KR20190107099A - Oxidative Desulfurization of Oil Fractions and Sulphone Management Using FCC - Google Patents

Abstract

Embodiments provide methods and apparatus for recovering components from hydrocarbon feedstocks. According to at least one embodiment, the method comprises feeding the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock is under conditions sufficient to selectively oxidize the sulfur and nitrogen compounds present in the hydrocarbon feedstock. Is oxidized in the presence of a catalyst; Separating the hydrocarbon, the oxidized sulfur compound, and the oxidized nitrogen compound by solvent extraction with a polar solvent; Collecting a residue stream comprising the oxidized sulfur compound and the oxidized nitrogen compound; Feeding the residue stream to a fluid catalytic cracking unit; And recycling the liquid product produced by the flow catalytic cracking unit to the oxidation reactor to selectively oxidize sulfur compounds in liquid product, wherein a portion of the liquid product is in light cycle oil and heavy cycle oil. At least one.

Description

Oxidative Desulfurization of Oil Fractions and Sulphone Management Using FCC

Embodiments relate to methods and apparatuses for recovering sulfur and nitrogen from hydrocarbon feedstocks. More specifically, embodiments relate to methods and apparatus for oxidative desulfurization and denitrogenation of hydrocarbon steam and subsequent disposal of the resulting oxidized sulfur and nitrogen compounds.

Crude oil is the world's major source of hydrocarbons used as fuel and petrochemical feedstock. At the same time, petroleum and petroleum-based products are also major sources of air and water pollution today. To address the increasing problems associated with pollution caused by petroleum and petroleum-based products, many countries have identified certain contaminants in fuels, such as petroleum products, in particular petroleum-refining operations and acceptable sulfur and nitrogen content in gasoline fuels There are strict regulations on acceptable concentrations. While the composition of natural petroleum or crude oil varies considerably, all crude oils contain some measurable amount of sulfur compounds and most crude oils also contain some measurable amount of nitrogen compounds. Crude oil may also contain oxygen, but the oxygen content of most crude oils is low. Generally, the sulfur concentration in crude oil is less than about 5 weight percent (wt%) and most crude oils have a sulfur concentration in the range of about 0.5 to about 1.5 wt%. The nitrogen concentration of most crude oils is generally less than 0.2 wt%, but can be as high as 1.6 wt%. In the United States, automotive gasoline fuels are regulated to have a maximum sulfur content of less than 10 parts per million weight sulfur.

Crude oil is refined in oil refineries to produce transport fuels and petrochemical feedstocks. Typically, the fuel for transportation is produced by treatment and blending of distilled fractions from crude oil to meet specific end use specifications. In general, most crude oils available today have high sulfur concentrations, so the distilled fractions typically require desulfurization to obtain products that meet various performance specifications, environmental criteria, or both.

Sulfur-containing organic compounds present in crude oil and the resulting refined fuel may be a major source of environmental pollution. Sulfur compounds are typically converted to sulfur oxides during the combustion process, which in turn can produce sulfur oxyacids and contribute to particulate emissions.

One method for reducing particulate emissions includes the addition of compounds with little or no carbon-to-carbon chemical bonds, such as various oxygenated fuel blending compounds, methanol and dimethylether, or both. However, most of these compounds may have high vapor pressures as indicated by their cetane number, or combinations thereof, and are almost insoluble in diesel fuel or have poor ignition quality.

Diesel fuels treated by chemical hydrogenation or hydrogenation to reduce their sulfur and aromatics content can have reduced fuel lubricity, which in turn is fuel pumps, injectors, and other moving parts that contact fuel at high pressures. May cause excessive wear.

For example, an intermediate distillate (ie, a distillate fraction nominally boiling in the range of about 180 to 370 ° C.) may be used as fuel, or alternatively for use in a compression ignition internal combustion engine (ie, diesel engine). It can be used as a blending component of a fuel. The middle distillate fraction typically contains about 1 to 3 wt% sulfur. Acceptable sulfur concentrations of the middle distillate fraction have been reduced from 3000 ppmw levels to 5 to 50 ppmw levels since 1993 in Europe and the United States.

In order to comply with ever more stringent regulations on ultra-low sulfur content fuels, refineries must produce fuels with lower sulfur levels at refinery gates so that they meet post-blending specifications.

Low pressure conventional hydrodesulfurization (HDS) processes can be used to remove the major portion of sulfur from petroleum distillates for blending refinery transportation fuels. However, these units are not efficient at removing sulfur from the compound under mild conditions when sulfur atoms are steric hindrance, such as in multi-ring aromatic sulfur compounds. This is especially true when the sulfur heteroatoms are hindered by two alkyl groups (eg 4,6-dimethyldibenzothiophene). Because of the difficulty of removal, the hindered dibenzothiophenes dominate at low sulfur levels such as 50 ppmw to 100 ppmw. Harsh operating conditions (eg, high hydrogen partial pressure, high temperature, or high catalyst volume) should be used to remove sulfur from these refractory sulfur compounds. Increasing the hydrogen partial pressure can only be achieved by increasing the recycle gas purity, or new grassroot units must be designed, which can be a very expensive option. The use of harsh operating conditions typically results in reduced yields, reduced catalyst life, and product quality degradation (eg, color), and therefore typically should be avoided.

However, conventional methods for oil upgrades typically have various limitations and disadvantages. For example, hydrogenation processes typically require large amounts of hydrogen gas to be supplied from external sources to achieve the desired level of upgrades and conversions. These methods may also undergo premature or rapid deactivation of the catalyst, as is typical during hydrotreatment of heavy feedstocks or under severe conditions, thus in turn leading to process unit downtime. Regeneration of the present catalyst or addition of a new catalyst is required. Thermal methods often involve the production of large quantities of coke as a by-product and limited ability to remove impurities such as sulfur and nitrogen. In addition, thermal methods require specialized equipment suitable for harsh conditions (eg, high temperature and high pressure), and require significant energy input, resulting in increased complexity and cost.

Thus, desulfurization, denitrification, or of hydrocarbons using low harsh conditions, which can provide a process for upgrading hydrocarbon feedstocks, in particular the recovery and disposal of available sulfur or nitrogen compounds, or both. There is a need to provide a process for both.

Embodiments provide methods and apparatus for upgrading hydrocarbon feedstocks that remove major portions of sulfur and nitrogen present and in turn utilize these compounds in related processes.

According to at least one embodiment, a method is provided for recovering a component from a hydrocarbon feedstock, the method comprising feeding the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock comprises a sulfur compound and a nitrogen compound; ; And under conditions sufficient to selectively oxidize the sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream comprising hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds. Contacting the hydrocarbon feedstock with an oxidant. The method further comprises separating the hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream, The mixed stream comprises the polar solvent, the oxidized sulfur compound, and the oxidized nitrogen compound, wherein the extracted hydrocarbon stream has a lower sulfur compound and nitrogen compound concentration than the hydrocarbon feedstock. The method comprises separating the mixed stream into a first recovered polar solvent stream and a first residue stream using a distillation column, wherein the first residue stream is oxidized sulfur compound and oxidized. Nitrogen compounds; And feeding the first residue stream to a fluid catalytic cracking unit, wherein the fluid catalyst cracking unit is operated to catalytically crack the oxidized sulfur and oxidized nitrogen. Catalyst and gas and liquid products are allowed and the recovery of hydrocarbons from the first residue stream is allowed. The method also includes recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize sulfur compounds in the liquid product, wherein the portion of the liquid product is light cycle oil and heavy cycle oil. At least one of the.

According to at least one embodiment, the method comprises feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped hydrocarbon stream; And recycling said first recovered polar solvent stream and second polar solvent stream to an extraction vessel for separation of said hydrocarbons, oxidized sulfur compounds, and said oxidized nitrogen compounds in said oxidized hydrocarbon stream. It includes more.

According to at least one embodiment, the method further comprises recycling a portion of the regenerated catalyst having a flow catalyst cracking feed stream to the flow catalyst cracking unit, wherein the recycle is from the first residue stream. Catalytically cracking the fluid catalyst cracking feed stream with a portion of the regenerated catalyst to recover hydrocarbons.

According to at least one embodiment, the oxidant is selected from the group consisting of air, oxygen, peroxides, hydrogen peroxide, ozone, nitrogen oxide compounds, and combinations thereof.

According to at least one embodiment, the step of contacting the hydrocarbon feedstock with an oxidant occurs in the presence of a catalyst comprising a metal oxide having the formula M _x O _y , where M is a group of IVB, VB, and VIB of the periodic table. Is an element selected from

According to at least one embodiment, the sulfur compound comprises sulfides, disulfides, mercaptans, thiophenes, benzothiophenes, dibenzothiophenes, alkyl derivatives of dibenzothiophenes, or combinations thereof. .

According to at least one embodiment, the oxidation reactor is maintained at a temperature of about 20 to about 350 ° C and a pressure of about 1 to about 10 bar.

According to at least one embodiment, the ratio of oxidant to sulfur compound present in the hydrocarbon feedstock is from about 4: 1 to about 10: 1.

According to at least one embodiment, the polar solvent has a Hildebrandt value of greater than about 19.

According to at least one embodiment, the polar solvent is acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and their It is selected from the group which consists of a combination.

According to at least one embodiment, the polar solvent is acetonitrile.

According to at least one embodiment, the polar solvent is methanol.

According to at least one embodiment, the solvent extraction is performed at a temperature of about 20 ° C to about 60 ° C and a pressure of about 1 to about 10 bar.

According to at least one embodiment, the method further comprises feeding the extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is an adsorbent suitable for removal of oxidized compounds present in the extracted hydrocarbon stream. Charged, the adsorption column produces a high purity hydrocarbon product stream and a second residue stream, the second residue stream comprising a portion of the oxidized compound.

According to at least one embodiment, the method further comprises feeding the second residue stream to the flow catalyst cracking unit.

According to at least one embodiment, the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays, silica-alumina, zeolites, and combinations thereof.

According to at least one embodiment, the adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, silica-alumina, zeolite, and activated carbon, the polymer being polysulfone , Polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, and combinations thereof.

According to at least one embodiment, feeding the first residue stream to the flow catalyst cracking unit comprises the steps of catalytically cracking a flow catalyst cracking feed stream to recover hydrocarbons from the first residue stream. Contacting the first residue stream in the presence with a flow catalyst cracking feed stream.

According to at least one embodiment, the flow catalyst cracking feed stream is vacuum gas oil, reduced crude oil, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker Gas oils, light cycle oils, heavy cycle oils, clarified slurry oils, or combinations thereof.

According to yet another embodiment, a method is provided for recovering a component from a hydrocarbon feedstock, the method comprising feeding the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock comprises a sulfur compound and a nitrogen compound; And under conditions sufficient to selectively oxidize the hydrocarbon feedstock to sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream comprising hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds. Contacting with an oxidant in the reactor. The method further includes separating the hydrocarbon, oxidized sulfur compound, and oxidized nitrogen compound in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream. Wherein the mixed stream comprises the polar solvent, the oxidized sulfur compound, and the oxidized nitrogen compound, wherein the extracted hydrocarbon stream has a lower sulfur compound and nitrogen compound concentration than the hydrocarbon feedstock. The method comprises using a distillation column to separate the mixed stream into a first recovered polar solvent stream and a first residue stream, wherein the first residue stream comprises the oxidized sulfur compound and the oxidized nitrogen compound. Includes; Supplying the first residue stream to a flow catalyst cracking unit, wherein the flow catalyst cracking unit produces regenerated catalyst and gas and liquid products and recovers hydrocarbons from the first residue stream. It is operated to catalytically crack the oxidized sulfur and oxidized nitrogen to allow. The method also includes contacting the first residue stream with a flow catalyst cracking feed stream in the presence of a catalyst that catalytically cracks the flow catalyst cracking feed stream to recover hydrocarbons from the first residue stream; And recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize a sulfur compound in the liquid product, wherein the portion of the liquid product comprises at least one of light cycle oil and heavy cycle oil. Include.

According to at least one embodiment, the method comprises feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped hydrocarbon stream; And recycling the first recovered polar solvent stream and the second polar solvent stream to an extraction vessel for separation of the hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds in the oxidized hydrocarbon stream. Wherein the oxidized sulfur compound and the oxidized nitrogen compound are in the oxidized hydrocarbon stream.

According to at least one embodiment, the method further comprises recycling a portion of regenerated catalyst having the flow catalyst cracking feed stream to the flow catalyst cracking unit, wherein the recycle is from the first residue stream. Catalytically cracking the flow catalyst cracking feed stream with a portion of the regenerated catalyst to recover the hydrocarbons.

According to at least one embodiment, the oxidant is selected from the group consisting of air, oxygen, peroxides, hydrogen peroxide, ozone, nitrogen oxide compounds, and combinations thereof.

According to at least one embodiment, the step of contacting said hydrocarbon feedstock with an oxidant occurs in the presence of a catalyst comprising a metal oxide having the formula M _x O _y , where M is Group IVB, VB, and VIB of the periodic table. Is selected from.

According to at least one embodiment, the sulfur compound comprises sulfides, disulfides, mercaptans, thiophenes, benzothiophenes, dibenzothiophenes, alkyl derivatives of dibenzothiophenes, or combinations thereof.

According to at least one embodiment, the oxidation reactor is maintained at a temperature of about 20 to about 350 ° C and a pressure of about 1 to about 10 bar.

According to at least one embodiment, the ratio of oxidant to sulfur compound present in the hydrocarbon feedstock is from about 4: 1 to about 10: 1.

According to at least one embodiment, the polar solvent has a Hildebrandt value of greater than about 19.

According to at least one embodiment, the polar solvent is acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and their It is selected from the group which consists of a combination.

According to at least one embodiment, the polar solvent is acetonitrile.

According to at least one embodiment, the polar solvent is methanol.

According to at least one embodiment, the solvent extraction is performed at a temperature of about 20 ° C to about 60 ° C and a pressure of about 1 bar to about 10 bar.

According to at least one embodiment, the method further comprises feeding the extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is charged with an adsorbent suitable for removal of oxidized compounds present in the extracted hydrocarbon stream. And the adsorption column produces a high purity hydrocarbon product stream and a second residue stream, the second residue stream comprising a portion of the oxidized compound.

According to at least one embodiment, the method further comprises feeding the second residue stream to the flow catalyst cracking unit.

According to at least one embodiment, the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays, silica-alumina, zeolites, and combinations thereof.

According to at least one embodiment, the adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, and activated carbon, the polymer being polysulfone, polyacrylonitrile, Polystyrene, polyester terephthalate, polyurethane, silica-alumina, zeolite, and combinations thereof.

According to at least one embodiment, the first residue oil stream and the flowing catalyst cracking feed stream are present in a weight ratio of the catalyst to the first residue oil stream and the flowing catalyst cracking feed stream in the range of about 1 to about 15.

According to at least one embodiment, the flow catalyst cracking feed stream comprises vacuum gas oil, reduced crude oil, demetalized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, Light cycle oil, heavy cycle oil, clarified slurry oil, or combinations thereof.

According to at least one embodiment, contacting said first residue stream with a flow catalyst cracking feed stream in the presence of a catalyst occurs in a temperature range of about 300 ° C to about 650 ° C.

According to at least one embodiment, contacting said first residue stream with a flowing catalyst cracking feed stream in the presence of a catalyst occurs within a residence time of about 0.1 seconds to about 10 minutes.

According to at least one embodiment, the method comprises separating the lower boiling component and catalyst particles from the first residue stream and the flowing catalyst cracking feed stream; And regenerating at least a portion of the catalyst particles.

According to at least one embodiment, regenerating at least a portion of the catalyst particles comprises fluidizing the portion of the catalyst particles under conditions to produce a gaseous product and a liquid product comprising a regenerated catalyst and carbon monoxide and carbon dioxide. contacting with a water-free oxygen-containing gas in a fluidized bed.

In a manner in which the features and advantages of the disclosed methods and systems, as well as others to be apparent, may be understood in more detail, more detailed descriptions of the methods and systems briefly summarized above are provided in the accompanying drawings which form a part hereof. It may be made with reference to the embodiments. However, the drawings show only various embodiments and therefore should not be considered as limiting the scope as this may include other effective embodiments. Like numbers refer to like elements throughout, and when used, prime notation refers to similar elements in alternative embodiments or locations.
1 provides a schematic diagram of one embodiment of a method of upgrading a hydrocarbon feedstock.
2 provides a schematic of one embodiment of a method of upgrading a hydrocarbon feedstock.
3 provides a schematic diagram of one embodiment of a method of upgrading a hydrocarbon feedstock.
4 provides a schematic of the process described in the Examples.

Although the following detailed description contains many specific details for the purpose of illustration, it is understood that one of ordinary skill in the art appreciates that many examples, modifications, and changes to the following details are within the scope and spirit. . Accordingly, the various embodiments described and provided in the accompanying drawings are described without loss of generality and without imposing a limitation on the claims.

Embodiments solve known problems associated with conventional methods of upgrading and recovering compounds from hydrocarbon feedstocks, in particular desulfurization, denitrogenation, or both, and subsequent removal and recovery of available hydrocarbons. do. According to at least one embodiment, a method is provided for the removal of sulfur and nitrogen from a hydrocarbon feedstock and for the use of oxidized sulfur species and oxidized nitrogen species in an FCC process.

As used, the term “upgraded” or “upgraded” in relation to petroleum or hydrocarbon is lighter than the original petroleum or hydrocarbon feedstock (ie, has fewer carbon atoms, such as methane, ethane, and propane), It means a petroleum or hydrocarbon product having at least one of high API specific gravity, high intermediate distillate yield, low sulfur content, low nitrogen content, or low metal content.

1 provides one embodiment for the recovery of hydrocarbons. The hydrocarbon recovery system 100 includes an oxidation reactor 104, an extraction vessel 112, a solvent regeneration column 116, a stripper 120, and an FCC unit 130.

According to at least one embodiment, a method is provided for the recovery of components from a hydrocarbon feedstock, in particular from a hydrocarbon feedstock comprising sulfur- and nitrogen-containing compounds. The method includes feeding a hydrocarbon feedstock 102 to an oxidation reactor 104 in which the hydrocarbon feedstock is contacted with an oxidant and a catalyst. The oxidant may be supplied to the oxidation reactor 104 via the oxidant supply line 106 and fresh catalyst may be supplied to the reactor via the catalyst supply line 108.

According to at least one embodiment, the hydrocarbon feedstock 102 may be any petroleum hydrocarbon, and may include various impurities such as compounds including elemental sulfur, sulfur or nitrogen, or both. In certain embodiments, hydrocarbon feedstock 102 may be a diesel oil having a boiling point of about 150 ° C to about 400 ° C. Alternatively, the hydrocarbon feedstock 102 may have a boiling point up to about 450 ° C, alternatively up to about 500 ° C. Alternatively, the hydrocarbon feedstock 102 may have a boiling point of about 100 ° C to about 500 ° C. Optionally, the hydrocarbon feedstock 102 may have a boiling point of up to about 600 ° C., alternatively up to about 700 ° C., or in certain embodiments, greater than about 700 ° C. According to at least one embodiment, the hydrocarbon is in a solid state after distillation called residue. In certain embodiments, hydrocarbon feedstock 102 may comprise heavy hydrocarbons. As used, heavy hydrocarbons means hydrocarbons having a boiling point above about 360 ° C. and may include aromatic hydrocarbons as well as alkanes and alkenes. Generally, in certain embodiments, hydrocarbon feedstock 102 is recovered from full range crude oil, topped crude oil, product stream from oil refinery, product stream from refinery steam cracking process, liquefied coal, oil or tar sands. Liquid products, bitumen, oil shale, asphaltenes, hydrocarbon fractions such as diesel and vacuum gas oils boiling within the range of about 180 to about 370 ° C. and about 370 to about 520 ° C., respectively, and mixtures thereof Can be.

Sulfur compounds present in hydrocarbon feedstock 102 include sulfides, disulfides, and mercaptans, as well as alkyl dibenzos such as thiophene, benzothiophene, dibenzothiophene, and 4,6-dimethyl-dibenzothiophene. Thiophene. Aromatic compounds are typically rich in higher boiling fractions than those found in lower boiling fractions.

The nitrogen-containing compound present in the hydrocarbon feedstock 102 may include a compound having the following structure:

It should be noted that sulfur oxidation is a limited target reaction in which nitrogen oxidation occurs during the reaction. Two types can be considered basic and neutral nitrogen.

According to at least one embodiment, the oxidation reactor 104 may be operated at mild conditions. More specifically, in certain embodiments, the oxidation reactor 104 may be maintained at a temperature of about 30 ° C to about 350 ° C, or alternatively, about 45 ° C to about 60 ° C. The operating pressure of the oxidation reactor 104 is about 1 bar to about 30 bar, alternatively about 1 bar to about 15 bar, alternatively about 1 bar to about 10 bar, or alternatively about 2 bar to about 3 bar. Can be. The residence time of the hydrocarbon feedstock in the oxidation reactor 104 is from about 1 minute to about 120 minutes, alternatively from about 15 minutes to about 90 minutes, alternatively from about 5 minutes to about 90 minutes, alternatively from about 5 minutes to About 30 minutes, alternatively about 30 minutes to about 60 minutes, with a sufficient amount of time for the oxidation of any sulfur or nitrogen compounds present in the hydrocarbon feedstock. According to at least one embodiment, the residence time of the hydrocarbon feedstock in the oxidation reactor 104 is from about 15 minutes to about 90 minutes.

According to at least one embodiment, the oxidation reactor 104 is suitably configured to ensure sufficient contact between the hydrocarbon feedstock 102 and the oxidant in the presence of a catalyst for the oxidation of sulfur- and nitrogen-containing compounds. May be any reactor). Sulfur and nitrogen compounds present in the hydrocarbon feedstock 102 are oxidized to sulfones, sulfoxides, and oxidized nitrogen compounds that can subsequently be removed by extraction or adsorption in the oxidation reactor 104. Various types of reactors can be used. For example, the reactor can be a batch reactor, a fixed bed reactor, an ebbulated bed reactor, a lifted reactor, a fluidized bed reactor, a slurry bed reactor, or a combination thereof. Other types of suitable reactors that may be used will be apparent to those skilled in the art and should be considered within the scope of various embodiments. Examples of suitable oxidized nitrogen compounds may include pyridine-based compounds and pyrrole-based compounds. The nitrogen atom is not directly oxidized and it is thought that what is actually oxidized is the carbon atom (s) next to nitrogen. Some examples of oxidized nitrogen compounds may include the following compounds:

Or combinations thereof.

According to at least one embodiment, the oxidant is fed to the oxidation reactor 104 via an oxidant feed stream 106. Suitable oxidizing agents may include air, oxygen, hydrogen peroxide, organic peroxides, hydroperoxides, organic peracids, peroxides, oxides of nitrogen, ozone and the like. The peroxide can be selected from hydrogen peroxide and the like. Hydroperoxide may be selected from t-butyl hydroperoxide and the like. The organic peracid can be selected from acetic acid peroxide and the like.

According to at least one embodiment, the molar ratio of oxidant to sulfur present in the hydrocarbon feedstock is from about 1: 1 to about 50: 1, preferably from about 2: 1 to about 20: 1, more preferably about 4: 1 To about 10: 1. According to at least one embodiment, the molar feed ratio of oxidant to sulfur may range from about 1: 1 to about 30: 1.

According to at least one embodiment, the molar feed ratio of oxidant to nitrogen compound may be about 4: 1 to about 10: 1. According to at least one embodiment, the feedstock is sulfur, such as, for example, an intermediate refinery stream such as South American crude oil, African crude oil, Russian crude oil, Chinese crude oil, or coker, thermal cracking, pyrolysis, gas oil, FCC cycle oil and the like. It may contain more nitrogen compounds.

According to at least one embodiment, the catalyst may be supplied to the oxidation reactor 104 via a catalyst feed stream 108. The catalyst can be a homogeneous catalyst. The catalyst may comprise at least one metal having the formula M _x O _y , where M is a metal selected from group IVB, VB, or VIB of the periodic table. The metal may include titanium, vanadium, chromium, molybdenum, and tungsten. Molybdenum and tungsten are two particularly effective catalysts that can be used in various embodiments. In certain embodiments, the catalyst used may be rejected from the system having an aqueous phase (eg, when using an aqueous oxidant) after the oxidation vessel.

According to at least one embodiment, the ratio of catalyst to oil is from about 0.1 wt% to about 10 wt%, preferably from about 0.5 wt% to about 5 wt%. In certain embodiments, the ratio is about 0.5 wt% to about 2.5 wt%. Alternatively, the ratio is about 2.5 wt% to about 5 wt%. Other suitable weight ratios of catalyst to oil will be apparent to those skilled in the art and should be considered to be within the scope of various embodiments.

The catalyst present in the oxidation reactor 104 can increase the oxidation rate of various sulfur- and nitrogen-containing compounds in the hydrocarbon feedstock 102, and can reduce the amount of oxidant required for the oxidation reaction, or both. have. In certain embodiments, the catalyst may be selective for the oxidation of sulfur species. In other embodiments, the catalyst may be selective for the oxidation of nitrogen species.

Oxidation reactor 104 produces an oxidized hydrocarbon stream 110 that may include hydrocarbons and oxidized sulfur- and oxidized nitrogen-containing species. Oxidized hydrocarbon stream 110 is fed to extraction vessel 112 in contact with oxidized hydrocarbon stream and oxidized sulfur- and oxidized nitrogen-containing species extraction solvent stream 137. Extraction solvent 137 may be a polar solvent, and in certain embodiments, may have a Hildebrandt solubility value of greater than about 19. In certain embodiments, when selecting specific polar solvents for use in extracting oxidized sulfur- and oxidized nitrogen-containing species, the selection is dependent on solvent density, boiling point, freezing point, viscosity, and surface tension, as non-limiting examples. Can be based. Suitable polar solvents for use in the extraction step are acetone (Hildebrand value of 19.7), carbon disulfide (20.5), pyridine (21.7), dimethyl sulfoxide (DMSO) (26.4), n-propanol (24.9), ethanol (26.2) , n-butyl alcohol (28.7), propylene glycol (30.7), ethylene glycol (34.9), dimethylformamide (DMF) (24.7), acetonitrile (30), methanol (29.7), and similar compositions or similar physical and chemical And compositions having properties. In certain embodiments, acetonitrile and methanol are preferred because of their low cost, volatility, and polarity. Methanol is a particularly suitable solvent for use in the embodiments. In certain embodiments, the solvent comprising sulfur, nitrogen, or phosphorus preferably has a relatively high volatility to ensure proper stripping of the solvent from the hydrocarbon feedstock.

According to at least one embodiment, the extraction solvent is non-acidic. The use of acid is typically avoided due to acid corrosiveness and the requirement that all equipment be designed specifically for corrosive environments. In addition, acids such as acetic acid can present difficulties in separation due to the formation of emulsions.

According to at least one embodiment, the extraction vessel 112 may be operated at about 20 ° C to about 60 ° C, preferably about 25 ° C to about 45 ° C, more preferably about 25 ° C to about 35 ° C. Extraction vessel 112 may operate at about 1 to about 10 bar, preferably about 1 to about 5 bar, more preferably about 1 to about 2 bar. In certain embodiments, extraction vessel 112 operates at a pressure of about 2 to about 6 bar.

According to at least one embodiment, the ratio of extraction vessel to hydrocarbon feedstock can be from about 1: 3 to about 3: 1, preferably from about 1: 2 to about 2: 1, more preferably about 1: 1. have. The contact time between the extraction solvent and the oxidized hydrocarbon stream 110 may be about 1 second to about 60 minutes, preferably about 1 second to about 10 minutes. In certain preferred embodiments, the contact time between the extraction solvent and the oxidized hydrocarbon stream 110 is less than about 15 minutes. In certain embodiments, extraction vessel 112 includes various means to increase the contact time between the extraction solvent and the oxidized sulfur- and oxidized nitrogen-containing hydrocarbon stream 110 or to increase the degree of mixing of the two solvents. can do. The mixing means may comprise a mechanical stirrer or agitator, a tray, or similar means.

According to at least one embodiment, the extraction vessel 112 comprises an extraction solvent, an oxidized species (eg, oxidized sulfur and nitrogen species originally present in the hydrocarbon feedstock 102), and trace amounts of hydrocarbon feedstock ( 102, and extracted hydrocarbon stream 118, which may include a hydrocarbon feedstock having a reduced sulfur and low nitrogen content relative to hydrocarbon feedstock 102.

The mixed stream 114 may be recovered from which the extraction solvent may be recovered as the first recovered solvent stream 117 and may be separated from the first residue stream 123 comprising oxidized sulfur and oxidized nitrogen compounds. The regeneration column 116 is supplied. Optionally, the mixed stream 114 may be separated into a recovered hydrocarbon stream 124 which may include hydrocarbons present in the mixed stream 114 from the hydrocarbon feedstock 102 in the solvent regeneration column 116. Can be. The solvent regeneration column 116 may be a distillation column arranged to separate the mixed stream 114 into a first recovered solvent stream 117, a first residue stream 123, and a recovered hydrocarbon stream 124. have.

The extracted hydrocarbon stream 118 may be fed to stripper 120, which may be a distillation column or similar vessel designed to separate the hydrocarbon product stream from the residual extraction solvent. In certain embodiments, a portion of the mixed stream 114 may be supplied to the stripper 120 via line 122 and optionally combined with the extracted hydrocarbon stream 118. In certain embodiments, solvent regeneration column 116 is a mixed stream 114 in which recovered hydrocarbon stream 124 may be fed to stripper 120 via selectively extracted hydrocarbon stream 118 or line 122. A recovered hydrocarbon stream 124 may be produced which may be fed to the stripper 120 which may be in contact with a portion of the.

The stripper 120 separates the various streams fed thereto into a stripped oil stream 126 having a reduced sulfur and nitrogen content relative to the hydrocarbon feedstock, and a second recovered solvent stream 128.

In certain embodiments, the first recovered solvent stream 117 may be combined with the second recovered solvent stream 128 and may be recycled to the extraction vessel 112. Optionally, make-up solvent stream 132, which may include fresh solvent, may be combined with first recovered solvent stream 117, second recovered solvent stream 128, or both, and the extraction vessel. May be supplied to 112.

The first residue stream 123, which includes oxidized compounds such as oxidized sulfur and nitrogen compounds, and which may include low concentrations of hydrocarbonaceous material, is the FCC unit in which the liquid product (including hydrocarbons) 136 is recovered. 130 may be supplied. According to at least one embodiment, the oxidized sulfur compound, such as sulfone, and the oxidized nitrogen compound are about 343 ° C. to about 524 ° C .; Or alternatively, it is embedded in a heavy hydrocarbon, such as a hydrocarbon having a boiling point in the range of about 360 ° C to about 550 ° C.

According to various embodiments in which the first residue stream 123 is sent to the FCC unit 130, the first residue stream 123 is in the presence of a catalyst for catalytic cracking the FCC feed stream 134. The liquid product 136 is recovered from the first residue stream 123 in contact with the feed stream 134. According to at least one embodiment, the catalyst may comprise hot solid zeolite active catalyst particles. According to at least one embodiment, the weight ratio of catalyst to FCC feed stream 134 is in the range of about 1 to 15 and forms a suspension at a pressure in the range of about 1 barg (gauge pressure) to about 200 barg. Other suitable ratios and operating conditions of catalyst to FCC feed stream 134 will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

According to at least one embodiment, the suspension then catalytically cracks the FCC feed stream 134 while avoiding thermal conversion of the feed stream 134 and providing a hydrocarbon residence time of about 0.1 seconds to about 10 minutes. And through a riser reaction zone or downer at a temperature (not shown) of from about 300 ° C to less than about 650 ° C.

According to at least one embodiment, the lower boiling component and the solid catalyst particles are then separated and recovered. At least a portion of the separated solid catalyst particles are oxygen-free without water in a fluidized bed operated at conditions for producing a regenerated catalyst 140 and a gas product 138 and a liquid product 136 consisting essentially of carbon monoxide and carbon dioxide. Is regenerated with gas. At least a portion of the regenerated catalyst is returned and combined with the FCC feed stream (not shown).

According to at least one embodiment, the type of components contained in the FCC feed stream 134 may vary. The FCC feed stream 134 is a vacuum gas oil, reduced crude oil, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, as non-limiting examples. , And FCC heavy products such as LCO, HCO, and CSO. Table 1 shows general yields from FCC units. As another example, the FCC feedstock 134 sent to the FCC unit 130 may have the characteristics shown in Table 2.

yield product Wt% Fuel gas 4.5 Liquefied Petroleum Gas (LPG) 12.2 Light gasoline 36.4 Heavy gasoline 11.5 Light Cycle Oils (LCO) 9.8 Purified Slurry Oil (CSO) 21.3 cokes 4.3 system 100.0

API 23.7 Sulfur (wt%) 2.40 Distillation range Initial boiling point (IBP) 507 ° C 10% 669 ° C 30% 754 ° C 50% 819 ° C 70% 874 ° C 90% 941 ° C Evaporation Point (EP) 970 ° C

Various types of catalysts may be used in the FCC unit 130. According to at least one embodiment, the FCC catalyst particles have a metal selected from IVB, VI, VII, VIIIB, IB, IIB, or a compound thereof, and catalyst particles of nominal diameter less than 200 microns. Zeolite matrix. Other suitable types of catalysts that may be used in FCC unit 130 will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

According to at least one embodiment, the operating parameters for the FCC unit 130 may vary depending on the type of FCC feed stream 134 sent to the FCC unit 130. FCC unit 130 is performed at a temperature range of about 400 ° C to about 850 ° C. According to another embodiment, the FCC unit 130 may be operated at a temperature in the range of about 1 barg to about 200 barg. According to another embodiment, the FCC unit 130 may be operated for a residence time ranging from about 0.1 seconds to about 3600 seconds. Other suitable operating parameters for the FCC unit 130 will be apparent to those skilled in the art and should be considered within the scope of various embodiments. The nature of the components recovered from the FCC unit 130 will vary based on the composition of the hydrocarbon FCC feed stream 134.

2 provides one embodiment for the recovery of hydrocarbons from a feed stream. The hydrocarbon recovery system 200 includes an oxidation reactor 104, an extraction vessel 112, a solvent regeneration column 116, a stripper 120, and an FCC unit 130.

As described above in connection with the embodiment shown in FIG. 1, a first residue stream 123 comprising oxidized compounds, such as oxidized sulfur and nitrogen compounds, which may include low concentrations of hydrocarbonaceous materials, Liquid product (including hydrocarbons) 136 may be supplied to the FCC unit 130 which is recovered. According to at least one embodiment, the sulfone and excess oxidized sulfur compound, and the oxidized nitrogen compound are about 343 ° C. to about 524 ° C .; Or alternatively, embedded in a heavy hydrocarbon, such as a hydrocarbon having a boiling point within the range of about 360 ° C. to about 550 ° C.

According to various embodiments, as shown in FIG. 2 where the first residue stream 123 is sent to the FCC unit 130, the first residue stream 123 catalyzes the FCC feed stream 134. The liquid product 136 is recovered from the first residue stream 123 in contact with the FCC feed stream in the presence of a cracking catalyst. According to at least one embodiment, the catalyst may comprise hot solid zeolite active catalyst particles. According to at least one embodiment, the weight ratio of catalyst to FCC feed stream 134 is in the range of about 1 to about 15 and forms a suspension at a pressure in the range of about 1 barg to about 200 barg. Other suitable ratios and operating conditions of catalyst and FCC feed stream 134 will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

According to at least one embodiment, the suspension is then passed through a riser reaction zone or downer at a temperature of about 300 ° C. to less than about 650 ° C. (not shown) to avoid heat conversion of the feed stream 134 and Catalyst feed stream 134 is catalytically cracked while providing a hydrocarbon residence time of 0.1 seconds to about 10 minutes.

According to at least one embodiment, the lower boiling component and the solid catalyst particles are then separated and recovered. At least a portion of the separated solid catalyst particles are oxygen-free without water in a fluidized bed operated at conditions for producing a regenerated catalyst 140 and a gas product 138 and a liquid product 136 consisting essentially of carbon monoxide and carbon dioxide. Is regenerated with gas. At least a portion of the regenerated catalyst is returned and combined with the FCC feed stream 134 (not shown).

As further shown in FIG. 2, in certain embodiments, at least a portion of the liquid product 136 is recycled back to the oxidation reactor 104 via line 202, where the liquid product 136 is a light cycle oil and It contains at least one of heavy cycle oils. The liquid product 136 is sulfur rich and may be desulfurized in the oxidative desulfurization process occurring in the oxidation reactor 104.

Various types of catalysts may be used in the FCC unit 130. According to at least one embodiment, the FCC catalyst particles comprise a zeolite matrix having a metal or compound thereof selected from Groups IVB, VI, VII, VIIIB, IB, IIB, and catalyst particles of nominal diameter less than 200 microns. Other suitable types of catalysts that may be used in FCC unit 130 will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

3 provides one embodiment for the recovery of hydrocarbons from a feedstock. The hydrocarbon recovery system 300 includes an oxidation reactor 104, an extraction vessel 112, a solvent regeneration column 116, a stripper 120, an FCC unit 130, and an adsorption column 302.

As shown in FIG. 3, in certain embodiments, the stripped oil stream 126 can be fed to an adsorption column 302, where the stripped oil stream 126 is a sulfur-containing compound, an oxidized sulfur compound. And one or more sorbents designed to remove one or more various impurities such as nitrogen-containing compounds, oxidized nitrogen compounds, and metals remaining in the hydrocarbon product stream after the oxidation and solvent extraction steps.

According to various embodiments, the one or more adsorbents include activated carbon; Silica gel; Alumina; Natural clay; Silica-alumina; Zeolites; And new, used, recycled or rejuvenated catalysts having affinity for oxidized sulfur and nitrogen compounds and other inorganic adsorbents. In certain embodiments, the adsorbent may include polar polymers applied to or coating various high surface area support materials such as silica gel, alumina, and activated carbon. Examples of polar polymers for use in coating various support materials include polysulfones, polyacrylonitrile, polystyrenes, polyester terephthalates, polyurethanes, other similar polymer species that show affinity for oxidized sulfur species, and their Combinations.

According to at least one embodiment, the adsorption column 302 may be operated at a temperature of about 20 ° C to about 60 ° C, preferably about 25 ° C to about 40 ° C, more preferably about 25 ° C to about 35 ° C. have. In certain embodiments, the adsorption column may be operated at a temperature of about 10 ° C to about 40 ° C. In certain embodiments, the adsorption column can be operated at a temperature above about 20 ° C, or alternatively at a temperature below about 60 ° C. Adsorption column 302 may be operated at a pressure of up to about 15 bar, preferably up to about 10 bar, more preferably from about 1 to about 2 bar. In certain embodiments, adsorption column 302 may be operated at a pressure of about 2 to about 5 bar. According to at least one embodiment, the adsorption column may be operated at a temperature of about 25 ° C to about 35 ° C and a pressure of about 1 to about 2 bar. The weight ratio of stripped oil stream to adsorbent can range from about 1: 1 to about 20: 1; Or in the alternative, about 10: 1.

The adsorption column 302 is used to extract the extracted hydrocarbon product stream 304 having a very low sulfur content (eg less than 15 ppmw sulfur) and a very low nitrogen content (eg less than 10 ppmw nitrogen), And a second residue stream 306. The second residue stream 306 comprises oxidized sulfur- and oxidized nitrogen-containing compounds, can optionally be combined with the first residue stream 123 and supplied to the FCC unit 130 and described above. Can be treated as one. The adsorbent may be regenerated by contacting the used adsorbent with a polar solvent such as methanol or acetonitrile to desorb the adsorbed oxidized compound from the adsorbent. In certain embodiments, heat, stripping gas, or both may also be used to allow removal of the adsorbed compound. Other suitable methods for removing adsorbed compounds will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

Example

4 shows a process flow diagram for oxidative desulfurization (oxidation and extraction steps) and FCC units. Vessels 10, 16, 20, and 25 are oxidation, extraction, solvent recovery, and FCC vessels, respectively.

Hydrotreated straight run diesel containing 500 ppmw of elemental sulfur, 0.28 wt% organic sulfur and a density of 0.85 kilograms (Kg / l) per liter was oxidatively desulfurized. The reaction conditions were as follows:

Hydrogen peroxide: sulfur molar ratio: 4: 1

Catalyst: Molybdenum Mo (VI)

Reaction time: 30 minutes

Temperature: 80 ℃

Pressure: 1 kilogram per square centimeter (kg / cm ² )

Extraction step substance resin Stream # 15 17 18 19 21 22 Component / Stream Oxidized diesel Methanol in Methanol sulfone out Extracted oil Methanol Sulfone Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h water Methanol 266,931 266,724 207 266,724 diesel 171,915 171,915 171,915 Organic sulfur 517 512 5 507 Acetic acid Na ₂ WO ₄ (kg) 5 5 Kgh total 172,437 266,931 267,241 172,127 438,639 507

According to at least one embodiment, the FCC unit was operated at 518 ° C. with a catalyst to oil ratio of 5 resulting in 67 wt% conversion of the feedstock. In addition to the sulfones produced in the oxidation step, direct vacuum gas oils derived from Arabian crude oil were used as blending components. The feedstock contained 2.65 wt% sulfur and 0.13 wt% fine carbon residue. The median and 95 wt% boiling points for the feedstock were 408 ° C and 455 ° C, respectively.

FCC conversion of feedstock was calculated using the following equation (1):

Conversion = Dry Gas + LPG + Gasoline + Coke (One)

The catalyst used was an equilibrium catalyst and was used without any treatment. The catalyst has a surface area of 131 square meters (m ² / g) per gram and a pore volume of 0.1878 cubic centimeters (cm ³ / g) per gram. Nickel and vanadium contents are 96 and 407 ppmw, respectively. The FCC process produced coke deposited on the following product and catalyst.

The coke produced in the FCC process was 2.5 wt% of the treated feedstock. Product yields are given in Table 5:

FCC stage substance resin Stream # 22 23 24 26 27 28 29 Stream name Sulfone Vacuum gas oil FCC feedstock gas Gasoline LCO HCO Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h Stream type Feed Feed Feed oil oil oil oil Prize oil oil oil oil oil oil oil Sulfur, wt% 0.05 2.67 2.5 0.27 2.65 4.70 Vacuum gas oil 10,000 10,000 Total gas 771 Sulfone 771 1,822 Gasoline 4,957 LCO 1,707 HCO 1,764 system 771 10,000 10,771 1,822 4,957 1,707 1,764

According to one embodiment, the LCO is recycled to the oxidation stage because the LCO boils in the same distillation range as the diesel used in the example. The FCC unit is designed to process 10,000 Kg / h vacuum gas oil for illustrative purposes. The FCC unit may be designed in any capacity, and design changes may be made to the oxidation / extraction step to handle additional feeds as would be apparent to those skilled in the art and should be considered within the scope of various embodiments. Process steps, oxidation, extraction and FCC are shown in Tables 6-8, respectively.

Oxidation Step Material Resin Stream # 11 12 13 14 Component / Stream diesel H ₂ O ₂ catalyst Catalytic waste Kg / h Kg / h Kg / h Kg / h water 0 983 0 8,837 Methanol 0 0 0 0 diesel 173,622 0 0 0 Organic sulfur 788 0 0 2 Acetic acid 0 0 10,747 10,747 H ₂ O ₂ 295 0 0 Na ₂ WO ₄ (kg) 0 0 4,841 4,793 Kgh total 174,410 1,278 15,588 24,379

Extraction step substance resin Stream # 15 17 18 19 21 22 Component / Stream Oxidized diesel Methanol in Methanol sulfone out
Extracted oil Methanol Sulfone Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h water 0 0 0 0 0 0 Methanol 0 269,990 269,781 210 269,781 0 diesel 173,622 0 0 173,622 173,622 0 Organic sulfur 787 0 779 8 0 771 Acetic acid 0 0 0 0 0 0 Na ₂ WO ₄ (kg) 5 0 5 0 0 0 Kgh total 174,414 269,990 270,565 173,839 443,403 771

FCC stage substance resin Stream # 22 23 24 26 27 28 29 Stream name Sulfone Vacuum gas oil FCC feedstock gas Gasoline LCO HCO Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h Kg / h Stream type Feed Feed Feed oil oil oil oil Prize oil oil oil oil oil oil oil Sulfur, wt% 0.05 2.67 2.5 0.27 2.65 4.70 Vacuum gas oil 10000 10000 Sulfone 771 771 Total gas 1822 Gasoline 4957 LCO 1707 HCO 1764 system 771 10000 10771 1822 4957 1707 1764

The methods and systems described herein are believed to increase the amount of aromatic sulfur, nitrogen compounds, and liquid hydrocarbons from aromatic streams by linking oxidative desulfurization and denitrification processes with fluid catalytic cracking units. It is also believed that there is no efficient way for the disposal of oxidation reaction by-products (ie oxidized sulfur and nitrogen compounds). Embodiments provide a method for discarding oxidized sulfur and nitrogen compounds without the need for discarding the compounds.

While various embodiments are described in detail, it should be understood that various modifications, substitutions, and alterations can be made herein without departing from the spirit and scope. Accordingly, the scope should be determined by the following claims and their appropriate legal equivalents.

The singular forms “a, an” and “the” include plural referents unless the context clearly dictates otherwise.

“Optional” or “optionally” means that an event or situation described subsequently may or may not occur. The description includes when an event or situation occurs and when it does not occur.

The range can be expressed from about one particular value to about another particular value. Where such ranges are expressed, it is to be understood that another embodiment is from one particular value or up to another particular value, with all combinations within that range.

Claims (42)

A method for recovering components from a hydrocarbon feedstock, the method comprising:
Feeding said hydrocarbon feedstock to an oxidation reactor, said hydrocarbon feedstock comprising a sulfur compound and a nitrogen compound;
In the oxidation reactor under conditions sufficient to selectively oxidize the sulfur and nitrogen compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream comprising hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds. Contacting the hydrocarbon feedstock with an oxidant;
Separating the hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream being the polar A solvent, an oxidized sulfur compound, and an oxidized nitrogen compound, wherein the extracted hydrocarbon stream has a lower sulfur compound and nitrogen compound concentration than the hydrocarbon feedstock;
Separating the mixed stream into a first recovered polar solvent stream and a first residue stream using a distillation column, the first residue stream comprising the oxidized sulfur compound and the oxidized nitrogen compound To;
Feeding the first residue stream to a fluid catalytic cracking unit, the fluid catalyst cracking unit being operated to catalytically crack the oxidized sulfur and oxidized nitrogen; Produce a liquid product and allow recovery of hydrocarbons from the first residue stream; And
Recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize sulfur compounds in the liquid product, wherein the portion of the liquid product comprises at least one of light cycle oil and heavy cycle oil. A method for recovering a component from a hydrocarbon feedstock comprising. The method according to claim 1,
The method includes feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped hydrocarbon stream; And
Recycling said first recovered polar solvent stream and second polar solvent stream to an extraction vessel for separation of said hydrocarbons, oxidized sulfur compounds, and said oxidized nitrogen compounds in said oxidized hydrocarbon stream. A method for recovering components from a hydrocarbon feedstock that is further characterized. The method according to claim 1 or 2,
The method is:
Recycled a portion of the regenerated catalyst having a fluidized catalyst cracking feed stream to the fluidized catalyst cracking unit, wherein the recycle is performed to recover the hydrocarbon from the first resid stream. A process for recovering components from a hydrocarbon feedstock further characterized by catalytic cracking a cracking feed stream with a portion of the regenerated catalyst. The method according to any one of claims 1 to 3,
Wherein the oxidant recovers components from a hydrocarbon feedstock selected from the group consisting of air, oxygen, peroxide, hydrogen peroxide, ozone, nitrogen oxide compounds, and combinations thereof. The method according to any one of claims 1 to 4,
Contacting the hydrocarbon feedstock with an oxidant occurs in the presence of a catalyst comprising a metal oxide having the formula M _x O _y , where M is a hydrocarbon feedstock that is an element selected from Groups IVB, VB, and VIB of the periodic table. Recovering the components from the composition. The method according to any one of claims 1 to 5,
The sulfur compound recovers components from a hydrocarbon feedstock comprising sulfides, disulfides, mercaptans, thiophenes, alkyl derivatives of benzothiophenes, dibenzothiophenes, dibenzothiophenes, or combinations thereof. Way. The method according to any one of claims 1 to 6,
The oxidation reactor recovers components from a hydrocarbon feedstock maintained at a temperature of about 20 to about 350 ° C. and a pressure of about 1 to about 10 bar. The method according to any one of claims 1 to 7,
Wherein the ratio of oxidant to sulfur compound present in the hydrocarbon feedstock is from about 4: 1 to about 10: 1. The method according to any one of claims 1 to 8,
Wherein said polar solvent recovers components from a hydrocarbon feedstock having a Hildebrandt value of greater than about 19. The method according to any one of claims 1 to 9,
The polar solvent is a hydrocarbon selected from the group consisting of acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and combinations thereof A method for recovering the components from the feedstock. The method according to any one of claims 1 to 10,
Wherein said polar solvent is acetonitrile. The method according to any one of claims 1 to 11,
And wherein said polar solvent is methanol. The method according to any one of claims 1 to 12,
Wherein said solvent extraction is carried out at a temperature of about 20 ° C. to about 60 ° C. and at a pressure of about 1 to about 10 bar. The method according to any one of claims 1 to 13,
The method is:
Further characterized by feeding the extracted hydrocarbon stream to an adsorption column, the adsorption column being packed with an adsorbent suitable for removal of oxidized compounds present in the extracted hydrocarbon stream, the adsorption column being of high purity Producing a hydrocarbon product stream and a second residue stream, wherein the second residue stream comprises a portion of the oxidized compound. The method according to claim 14,
The method is:
And recovering the components from the hydrocarbon feedstock further characterized by feeding the second residue stream to the fluid catalytic cracking unit. The method according to claim 14,
Said adsorbent recovering components from a hydrocarbon feedstock selected from the group consisting of activated carbon, silica gel, alumina, natural clay, silica-alumina, zeolite, and combinations thereof. The method according to claim 14,
The adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, silica-alumina, zeolite, and activated carbon, the polymer being polysulfone, polyacrylonitrile, polystyrene, A method for recovering components from a hydrocarbon feedstock selected from the group consisting of polyester terephthalates, polyurethanes, and combinations thereof. The method according to any one of claims 1 to 17,
Feeding the first residue stream to the flow catalyst cracking unit may comprise the first residue stream in the presence of a catalyst catalytically cracking the flow catalyst cracking feed stream to recover hydrocarbons from the first residue stream. Recovering the components from the hydrocarbon feedstock characterized by contacting the fluidized catalyst cracking feed stream with water. The method according to claim 18,
The flow catalyst cracking feed stream includes vacuum gas oil, reduced crude oil, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy A process for recovering components from a hydrocarbon feedstock comprising cycle oil, clarified slurry oil, or combinations thereof. A method for recovering components from a hydrocarbon feedstock, the method comprising:
Feeding said hydrocarbon feedstock to an oxidation reactor, said hydrocarbon feedstock comprising a sulfur compound and a nitrogen compound;
The hydrocarbon feedstock under conditions sufficient to selectively oxidize the sulfur and nitrogen compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream comprising a hydrocarbon, an oxidized sulfur compound, and an oxidized nitrogen compound. Contacting with an oxidant in the reactor;
Separating the hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream being the A polar solvent, an oxidized sulfur compound, and an oxidized nitrogen compound, wherein the extracted hydrocarbon stream has a lower sulfur compound and nitrogen compound concentration than the hydrocarbon feedstock;
Separating the mixed stream into a first recovered polar solvent stream and a first residue stream using a distillation column, the first residue stream comprising the oxidized sulfur compound and the oxidized nitrogen compound;
Feeding the first residue stream to a flow catalyst cracking unit, wherein the flow catalyst cracking unit produces the regenerated catalyst and gas and liquid product and permits the oxidation to recover the hydrocarbons from the first residue stream. Operates to catalytically crack the sulfur and oxidized nitrogen;
Contacting the first residue stream with a flow catalyst cracking feed stream in the presence of a catalyst catalytically cracking the flow catalyst cracking feed stream to recover hydrocarbons from the first residue stream; And
Recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize sulfur compounds in the liquid product, wherein the portion of the liquid product comprises at least one of light cycle oil and heavy cycle oil. A method for recovering a component from a hydrocarbon feedstock comprising. The method of claim 20,
The method is:
Feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped hydrocarbon stream; And
Further characterized by recycling said first recovered polar solvent stream and second polar solvent stream to an extraction vessel for separation of said hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds in said oxidized hydrocarbon stream. A method for recovering components from hydrocarbon feedstocks. The method according to claim 20 or 21,
The method is:
Recycling a portion of the regenerated catalyst having the flow catalyst cracking feed stream to the flow catalyst cracking unit, wherein the recycle is performed to recover the hydrocarbon from the first residue stream. A process for recovering components from a hydrocarbon feedstock further characterized by catalytic cracking a cracking feed stream with a portion of the regenerated catalyst. The method according to any one of claims 20 to 22,
Wherein the oxidant recovers components from a hydrocarbon feedstock selected from the group consisting of air, oxygen, peroxide, hydrogen peroxide, ozone, nitrogen oxide compounds, and combinations thereof. The method according to any one of claims 20 to 23,
Contacting the hydrocarbon feedstock with an oxidant occurs in the presence of a catalyst comprising a metal oxide having the formula M _x O _y , wherein M is a component from a hydrocarbon feedstock selected from Groups IVB, VB, and VIB of the periodic table. How to recover. The method according to any one of claims 20 to 24,
Wherein the sulfur compound comprises a sulfide, disulfide, mercaptan, thiophene, benzothiophene, an alkyl derivative of dibenzothiophene, dibenzothiophene, or a combination thereof. The method according to any one of claims 20 to 25,
The oxidation reactor recovers components from a hydrocarbon feedstock maintained at a temperature of about 20 to about 350 ° C. and a pressure of about 1 to about 10 bar. The method according to any one of claims 20 to 26,
Wherein the ratio of oxidant to sulfur compound present in the hydrocarbon feedstock is from about 4: 1 to about 10: 1. The method according to any one of claims 20 to 27,
Wherein said polar solvent recovers components from a hydrocarbon feedstock having a Hildebrandt value of greater than about 19. The method according to any one of claims 20 to 28,
The polar solvent is a hydrocarbon selected from the group consisting of acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and combinations thereof A method for recovering the components from the feedstock. The method of claim 20, wherein
Wherein said polar solvent is acetonitrile. The method according to any one of claims 20 to 30,
And wherein said polar solvent is methanol. The method according to any one of claims 20 to 31,
Wherein said solvent extraction is carried out at a temperature of about 20 ° C. to about 60 ° C. and a pressure of about 1 bar to about 10 bar. The method according to any one of claims 20 to 32,
The method is:
Further characterized by feeding the extracted hydrocarbon stream to an adsorption column, the adsorption column being packed with an adsorbent suitable for removal of oxidized compounds present in the extracted hydrocarbon stream, the adsorption column being of high purity Producing a hydrocarbon product stream and a second residue stream, wherein the second residue stream comprises a portion of the oxidized compound. The method according to claim 33,
The method is:
And recovering the components from the hydrocarbon feedstock further characterized by feeding the second residue stream to the fluid catalytic cracking unit. The method according to claim 33,
Wherein said adsorbent recovers components from a hydrocarbon feedstock selected from the group consisting of activated carbon, silica gel, alumina, natural clays, silica-alumina, zeolites, and combinations thereof. The method according to claim 33,
The adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, and activated carbon, the polymer being polysulfone, polyacrylonitrile, polystyrene, polyester terephthalate, poly A method for recovering components from a hydrocarbon feedstock selected from the group consisting of urethanes, silica-aluminas, zeolites, and combinations thereof. The method according to any one of claims 20 to 36,
Wherein the first residue oil stream and the flow catalyst cracking feed stream are present in a weight ratio of the catalyst to the first residue oil stream and the flow catalyst cracking feed stream in the range of about 1 to about 15. The method according to any one of claims 20 to 37,
The flow catalyst cracking feed stream includes vacuum gas oil, reduced crude oil, demetalized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy cycle oil, A method for recovering components from a hydrocarbon feedstock comprising clarified slurry oil, or combinations thereof. The method according to any one of claims 20 to 38,
Contacting said first residue stream with a flow catalyst cracking feed stream in the presence of a catalyst recovers components from a hydrocarbon feedstock that occurs in a temperature range of about 300 ° C to about 650 ° C. The method according to any one of claims 20 to 39,
Contacting said first residue stream with a flow catalyst cracking feed stream in the presence of a catalyst recovers components from a hydrocarbon feedstock that occurs within a residence time of about 0.1 seconds to about 10 minutes. The method according to any one of claims 20 to 40,
The method is:
Separating the lower boiling component and catalyst particles from the first residue stream and the flowing catalyst cracking feed stream; And
Recovering components from a hydrocarbon feedstock further characterized by regenerating at least a portion of said catalyst particles. The method of claim 41,
Regenerating at least a portion of the catalyst particles may comprise water in a fluidized bed operated under conditions for producing a portion of the catalyst particles and a gaseous product and a liquid product comprising carbon monoxide and carbon dioxide. A method for recovering a component from a hydrocarbon feedstock comprising the step of contacting with a free oxygen-containing gas.

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