JP2020514485A - Oxidative desulfurization of oils and control of sulfones using FCC - Google Patents

Abstract

Embodiments provide methods and apparatus for recovering components from hydrocarbon feedstocks. According to at least one embodiment, the method is a step of feeding a hydrocarbon feedstock to an oxidation reactor under conditions sufficient to selectively oxidize sulfur and nitrogen compounds present in the hydrocarbon feedstock. Hydrocarbon feedstock oxidizes in the presence of a catalyst, feeding step, separating hydrocarbon, oxidised sulfur compound and oxidised nitrogen compound by solvent extraction, oxidised sulfur compound and oxidised nitrogen compound Collecting the residual stream containing the liquid product, supplying the residual stream to the fluid catalytic cracking unit, and selectively oxidizing the liquid compounds produced by the fluid catalytic cracking unit to selectively oxidize sulfur compounds in the liquid product. Recirculating to the oxidation reactor, wherein a portion of the liquid product comprises at least one of light cycle oil and heavy cycle oil.

Description

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

  Crude oil is the world's leading source of hydrocarbons used as fuel and petrochemical feedstock. At the same time, petroleum and petroleum-based products are also a major source of air and water pollution today. To address the growing concern over pollution caused by petroleum and petroleum-based products, many countries have adopted acceptable levels of certain pollutants in petroleum products, especially oil refining operations and fuels, such as the acceptable sulfur in gasoline fuels. Strict regulations regarding nitrogen content and nitrogen content have been implemented. The exact composition of natural petroleum or crude oils varies widely, but all crudes contain some measurable amount of sulfur compounds, and most crudes also contain some measurable amount of nitrogen compounds. In addition, while crude oil may contain oxygen, most crude oils have low oxygen content. Generally, the concentration of sulfur in crude oil is less than about 5 weight percent (wt%), with most crude oils having a sulfur concentration in the range of about 0.5 to about 1.5 wt%. Nitrogen concentrations in most crude oils are usually less than 0.2% by weight, but can be as high as 1.6% by weight. In the United States, automotive gasoline fuels are regulated to have a maximum total sulfur content of less than 10 parts per million by weight (ppmw).

  Crude oil is refined at refineries that produce transportation fuels and petrochemical feedstocks. Fuels for transportation are typically produced by processing and mixing the distillation fractions obtained from crude oil to meet the specifications of a particular end use. Since most of the crude oil commonly available today contains high levels of sulfur, the distillate fraction usually requires desulfurization to obtain products that meet various performance specifications, environmental standards, or both. And

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

  One method for reducing particulate emissions involves the addition of various oxygenated fuel compounding compounds, compounds with little or no carbon-carbon chemical bonds, such as methanol and dimethyl ether, or both. However, most of these compounds say that they can have high vapor pressures and are almost insoluble in diesel fuel, or they can have poor ignitability as indicated by their cetane number. Frustrated at the points, or a combination thereof.

  Diesel fuels that have been treated by chemical hydrotreating, or hydrotreating to reduce sulfur and aromatics content, may have reduced fuel lubricity, resulting in fuels that come into contact with the fuel under high pressure. Pumps, injectors and other moving parts can lead to excessive wear.

  For example, a middle distillate (ie, a distillate fraction that nominally boils in the range of about 180-370 ° C.) can be used as a fuel or used in a compression ignition internal combustion engine (ie, a diesel engine). Can be used as a mixed component of fuel for. The middle distillate fraction typically contains about 1-3 wt% sulfur. The allowable sulfur concentration of the middle distillate fraction has been reduced from 3,000 ppmw level to 5 to 50 ppmw level in Europe and America since 1993.

  In order to comply with ever more stringent regulations for ultra-low sulfur fuels, refiners must produce fuels with much lower sulfur levels at refinery gates so that they can meet specifications after mixing. I won't.

  Conventional low pressure hydrodesulfurization (HDS) processes can be utilized to remove most of the sulfur from petroleum distillates for mixing refinery transportation fuels. However, these devices, under mild conditions (ie, pressures up to about 30 bar), remove sulfur from the compound when the sulfur atom is sterically hindered, as in polycyclic aromatic sulfur compounds. Not efficient to remove. This is especially true when the sulfur heteroatoms are hindered by two alkyl groups (eg 4,6-dimethyldibenzothiophene). Because it is difficult to remove, the hindered dibenzothiophenes account for low sulfur levels, such as 50-100 ppmw. In order to remove sulfur from these refractory sulfur compounds, severe operating conditions (eg high hydrogen partial pressure, high temperature or high catalyst capacity) must be utilized. Increasing the hydrogen partial pressure can only be achieved by increasing the recycle gas purity or new grass root units have to be designed, which can be a very expensive option. The use of harsh operating conditions typically results in reduced yields, reduced catalyst life cycles, and product quality degradation (eg, color), which is typically sought to be avoided. .

  However, conventional methods for upgrading petroleum have various limitations and drawbacks. For example, hydrogenation processes typically require the supply of large amounts of hydrogen gas from an external source to achieve the desired upgrades and conversions. These processes may also suffer from premature or rapid deactivation of the catalyst, as is usually the case during hydrotreating of heavy feedstocks or hydrotreating under harsh conditions, This requires catalyst regeneration or new catalyst addition, which can lead to downtime of the process unit. Thermal methods are often plagued by the production of large amounts of coke as by-products and their limited ability to remove impurities such as sulfur and nitrogen. Moreover, thermal methods require specialized equipment suitable for harsh conditions (eg, high temperatures and pressures) and require significant energy input, thereby increasing complexity and cost.

  Thus, hydrocarbon feedstock upgrading processes, especially hydrocarbon desulfurization, desulfurization, that utilize less severe conditions that can also provide a means for recovery and disposal of available sulfur and / or nitrogen compounds. There is a need to provide a process for nitrogen, or both.

  Embodiments provide methods and apparatus for upgrading hydrocarbon feedstocks that removes most of the sulfur and nitrogen present and then utilizes these compounds in related processes.

  According to at least one embodiment, a method of recovering components from a hydrocarbon feedstock, the step of feeding the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock comprises a sulfur compound and a nitrogen compound Step, conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock to produce a hydrocarbon and an oxidized hydrocarbon stream comprising oxidized sulfur compounds and oxidized nitrogen compounds. Below, a method is provided that includes the step of contacting a hydrocarbon feedstock with an oxidant in an oxidation reactor. This method consists of separating hydrocarbons and oxidized sulfur compounds and oxidized nitrogen compounds in an oxidized hydrocarbon stream by solvent extraction using a polar solvent to produce an extracted hydrocarbon stream and a mixed stream. Wherein the mixed stream comprises a polar solvent, an oxidized sulfur compound and an oxidized nitrogen compound, and the extracted hydrocarbon stream comprises a lower concentration of sulfur and nitrogen compounds than the hydrocarbon feedstock. Including. The method further comprises the step of separating the mixed stream into a first recovered polar solvent stream and a first residual stream using a distillation column, the first residual stream being oxidized with the oxidized sulfur compounds. A separation step including a nitrogen compound and a step of supplying a first residual stream to a fluid catalytic cracking unit, wherein the fluid catalytic cracking unit catalytically cracks oxidized sulfur and oxidized nitrogen to produce a regenerated catalyst. And a feeding step operative to generate gaseous and liquid products to allow recovery of hydrocarbons from the first residual stream. Further, the method is a step of recycling at least a portion of the liquid product to an oxidation reactor to selectively oxidize sulfur compounds in the liquid product, the portion of the liquid product comprising: Recycling, comprising at least one of a light cycle oil and a heavy cycle oil.

  According to at least one embodiment, the method comprises feeding an extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a removed hydrocarbon stream, and in the oxidized hydrocarbon stream. The method further comprises recycling the first recovered polar solvent stream and the second polar solvent stream to the extraction vessel to separate the hydrocarbons, the oxidized sulfur compounds, and the oxidized nitrogen compounds.

  According to at least one embodiment, the method comprises the step of recirculating a portion of the regenerated catalyst to a fluid catalytic cracking unit using a fluid catalytic cracking feed stream, the fluid catalytic cracking feed stream containing a portion of the regenerated catalyst. The method further comprises the step of recycling, further comprising the step of catalytically cracking with and recovering hydrocarbons from the first residual stream.

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

According to at least one embodiment, contacting the hydrocarbon feedstock with an oxidant comprises a metal oxide having the formula M _x O _y , where M is selected from Group IVB, Group VB and Group VIB of the Periodic Table. It occurs in the presence of an elemental catalyst.

  According to at least one embodiment, the sulfur compound comprises a sulfide, disulfide, mercaptan, thiophene, benzothiophene, dibenzothiophene, alkyl derivative of dibenzothiophene, or a combination 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 oxidizing agent 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 Hildebrand value greater than about 19.

  According to at least one embodiment, the polar solvent is acetone, carbon disulfide, pyridine, dimethylsulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and combinations thereof. Is selected from the group consisting of

  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 is a step of feeding an extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is a suitable adsorbent for removing oxidised compounds present in the extracted hydrocarbon stream. And charging the adsorber column to produce a high purity hydrocarbon product stream and a second retentate stream, the second retentate stream comprising a portion of the oxidized compound.

  According to at least one embodiment, the method further comprises feeding the second residual stream to a fluid catalytic cracking unit.

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

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

  According to at least one embodiment, supplying the first residual stream to a fluid catalytic cracking feed unit comprises contacting the first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst to produce a fluid catalytic cracking feed stream. The method further comprises catalytically cracking to recover hydrocarbons from the first residual stream.

  According to at least one embodiment, the fluid catalytic cracking feed stream comprises vacuum gas oil, atmospheric residue, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy cycle oil. Includes quality cycle oils, clarified slurry oils, or combinations thereof.

  According to another embodiment, a method of recovering components from a hydrocarbon feedstock, the step of feeding the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock comprises a sulfur compound and a nitrogen compound. Step, conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock to produce a hydrocarbon and an oxidized hydrocarbon stream comprising oxidized sulfur compounds and oxidized nitrogen compounds. Below, a method is provided that includes the step of contacting a hydrocarbon feedstock with an oxidant in an oxidation reactor. The method is a process of separating hydrocarbons and oxidized sulfur compounds and oxidized nitrogen compounds in an oxidized hydrocarbon stream by solvent extraction using a polar solvent to produce an extracted hydrocarbon stream and a mixed stream. And the mixed stream comprises a polar solvent, an oxidized sulfur compound and an oxidized nitrogen compound, and the extracted hydrocarbon stream comprises a lower concentration of sulfur and nitrogen compounds than the hydrocarbon feedstock. Including. The method further comprises separating the mixed stream into a first recovered polar solvent stream and a first retentate stream using a distillation column, the first retentate stream comprising oxidized sulfur compounds and oxidized nitrogen. A step of separating containing a compound and a step of supplying a first residual stream to a fluid catalytic cracking unit, wherein the fluid catalytic cracking unit catalytically cracks oxidized sulfur and oxidized nitrogen to produce a regenerated catalyst and A feeding step operative to generate gaseous and liquid products to allow recovery of hydrocarbons from the first residual stream. Further, the method comprises contacting a first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst to catalytically crack the fluid catalytic cracking feed stream to recover hydrocarbons from the first residual stream, and a liquid. Recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize sulfur compounds in the product, the portion of the liquid product comprising light cycle oil and heavy cycle Recirculating with at least one of the oils.

  According to at least one embodiment, the method comprises feeding an extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a removed hydrocarbon stream, and in the oxidized hydrocarbon stream. The method further comprises the step of recycling the first recovered polar solvent stream and the second polar solvent stream to the extraction vessel to separate the hydrocarbons, the oxidized sulfur compounds, and the oxidized nitrogen compounds.

  According to at least one embodiment, the method comprises the step of recirculating a portion of the regenerated catalyst to a fluid catalytic cracking unit using a fluid catalytic cracking feed stream, the fluid catalytic cracking feed stream containing a portion of the regenerated catalyst. The method further comprises the step of recycling further comprising the step of catalytically cracking with and recovering hydrocarbons from the first residual stream.

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

According to at least one embodiment, contacting the hydrocarbon feedstock with an oxidant comprises a metal oxide having the formula M _x O _y , where M is selected from Group IVB, Group VB and Group VIB of the Periodic Table. It occurs in the presence of an elemental catalyst.

  According to at least one embodiment, the sulfur compound comprises a sulfide, disulfide, mercaptan, thiophene, benzothiophene, dibenzothiophene, alkyl derivative of dibenzothiophene, or a combination 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 oxidizing agent 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 Hildebrand value greater than about 19.

  According to at least one embodiment, the polar solvent is acetone, carbon disulfide, pyridine, dimethylsulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethylformamide, acetonitrile, methanol and combinations thereof. Is selected from the group consisting of

  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 is a step of feeding an extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is a suitable adsorbent for removing oxidised compounds present in the extracted hydrocarbon stream. Further comprising the step of charging, the absorption tower producing a high purity hydrocarbon product stream and a second retentate stream, the second retentate stream comprising a portion of the oxidized compound.

  According to at least one embodiment, the method further comprises feeding the second residual stream to a fluid catalytic cracking unit.

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

  According to at least one embodiment, the adsorbent is a polymer coated support, the support having a large surface area is selected from the group consisting of silica gel, alumina, and activated carbon, and the polymer is polysulfone, polyacrylonitrile, polystyrene, It is selected from the group consisting of polyester terephthalate, polyurethane, silica-alumina, zeolites, and combinations thereof.

  According to at least one embodiment, the first retentate stream and fluid catalytic cracking feed stream is present in a weight ratio of catalyst to first retentate stream and fluid catalytic cracking feed stream in the range of about 1 to about 15.

  According to at least one embodiment, the fluid catalytic cracking feed stream comprises vacuum gas oil, atmospheric residue, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy cycle oil. Includes quality cycle oils, clarified slurry oils, or combinations thereof.

  According to at least one embodiment, contacting the first residual stream with the fluid catalytic 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 the first retentate stream with the fluid catalytic cracking feed stream in the presence of a catalyst occurs in a residence time range of from about 0.1 seconds to about 10 minutes.

  According to at least one embodiment, the method further comprises separating low boiling components and catalyst particles from the first residual stream and the fluid catalytic 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 in a fluidized bed operated under conditions that produce a regenerated catalyst and a gaseous and liquid product comprising carbon monoxide and carbon dioxide, Contacting a portion of the catalyst particles with an anhydrous oxygen-containing gas.

  For a better understanding of the features and advantages of the disclosed methods and systems, as well as others that will become apparent, a more detailed description of the methods and systems that have already been briefly summarized is included as part of this specification. By referring to the embodiment shown in the drawings. However, it should be noted that the drawings are merely illustrative of various embodiments and therefore should not be considered limiting as they may include other valid embodiments as well. Like numbers refer to like elements throughout, and where prime notation is used, indicate similar elements in alternative embodiments or locations.

1 presents a schematic diagram of one embodiment of a method for upgrading a hydrocarbon feedstock. 1 presents a schematic diagram of one embodiment of a method for upgrading a hydrocarbon feedstock. 1 presents a schematic diagram of one embodiment of a method for upgrading a hydrocarbon feedstock. A schematic of the process described in the examples is presented.

  While the following detailed description includes many specific details for purposes of illustration, one of ordinary skill in the art will recognize that many examples, variations and modifications to the following details are within the scope and spirit. To be understood. Accordingly, the various embodiments described and provided in the accompanying drawings are described with respect to the claims without any loss of generality or limitation.

  Embodiments include conventional methods for upgrading hydrocarbon feedstocks and recovering compounds from hydrocarbon feedstocks, particularly desulfurization, denitrification, or both of hydrocarbon feedstocks, and subsequent use of available hydrocarbons. Address known issues with removal and collection. According to at least one embodiment, there is provided a method of removing sulfur and nitrogen compounds from a hydrocarbon feedstock and a method of using oxidized sulfur species and oxidized nitrogen species in a FCC process.

  As used, the term “enhanced” or “enhanced” with respect to petroleum or hydrocarbons is lighter (ie, methane, ethane, and propane) than the original crude or hydrocarbon feedstock. Petroleum or hydrocarbon products having at least one of (i.e. relatively less carbon atoms), high API gravity, high middle distillate yield, low sulfur content, low nitrogen content, or low metal content. Point to.

  FIG. 1 presents one embodiment for recovering hydrocarbons. The hydrocarbon recovery system 100 includes an oxidation reactor 104, an extraction vessel 112, a solvent regeneration tower 116, a stripper 120, and an FCC unit 130.

  According to at least one embodiment, there is provided a method of recovering components from a hydrocarbon feedstock, especially a hydrocarbon feedstock comprising a sulfur-containing compound and a nitrogen-containing compound. The method includes feeding hydrocarbon feedstock 102 to oxidation reactor 104, where the hydrocarbon feedstock is contacted with an oxidant and a catalyst. The oxidant can be fed to the oxidation reactor 104 via the oxidant feed line 106 and the fresh catalyst can be fed to the reactor via the catalyst feed line 108.

  According to at least one embodiment, the hydrocarbon feedstock 102 can be any petroleum-based hydrocarbon and can include various impurities such as elemental sulfur, compounds containing sulfur or nitrogen, or both. In certain embodiments, the hydrocarbon feedstock 102 can be diesel oil having a boiling point of about 150 ° C to about 400 ° C. Alternatively, the hydrocarbon feedstock 102 can have a boiling point of up to about 450 ° C, or up to about 500 ° C. Alternatively, the hydrocarbon feedstock 102 can have a boiling point of about 100 ° C to about 500 ° C. Optionally, the hydrocarbon feedstock 102 can have a boiling point of up to about 600 ° C, or up to about 700 ° C, or in certain embodiments above about 700 ° C. According to at least one embodiment, the feedstock is present in a solid state called a residue after distillation. In particular embodiments, hydrocarbon feedstock 102 can include heavy hydrocarbons. Heavy hydrocarbons, when used, refers to hydrocarbons having a boiling point greater than about 360 ° C. and may include aromatic hydrocarbons, as well as alkanes and alkenes. Generally, in certain embodiments, the hydrocarbon feedstock 102 is a full range of crude oil, top crude oil, refinery derived product streams, refinery steam cracking process product streams, liquefied coal, petroleum or tar. Liquid products recovered from the sand, bitumen, oil shale, asphaltene, hydrocarbon fractions such as diesel and vacuum gas oil boiling in the range of about 180 to about 370 ° C and about 370 to about 520 ° C, respectively, and their It can be selected from a mixture.

  Sulfur compounds present in hydrocarbon feedstock 102 may include sulfides, disulfides, and mercaptans, as well as aromatic molecules such as thiophene, benzothiophene, dibenzothiophene, and alkyldibenzothiophenes, such as 4,6-dimethyldibenzothiophene. .. Aromatic compounds are typically present in higher boiling fractions than are normally found in lower boiling fractions.

硫黄酸化は制限された標的反応であり、その間に窒素酸化が起こることに留意されたい。２つのタイプは塩基性窒素と中性窒素と考えられる。 The nitrogen-containing compound present in the hydrocarbon feedstock 102 may include compounds having the structure:

Note that sulfur oxidation is a limited target reaction, during which nitrogen oxidation occurs. The two types are considered basic nitrogen and neutral nitrogen.

  According to at least one embodiment, the oxidation reactor 104 can operate in mild conditions. More specifically, in certain embodiments, the oxidation reactor 104 can be maintained at a temperature of about 30 ° C to about 350 ° C, or about 45 ° C to about 60 ° C. The operating pressure of the oxidation reactor 104 can be about 1 bar to about 30 bar, or about 1 bar to about 15 bar, or about 1 bar to about 10 bar, or about 2 bar to about 3 bar. The residence time of the hydrocarbon feedstock in the oxidation reactor 104 is about 1 minute to about 120 minutes, or about 15 minutes to about 90 minutes, or about 5 minutes to about 90 minutes, or about 5 minutes to about 30 minutes, or It can be from about 30 minutes to about 60 minutes, preferably for a time sufficient to oxidize any sulfur or nitrogen compounds present in the hydrocarbon feed. According to at least one embodiment, the residence time of the hydrocarbon feedstock in the oxidation reactor 104 is between about 15 minutes and about 90 minutes.

またはそれらの組み合わせ。 According to at least one embodiment, the oxidation reactor 104 ensures sufficient contact between the hydrocarbon feedstock 102 and the oxidant in the presence of the catalyst to oxidize sulfur-containing compounds and nitrogen-containing compounds. Can be any reactor configured appropriately. Sulfur and nitrogen compounds present in hydrocarbon feedstock 102 are oxidized in oxidation reactor 104 to sulfones, sulfoxides, and oxidized nitrogen compounds, which can subsequently be removed by extraction or adsorption. Various types of reactors can be used. For example, the reactor can be a batch reactor, fixed bed reactor, ebullated bed reactor, lift-up reactor, fluidized bed reactor, 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. It is believed that the nitrogen atom is not directly oxidized, but rather it is the carbon atom next to the nitrogen that is actually oxidized. Some examples of oxidized nitrogen compounds can include the following compounds:

Or a combination of them.

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

  According to at least one embodiment, the molar ratio of oxidizer 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 can range from about 1: 1 to about 30: 1.

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

According to at least one embodiment, the catalyst can be fed to the oxidation reactor 104 via the catalyst feed stream 108. The catalyst can be a homogeneous catalyst. The catalyst may comprise at least one metal oxide having the formula M _x O _y, in this case M is, IVB of the Periodic Table, a metal selected from Group VB or VIB. Metals can 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, spent catalyst may be removed from the system with the aqueous phase after the oxidation vessel (eg, when using an aqueous oxidant).

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

  The catalyst present in the oxidation reactor 104 increases the rate of oxidation of various sulfur-containing compounds and nitrogen-containing compounds in the hydrocarbon feedstock 102, reduces the amount of oxidizing agent required for the oxidation reaction, or both. To enable. 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, which can include hydrocarbons and oxidized sulfur-containing species and oxidized nitrogen-containing species. Oxidized hydrocarbon stream 110 is fed to extraction vessel 112, where the oxidized hydrocarbon stream and the oxidized sulfur-containing species and oxidized nitrogen-containing species contact extraction solvent stream 137. The extraction solvent 137 can be a polar solvent and, in certain embodiments, can have a Hildebrand solubility value of greater than about 19. In certain embodiments, when selecting a particular polar solvent for use in extracting oxidized sulfur-containing species and oxidized nitrogen-containing species, the selection includes solvent density, as a non-limiting example, It may be based in part on boiling point, freezing point, viscosity, and surface tension. Suitable polar solvents for use in the extraction process include acetone (Hildebrand value 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 compositions having similar physical and chemical 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, it is preferred that the solvent containing sulfur, nitrogen, or phosphorus have a relatively high volatility to ensure proper removal of the solvent from the hydrocarbon feed.

  According to at least one embodiment, the extraction solvent is non-acidic. The use of acids is usually avoided due to the corrosive nature of the acids and the requirement that all equipment be specially designed for corrosive environments. In addition, acids such as acetic acid can make separation difficult due to the formation of emulsions.

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

  According to at least one embodiment, the ratio of extraction solvent to hydrocarbon feedstock is from about 1: 3 to about 3: 1, preferably from about 1: 2 to about 2: 1, more preferably about 1: 1. obtain. The contact time between the extraction solvent and the oxidized hydrocarbon stream 110 can be between about 1 second and about 60 minutes, preferably between about 1 second and 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, the extraction vessel 112 increases the contact time between the extraction solvent and the oxidized sulfur-containing hydrocarbon and oxidized nitrogen-containing hydrocarbon stream 110, or the degree of mixing of the two solvents. Various means for increasing can be included. The mixing means may include a mechanical stirrer or stirrer, a tray, or similar means.

  According to at least one embodiment, the extraction vessel 112 includes an extraction solvent, oxidizing species (eg, oxidized sulfur species and oxidized nitrogen species originally present in the hydrocarbon feedstock 102), and trace hydrocarbon feedstock. 102, and a mixed stream 114, which may include an extracted hydrocarbon stream 118, the extracted hydrocarbon stream 118 having a reduced sulfur and low nitrogen content compared to the hydrocarbon feedstock 102. Can be included.

  The mixed stream 114 is fed to a solvent regeneration column 116 where the extraction solvent is recovered as a first recovery solvent stream 117 and may be separated from a first residual stream 123 containing oxidized sulfur compounds and oxidized nitrogen compounds. .. Optionally, mixed stream 114 can be separated in solvent regeneration column 116 into recovered hydrocarbon stream 124, which can include hydrocarbons present in mixed stream 114 from hydrocarbon feedstock 102. The solvent regeneration column 116 can be a distillation column configured to separate the mixed stream 114 into a first recovered solvent stream 117, a first residual stream 123, and a recovered hydrocarbon stream 124.

  Extracted hydrocarbon stream 118 can be fed to stripper 120, which can be like a distillation column or a vessel designed to separate the hydrocarbon product stream from residual extraction solvent. In certain embodiments, a portion of the mixed stream 114 can be fed to the stripper 120 via line 122 and optionally combined with the extracted hydrocarbon stream 118. In certain embodiments, the solvent regeneration column 116 can produce a recovered hydrocarbon stream 124, which can be fed to the stripper 120, which recovered hydrocarbon stream 124 is optionally an extracted hydrocarbon stream 118 or It can be contacted with a portion of the mixed stream 114, which can be fed to the stripper 120 via line 122.

  Stripper 120 separates the various streams provided therein into a removed oil stream 126 and a second recovered solvent stream 128 that have a reduced sulfur and nitrogen content compared to hydrocarbon feedstock 102.

  In particular embodiments, the first recovered solvent stream 117 can be mixed with the second recovered solvent stream 128 and recycled to the extraction vessel 112. A make-up solvent stream 132, which may optionally include fresh solvent, may be mixed with the first recovered solvent stream 117, the second recovered solvent stream 128, or both and provided to the extraction vessel 112. ..

  A first retentate stream 123, which may include oxidized compounds such as oxidized sulfur compounds and oxidized nitrogen compounds, and may also include low concentrations of hydrocarbon-based materials, may be provided to FCC unit 130. , Where the liquid product (including hydrocarbons) 136 can be recovered. According to at least one embodiment, the oxidized sulfur compounds such as sulfones, and the oxidized nitrogen compounds include hydrocarbons having boiling points in the range of about 343 ° C to about 524 ° C, or about 360 ° C to about 550 ° C. Embedded in heavy hydrocarbons.

  According to various embodiments in which the first retentate stream 123 is sent to the FCC unit 130, the first retentate stream 123 is contacted with the FCC feed stream 134 in the presence of a catalyst to remove liquid from the first retentate stream 123. Product 136 is catalytically cracked with FCC feed stream 134 to recover. According to at least one embodiment, the catalyst may include high temperature solid zeolite active catalyst particles. According to at least one embodiment, at a pressure in the range of about 1 barg (gauge pressure) to about 200 barg to form a suspension, the weight ratio of catalyst to FCC feed stream 134 is in the range of about 1 to about 15. Is. Other suitable ratios of catalyst and FCC feed stream 134 and operating conditions 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 (not shown) between about 300 ° C and less than about 650 ° C to avoid thermal conversion of the feed stream 134. And catalytically crack the FCC feed stream 134 while providing a hydrocarbon residence time of about 0.1 seconds to about 10 minutes.

  According to at least one embodiment, the low boiling components and solid catalyst particles are then separated and recovered. At least a portion of the separated solid catalyst particles is operated under conditions that produce a regenerated catalyst 140, a gaseous product 138 consisting essentially of carbon monoxide and carbon dioxide, and a liquid product 136. Regenerated with anhydrous oxygen-containing gas in the bed. At least a portion of the regenerated catalyst is returned and mixed with FCC feed stream 134 (not shown).

According to at least one embodiment, the types of components included in FCC feed stream 134 can vary. FCC feed stream 134 includes, by way of non-limiting example, vacuum gas oil, atmospheric residue, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, and LCO, HCO and CSO. FCC heavy product of Table 1 shows typical yields from FCC units. As another example, the FCC feed stream 134 sent to the FCC unit 130 can have the characteristics shown in Table 2. Other suitable compounds that can be used in the FCC feed stream 134 to the FCC unit 130 will be apparent to those skilled in the art and should be considered within the scope of various embodiments.

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

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

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

  As described above with respect to the embodiment shown in FIG. 1, a first retentate stream containing oxidized compounds such as oxidized sulfur compounds and oxidized nitrogen compounds, which may also include low concentrations of hydrocarbon-based materials. 123 can be fed to the FCC unit 130, where liquid products (including hydrocarbons) 136 can be recovered. According to at least one embodiment, the oxidized sulfur compounds such as sulfones, and the oxidized nitrogen compounds include hydrocarbons having boiling points in the range of about 343 ° C to about 524 ° C, or about 360 ° C to about 550 ° C. Embedded in heavy hydrocarbons.

  According to various embodiments in which the first retentate stream 123 is sent to the FCC unit 130, the first retentate stream 123 is contacted with an FCC feed stream 134 in the presence of a catalyst, as shown in FIG. Catalytic cracking with FCC feed stream 134 to recover liquid product 136 from first residual stream 123. According to at least one embodiment, the catalyst may include high temperature solid zeolite active catalyst particles. According to at least one embodiment, at a pressure in the range of about 1 barg to about 200 barg to form a suspension, the weight ratio of catalyst to FCC feed stream 134 is in the range of about 1 to about 15. Other suitable ratios of catalyst and FCC feed stream 134 and operating conditions 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 (not shown) between about 300 ° C. and less than about 650 ° C. to avoid thermal conversion of FCC feed stream 134. The feed stream 134 is then catalytically cracked, providing a hydrocarbon residence time of about 0.1 seconds to about 10 minutes.

  According to at least one embodiment, the low boiling components and solid catalyst particles are then separated and recovered. At least a portion of the separated solid catalyst particles is operated under conditions that produce a regenerated catalyst 140, a gaseous product 138 consisting essentially of carbon monoxide and carbon dioxide, and a liquid product 136. Regenerated with anhydrous oxygen-containing gas in the bed. At least a portion of the regenerated catalyst is returned and mixed with FCC feed stream 134 (not shown).

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

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

  FIG. 3 provides one embodiment for recovering hydrocarbons from a feed stream. The hydrocarbon recovery system 300 includes an oxidation reactor 104, an extraction container 112, a solvent regeneration tower 116, a stripper 120, an FCC unit 130, and an adsorption tower 302.

  As shown in FIG. 3, in certain embodiments, the depleted oil stream 126 can be fed to the adsorption tower 302 where the removed oil stream 126 is fed with sulfur-containing compounds, oxidized sulfur compounds, nitrogen-containing compounds, oxidation. Of the nitrogen compound and one or more adsorbents designed to remove one or more various impurities such as metals remaining in the hydrocarbon product stream after the oxidation and solvent extraction steps.

  According to various embodiments, the one or more adsorbents are activated carbon, silica gel, alumina, natural clay, silica-alumina, zeolites, and oxidized sulfur compounds and oxidized nitrogen compounds and other inorganic adsorbents. It may include fresh, spent, regenerated or reclaimed catalyst having an affinity for. In certain embodiments, adsorbents can 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, polyacrylonitriles, polystyrenes, polyester terephthalates, polyurethanes, and other similar polymer species that have an affinity for oxidized sulfur species, and A combination thereof can be mentioned.

  According to at least one embodiment, the adsorption tower 302 can operate at a temperature of about 20 ° C to about 60 ° C, preferably about 25 ° C to about 40 ° C, and even more preferably about 25 ° C to about 35 ° C. .. In certain embodiments, the adsorption column can operate at temperatures of about 10 ° C to 40 ° C. In certain embodiments, the adsorption column can operate at temperatures above about 20 ° C, or at temperatures below about 60 ° C. The adsorption column 302 can operate at pressures of up to about 15 bar, preferably up to about 10 bar, and even more preferably from about 1 to about 2 bar. In certain embodiments, the adsorption column 302 can operate at a pressure of about 2 to about 5 bar. According to at least one embodiment, the adsorption column can operate 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 removed oil stream to adsorbent is from about 1: 1 to about 20: 1, or about 10: 1.

  The adsorption column 302 provides the feed with an 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). 2 and the residual stream 306. The second retentate stream 306 comprises an oxidized sulfur-containing compound and an oxidized nitrogen-containing compound, optionally mixed with the first retentate stream 123 and fed to the FCC unit 130, which can be processed as described above. .. The adsorbent can be regenerated by contacting the spent 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 can also be used to facilitate removal of adsorbed compounds. 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]
FIG. 4 shows a process flow diagram for oxidative desulfurization (oxidation and extraction steps) and FCC unit. Vessels 10, 16, 20 and 25 are oxidation, extraction, solvent recovery and FCC vessels, respectively.

Hydrotreated straight run diesel containing 500 ppmw elemental sulfur, 0.28 wt% organic sulfur, a density of 0.85 kilograms per liter (Kg / l) was oxidatively desulfurized. The reaction conditions were as follows.
Hydrogen peroxide: Sulfur molar ratio: 4: 1
Catalyst: Mo (VI) based on molybdenum
Reaction time: 30 minutes Temperature: 80 ° C
Pressure: 1 kilogram per square centimeter (Kg / cm ² )

  According to at least one embodiment, the FCC unit was operated at 518 ° C. with a catalyst to oil ratio of 5, which resulted in 67 wt% conversion of the feedstock. In addition to the sulfone produced in the oxidation step, a straight run vacuum gas oil derived from Arabian crude oil was used as a compounding ingredient. The feedstock contained 2.65 wt% sulfur and 0.13 wt% microcarbon residue. The intermediate and 95 wt% boiling points of the feedstock were 408 ° C and 455 ° C, respectively.

The FCC conversion of the feedstock was calculated as follows using equation (1).
Conversion rate = dry gas + LPG + gasoline + coke (1)

The catalyst used was an equilibrium catalyst and was used as is without any treatment. The catalyst has a surface area of 131 square meters per gram (m ² / g) and a pore volume of 0.1878 square centimeters per gram (cm ³ / g). The contents of nickel and vanadium are 96 ppmw and 407 ppmw, respectively. The FCC process caused the following products to deposit coke on the catalyst.

Dry gas _{H 2, CH 4, C 2} H 6, C 2 H 4
Wet gas C ₃ , C ₄ compound (LPG)
Liquid product containing gasoline C ₅ -C ₁₂ hydrocarbons.
Typical final boiling point is 221 ° C
Light cycle oil containing hydrocarbons LCO C ₁₂ ~C _20.
Typical boiling point is 221 to 343 ° C
_{C 20} + solid carbonaceous deposits of heavy cycle oil coke catalyst containing hydrocarbons HCO lowest boiling 343 ° C.. Typical C / H ratio = 1

The coke produced by the FCC process was 2.5% by weight of the treated feedstock. Product yields are shown in Table 5.

According to one example, the LCO boils in the same range of distillation as the diesel used in the example, so the LCO was recycled to the oxidation step. Note that the FCC unit is designed to process 10,000 Kg / hr vacuum gas oil for purposes of illustration. As will be apparent to one of ordinary skill in the art and the FCC unit can be designed with any capacity as will be considered within the scope of various embodiments, modifications in the design may result in oxidation / extraction to handle additional feeds. It can be performed for a process. Material balance is proportional to the amount of feedstock processed. The processing steps, oxidation, extraction and FCC are shown in Table 6 to Table 8, respectively.

  The methods and systems described herein increase the amount of liquid hydrocarbons from aromatic sulfur, nitrogen compounds, and aromatic streams by coupling an oxidative desulfurization and denitrification process with a fluid catalytic cracking unit. It is thought that Furthermore, it is believed that there is no efficient way to dispose of oxidation reaction byproducts (ie, oxidized sulfur compounds and oxidized nitrogen compounds). Embodiments provide a method of discarding oxidized sulfur compounds and oxidized nitrogen compounds without having to discard the compounds.

  While various embodiments have been described in detail, it should be understood that various changes, substitutions, and alterations can be made without departing from the present principles and scope. Accordingly, the scope should be determined by the appended 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 the events or circumstances described below may or may not occur. The description includes when an event or situation occurred and when it did not occur.

Ranges can be expressed as approximately one particular value to approximately another particular value. When such a range is expressed, it is to be understood that other embodiments, along with all combinations within that range, are from one particular value to the other. .

Claims (42)

A method of recovering components from a hydrocarbon feedstock,
A step of supplying the hydrocarbon raw material to an oxidation reactor, wherein the hydrocarbon raw material contains a sulfur compound and a nitrogen compound,
Conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in said hydrocarbon feedstock to produce a hydrocarbon and an oxidized hydrocarbon stream comprising oxidized sulfur compounds and oxidized nitrogen compounds. And a step of contacting the hydrocarbon raw material with an oxidant in the oxidation reactor,
Separating the hydrocarbons and the oxidized sulfur compounds and oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction using a polar solvent to produce an extracted hydrocarbon stream and a mixed stream. The mixed stream contains the polar solvent, the oxidized sulfur compound and the oxidized nitrogen compound, and the extracted hydrocarbon stream contains a lower concentration of sulfur compounds and nitrogen compounds than the hydrocarbon feedstock, The process of generating,
Separating the mixed stream into a first recovered polar solvent stream and a first retentate stream using a distillation column, wherein the first retentate stream is the oxidized sulfur compound and the oxidized nitrogen. Separating step including the compound,
Supplying the first residual stream to a fluid catalytic cracking unit, wherein the fluid catalytic cracking unit catalytically cracks oxidized sulfur and oxidized nitrogen to produce a regenerated catalyst and gaseous and liquid products. Operating to enable hydrocarbons to be produced and recovering hydrocarbons from the first residual stream; and the liquid product for selectively oxidizing sulfur compounds in the liquid product. Recirculating at least a portion of the liquid product to the oxidation reactor, wherein a portion of the liquid product comprises at least one of a light cycle oil and a heavy cycle oil. And how to. Feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a removed hydrocarbon stream, and the hydrocarbons in the oxidized hydrocarbon stream, the oxidized sulfur Recycling the first recovered polar solvent stream and the second polar solvent stream to an extraction vessel to separate the compound and the oxidized nitrogen compound.
The method of claim 1, further characterized by: Recirculating a portion of the regenerated catalyst to the fluid catalytic cracking unit using a fluid catalytic cracking feed stream, the fluid catalytic cracking feed stream being catalytically cracked using a portion of the regenerated catalyst to The method of any one of claims 1 or 2, further characterized by the step of recycling, further characterizing the step of recovering hydrocarbons from the first residual stream.   4. The method of any one of claims 1-3, wherein the oxidant is selected from the group consisting of air, oxygen, peroxides, hydroperoxides, ozone, nitrogen-oxidized compounds, and combinations thereof. .. Presence of a catalyst wherein said contacting said hydrocarbon feedstock with an oxidant comprises a metal oxide having the formula M _x O _y , where M is an element selected from Group IVB, Group VB and Group VIB of the Periodic Table. 5. The method according to any one of claims 1 to 4, which occurs below.   6. The method of any one of claims 1-5, wherein the sulfur compound comprises a sulfide, disulfide, mercaptan, thiophene, benzothiophene, dibenzothiophene, an alkyl derivative of dibenzothiophene, or a combination thereof.   7. The method of any one of claims 1-6, wherein the oxidation reactor is maintained at a temperature of about 20 to about 350 <0> C and a pressure of about 1 to about 10 bar.   8. The method of any one of claims 1-7, wherein the ratio of the oxidizer to sulfur compound present in the hydrocarbon feedstock is from about 4: 1 to about 10: 1.   9. The method of any one of claims 1-8, wherein the polar solvent has a Hildebrand value greater than about 19.   The polar solvent is 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, The method according to any one of claims 1 to 9.   11. The method according to any one of claims 1-10, wherein the polar solvent is acetonitrile.   The method according to any one of claims 1 to 11, wherein the polar solvent is methanol.   13. The method of any one of claims 1-12, wherein the solvent extraction is performed at a temperature of about 20 <0> C to about 60 <0> C and a pressure of about 1 to about 10 bar. A step of supplying the extracted hydrocarbon stream to an adsorption tower, wherein the adsorption tower is charged with an adsorbent suitable for removing oxidized compounds present in the extracted hydrocarbon stream, Producing a high purity hydrocarbon product stream and a second retentate stream, wherein the second retentate stream comprises a portion of the oxidized compound. The method described in paragraph 1. 15. The method of claim 14, further characterized by: providing the second residual stream to the fluid catalytic cracking unit.   15. The method of claim 14, wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clay, silica-alumina, zeolites, and combinations thereof.   The adsorbent is a polymer coated support, the support has a large surface area and is selected from the group consisting of silica gel, alumina, silica-alumina, zeolites, and activated carbon, and the polymer is polysulfone, polyacrylonitrile, polystyrene. 15. The method of claim 14, selected from the group consisting of :, polyester terephthalate, polyurethane, and combinations thereof.   Providing the first residual stream to the fluid catalytic cracking unit comprises contacting the first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst to catalytically crack the fluid catalytic cracking feed stream. 18. The method of any of claims 1-17, further characterized by recovering hydrocarbons from the first residual stream.   Fluid catalytic cracking feed stream is vacuum gas oil, atmospheric residual oil, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy cycle oil, clarified slurry oil 19. The method of claim 18, comprising: or a combination thereof. A method of recovering components from a hydrocarbon feedstock,
A step of supplying the hydrocarbon raw material to an oxidation reactor, wherein the hydrocarbon raw material contains a sulfur compound and a nitrogen compound,
Conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in said hydrocarbon feedstock to produce a hydrocarbon and an oxidized hydrocarbon stream comprising oxidized sulfur compounds and oxidized nitrogen compounds. And a step of contacting the hydrocarbon raw material with an oxidant in the oxidation reactor,
Separating the hydrocarbons and the oxidized sulfur compounds and oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction using a polar solvent to produce an extracted hydrocarbon stream and a mixed stream. The mixed stream contains the polar solvent, the oxidized sulfur compound and the oxidized nitrogen compound, and the extracted hydrocarbon stream contains a lower concentration of sulfur compounds and nitrogen compounds than the hydrocarbon feedstock, The process of generating,
Separating the mixed stream into a first recovered polar solvent stream and a first retentate stream using a distillation column, wherein the first retentate stream is the oxidized sulfur compound and the oxidized nitrogen. Separating step including the compound,
Supplying the first residual stream to a fluid catalytic cracking unit, wherein the fluid catalytic cracking unit catalytically cracks the oxidized sulfur and the oxidized nitrogen to produce a regenerated catalyst and a gaseous and liquid product. A feed operation operative to produce a product to recover hydrocarbons from the first residual stream;
Contacting the first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst to catalytically crack the fluid catalytic cracking feed stream to recover hydrocarbons from the first residual stream; and the liquid Recycling at least a portion of the liquid product to the oxidation reactor to selectively oxidize sulfur compounds in the product, the portion of the liquid product comprising light cycle oil and A method of recycling comprising at least one of heavy cycle oils. Feeding the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a removed hydrocarbon stream, and the hydrocarbons in the oxidized hydrocarbon stream, the oxidized sulfur Recycling the first recovered polar solvent stream and the second polar solvent stream to an extraction vessel to separate the compound and the oxidized nitrogen compound;
21. The method of claim 20, further characterized by:   Recirculating a portion of the regenerated catalyst to the fluid catalytic cracking unit using the fluid catalytic cracking feed stream, wherein the fluid catalytic cracking feed stream is catalytically cracked using a portion of the regenerated catalyst. 22. The method of any one of claims 20-21, further characterized by a recycling step further characterized by a step of recovering the hydrocarbon from the first residual stream.   23. The method of any one of claims 20-22, wherein the oxidant is selected from the group consisting of air, oxygen, peroxides, hydroperoxides, ozone, nitrogen-oxidized compounds, and combinations thereof. .. Presence of a catalyst wherein said contacting said hydrocarbon feedstock with an oxidant comprises a metal oxide having the formula M _x O _y , where M is an element selected from Group IVB, Group VB and Group VIB of the Periodic Table. 24. The method according to any one of claims 20-23, which occurs below.   25. The method of any one of claims 20-24, wherein the sulfur compound comprises a sulfide, disulfide, mercaptan, thiophene, benzothiophene, dibenzothiophene, alkyl derivative of dibenzothiophene, or a combination thereof.   26. The method of any one of claims 20-25, wherein the oxidation reactor is maintained at a temperature of about 20 to about 350 <0> C and a pressure of about 1 to about 10 bar.   27. The method of any one of claims 20-26, wherein the ratio of the oxidizer to sulfur compound present in the hydrocarbon feed is from about 4: 1 to about 10: 1.   28. The method of any one of claims 20-27, wherein the polar solvent has a Hildebrand value greater than about 19.   The polar solvent is 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, The method according to any one of claims 20 to 28.   30. The method according to any one of claims 20-29, wherein the polar solvent is acetonitrile.   31. The method of any of claims 20-30, wherein the polar solvent is methanol.   32. The method of any one of claims 20-31, wherein the solvent extraction is performed at a temperature of about 20 <0> C to about 60 <0> C and a pressure of about 1 to about 10 bar. A step of supplying the extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is charged with an adsorbent suitable for removing the oxidized compound present in the extracted hydrocarbon stream, and the absorption 33. The method of claim 20 further comprising the step of providing a column to produce a high purity hydrocarbon product stream and a second retentate stream, the second retentate stream comprising a portion of the oxidized compound. The method according to any one of items. 34. The method of claim 33, further comprising: supplying the second residual stream to the fluid catalytic cracking unit.   34. The method of claim 33, wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clay, silica-alumina, zeolites, and combinations thereof.   The adsorbent is a polymer coated support, the support has a large surface area and is selected from the group consisting of silica gel, alumina, and activated carbon, and the polymer is polysulfone, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, 34. The method of claim 33, selected from the group consisting of silica-alumina, zeolites, and combinations thereof.   37. The first residue stream and the fluid catalytic cracking feed stream are present in a weight ratio of the catalyst to the first residue stream and the fluid catalytic cracking feed stream in the range of about 1 to about 15. The method according to any one of 1.   The fluid catalytic cracking feed stream is vacuum gas oil, atmospheric residual oil, demetallized oil, whole crude oil, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oil, light cycle oil, heavy cycle oil, clarified slurry. 38. The method of any one of claims 20-37 comprising oil, or a combination thereof.   39. The method of any one of claims 20-38, wherein the contacting the first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst occurs in a temperature range of about 300 <0> C to about 650 <0> C. the method of.   40. Any of claims 20-39, wherein said contacting said first residual stream with a fluid catalytic cracking feed stream in the presence of a catalyst occurs with a residence time of from about 0.1 seconds to about 10 minutes. The method described. 41. Any of claims 20-40, further characterized by: separating low boiling components and catalyst particles from the first residual stream and the fluid catalytic cracking feed stream, and regenerating at least a portion of the catalyst particles. The method described in paragraph 1. Wherein the regenerating of at least a portion of the catalyst particles produces a regenerated catalyst and a gaseous product containing carbon monoxide and carbon dioxide and a liquid product, wherein 42. The method of claim 41, comprising contacting a portion of the with an anhydrous oxygen-containing gas.

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