Reaction system and products therefrom.

(54) Title: REACTION SYSTEM AND PRODUCTS THEREOF. (54) Title: REACTION SYSTEM AND PRODUCTS THEREFROM.

(57) Summary

A reaction system and method for removing or removing heteroatoms from hydrocarbon feed streams containing oxidized heteroatoms and products derived therefrom is described. A hydrocarbon feed containing oxidized heteroatoms is reacted in a reaction system to thereby form nonionic hydrocarbon products. The products derived from them are useful in transportation fuels, lubricants, refinery intermediaries, or refinery feeds.

(57) Abstract

A reaction system and method for removing heteroatoms from oxidized-heteroatom-containing hydrocarbon streams and products derived therefrom are disclosed. An oxidized-heteroatom-containing hydrocarbon feed is reacted in a reaction system thereby forming non-ionic hydrocarbon products. The products derived therefrom are useful as transportation fuels, lubricants, refinery intermediates, or refinery feeds.

REACTION SYSTEM AND PRODUCTS THEREOF

FIELD AND BACKGROUND

The present description is directed to systems and 5 methods to treat the. crude oil, intermediate refining streams, and refining products to substantially reduce the content of unwanted heteroatoms, specifically sulfur, nitrogen, nickel, vanadium, iron, and to reduce the total acid number and to do this you have equipment that has an investment of relatively low capital and which is economical to operate.

Systems and methods are described for removing contaminants with oxidized heteroatoms that include, but are not limited to, sulfur, nitrogen, nickel, vanadium, iron * 15 and for reducing the total acid number of liquid hydrocarbon feed streams. After subjecting a stream of liquid hydrocarbons to oxidation conditions, to thereby oxidize at least a portion of the heteroatom compounds (eg, oxidizing dibenzothiophenes into sulfones), the oxidized heteroatom compounds are reacted with caustic. (eg hydroxide. sodium, potassium hydroxide, eutectic mixtures thereof etc.) and a selectivity promoter to produce substantially lower heteroatom containing hydrocarbon products.

As is well known in the industry, crude oil contains heteroatoms such as sulfur, nitrogen, nickel, vanadium, and acidic oxygenates in amounts that negatively impact the refining process of crude oil fractions. Light or condensed crude oils contain heteroatoms, in concentrations as low as

0.001% by weight. In contrast, heavy crude oils contain heteroatoms as high as 5-7% by weight. The heteroatom content of crude oil increases with an ever-increasing boiling point and the heteroatom content increases. increases with decreasing API severity .. These impurities must be removed during refining operations to comply with the environmental regulations of the specifications for final products (for example, gasoline, diesel, fuel) or to prevent the reduction of the catalytic activity, selectivity, and duration of the contaminants in operations of subsequent refining. Contaminants such as sulfur, nitrogen, residual metals, and total acid number (TAN) in the crude oil fractions negatively impact these subsequent processes, and others, including hydrotreatment, hydrocracking. and FCC to name just a few. These pollutants are present in the crude oil fractions in varying structures and concentrations.

It is widely recognized that the emission of sulfur oxides from fossil fuel combustion causes a serious problem of air pollution. In fact, sulfur is converted through. combustion into various sulfur oxides that can be converted into acids, therefore it is believed that .. S0 emissions_x they contribute to the formation of acid rain and also to the reduction of the efficiency of catalytic converters in automobiles. Furthermore, sulfur compounds are believed to ultimately increase the particle content of the combustion products.

A variety of methods have been proposed to remove sulfur compounds either from fuels before combustion or from exhaust gases thereafter. Most refineries use hydrodesulfurization (HDS) as the predominant process to remove sulfur from hydrocarbon streams. HDS remains an inexpensive option for light currents with sulfur levels up to approximately 2% (w / w) elemental sulfur. Although the environmental benefits of HDS are compensated in very heavy and acidic currents (> 2% elemental sulfur) due to the input of energy in the reaction, the high pressures and the amount of hydrogen necessary to remove the sulfur paradoxically. create a CO emission problem₂ substantial.

Due to these problems, the reduction of pollutants and, in particular, of the sulfur content in hydrocarbon streams has become a main objective of environmental legislation worldwide. The pending sulfur regulations in the United States for road diesel will be 15 ppm in NRLM diesel fuel. For

October 2012, the sulfur specifications for road diesel will be 15 ppm for NRLM diesel fuel. In the

European Union that specification is expected to be. Restrict to ppm in January 2011 for intended diesel for inland waterways and for equipment operated with road and non-road diesel. In China, the specification for road diesel will be 10 ppm by 2012. Currently the most stringent specifications in the world are in Japan, where the specification for road diesel is 10 ppm.

Refiners typically use catalytic hydrodesulfurization (HDS, commonly referred to as hydrotreating) methods to reduce the sulfur content of hydrocarbon fuels. In HDS, a hydrocarbon stream derived from a petroleum distillation is treated in a reactor that operates at temperatures ranging from 575 to 750 degrees F (about 300 to about 400 degrees C), a hydrogen pressure that varies from 430 to 14,500 psi (3,000 to 10,000 kPa or 30 to 100 atmospheres) and space speeds per hour ranging from 0.5 to 4 hr sup -1. Dibenzothiophenes in the feed react with hydrogen. when contacting a

<td colspan="2">catalyst are placed in a</td><td colspan="2">bed</td><td>permanent</td><td>than</td><td>understands</td>

<td>sulfides</td><td>metal groups</td><td>SAW</td><td>and</td><td>VIII</td><td>(by</td><td>example,</td>

<td>sulfides</td><td>cobalt and molybdenum</td><td> 0</td><td colspan="2">sulfides</td><td>of</td><td>nickel and</td>

molybdenum) held in alumina. Due to the conditions of

<td>operation and use</td><td>hydrogen, these</td><td>methods</td><td>they can</td><td>to be</td>

<td>expensive both in</td><td>capital investment</td><td>like in</td><td>costs</td><td>of</td>

<td>operation.</td><td></td><td></td><td></td><td></td>

<td>As you know</td><td>currently the HDS</td><td colspan="3">or hydrotreatment</td>

can provide a product treated in accordance with current strict sulfur level targets. However, due to the presence of spherically restricted refractory sulfur compounds such as unsubstituted and substituted dibenzothiophenes, the process is not smooth. For example, it is particularly difficult to remove sulfur residues using such catalytic processes when sulfur is contained in molecules such as dibenzothiophene with alkyl substituents at the 4, or 4 and 6 position. Attempts to completely convert these species, which are more prevalent into heavier reserves such as diesel fuel and fuel, have resulted in increased equipment costs, more frequent catalyst replacements, degradation of product quality due to side reactions, and the continued inability to meet the strictest sulfur requirements for some feeds.

This has led many to seek alternatives to hydrogen for desulfurization, such as oxidesulfurization. An attempt to solve the thiophene problem discussed above includes selectively desulfurizing the dibenzothiophenes contained in the hydrocarbon stream by oxidizing the dibenzothiophenes in a sulfone in the presence of an oxidizing agent, followed by optionally separating the sulfone compounds from the remainder of the stream. hydrocarbons. Oxidation has been found to be beneficial because oxidized sulfur compounds can be removed using a variety of separation processes that are based on altered chemical properties such as the solubility, volatility, and reactivity of the sulfone compounds. A specific sulfoxidation method and system is described in International Publication Number WO 2009/120238 Al, by Litz et al., The disclosure of which is incorporated herein by reference to the extent consistent with the present disclosure.

An issue with sulfoxidation lies in the waste of sulfones. If the sulfones are hydrotreated, they can be converted back to the original dibenzothiophene compounds thus re-generating the original problem. The sulfur content of the feed can probably be in the range of 0% to 10% by weight of sulfur. Sulfur, on average, comprises approximately 15% by weight of substituted and unsubstituted dibenzothiophene molecules. Therefore, up to 67% by weight of the oil can be removed as a sulfone extract. For typical refinery processing, 40,000 barrels per day of crude oil will be generated, up to 27,000 barrels per day of sulfone oil, which is believed to be too much to conventionally dispose of as a waste product. In addition, removal of sulfone oil also discards valuable hydrocarbons, which could theoretically be recycled if an efficient process were available.

As stated above, the main challenge presented for oxidesulfurization remains the removal of S0_x of the sulfone and sulfoxide groups created by the oxidation of the initial organic sulfur species. Kocal et al., US Patent Number 7,790,021 B2, the disclosure of which is incorporated herein by reference to the extent not inconsistent with the present disclosure, teaches the use of an aqueous caustic stream and a caustic waste stream for Treat sulfones and sulfoxide streams to produce substituted biphenyls. The problem with the method described is the costly extra steps to remove the substituted biphenyl products from the aqueous caustic stream and the lack of selectivity towards unsubstituted biphenyls, and the failure to teach any effect on other species containing heteroatoms.

A similar teaching of the use of melted caustic substance was described by Aída et al (reference) to treat sulfones in oxidized coal. Aida's teaching gives rise to ionizable and non-ionizable biphenyls with no apparent selectivity in product formation. Aída later teaches (Tetrahedron Letters publication) that desulfonylation with caustic alkoxide ions continues with the predominant formation of the formation of the carbon oxygen bond although with substantive formation of hydroxybiphenyls which constitute an extremely challenge to separate from the substance stream caustic because they are ionizable.

García et al. (J. Mol Catalysis 2008), teaches a nickel compound catalyzed desulfonylation reaction. Aída and Kocal et al., Showed that caustic substances react with sulfones, although their methods do not show selectivity with unsubstituted products and have not been shown to be capable of removing other heteroatoms. García et al., Showed that there is a way to selectively make unsubstituted biphenyls from sulfones, although it fails to do so in a cost-effective way and they did not demonstrate the ability to remove other heteroatoms. The method unfortunately employs an expensive stoichiometric Grignard reagent to selectively form unsubstituted biphenyl products and is therefore not suitable for the treatment of commercial fuels for economic reasons.

Below are the documents and references that are considered relevant to this description:

Reaction of Dibenzothiophene Sulfone with Alkoxides Aída, T .; Squires, TG; Venier, CG Tetrahedron Letters, (1983), 24 (34) p 3543-3546.

Developmént of an efficient coal-desulfurization process: oxy-alkalinolysis Authors Aída, T .; Venier, CG;

Squires, TG

Publication Date 1982 Sep 01 Technical Report Resource

Conference: American Chemical Society symposium on coal liquefaction, pages 328-334 Kansas City, MO, USA, 1 Sep 1982

<td>Times Lab., IA (USA); Advanced</td><td colspan="3">Fuel Research, Inc., East</td>

<td>Hartford, CT (USA).</td><td></td><td></td><td></td>

<td>Deoxydesulfurization of</td><td>Sulphons</td><td>Derived</td><td>desde</td>

<td>Dibenzothiophene using Nickel</td><td>Compounds,</td><td>Authors:</td><td>Alberto</td>

Oviedo, Jorge Torres-Nieto, Alma Arevalo, and Juventino J.

Garcia. J. Mol. Catalysis A: Chemical, (2008) 293, p 65-71.

Various metallic elements have long been known to occur in nature and in synthetic crude oils (see OI Miller et al, Anal. Chem., 24,

1728 [1952]).

Some of these metal impurities are known to be harmful when present in cargo reserves for oil refining, for example molecular decomposition or cracking, when present in boiler and turbine fuels and similar uses.

A process for removing vanadium and sodium from crude oil is described in US Patent No. 2,764,525 (FW Porter et al) where the oil comes into contact in the presence of hydrogen with alumina containing a smaller amount of ferric oxide .

A method of treating crude oil containing the residual metal components is described in the Patent

North American No. 2,910,434 (V.. V. Hess, et al) where oil is in contact with an inert packing material in the presence of hydrogen gas.

In US Patent No. 2,987,470 (M. Turken) a process is described for demineralizing oil by contacting it in a boiling bed with materials in contact with particles, for example, bauxite, alumina and the like.

US Patent No. 3, 819, 509 (RH Walk et al) metal and sulfur containing contaminants in a residual oil are removed from the fuel by contact with the oil in the presence of the desulfurization catalyst and an intimate combination of solids inert demetalization inert.

, In US Patent No. 3,964,995 (RH Walk et al) metals are removed from sulfur-contaminated petroleum and metals using porous alumina solids activated with a Fe group oxide promoter₂C&gt; 3, TiO₂ and SiO₂.

In US Patent No. 4,192,736 (Kluksdahl) metals are removed from petroleum by contact with alumina containing a phosphorous oxide promoter.

In US Patent No. 4,645,589 (FJ

Krambeck et al) are removed from the oil by extraction in aqueous phase with a phosphorous compound.

A process for removing metals and coke precursors is described in US Patent No. 6,245,223 (ML

Gorbaty et al) where the oil is in contact with a solid, low surface area adsorbent.

Therefore, there is a need for a selective process.

I to remove heteroatoms (including, but not limited to, sulfur, nitrogen, nickel, vanadium, iron, and the like) from a hydrocarbon stream containing oxidized heteroatoms thus avoiding the need for costly reagents, waste disposal, and other separation and management as well as cost issues associated with waste streams.

The inventors of the present disclosure have unexpectedly discovered that removal of heteroatoms from hydrocarbon streams containing substantially oxidized heteroatoms can be facilitated by employing the novel reaction system detailed herein. What is described herein are systems and methods that show selectivity towards nonionic hydrocarbon products using a novel caustic reaction system. Not only have we learned that our reaction system works for sulfur removal but. We have also learned that it has the beneficial ability to remove nitrogen, residual metals and reduces the total acid number of a hydrocarbon fuel and increases API gravity.

BRIEF DESCRIPTION OF THE INVENTION

A reaction method and system is described for reducing the content of heteroatoms, reducing the total acid number, and for increasing the API gravity of hydrocarbon feed streams containing substantially oxidized heteroatoms, including but not limited to, streams of internal refinery, crude oil or distilled fraction of crude oil. The reaction system for now can preferably be used in hot form and can

- comprise a feed input region, a reaction region and an output region; the reaction region may comprise a caustic compound, optionally a mixture of caustic compounds, and optionally held in an inert metal oxide, and a melted caustic liquid, and optionally a melted caustic mixture; the inlet region is fed independently or as a mixture comprising a hydrocarbon rich in oxidized heteroatoms and a selectivity promoter which combine in contact with the caustic compound (s); wherein the hydrocarbons rich in oxidized heteroatoms react with the caustic substance and selectivity promoter that selectively produce products of substantially non-ionic hydrocarbons that leave through the exit region with a content of heteroatoms lower than that of the feed .

The caustic component of the reaction region of the system of the present disclosure can be any inorganic compound that exhibits basic properties; for now preferably inorganic oxides of the elements of group IA and IIA; for now more preferably inorganic hydroxides of the elements of group IA and IIA, or optionally mixtures of oxides and hydroxides of the elements of group IA and IIA; for now even more preferably melted hydroxides of the elements of group IA and IIA, or optionally mixtures of the hydroxides of said elements; and for now more preferably melted NaOH. KOH, or a mixture thereof. Non-limiting examples may include, but are not limited to, Li₂O, Na₂OKAY₂O, Rb₂O, Cs₂O, · Fr₂O, BeO, MgO,

CaO, SrO, BaO, and the like as well as LiOH, NaOH, KOH, RbOH,

CsOH, FrOH, Be (OH)₂, Mg (OH)₂, Ca (OH)₂, Sr (OH)₂, Ba (OH)₂, and the like, and their mixtures or melted mixtures thereof.

Optional support components of the reaction region of the reaction system of the present disclosure

14 · can be any inorganic oxide, either inert or active; in particular a porous support such as talc or inorganic oxides can be used as support components .

Suitable inorganic oxides can be 5-element oxides from groups 2, 3, 4, 5, 13, 14, 15 and 16 of

Periodic Table of the Elements. Examples of preferred oxides as supports may include silicon dioxide, aluminum oxide, and also mixed oxides of the two elements and corresponding oxide mixtures. Other inorganic oxides which can be used alone or in combination with the aforementioned preferred oxide supports can be, for example, MgO, ZrO₂, Uncle₂ or CaO, to name just a few.

The support materials used can have a specific surface area in the range of 10 to 1000 m²/ g, a pore volume in the range of 0.1 to 5 ml / g and an average particle size, in the range of 0.1 to 10 cm. Preference can be given to supports that have a specific surface area in the range of 0.5 to 500 m²/ g, a pore volume in the range of 0.5 to 3.5 ml / g and an average particle size in the range of 0.5 to 3 cm. Preference can be given to supports that have a specific surface area in the range of 200 to 400 m²/ g, and a pore volume in the range of 0.8 to 3.0 ml / g.

The selectivity promoter may be an organic alcohol, ROH, where R is a C1-C18 alkyl, aryl, or alkenyl group, which produces a nonionic hydrocarbon product. The hydrocarbon product may be substantially insoluble in the melted caustic substance and leaves the exit region and may be preferred for a reaction system that does not contain a selectivity promoter because reaction products with caustic substances may tend to be hydroxides. organics which are substantially in the ionic form in severely caustic environments and therefore can be challenging to separate from the caustic without cost considerable. The selectivity promoter can most preferably be an alcohol, a diol, or a polyol and mixtures thereof. Non-limiting examples include, but are not limited to: methanol, benzyl alcohol, ethylene glycol, propylene glycol, glycerol, pinacol, 1,3-propanediol, and the like that can produce a nonionic product from the feed of oxidized heteroatoms. The nonionic product can be substantially insoluble and / or inert in the caustic substance and leaves the exit region and may be more preferred for a reaction system containing ionic products.

In order to provide a reaction system to decrease the content of heteroatoms (sulfur, nitrogen, vanadium, and nickel), decrease the Total Acid Number, and increase the API gravity of hydrocarbon feed streams containing heteroatoms, the Reaction is preferably heated and comprises a feed inlet region, a reaction region and an outlet region; the reaction region comprises a caustic compound, optionally a mixture of caustic compounds, and optionally held in an inert metal oxide, and optionally a melted caustic liquid, and optionally a melted caustic mixture; the inlet region is fed with hydrocarbons independently or as a mixture comprising a hydrocarbon rich in oxidized heteroatoms and a selectivity promoter that combine to come into contact with the caustic compound (s); wherein the hydrocarbons rich in oxidized heteroatoms react with the caustic substance and selectivity promoter which produce substantially non-ionic hydrocarbon products exiting through the exit region with a lower heteroatom content than in the feed.

The caustic component operably positioned in the reaction region of the system of the present disclosure may be any inorganic compound exhibiting basic properties which includes, but is not limited to, inorganic oxides of group IA and IIA elements, inorganic hydroxides of the Group IA and IIA elements, or optionally mixtures of oxides and hydroxides of Group IA and IIA elements, melted hydroxides of Group IA and TIA elements, or optionally the hydroxide mixtures of said elements. For now preferably inorganic oxides or hydroxides of the elements of group ΙΆ and IIA. For now more preferably inorganic hydroxides of the elements of group IA and IIA, or optionally mixtures of oxides and hydroxides of the elements of group IA and IIA. For now even more preferably melted hydroxides of group IA and IIA elements, or optionally hydroxide mixtures of said elements. For now more preferably

Melted NaOH, KOH, or a mixture thereof. Non-limiting examples may include Li₂O, Na₂0, K₂Or, -Rb₂O, Cs₂O, Fr₂OR,

BeO, MgO, CaO, SrO, BaO, and the like as well as LiOH, NaOH, KOH,

RbOH, CsOH, FrOH, Be (OH)₂, Mg (OH)₂, Ca (OH)₂, Sr (OH)₂, Ba (OH)₂, and the like, and their mixtures or melted mixtures thereof.

Optional support components of the reaction region of the reaction system of the present disclosure may be any inert, inert, or active oxide, such as, for example, a porous support such as talc or inorganic oxides.

Suitable inorganic oxides may be element oxides of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the

Periodic table of elements. Examples of preferred oxides as supports include silicon dioxide, aluminum oxide and also mixed oxides of the two elements and corresponding oxide mixtures. Other inorganic oxides which can be used. alone or in combination with the aforementioned preferred oxide supports are, for example, MgO, ZrO₂, Uncle₂ or CaO, to name just a few.

The support materials used can have a specific surface area in the range of 10 to 1000 m²/ g, a pore volume in the range of 0.1 to 5 ml / g and an average particle size in the range of 0.1 to 10 cm. Preference can be given to supports that have a specific surface area in the range of 0.5 to 500 m²/ g, a pore volume in the range of 0.5 to 3.5 ml / g and an average particle size in the range of 0.5 to 3 cm. Preference can be given to supports that have a specific surface area in the range of 200 to 400 m²/ g, and a pore volume in the range of 0.8 to 3.0 ml / g.

Other advantages and characteristics will become apparent from the following detailed description when read in conjunction with the accompanying drawings which include the application of the techniques described to currents other than diesel, such as, for example, crude oil, tar, diesel, kerosene. , transportation fuels, lubricants, and refinery intermediaries and other contaminated hydrocarbon streams containing sulfur and other contaminants.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the systems and methods described, reference will be made to the flow diagrams in Figures 1 and the equations in Figure 2.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise indicated, it is understood that all numbers expressing ingredient amounts, properties such as molecular weight, reaction conditions, etc., used in this specification and claims are modified in all cases by the term approximately.

Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations which may vary depending on the desired properties intended to be obtained by the present disclosure. At least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in view of the number of significant digits reported and applying ordinary rounding techniques.

Although the numerical ranges and parameters that establish the broad scope of the description are approximations, the numerical values ​​established in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective analysis measurements.

Unless otherwise indicated, the term effective amount used herein includes that amount of a substance capable of either increasing (directly or indirectly) the yield of the desulfonylation product or increasing selectivity towards formation of sulfur-free products. Unless otherwise indicated, optimal amounts of a given catalyst, heat, or steam can be varied based on reaction conditions, and the identity of other constituents can even be readily determined in view of the discrete circumstances of an application. Dadaist. Unless otherwise indicated, the term conversion or more precisely percent conversion (conv%), used herein, describes the mole ratio of sulfone converted by the combination of desulfonylation and deoxygenation reactions. in relation to the feed of - sulfone in the reaction. Unless otherwise indicated, the term selectivity used herein describes the percentage by mole of converted sulfur-free products. Unless. otherwise indicated, the term "yield" is used herein and describes the mole percent of products converted to a nonionic hydrocarbon.

Reaction systems and methods for removing heteroatoms from hydrocarbon streams containing oxidized heteroatoms and hydrocarbon products containing low amounts of heteroatoms derived therefrom are described. A hydrocarbon feed rich in oxidized heteroatoms, such as, for example, that provided by the sulfoxidation method and system described in the Publication

International Number WO 2009/120238 Al, by Litz et al., Can be reacted in the reaction system whereby hydrocarbon products substantially free of heteroatoms are formed which are easily separated from each other by conventional separation methods (i.e. vapor-liquid, liquid-liquid, or adsorption). Hydrocarbon products derived from the reaction system and method can be useful as transportation fuels, lubricants, and refinery feeds, intermediates, and refinery products.

In order to provide a reaction system and method to reduce heteroatom content and to increase API gravity, by decreasing the TAN of hydrocarbon feed streams containing oxidized heteroatoms, the reaction system may preferably be heated and comprises a region of feed inlet, reaction region, and outlet region; the reaction region comprises a caustic compound, optionally a mixture of caustic compounds, and optionally held in an inert metal oxide, and optionally a melted liquid, and optionally a melted mixture; the inlet region may receive the hydrocarbon feed independently or as a mixture comprising a sulfone-rich hydrocarbon and a selectivity promoter that combine to be in contact with the caustic compound (s); wherein the hydrocarbons rich in oxidized heteroatoms react with the caustic substance and selectivity promoter that produce substantially non-ionic hydrocarbon products that leave through the exit region with a content of heteroatoms lower than that of the feed.

The caustic compound operably positioned in the reaction region of the system of the present disclosure can be any inorganic compound that exhibits basic properties which includes, but is not limited to, inorganic oxides of group IA and IIA elements, inorganic hydroxides of the elements of group IA and IIA, or optionally mixtures of oxides and hydroxides of elements of group IA and IIA, melted hydroxides of elements of group IA and IIA, or optionally mixtures of said elements. Non-limiting examples may include, Li₂OR,

Na₂0, K₂0, Rb₂O, Cs₂O, Fr₂O, BeO, MgO, · CaO, SrO, BaO, and the like as well as LiOH, NaOH, KOH, RbOH, CsOH, FrOH, Be (OH)₂,

Mg (OH)₂, Ca (OH)₂, Sr (OH)₂, Ba (OH)₂, and the like, and their mixtures or molten mixtures thereof.

Optional support components of the reaction region of the reaction system of the present disclosure may be any inert, inert, or active oxide, such as, for example, a porous support such as talc or inorganic oxides.

Suitable inorganic oxides can be oxides of the elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the

Periodic table of elements. Examples of preferred oxides as supports include silicon dioxide, aluminum oxide, and also mixed oxides of the two elements and corresponding oxide mixtures. Other inorganic oxides which can be used alone or in combination with the aforementioned preferred oxide supports can be, for example, MgO, ZrO₂, Uncle₂ or CaO, to name just a few.

The support materials used can have a specific surface area in the range of 10 to 1000 m²/ g, a pore volume in the range of 0.1 to 5 ml / g and an average particle size in the range of 0.1 to 10 cm. Preference can be given to supports that have a specific surface area in the range of 0.5 to 500 m²/ g, a pore volume in the range of 0.5 to 3.5 ml / g and an average particle size in the range of 0.5 to 3 cm. Preference can be given to supports that have a specific surface area in the range of 200 to 400 m²/ g, and a pore volume in the range of 0.8 to 3.0 ml / g.

The selectivity promoter can be an organic alcohol, ROH, where R is a C1-C18 alkyl, aryl, or alkenyl group, which produces a nonionic hydrocarbon product. The hydrocarbon product can be substantially insoluble in the melted caustic substance and leaves the exit region and may be preferred for a reaction system that does not contain a selectivity promoter because the reaction products without the promoter tend to be organic hydroxides which are substantially in the ionic form in severely caustic environments and therefore it can be challenging to separate them from the caustic substance without considerable expense. The selectivity promoter for now more preferably may be an alcohol, a diol, 'or a polyol and mixtures thereof. Non-limiting examples include, but are not limited to: methanol, benzyl alcohol, ethylene glycol, propylene glycol, glycerol, pinacol, 1,3-propanediol, and the like that can produce a nonionic product from the feed of oxidized heteroatoms. For now, selectivity promoters falling in the class of compounds, referred to as neighborhood diols, which may have hydroxyl groups attached to adjacent carbon atoms, or the class of alcohols known as primary alcohols, where the group of Hydroxyl is attached to one carbon atom that is attached to at most one other carbon atom. For now, ethylene glycol or methanol may be more preferred. The nonionic hydrocarbon product can be substantially insoluble and / or inert to the caustic substance and leaves the exit region and may be more preferred for a reaction system containing ionic products.

Figure 1 illustrates how the selectivity of the reaction of the present description is improved to form more precious or valuable products. Dibenzothiophene sulfone was chosen as a model sulfur compound because most of the sulfur in an average diesel fuel is in the form of substituted or unsubstituted dibenzothiophene. Equation (1) illustrates how the hydroxide attacks the sulfur atom of dibenzothiophene sulfone (A), which forms biphenii-2-sulfonate (B). Equation (2) illustrates how hydroxide can attack B at the carbon atom adjacent to the sulfur atom, which forms biphenyl-2-ol (C) and sulfite salts (D). Compound C can be ionized in basic media, and can be dissolved in the aqueous or melted salt layer. Equation (3) illustrates how hydroxide can attack the sulfur atom in B to form biphenyl (E) and sulfate salts (F). Equation (4) illustrates how, in the presence of a primary alcohol, which includes, but is not limited to, methanol, in situ generated methoxide ions can attack the carbon atom, which forms

<td>compounds</td><td>of</td><td colspan="2">ether, such as 2-</td><td colspan="2">methoxybiphenyl (G).</td><td>The</td>

<td>Equation</td><td> (5)</td><td>illustrates the</td><td>reaction</td><td>of the</td><td>sulfone</td><td>of</td>

<td colspan="2">dibenzothiophene</td><td>with alkoxides</td><td>alone,</td><td>not in the</td><td>presence</td><td>of</td>

<td>hydroxide,</td><td>how</td><td>is taught by</td><td>Aida et</td><td>al., for</td><td>form the</td><td>Salt</td>

of biphenyl-2-methoxy-2'-sulphinate · (H), which can be substantially soluble in the caustic substance. Use of the aqueous or melted hydroxide without the selectivity promoter currently described will cause reaction (1) to occur, followed predominantly by reaction (2). When the neighborhood diol selectivity promoter described herein is used, reaction (1) occurs, followed predominantly by reaction (3). When the primary selectivity promoter (alcohol) described herein is used, reaction (1) occurs, followed predominantly by reaction (4). It can be seen that the hydrogen atoms that adhere to the biphenyl come from the hydroxide. When water is used in the regeneration of the caustic substance, the last source of the hydrogen atoms added to the biphenyl may be water.

The two representative modalities of a plurality of possible representative modalities of systems and methods for removing contaminants from hydrocarbon streams and contaminated feed products derived therefrom are shown in FIGURE 2. Both systems and methods can start with a heteroatom-contaminated hydrocarbon feed that undergoes treatment to meet current and future environmental standards. In a representative system and method, a hydrocarbon feed containing oxidized heteroatoms can be supplied via line A, to a mixing vessel 10 via a feed inlet where the contaminated feed can be combined with a caustic substance and a selectivity promoter where it is allowed to react in the mixing container 10 to decontaminate the contaminated feed. The reaction combination can preferably be heated generally in a temperature range of 50-450 ° C at a pressure of 0 - 56.24 kg / cm² (0-800 psi).

Mixing vessel 10 may comprise a feed inlet 12, a reaction mixture comprising a stream of hydrocarbons containing oxidized heteroatoms, caustic, glycol, and intermediates and reaction products, an outlet 14 operatively connected to a settling vessel 16 , where clean petroleum (substantially non-ionic hydrocarbon products having a lower heteroatom content than hydrocarbon feed streams containing oxidized heteroatoms) can optionally be flushed with water and / or spun 18 to produce a substantially hydrocarbon product free of heteroatoms. The settled caustic and the selectivity promoter can be removed by gravity sedimentation from the bottom of the decanter vessel 16 to a process gas / caustic desulfurization recovery unit 22. The recovered caustic substance and the selectivity promoter are then sent back to the mixing vessel 10 to allow a continuous decontamination reaction process. The decanter container 16 may comprise a feed inlet 24 from the mixer

10, a clean oil outlet 26 to an optional water wash / centrifuge 18 and then to a clean oil recovery location (not shown) and a caustic / selectivity promoter outlet which can be operatively connected to unit 22 for the recovery of caustic substance through the desulphurisation of the process gas. The caustic recovery unit 22 by process gas desulfurization of the process gas may comprise the outlet 28 of the recovered caustic / selectivity promoter which is operatively connected to mixer 10 to transport the recovered caustic / promoter selectivity of the caustic recovery unit 22 by desulphurizing the process gas to the mixer 10, providing the continuous process mentioned above.

The caustic recovery unit 22 by process gas desulfurization may also comprise a gypsum outlet 30 for transporting the gypsum to a gypsum storage or distribution unit (not shown).

In a second representative method and system, a hydrocarbon feed stream containing oxidized heteroatoms a can be provided. Through line B to a continuous countercurrent reaction column 40 (CCR column), at the top of said column, a stream of recovered caustic substance and selectivity promoter is fed to it, the two streams are in contact between yes in a countercurrent mode and the selectivity promoter, the caustic. and the sulfite exit through an outlet 42 at the bottom of column 40 and are transported to a caustic recovery unit 22 by process gas desulfurization, where the caustic and the selectivity promoter are regenerated and recovered . Clean oil 44 exits the top of the countercurrent recovery column where it can optionally be washed with water and centrifuged to produce a hydrocarbon product substantially free of heteroatoms.

In both systems and methods, route A where a mixer / decanter is used and route B using a countercurrent reaction column, generate a used caustic substance / selectivity promoter stream that exits to the caustic recovery unit 22 by desulphurizing the process gas to produce a regenerated caustic substance and selectivity promoter that is recycled to the initial stage of the systems and methods and a gypsum by-product containing the heteroatoms that previously reside in the untreated feed stream.

EXAMPLES

In order to demonstrate the significant benefit of the present disclosure, examples of the systems and methods of the present disclosure were made. For comparative purposes, various control reactions were performed. The reaction vessel consisted of a stainless steel Parr type reaction vessel. The reactor was charged with a hydrocarbon feed rich in oxidized heteroatoms and heated to a temperature of 275 ° C at a constant feed rate. The heteroatom content of the products was analyzed.

EXAMPLE 1

A stainless steel Parr type pressure reactor (type 316) with a volume of 1000 mL was charged with 29 grams of

1: 1 mol of a mixture of sodium hydroxide and potassium hydroxide, 11 grams of dibenzothiophene sulfone, and 202 grams of 1,2,3,4-tetrahydronaphthalene. The vessel was heated under rapid stirring to 300 ° C. The reactor was held at this temperature for 60 minutes, during which the pressure was raised to a maximum of 10.54 kg / cm² (150 psi), then removed from the heat and allowed to cool without stirring. 200 grams of liquid were decanted from the reactor, and 41 grams of solids remained. The tetralin layer was analyzed by HPLC. The solids were acidified by adding 125 mL of 5.0 M HC1. Vigorous bubbling of sulfur dioxide released from neutralization of sulfites occurred, which was confirmed by a sulfur dioxide detector. Dichloromethane was added to extract organic materials, which were then evaporated, leaving a light brown oil, which was analyzed by HPLC. &gt; 99% of the dibenzothiophene sulfone was found to be converted into the following products:

ortho-phenylphenol (56%), biphenyl (21%), dibenzofuran (4%), and dibenzothiophene (4%), to a total sulfur-free yield of 81%. The performance of all organic materials was

95%.

EXAMPLES 2-4

The EXAMPLE 1 experiment was repeated three times, except that the temperature was 275 ° C. The average results were: 94.5% conversion of dibenzothiophene sulfone, in the following products: ortho-phenylphenol (58%), biphenyl (9%), and dibenzof uran (5%)., No dibenzothiophene was detected (&lt;1% ). Total sulfur free yield was 73%. The average yield of all organic materials was 97%.

EXAMPLE 5

The EXAMPLE 2 experiment was repeated except that 20 grams of methanol was added to the reactor with the other reagents. The pressure rose to 24.60 kg / cm² (350 psi) during the reaction. It was found that 92% of the dibenzot'iofen sulfone has been converted into the following products: 2-methoxybiphenyl (40%), ortho-phenylphenol (30%), biphenyl (6%),. 5 and dibenzofuran (3%). No dibenzothiophene was detected (&lt;1%). Total sulfur-free yield was 79%, with 49% being non-ionizable products. In addition, sulfur dioxide was detected after the run when the pressure was released, before any acid had been added. The yield of all organic materials was 97%, not including methanol, which was cleaned with water in the acid treatment.

EXAMPLE 6

EXAMPLE 2 experiment was repeated except 45 grams of tert-butanol were added. The results were similar to those of EXAMPLE 2, and the expected tere-butyl ether was not detected. Sulfur dioxide was detected just after the run cooled down. The yield of all organic materials was 92%.

EXAMPLE 7

0 The EXAMPLE 5 experiment was repeated except that 33 grams of sodium methoxide were added to the reactor with the other reagents. The results were similar to those of EXAMPLE 5.

EXAMPLE 8

The EXAMPLE 5 experiment was repeated except that the 29 grams of the 1: 1 molar sodium hydroxide / potassium hydroxide mixture were omitted, and 33 grams of sodium methoxide (which contains some sodium hydroxide as impurity) were added ). The results were analyzed by GC-MS, which showed the conversion of dibenzothiophene sulfone to only ~ 80%, and that the main product formed was ortho-phenylphenol, followed by 2-methoxybiphenyl and biphenyl. Sulfur dioxide was detected immediately after the run cooled down. The yield of all organic materials was 90%.

EXAMPLE 9

The EXAMPLE 5 experiment was repeated except that the reaction was held at temperature for 90 minutes. The results were similar to those of EXAMPLE 5. The yield of all organic materials was 95%.

EXAMPLE 10

The EXAMPLE 5 experiment was repeated except 60 grams of methanol were used. The pressure rose to 52.72 kg / cm² (750 psi) during the reaction. It was found that 95% of the dibenzothiophene sulfone had been converted to the following products: ortho-phenylphenol (54%), dibenzofuran (10%), 2-methoxybiphenyl (9%), and biphenyl (8%). No dibenzothiophene was detected (&lt;1%). Total sulfur free yield was 81%. Sulfur dioxide was detected only after the run cooled down. The yield of all organic materials was 100%, not counting methanol.

EXAMPLE 11

The EXAMPLE 5 experiment was repeated except that 87 grams of the 1: 1 mole mixture of sodium hydroxide and potassium hydroxide were used. It was found that 97% of the dibenzothiophene sulfone was converted. The distribution of the product was similar to that of EXAMPLE 5. The yield of all organic materials was 91%.

EXAMPLE 12

The EXAMPLE 2 experiment was repeated except that 48 grams of phenol were added to the reactor along with the other reagents. The pressure reached 14.06 kg / cm² (200 psi) during the run. No sulfur dioxide was detected after the run, nor was it detected at all when the solids were acidified with HC1. The products were analyzed by GCMS, which did not detect dibenzothiophene sulfone at all. The main products were ortho-phenylphenol and dibenzothiophene.

The yield of all organic materials was 96%.

EXAMPLE 13

The EXAMPLE 1 experiment was repeated except that the reactor was kept at temperature for 120 minutes. The results were similar to EXAMPLE 1. The oil layer was decanted from the rector, and 200 grams of methanol was added to the solids. These were sealed and shaken together at 60 ° C for 5 hours. A sample of this product was extracted with dichloromethane and water, and the dichloromethane layer was analyzed by GC-MS. Only one trace of 2methoxybiphenyl was detected.

EXAMPLE 14

The EXAMPLE 2 experiment was repeated except that 40 grams of dicyclopentadiene was added to the reactor with the other reagents. The sample was analyzed by GC-MS, which showed a large number of different products, including a substantial amount of dibenzothiophene.

EXAMPLE 15

The 1L pressure reactor was charged with 200 grams of ethanol, 2.4 grams of magnesium residues, and 11 grams of dibenzothiophene sulfone. The mixture was stirred at room temperature for 60 minutes. The product was analyzed as is by GC-MS. Approximately 25% of the dibenzothiophene sulfone had been converted, and the only product was dibenzothiofen.

EXAMPLE 16

The EXAMPLE 5 'experiment was repeated except that only 10 grams of methanol were added to the reactor with the other reagents. The product was developed similarly to EXAMPLE 1. 97% of dibenzothiofen was found to have been converted into the following products: ortho-phenylphenol (15%), dibenzofuran (2%), 2-methoxybiphenyl (47%), and biphenyl (8%), dibenzothiophene (2%). Total sulfur free yield was 72%. Sulfur dioxide was detected just after the run cooled down. The yield of all organic materials was 97%, not counting methanol.

EXAMPLE 17

A 1L Parr pressure reactor was charged with 200 grams of tetralin, 12 grams of sodium hydroxide, 17 grams of potassium hydroxide, 11 grams of dibenzothiophene sulfone, and 28 grams of ethylene glycol. The reactor was purged with nitrogen prior to the run, until oxygen could not be detected on an oxygen sensor (&lt;0.1%). The reactor was sealed and heated at 275 ° C for one hour. The product was developed using the procedure in EXAMPLE 1. However, no sulfur dioxide was detected after the run, or during acidification. Also, very few bubbles formed during the acidification step. 100% of the dibenzothiophene sulfone was found to have been converted to the following products: biphenyl (&gt; 75%), ortho-phenylphenol (&lt;25%).

The total sulfur-free yield was 100%. The yield of all organic materials was 97%, excluding ethylene glycol, which was cleaned with water in the acid treatment. '

EXAMPLE 18

The EXAMPLE 17 experiment was repeated except that instead of tetralin and dibenzothiophene sulfone, 100 grams of a diesel stream containing heteroatoms oxidized with ~ 2000 ppm sulfur in the form of sulfones were used. Additionally, 1.5 grams of sodium hydroxide, 2.2 grams of potassium hydroxide, and 3.2 grams of ethylene glycol were added. The petroleum product was washed with water and dried, then the sulfur content was analyzed by XRF. The process was repeated a total of three times. The sulfur content of the fuel was significantly reduced, to less than 430 ppm S. The nitrogen content was decreased to at least 85%, and the total acid number was decreased below measurable concentrations, at least a decrease of 60 %.

EXAMPLE 19

The EXAMPLE 18 experiment was repeated except that a tar stream containing ~ 4% sulfur was used in place of a diesel. The sulfur content after the reaction was significantly reduced, to less than 1.75% by weight of sulfur.

EXAMPLE 20

A 1L stainless steel Parr reactor was charged with 100 grams of 2.75 wt% sulfur-containing tar oil containing oxidized heteroatoms, 21 grams of sodium hydroxide, 29 grams of potassium hydroxide, and -64 grams of ethylene glycol. The reactor was purged with nitrogen, then heated to 275 degrees C and held at that temperature for 1 hour, then cooled. The oil was washed with water to remove the caustic and ethylene glycol until the pH of the wash water was below 8.5, then dried. The sulfur content after the reaction was at most 1% sulfur, the vanadium content had been reduced from 175 ppm 'to less than 65 ppm, and the nickel content had been reduced from 67 ppm to below 33 ppm.

PRE-FIGURATIVE EXAMPLE 1

A 1000 mL volume stainless steel Parr pressure reactor (type 316) was charged with approximately 11 grams of dibenzothiofenq sulfone, approximately 202 grams of 1,2,3,4-tetrahydronaphthalene, approximately 24 g of benzyl alcohol and approximately 5.7 g of potassium hydroxide. The vessel was heated under rapid stirring to 195 ° C. The reactor was kept at this

<td>temperature</td><td>during</td><td colspan="2">about 60 minutes,</td><td>and later</td><td>I know</td>

<td>withdrew from</td><td>hot</td><td>and let it cool</td><td>without</td><td colspan="2">agitation.</td>

<td colspan="2">About 210</td><td>grams of liquid</td><td colspan="2">they decanted</td><td>of the</td>

<td>reactor, and</td><td>they were</td><td>about 8 grams</td><td>of</td><td>solid.</td><td>The</td>

<td colspan="3">tetralin layer was analyzed by HPLC.</td><td>The</td><td>solids</td><td>I know</td>

<td>acidified</td><td colspan="2">adding approximately</td><td> 25</td><td>mL</td><td>of</td>

approximately HC1 5.0 M. Sulfur dioxide is released when neutralization of the sulfites occurs. Dichloromethane is added to extract organic materials, which are then evaporated, leaving an oil, which is analyzed by HPLC. The conversion of the dibenzothiophene sulfone is at least as good as that presented in EXAMPLE 5 with a similar product distribution: 2-benzyloxy-biphenyl (approximately 40%), ortho-phenylphenol (approximately 30%), biphenyl (approximately 6 %), and dibenzofuran (approximately 3%).

PRE-FIGURATIVE EXAMPLE 2

A 1000 mL volume stainless steel Parr-type pressure reactor (type 316) was charged with approximately 200 grams of tar oil which · has a sulfur content of 2% by weight, 15 grams of sodium hydroxide, 21 grams of potassium hydroxide, and 35 grams of ethylene glycol. The vessel was heated under rapid stirring to 275 ° C. The reactor was held at this temperature for approximately 60 minutes, and then removed from the heat and allowed to cool without stirring. Approximately 20 grams of liquid is decanted from the reactor, and approximately 70 grams of solids remain. The removal of sulfur and metals is at least as good as that presented in EXAMPLE 18 and EXAMPLE 20. The sulfur content is decreased to less than 1% by weight, nitrogen and metal content is decreased to more than 50%.

The API gravity of the feed was increased to at least 5 units.

The results of the previous examples are illustrated in Table 1 below.

<td>EXAMPLE</td><td>% of</td><td> 2-</td><td>ortho-</td><td></td><td></td><td></td>

<td> #</td><td>Conversion</td><td>methoxybiphenyl</td><td>phenithphenol</td><td>biphenyl</td><td>dibenzofuran</td><td>dibenzothiophene</td>

<td> 1</td><td> 99%</td><td> 0%</td><td> 56%</td><td> 21%</td><td> 4%</td><td> 4%</td>

<td> 2</td><td> 95%</td><td> ' 0%</td><td> 58%</td><td> 9%</td><td> 5%</td><td> 0%</td>

<td> 3</td><td> 95% ’</td><td> 0%</td><td> 58%</td><td> 9%</td><td> 5%</td><td> 0%</td>

<td> 4</td><td> 95%</td><td> 0%</td><td> 58%</td><td> 9%</td><td> 5%</td><td> 0%</td>

<td> 5</td><td> 92%</td><td> 40%</td><td> 30%</td><td> 6%</td><td> 3%</td><td> 0%</td>

<td> 6</td><td> 95%</td><td> 0%</td><td> 58%</td><td> 9%</td><td> 5%</td><td> 0%</td>

<td> 7</td><td> 92%</td><td> 40%</td><td> 30%</td><td> 6%</td><td> 3%</td><td> 0%</td>

<td> 8</td><td> -80%</td><td></td><td>higher</td><td></td><td></td><td></td>

<td> 9</td><td> 92%</td><td> 40%</td><td> 30%</td><td> 6%</td><td> 3%</td><td> 0%</td>

<td> 10</td><td> 94%</td><td> 9%</td><td> 54%</td><td> 8%</td><td> 10%</td><td> 0%</td>

<td> 11</td><td> 92%</td><td> 40%</td><td> 30%</td><td> 6%</td><td> 3%</td><td> 0%</td>

<td> 12</td><td>N / A</td><td></td><td></td><td></td><td></td><td>higher</td>

<td> 13</td><td> 99%</td><td> 0%</td><td> 56%</td><td> 21%</td><td> 4%</td><td> 4%</td>

<td> 14</td><td>N / A</td><td></td><td></td><td></td><td></td><td>higher</td>

<td> 15</td><td>N / A</td><td></td><td></td><td></td><td></td><td>higher</td>

<td> 16</td><td> 97%</td><td> 47%</td><td> 15%</td><td> 8%</td><td> 2%</td><td> 2%</td>

<td> 17</td><td> 100%</td><td> 0%</td><td> 25%</td><td> 75%</td><td> 0%</td><td> 0%</td>

Although only certain modalities have been established, alternatives and alternative modifications of the foregoing description will be apparent to those skilled in the art such as applying the techniques and apparatus described to crude oil, tar, kerosene, and other fuel streams and the use of Similar reagents to convert hydrocarbons containing oxidized heteroatoms into nonionic hydrocarbon products. These and other alternatives are considered equivalent and within the spirit and scope of this description and the appended claims.