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Desulfurization and denitrogenation with ionic liquids and metal ion systems / Saudi Arabian Oil Company




Title: Desulfurization and denitrogenation with ionic liquids and metal ion systems.
Abstract: This invention relates to a process for the desulfurization and denitrogenation of petroleum based hydrocarbon feeds with a mixture of at least one ionic liquid and at least one metal salt. Liquid or gas phase hydrocarbons contacted with the mixture to allow complexation of the sulfur and nitrogen species that are present in the processed stream. ...


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USPTO Applicaton #: #20100270211
Inventors: Ryszard A. Wolny


The Patent Description & Claims data below is from USPTO Patent Application 20100270211, Desulfurization and denitrogenation with ionic liquids and metal ion systems.

BACKGROUND

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OF THE INVENTION

1. Technical Field of the Invention

This invention generally relates to the field of the upgrading of hydrocarbons. In particular, the invention is directed to a process for the improved removal of sulfur and nitrogen from petroleum based hydrocarbon feeds.

2. Description of the Prior Art

In the petroleum industry, it is common for gas oils, particularly middle distillate petroleum fuels, to contain sulfur and nitrogen species. Engines utilizing sulfur-containing petroleum based fuels produce emissions of nitrogen oxide, sulfur oxide and particulate matter. Government regulations have become more stringent in recent years with respect to allowable levels of theses potentially harmful emissions.

Currently, many countries around the world limit allowable sulfur content in gasoline fuels to less than 50 ppm, and in some cases as low as 10 ppm or less. Thus, catalysts and processes for the production of gasoline fuels having a sulfur content of 10 ppm or less are of great interest.

Gasoline is typically produced as a blend of multiple components, from refining processes that use a variety of equipment, such as for example, distillation columns, catalytic crackers (FCC), hydro-crackers, and cokers. The sulfur content of the gasoline component from an FCC can be as high as 1000 to 5000 ppm, thus requiring extensive treatment to meet the current regulations by reducing the sulfur content to an acceptable level for use in automobile engines. Although several different methods can be employed, most commonly the FCC feed is pre-treated prior to being supplied to the FCC unit, or the gasoline component from the FCC is treated before being used as a fuel.

Conventional pre-treatment of an FCC feed can include hydrotreating of the feed to reduce the content of sulfur, nitrogen and metals, hydrofinishing all or a portion of the FCC naphtha, and hydrotreating the straight run kerosene and distillate, coker distillate and light cycle oil.

Post treatment processes can include hydrotreating all or a portion of an FCC naphtha, and hydrotreatment of the straight run kerosene and distillate, coker distillate and FCC light cycle oil.

In addition, products from straight run distillation columns can be hydrotreated to reduce the sulfur, nitrogen and metal content in finished products.

Post-treatment of the FCC naphtha is the least costly route to desulfurization. However, conventional FCC naphtha hydrotreating processes are expensive because they are not selective. In the process of removing sulfur, the hydrotreating process also results in saturation of essentially all of the olefins present in FCC naphtha. This in turn leads to substantial loss of research octane number (RON) (up to 10 octane numbers), as well as high hydrogen consumption, thus accounting for the high cost of conventional hydrotreating.

Furthermore, the reactivity of various organosulfur compounds over traditional hydrodesulfurization catalysts can depend on a variety of factors, including the molecular structures of the sulfur containing compounds. Aliphatic organosulfur compounds are typically highly reactive in conventional hydrotreating processes, and in general, are completely removed from fuels and feedstocks with little difficulty. In contrast, aromatic sulfur compounds, which can include thiophenes, dibenzothiophenes and alkylated dibenzothiophenes, are generally more difficult to remove over traditional hydrodesulfurization catalysts.

There are also other disadvantages associated with previously proposed desulfurization methods. For example, hydrodesulfurization in catalytic reactors requires that the reactors operate under relatively severe reaction conditions; i.e., low flow rates, high temperatures, high pressures and hydrogen consumption conditions. The relatively severe reaction conditions are necessary to overcome strong inhibition of refractory sulfur and nitrogen compounds against hydrodesulfurization. Therefore, strict conditions are also imposed on a process design, thereby typically incurring high construction costs.

Other methods for the removal of sulfur and nitrogen containing compounds can include various oxidative methods, which are typically followed by extraction of polar oxidized species, reactive adsorption, and fixed bed metal ion complexation methods. The main disadvantage to oxidative/extraction technologies are disposal of the oxidized sulfur species, difficulties associated with separation of the oxidizing media, and oxidant selectivity. Generally, while fixed bed metal complexation technologies offer a relatively simple route to the removal of sulfur containing compounds form motor fuels, when compared with oxidation/extraction technologies, fixed bed metal complexation technologies frequently suffer from metal leaching. In addition, fixed bed technologies can be limited by liquid-solid diffusion and progressive deterioration of the catalyst bed.

The present invention described herein can achieve sulfur removal of nearly 100% yield of the original feed stream. Additionally, the processes described herein typically do not create light compounds, which can increase the vapor pressure of the effluent. Because the methods described herein are not a hydrotreating technique, high hydrogen consumption, hydrogen purity, and the associated operating costs are not an issue.

SUMMARY

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OF THE INVENTION

In one aspect, a method for the desulfurization of a sulfur containing hydrocarbon feed is provided. The method includes the steps of: contacting a feed stream that includes a sulfur containing hydrocarbon feed with an extracting stream, wherein the extracting stream includes at least one metal salt and at least one ionic liquid solution, to create a mixed stream. During the contacting step, the metal ion of the metal salt binds with sulfur contained in the feed stream such that a significant amount of sulfur is removed from the hydrocarbon feed and bound to the metal. The mixed stream is separated into a sulfur-lean stream and a sulfur-rich stream and the sulfur-lean stream is collected as a product stream.

In certain embodiments, the ionic liquid includes an ion selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion and a phosphonium ion. In certain other embodiments, the metal salt can be a salt of a Group IB, IIB, VIB, or VIIIB metal, preferably selected from copper, nickel, zinc, cobalt, molybdenum, silver or palladium.

In certain embodiments, the method further includes the steps of: feeding the sulfur-lean product stream to a distillation column, separating the sulfur-lean product stream containing residual extracting media into a vapor stream and a residual liquid stream; and collecting the vapor stream as a purified product stream.

In another aspect, a method for the denitrogenation of a nitrogen containing hydrocarbon feed is provided. The method includes the steps of: contacting a feed stream that includes a nitrogen containing hydrocarbon feed with an extracting stream that includes at least one ionic liquid and at least one metal salt, to produce a mixed stream. During the step of contacting the feed stream and the extracting stream, the metal ion of the metal salt binds with the nitrogen contained in the feed stream such that a significant amount of the sulfur is removed from the hydrocarbon feed. The mixed stream is separated into a nitrogen-lean stream from a nitrogen-rich stream; and the nitrogen-lean stream is collected as a product stream.

In certain embodiments, the ionic liquid includes an ion selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion and a phosphonium ion. In certain other embodiments, the metal salt can be a salt of a Group IB, IIB, VIB, or VIIIB metal, preferably selected from copper, nickel, zinc, cobalt, molybdenum, silver or palladium.

In another aspect, a process for upgrading of a hydrocarbon feed is provided. The process includes the steps of: mixing the hydrocarbon feed and an adsorbent containing solution in a mixing vessel, wherein the adsorbent containing solution includes at least one ionic liquid and at least one metal salt. During the step of mixing the hydrocarbon feed and the adsorbent containing solution, the metal ion of the metal salt can bind to and remove one or more contaminants present in the hydrocarbon feed. The mixture is separated into a contaminant-lean hydrocarbon product stream and a contaminant-rich stream, and the contaminant-lean hydrocarbon stream is supplied to a first distillation column. Residual extracting solution is separated from the contaminant-lean hydrocarbon stream to produce a hydrocarbon product stream having a reduced contaminant content in comparison to the hydrocarbon feed stream. The sulfur-rich stream is supplied to a second distillation column to produce a top stream and a bottom stream, wherein the top stream includes a contaminant-rich stream and the bottom stream comprises ionic liquid. Ionic liquid is recycled back to the mixing vessel.

BRIEF DESCRIPTION OF THE DRAWINGS

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So that the manner in which the features, advantages and objects of the invention, as well as others that will become apparent, can be understood in more detail, more particular description of the invention briefly summarized above can be had by reference to the embodiment thereof which is illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only a preferred embodiment of the invention and is therefore not to be considered limiting of the invention\'s scope as it can admit to other equally effective embodiments.

FIG. 1 depicts a schematic of one embodiment of a process of producing desulfurized and/or denitrogenated hydrocarbons according to one of the invention.

FIG. 2 is an expanded stacked chromatogram showing an untreated Arabian Light fraction 400-600° F. (top), an Arabian Light fraction 400-600° F. treated with 1-ethyl-3-methylimidazolium tosylate/copper mixture (second from top), an Arabian Light fraction 400-600° F. treated with 1-butyl-4-methylpyridinium tetrafluoroborate/copper mixture (third from top), and an Arabian Light fraction 400-600° F. treated with 1-butyl-3-methylimidazolium octyl sulfate/copper mixture (bottom).

FIG. 3 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-ethyl-3-methylimidazolium tosylate/copper mixture (bottom).

FIG. 4 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-butyl-4-methylpyridinium tetrafluoroborate/copper mixture (bottom).

FIG. 5 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-butyl-3-methylimidazolium octyl sulfate/copper mixture (bottom).

FIG. 6 is an expanded stacked chromatogram showing an untreated Arabian Light fraction 400-600° F. (top), an Arabian Light fraction 400-600° F. treated with 1-ethyl-3-methylimidazolium tosylate/palladium mixture (second from top), an Arabian Light fraction 400-600° F. treated with 1-butyl-4-methylpyridinium tetrafluoroborate/palladium mixture (third from top), and an Arabian Light fraction 400-600° F. treated with 1-butyl-3-methylimidazolium octyl sulfate/palladium mixture (bottom).

FIG. 7 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-ethyl-3-methylimidazolium tosylate/palladium mixture (bottom).

FIG. 8 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-butyl-4-methylpyridinium tetrafluoroborate/palladium mixture (bottom).

FIG. 9 is an expanded stacked chromatogram for an untreated Arabian Light fraction 400-600° F. (top) and an Arabian Light fraction 400-600° F. treated with 1-butyl-3-methylimidazolium octyl sulfate/palladium mixture (bottom).




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stats Patent Info
Application #
US 20100270211 A1
Publish Date
10/28/2010
Document #
File Date
12/31/1969
USPTO Class
Other USPTO Classes
International Class
/
Drawings
0




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Saudi Arabian Oil Company


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Mineral Oils: Processes And Products   Refining   Sulfur Removal (free Or Combined Sulfur)   With Group Vi Metal Or Compound  

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20101028|20100270211|desulfurization and denitrogenation with ionic liquids and metal ion systems|This invention relates to a process for the desulfurization and denitrogenation of petroleum based hydrocarbon feeds with a mixture of at least one ionic liquid and at least one metal salt. Liquid or gas phase hydrocarbons contacted with the mixture to allow complexation of the sulfur and nitrogen species that |Saudi-Arabian-Oil-Company
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