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Upgrading of peroxide treated petroleum streams

a technology of peroxide and petroleum stream, which is applied in the direction of hydrocarbon oil treatment, aromatic hydrocarbon hydrogenation, refining to change the structural skeleton of hydrocarbon, etc., can solve the problems of presenting corrosion problems, relatively expensive peroxide, and raising operational concerns

Inactive Publication Date: 2007-06-21
EXXON RES & ENG CO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These crudes may, for example, present corrosion problems because they have high levels of naphthenic acids.
As many sulfur and nitrogen contaminants occur in aromatic compounds, they tend to accumulate in the aromatic extract.
Peroxides are, however, relatively expensive and may raise operational concerns.
A problem presented by the conventional upgrading process is that the raffinate from the solvent extraction contains levels of sulfur and / or nitrogen contaminants that would adversely impact subsequent catalytic dewaxing steps.

Method used

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  • Upgrading of peroxide treated petroleum streams
  • Upgrading of peroxide treated petroleum streams
  • Upgrading of peroxide treated petroleum streams

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0064] Experiments were conducted using a dewaxed HNN distillate as a test fluid and heated to 150° C. in the presence of air bubbling through the fluid. The oxidation products were measured by Fourier Transform Inferred Spectroscopy (FTIR) to determine the existence of oxidation products. Additionally a sample was heated in the presence of a nitrogen gas instead of air to determine the effect of any thermal degradation of the fluid under these test conditions. This sample was also measured by FTIR and used as a baseline reading. A subtraction spectra was generated at four different times during the oxidation experiments using the FTIR readings minus the baseline reading. The results are given in FIGS. 2 and 3, where FIG. 2 shows the FTIR subtraction spectra of four sequential samples undergoing oxidation across a wavelength ranging from 600 to 2000 cm−1. FIG. 3 shows FTIR subtraction spectra of four sequential samples undergoing oxidation reactions generally associated with the reg...

example 2

[0066] The current example uses real feeds of which are a combination of many species in their native environment. This example is directed to a series of runs comparing various catalyst / peroxide configurations as compared to a base case of a distillate undergoing extraction without the oxidation step (run 1 below). The series of runs include: [0067] 1. the heating of the distillate followed by extraction, [0068] 2. the addition of an oil-soluble catalyst, air and heat without peroxides followed by extraction, [0069] 3. the formation of in-situ peroxides, addition of air and heat without the oil soluble catalyst followed by extraction, [0070] 4. the formation of in-situ peroxides, addition of oil soluble catalyst, air and heat followed by extraction, [0071] 5. the formation of in-situ peroxides, addition of hydrogen peroxide, oil soluble catalyst, air, and heat followed by extraction.

[0072] The results of these runs have been shown in Table 1 as an improvement over the sulfur and n...

example 3

[0073] A set of experiments have been conducted using ZSM-48 followed by MCM-41 on hydrocracker bottoms with a pressure of 400 psig. The material contained approximately 25 wppm sulfur and 1.5 wppm nitrogen with a VI of 99. After hydroprocessing, the data showed a potential VI uplift of about 5 points with a conversion of 6-7 wt. % (FIG. 4). FIG. 4 is a graph showing the performance of ZSM-48 followed by MCM-41 at moderate operating pressures.

[0074] The yield loss is associated with the conversion of normal paraffinic species to iso-paraffinic species, beneficial to the VI. Similar data was generated at a pressure of 900 psig using various other feedstocks. These runs also showed significant VI improvements with minimal yield losses. These experiments provide support for an embodiment using air oxidation followed by solvent extraction followed by ZSM-48 catalytic dewaxing followed by MCM-41 aromatic saturation to improve basestock quality.

[0075] Additionally, this invention would ...

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Abstract

This invention relates to a method for upgrading petroleum streams which have been treated with peroxide, extracted to remove oxidized sulfur and nitrogen compounds, dewaxed and hydrofinished. More particularly, peroxides are generated in-situ by combining the petroleum stream with a high neutralization number (HNN) crude and adding an oxygen-containing stream. Alternatively, the oxidation of sulfur and nitrogen compounds may be accomplished by adding peroxides in the presence of oil soluble metal catalysts. The peroxides oxidize nitrogen and sulfur compounds in the petroleum stream to more polar compounds which are solvent extracted.

Description

FIELD OF THE INVENTION [0001] This invention relates to a method for upgrading petroleum streams which have been treated with peroxide, extracted to remove oxidized sulfur and nitrogen compounds, dewaxed and hydrofinished. More particularly, peroxides are generated in-situ by combining the petroleum stream with a high neutralization number (HNN) crude and adding an oxygen-containing stream. HNN crudes contain molecules sufficient for peroxide generation. Alternatively, the oxidation of sulfur and nitrogen compounds may be accomplished by adding peroxides in the presence of oil soluble metal catalysts. The peroxides oxidize nitrogen and sulfur compounds in the petroleum stream to more polar compounds which are solvent extracted. The raffinate from solvent extraction is then upgraded. BACKGROUND OF THE INVENTION [0002] Opportunity crudes are crudes that present some difficulties to the refiner and are therefore sold at discount. These crudes may, for example, present corrosion problem...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C10G65/00C10G45/00C10G17/00
CPCC10G21/00C10G27/04C10G27/12C10G45/44C10G45/58C10G67/04C10G67/12
Inventor PALMER, THOMAS R.MURPHY, WILLIAM J.PAGE, NANCY M.HANTZER, SYLVAIN S.
Owner EXXON RES & ENG CO
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