Simultaneous metal, sulfur and nitrogen removal using supercritical water

a technology of supercritical water and metals, applied in the direction of hydrocarbon oil treatment, liquid carbonaceous fuels, fuels, etc., can solve the problems of high operating cost of hydrogen-addition process, and negative effect of contaminants on catalysts and equipment used in many processes

Inactive Publication Date: 2009-07-02
CHEVROU USA INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0012]The present invention relates to a process for removing metals, sulfur and nitrogen in the upgrading of hydrocarbons comprising: mixing hydrocarbons containing metals, sulfur and nitrogen with a fluid comprising water that has been heated to a temperature higher than its critical temperature in a mixing zone to form a mixture; passing the mixture to a reaction zone; reacting the mixture in the reaction zone under supercritical water conditions in the absence of externally added hydrogen for a residence time sufficient to allow upgrading reactions including demetalation and desulfurization to occur while maintaining an effective amount of metals, derived from the hydrocarbon undergoing upgrading, in the reaction zone to catalyze desulfurization reactions; and recovering upgraded hydrocarbons having a lower concentration of metals, sulfur and nitrogen than the hydrocarbons containing metal and sulfur.

Problems solved by technology

Such contaminants have very negative effects on the catalysts and equipment used in many processes for further refining to produce high value products.
Hydrotreating process typically takes place in a trickle bed or fixed-bed reactor using expensive catalyst such as Mo and requires the use, of high pressure hydrogen which becomes more and more expensive.
Hydrogen-addition processes also have high operating costs, since hydrogen production costs are highly sensitive to natural gas prices.
Some remote heavy oil reserves may not even have access to sufficient quantities of low-cost natural gas to support a hydrogen plant.
These hydrogen-addition processes also generally require expensive catalysts and resource intensive catalyst handling techniques, including catalyst regeneration.
Without externally supplied catalyst or hydrogen, the contaminate removal rate was not satisfactory.
Further, the process in the present Invention does not produce an appreciable coke by-product.

Method used

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  • Simultaneous metal, sulfur and nitrogen removal using supercritical water
  • Simultaneous metal, sulfur and nitrogen removal using supercritical water

Examples

Experimental program
Comparison scheme
Effect test

example 1

Experimental Process Description

[0047]A bomb reactor was loaded with a water and a heavy oil feed with API=12.8, which was a heavy crude oil which was diluted with a diluent hydrocarbon at a ratio of 5:1 (20 vol % of diluent). The reactor was immersed in a sand bath at reaction temperature so the temperature inside the reactor was quickly raised to ˜400° C., typically in 3 to 5 minutes. The reaction time was 30 minutes, and after reaction the reactor was quickly cooled down. The upgraded oil product and water were then recovered from the bomb reactor.

[0048]The properties of the heavy crude feed were as follows: 12.8 API gravity at 60 / 60; 1329 CST viscosity @40° C.; 13.04 wt % MCRT; 3.54 wt % sulfur; 0.56 wt % nitrogen; 3.05 mg KOH / gm acid number; 1.41 wt % water; 371 ppm Vanadium; and 86 ppm Nickel.

[0049]After the super critical water treatment upgraded product (syncrude) had the following properties: 19.2 API gravity at 60 / 60; 3.15 wt % MCRT; 0.54 wt % sulfur; 0.21 wt % nitrogen; 5...

example 2

[0050]The following procedure was performed using a continuous system. The feed oil was heated to 130° C. before entering a mixer. The heated crude was injected into a stream of supercritical water at temperature of 400° C. The water to oil ratio (volume at room temperature) was 3:1. The oil-supercritical water mixture was then injected into a reactor at temperature of 400° C. and pressure of 3400 psig. The upgraded product, which formed a homogeneous phase with supercritical water, was withdrawn from the top of the reactor and send to high pressure separator which was operated at the same pressure but lower temperature to achieve oil-water separation. The dreg stream was removed from reactor bottom.

[0051]The properties of the feed crude in Example 2 were as follows: 8 API gravity at 60 / 60; 65689 CST viscosity @40° C.;. 15.7 wt % MCRT; 4.17 wt % sulfur; 0.68 wt % nitrogen; 5.8 mg KOH / gm acid number; 435 ppm Vanadium; and 104 ppm Nickel.

[0052]After the super critical water treatment ...

example 3

[0053]The procedure of Example 2 was repeated except that the properties of the feed crude were as follows: 8 API gravity at 60 / 60; 20,400 CST viscosity @40° C.; 13 wt % MCRT; 5 wt % sulfur; 0.48 wt % nitrogen; 3.8 mg KOH / gm acid number; 215 ppm Vanadium; and 80 ppm Nickel.

[0054]After the super critical water treatment upgraded product (syncrude) had the following properties: 18 API gravity at 60 / 60; 21 CST viscosity @40° C. 3 wt % MCRT; 4 wt % sulfur; 0.27 wt % nitrogen; 41 ppm Vanadium; and 8 ppm Nickel.

[0055]For Examples 2 and 3, substantial reductions in metals, nitrogen and sulfur were observed, with simultaneous increase in the API gravity and a significant decrease in the viscosity of the original crude oil feedstock.

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Abstract

A process for removing metals, sulfur and nitrogen in the upgrading of hydrocarbons comprising: mixing hydrocarbons containing metals, sulfur and nitrogen with a fluid comprising water that has been heated to a temperature higher than its critical temperature in a mixing zone to form a mixture; passing the mixture to a reaction zone; reacting the mixture in the reaction zone under supercritical water conditions in the absence of externally added hydrogen for a residence time sufficient to allow upgrading reactions to occur while maintaining an effective amount of metals, derived from the hydrocarbon undergoing upgrading, in the reaction zone to catalyze the upgrading reactions; and recovering upgraded hydrocarbons having a lower concentration of metals, sulfur and nitrogen than the hydrocarbons before reaction is disclosed.

Description

FIELD OF THE INVENTION[0001]The present invention relates to a process for simultaneous removal of metals, sulfur and nitrogen from heavy oil using supercritical water.BACKGROUND OF THE INVENTION[0002]Heavy oil typically contains high concentration of sulfur, metals and nitrogen. Such contaminants have very negative effects on the catalysts and equipment used in many processes for further refining to produce high value products. Hydroprocessing is currently the process of choice to remove metal and sulfur from heavy oil. Hydrotreating process typically takes place in a trickle bed or fixed-bed reactor using expensive catalyst such as Mo and requires the use, of high pressure hydrogen which becomes more and more expensive. Hydrogen-addition processes such as hydrotreating or hydrocracking require significant investments in capital and infrastructure. Hydrogen-addition processes also have high operating costs, since hydrogen production costs are highly sensitive to natural gas prices....

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C10G45/00
CPCC10G31/08C10L1/026C10G2300/1011Y02P30/20
Inventor HE, ZUNQINGLI, LIN
Owner CHEVROU USA INC
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