KR20200000240A - Reduction method of asphaltenes - Google Patents

Abstract

Provided is an asphaltene reduction method. The asphaltene reduction method comprises the following steps: supplying an asphaltene-containing material, a solvent, and a metal oxide precursor to a reactor; and adjusting the reactor to supercritical condition to perform a deasphaltene reaction.

Description

Asphaltene reduction method {REDUCTION METHOD OF ASPHALTENES}

The present invention relates to a method for reducing asphaltenes and to a method for reducing asphaltenes using a supercritical fluid and a metal oxide precursor.

According to the United States Department of Energy (DOE), ultra-heavy crude oil is expected to cover 2.4 billion barrels / year of total crude oil consumption of 36 billion barrels / year since 2020. However, super heavy crude oil has high density and viscosity, and high sulfur and asphaltene content, so it is impossible to separate crude oil through conventional atmospheric distillation tower, and thus pretreatment process is essential. Currently, pretreatment to reduce the sulfur and asphaltene content in ultra heavy crude oil is carried out through decompression process, high temperature pyrolysis process, catalytic hydrolysis process, but the cost of hydrogen added to form hydrogen atmosphere is high. Due to the high sulfur content of the crude oil, there are problems such as deactivation of the catalyst and additives used, and it is a situation that does not solve the process problems in the transportation and fractionation process due to coke generated in the pretreatment process.

In order to solve the above problems, the present invention provides a method that can effectively reduce the asphaltene in the asphaltene-containing material.

Other objects of the present invention will become apparent from the following detailed description and the accompanying drawings.

According to embodiments of the present invention, a method for reducing asphaltenes includes supplying an asphaltene-containing material, a solvent, and a metal oxide precursor to a reactor, and changing the reactor to supercritical conditions to perform a deasphaltene reaction. Include.

The solvent may comprise one or more of water and alcohols. The solvent may comprise -OH.

The metal oxide precursor may comprise one or more of metal salts and metal salt hydrates. The metal oxide precursor may comprise one or more of zinc nitrate and zinc nitrate hydrate.

The reactor is a continuous reactor, and the metal oxide precursor may include the metal salt hydrate.

The metal oxide precursor may include a metal hydroxide and an acid. The metal oxide precursor may include zinc hydroxide and nitric acid.

The asphaltene-containing material and the solvent may be supplied in a weight ratio of 1: 1 to 1:10.

The asphaltene containing material may comprise crude oil or hydrocarbons.

According to embodiments of the present invention, it is possible to effectively reduce asphaltene in asphaltene-containing materials such as crude oil. Process efficiency can be improved while simplifying the deasphalten and advanced processes. In addition, the process can be applied to a continuous reactor to increase the throughput of asphaltene containing material.

1 is a view for explaining a process for reducing asphaltenes of crude oil according to an embodiment of the present invention.
Figure 2 shows the composition of Venezuela's Boskan regional high-sulfur crude oil.
Figure 3 shows the hydration and molecular weight of the metal oxide precursor according to embodiments of the present invention.
Figure 4 shows the mass and content of maltene, asphaltenes, coke, and metal oxides according to the type of metal oxide precursor according to embodiments of the present invention.
5 illustrates asphaltene conversion and coke formation rate according to the type of metal oxide precursor when water is used as a supercritical fluid.
6 illustrates asphaltene conversion and coke formation rate according to the type of metal oxide precursor when methanol is used as a supercritical fluid.
FIG. 7 shows the conversion of asphaltenes to coke depending on the type of metal oxide precursor when water is used as the supercritical fluid.
8 shows the conversion of asphaltenes to coke according to the type of metal oxide precursor when methanol is used as the supercritical fluid.

Hereinafter, the present invention will be described in detail through examples. The objects, features and advantages of the present invention will be readily understood through the following examples. The invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and the spirit of the present invention may be sufficiently delivered to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

According to embodiments of the present invention, a method for reducing asphaltenes includes supplying an asphaltene-containing material, a solvent, and a metal oxide precursor to a reactor, and changing the reactor to supercritical conditions to perform a deasphaltene reaction. Include.

The solvent may comprise one or more of water and alcohols. The solvent may comprise -OH.

The metal oxide precursor may comprise one or more of metal salts and metal salt hydrates. For example, the metal oxide precursors include cerium (III) nitrate, zinc nitrate, copper (II) sulfate, aluminum nitrate, iron (III) nitrate, silver nitrate, cobalt (II) hydrochloride, nickel (II) acetate, and One or more of these hydrates. Preferably, the metal oxide precursor may comprise one or more of zinc nitrate and zinc nitrate hydrate.

The reaction can be carried out in a continuous reactor. The metal oxide precursor may include the metal salt hydrate, the metal salt hydrate may be continuously supplied to the reactor and treated with the asphaltene-containing material and solvent in a liquid phase, and the resulting metal oxide may have a particle size. Small to reduce the pressure drop when discharged with the reaction product.

The metal oxide precursor may include a metal hydroxide and an acid. The metal oxide precursor may include zinc hydroxide and nitric acid.

The asphaltene containing material may comprise crude oil or hydrocarbons.

The asphaltene-containing material and the solvent may be supplied in a weight ratio of 1: 1 to 1:10. If the amount of the solvent is less than 1: 1, the asphaltene reduction reaction may not be performed well, and if the amount of the solvent is greater than 1:10, the amount of the supercritical fluid may increase, which may be uneconomic.

The reaction conditions in the reaction should be set to conditions that can change the solvent into a supercritical fluid. For example, the temperature may be set above 400 ° C. or above the critical point and the pressure above the critical point. The reaction time may be set in consideration of the amount of the asphaltene-containing material, the mixing ratio of the asphaltene-containing material and the solvent, the reaction conditions, the reactor type, the type and the amount of the metal oxide precursor, and the like. For example, the reaction may be performed for 30 minutes or longer, for example, 0.5 to 3 hours.

1 is a view for explaining a process for reducing asphaltenes of crude oil according to an embodiment of the present invention.

Referring to FIG. 1, water and methanol, which are solvents used in the embodiments of the present invention, have the ability to donate hydrogen by radical reaction under supercritical conditions, thereby suppressing the formation of coke generated during pretreatment. It forms a homogeneous phase with the ability to dissolve in organic matter and can act as an excellent reaction medium.

In addition, the metal oxide used as a catalyst in the reaction contains a substance that acts as a catalyst for desulfurization, and serves to promote the oxidation-reduction reaction of water or methanol, which acts as a solvent and a hydrogen donor, to promote asphaltene and sulfur. It is possible to increase the removal rate of components and to improve the production of high value oil.

 Since the catalyst is reacted at the surface, the smaller the particle size, the larger the surface area and the higher the efficiency. In the embodiments of the present invention, the catalyst is formed from the metal oxide precursor under supercritical conditions with a very small particle size. The efficiency of the reaction can be improved. In addition, since the catalyst is formed under supercritical solvent conditions and deasphaltene and an advanced reaction are performed using the catalyst, the supercritical process can be simplified and the process efficiency can be improved.

EXAMPLE

Example  One

In a 22 mL batch reactor made of stainless steel (SUS316 steel), Venezuela's Boskan local high-sulfur crude oil (see FIG. 2), water, and zinc nitrate hydrate (200 mg) were added. Adjusted. Under the supercritical conditions, the zinc nitrate hydrate was changed to zinc oxide and nitric acid, and the water was changed to supercritical water to advance the reaction. The ultra heavy crude oil and the water were added to the reactor in a weight ratio of 1: 4, and the reaction was performed for 1 hour. While the reaction was in progress, stirring was performed using a horizontal stirrer at a constant speed. The reaction time is set to 1 hour to compare the results for the same energy use, but may be set differently depending on the throughput of crude oil, the mixing ratio of crude oil and water, the reaction conditions, the type of reactor, the type and the amount of the metal oxide precursor. In addition, the reaction is carried out in a batch reactor, but may be made through a continuous reactor.

After the reaction, all of the products were extracted using dichloromethane, water was added thereto to separate inorganic materials through liquid separation, and dichloromethane was evaporated using a rotary evaporator. The resultant was dissolved and filtered with heptane in a Soxhlet extractor and partitioned between malten and heptane insoluble in heptane. In addition, the components insoluble in heptane were dissolved and filtered with toluene at 80 degrees and fractionated into asphalt components dissolved in toluene and solid components insoluble in toluene. The solid component was burned in a furnace at 800 ° C. and the weight of the coke component in the solid and the weight of the metal oxide were measured by changing the weight of the filter paper.

Example  2

The reaction was carried out in the same manner as in Example 1, except that the solvent was changed from water to methanol in Example 1, and the reaction product was analyzed.

Example  3 to 18

The reaction was carried out in the same manner as in Examples 1 and 2 except that the metal oxide precursor was changed from zinc nitrate hydrate to another metal salt or metal salt hydrate in Examples 1 and 2 and the reaction product was analyzed. The metal oxide precursors used in the above examples are shown in FIG. 3, and the analysis results for the reaction products are shown in FIG. 4. Referring to FIG. 4, when the metal oxide precursor was used under supercritical solvent conditions of water or methanol, the conversion of asphaltenes was high and the formation of coke was low. Therefore, the metal oxide precursor may be appropriately selected or used in combination of two or more metal oxide precursors according to the process conditions or the desired result in a specific process.

5 shows asphaltene conversion and coke formation rate according to the type of metal oxide precursor when water is used as the supercritical fluid, and FIG. 6 illustrates asphaltene conversion and coke formation according to the type of metal oxide precursor when methanol is used as the supercritical fluid. Show production rate. 7 shows the conversion of asphaltenes to coke according to the type of metal oxide precursor when water is used as the supercritical fluid, and FIG. 8 shows the coke of asphaltenes according to the type of metal oxide precursor when methanol is used as the supercritical fluid. The conversion rate to. 7 and 8 show the degree of coke generation according to the conversion of asphaltenes, and the lower the value of the y-axis, the lower the selectivity of the coke formation reaction means that the deasphaltene reaction was made in the desired direction. 5 to 8, the metal oxide precursors represent cerium (III) nitrate, zinc nitrate, aluminum nitrate, iron (III) nitrate, cobalt (II) hydrochloride, and nickel (II) acetate.

5 to 8, when zinc nitrate hydrate was used as the metal oxide precursor, high asphaltene conversion and low coke formation were shown in both solvents of water and methanol. In other words, when zinc nitrate hydrate is used as the metal oxide precursor at the same temperature and time, high asphaltene conversion can be achieved and process problems caused by coke formation during transportation and fractionation can be reduced.

So far, specific embodiments of the present invention have been described. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in descriptive sense only and not for purposes of limitation. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

Claims (10)

Feeding the asphaltene containing material, solvent, and metal oxide precursor to the reactor; And
Changing the reactor to supercritical conditions to perform deasphaltene reaction. The method of claim 1,
Wherein said solvent comprises at least one of water and an alcohol. The method of claim 1,
The solvent is asphaltene reduction method characterized in that it comprises -OH. The method of claim 1,
Said metal oxide precursor comprises at least one of a metal salt and a metal salt hydrate. The method of claim 4, wherein
Wherein said metal oxide precursor comprises at least one of zinc nitrate and zinc nitrate hydrate. The method of claim 4, wherein
The reactor is a continuous reactor,
And said metal oxide precursor comprises said metal salt hydrate. The method of claim 1,
And said metal oxide precursor comprises a metal hydroxide and an acid. The method of claim 7, wherein
And said metal oxide precursor comprises zinc hydroxide and nitric acid. The method of claim 1,
The asphaltene-containing material and the organic solvent are supplied in a weight ratio of 1: 1 to 1:10. The method of claim 1,
The asphaltene-containing material is a method for reducing asphaltenes, characterized in that it comprises crude oil or hydrocarbons.

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