RU2812183C1 - Method for desulphurization of petroleum coke - Google Patents

Abstract

FIELD: petrochemical industry.

SUBSTANCE: invention relates to a method for desulphurizing petroleum coke. The method includes the following steps: petroleum coke, crushed to sizes less than 2 mm, and water or an aqueous solution are added to the reactor, and a desulphurizing agent, which is air oxygen or gaseous oxygen, or an oxygen-containing gas mixture, is supplied to the reactor. Moreover, by supplying the desulphurizing agent, an excess pressure of 1.0 to 5.0 MPa is created in the reactor, and the reactor is heated to a temperature of 150°C up to 230°C, which is maintained for 0.5-8 hours, during which water or aqueous solution is stirred.

EFFECT: efficient removal of sulphur from petroleum coke using widely available substances - water, air, and oxygen; facilitated management and implementation of the desulphurization process, which leads to increased process reliability, reduced process time, increased explosion safety, and reduced release of pollutants.

13 cl, 1 tbl, 68 ex

Description

TECHNICAL FIELD

This invention relates to the field of oil refining and coke chemistry, namely, desulfurization (desulfurization) technology and, more specifically, to a method for oxidative desulfurization of petroleum coke and petroleum coke obtained by this method.

BACKGROUND OF THE ART

Currently, in industry, energy and metallurgy, petroleum coke is widely used, obtained mainly from the delayed coking of heavy oil residues as a by-product in the main production - the production of distillates in the production of motor fuels. Petroleum coke is a solid product consisting mainly of carbon, has a low ash content (less than 1.2% by weight) when burned, and, after heat treatment at 400-500°C, has a developed porous structure. Petroleum coke is the main raw material for the production of aluminum pot anodes in the aluminum industry and the main raw material for the production of graphite electrodes for arc furnaces in the steel industry; raw materials for the production of calcium and silicon carbides in the production of acetylene, a promising technological fuel, a reducing agent and a sulfiding agent in a number of other industries, as well as a structural material for various purposes.

Petroleum coke in the world is classified as green coke (in the Russian Federation - raw or non-calcined coke) and calcined coke. These two categories are grouped based on the similarity of their production processes - cracking and carbonization of heavy petroleum residues under elevated pressure, which lead to similar physicochemical characteristics and chemical composition of the final product. The fundamental difference is the amount of residual hydrocarbons (so-called volatile substances). To increase the carbon: hydrogen ratio to produce calcined coke, green coke (primary processing product) containing 88-95% carbon, 3-4% hydrogen, 1-2% nitrogen, 0.5-6% sulfur and 1-7 % oxygen, is subjected to additional heat treatment at 1200-1350°C, which reduces the content of volatile substances and sulfur compounds. Low and medium sulfur petroleum coke (containing 0.5-3.5% sulfur) is most widely used in the production of electrodes and as a metallurgical fuel. Along with traditional methods of using petroleum coke, in the medium term it is considered as an alternative raw material in gasification technology due to its low cost, economic competitiveness, versatility of its use, and diversity of applications for coke gasification products.

The main disadvantage of using petroleum coke is its significant sulfur content (more than 1.5% for sulfur cokes and more than 4% for high-sulfur cokes), which complicates or limits its direct use as a carbon product, as it causes corrosion of equipment and an increased number of cracks in electrode products , destruction of the masonry of calcination furnaces, and causes environmental problems that require additional costs to solve them.

Thus, reducing the content of sulfur compounds in petroleum coke is a significant problem for the development of modern technologies for its use in various fields of industry and reducing the impact of sulfur compounds on the environment.

There is a known thermal method for desulfurization of petroleum coke, which consists in the desorption of inorganic sulfur compounds in a flow of inert gas under high temperatures (T. Liu, M. Long, W. Jiang, D. Chen, Sh. Yu, H. Duan, J. Sheng, Ch. Chen. Variations in the True Density and Sulfur Removal Forms of Petroleum Coke during an Ultrahigh-Temperature Desulfurization Process. / T. Liu / / Energy & Fuels. - 2017. - 31 (7). - P. 7693-7699. DOI: 10.1021/acs.energyfuels.7b01085). However, the efficiency of this method is low - with this method at temperatures below 1300°C it is possible to remove only up to 10% of sulfur, while up to 90% of sulfur present in the form of high-strength organosulfur compounds of sulfur associated with the carbon frame of coke is not removed. In addition, this method is energy-consuming, as it requires reaching high and ultra-high temperatures, also requires the use of special heat-resistant equipment, deteriorates the quality of coke, does not solve environmental problems and requires additional technological solutions for the disposal of released sulfur compounds.

There is a known extraction method for desulfurization of petroleum coke, which consists in extracting sulfur compounds with various extractants, including o-chlorophenol, pyridine, aqua regia, phenol, furfural, ionic liquids ([Bmim]BF4) at temperatures of 20-160°C (Ibrahim H. Desulfurization of petroleum coke: Areview. / N. Ibrahim, I. V. Morsi // Ind. Eng. Chem. Res. - 1992. - 31. - P. 1835-1840; H. Ibrahim Desulfurization of Petroleum Coke by Solvent Extraction. / H. Ibrahim // Recent Adv. Petrochem. Sci. - 2019 - 6(3) - P. 0044-0049:RAPSCI.MS.ID.555686;

https://juniperpublishers.com/rapsci/pdf/RAPSCI.MS.ID.555686.pdf). In this case, the efficiency of petcoke desulfurization ranges from 1 to 24% with an extraction time from 2 to 120 hours. The main disadvantages of this method are the high cost of reagents, and, in some cases, the lack of their industrial production, the long duration of the process, and complex extraction equipment , the need to solve the problems of isolating sulfur compounds from the extract, their separation and disposal, the need to regenerate the extractant.

There is a known combined extraction-oxidation method for desulfurization of petroleum coke (H. Liu. Extraction combined catalytic oxidation desulfurization of petcoke in ionic liquid under mild conditions/ H. Liu, H. Xu, M. Hua, L. Chen, Ya. Wei, C. Wang, P. Wu, F. Zhu, X. Chu, H. Li, W. Zhu // Fuel - 2020. - 260. P. 116200. https.//doi.org/10.1016/j.fuel.2019.116200, https://www.sciencedirect.com/science/article/pii/S0016236119315546), according to which pre-treatment of petroleum coke is carried out by extraction of sulfur compounds from petroleum coke with tetrabutylammonium chloride at 150°C for 4 hours, and then oxidation of sulfur compounds in the composition is carried out petroleum coke in the green solvent [Bmim] BF4 using polyoxometalate ionic liquid [Bmim]3PW12O40 and hydrogen peroxide H2O2 as a catalyst and oxidizer, respectively, at a temperature of 80°C for 5 hours, followed by washing the petroleum coke sequentially with acetonitrile, hydrogen peroxide and water. In this case, the efficiency of petcoke desulfurization is 36.1%. The main disadvantages of this method are also the high cost of reagents and the complete lack of their industrial production, the long duration of the process, complex extraction equipment, the need to solve the problems of isolating sulfur compounds from the extract, their separation and disposal, the need to isolate and regenerate the catalyst and regenerate the extractant, and the multi-stage process process.

A combined oxidative-extraction method for desulfurization of petroleum coke is known (N. Ibrahim. Desulphurization of Petroleum Coke by Solvent Extraction. / H. Ibrahim // Recent Adv. Petrochem. Sci. - 2019 - 6(3) - P. 0044-0049: RAPSCI .MS.ID.555686; https://juniperpublishers.com/rapsci/pdf/RAPSCI.MS.ID.555686.pdf; H. Ibrahim, Upgrading of Syrian petroleum coke by pre-oxidation / H. Ibrahim // Periodica Polytechnica Chemical Engineering. - 2011 - 55(1) - P. 21-25. https://doi.org/10.3311/pp.ch.2011-1.04), according to which oxidative pretreatment of petroleum coke is carried out at temperatures of 330-350° C for 15 minutes, and then extraction with ortho-chlorophenol or pyridine at 160°C for 2 hours, while the maximum efficiency of petroleum coke desulfurization is 76% when using ortho-chlorophenol. The main disadvantages of this method are also the high cost of reagents, complex extraction equipment, the need to solve the problems of isolating sulfur compounds from the extract, their separation and disposal, the need to isolate and regenerate the extractant, and the multi-stage technological process.

There is a known method of oxidative desulfurization of petroleum coke, disclosed in the RF patent application No. 2013120503 (C10B 55/00, filing date 05/07/2013), including grinding the coke, mixing it with a catalyst and a desulfurizing agent, while 30% is used as a desulfurizing agent hydrogen peroxide and the process is carried out with intense stirring in the presence of 0.5-2.0% ammonium salt of nitric acid, taken as a catalyst, for 30 minutes under conditions of self-heating of the reaction mixture at a temperature of 30-80°C, followed by heating of the reaction mass up to 500-700°C for 4 hours. A vibrating mixer is used to mix the reaction mass. In this case, air heated to 280-300°C is passed through the reaction mass for 4 hours at atmospheric pressure.

The considered method of oxidative desulfurization of petroleum coke solves the problem of reducing the content of sulfur compounds in petroleum coke by oxidizing sulfur compounds with the formation of oxidation products released into the aqueous solution and into the atmosphere.

However, this method has significant drawbacks that complicate its practical implementation:

1) the complexity of controlling the desulfurization process under conditions of self-heating of the reaction mixture and a multi-stage process;

2) the need to solve environmental problems associated with the formation of environmentally hazardous waste - in solution during the oxidation of sulfur-containing compounds of petroleum coke and other organosulfur compounds (sulfoxides and sulfones) with hydrogen peroxide and the release of sulfur dioxide, organic substances and carbon monoxide into the atmosphere;

3) the high cost of reagents and the need to organize and maintain a reagent facility;

4) high energy costs for heating the reaction mixture to 500-700°C;

5) a fairly long total duration of the petroleum coke desulfurization process (about 5 hours);

6) the explosion hazard of the process of blowing the hot reaction mass with air heated to 280-300°C.

The closest analogue to the proposed solution is the method disclosed in US patent 2693999, published 11/09/1954, in which the sulfur content in petroleum coke particles 1-100 mesh in size is reduced by rapidly heating them with a flow of oxygen-containing gas to 2500-3200°F (1371- 1760°C) and maintaining at this temperature for approximately 1/4-8 hours. Based on its sulfur content, the resulting petroleum coke is suitable for metallurgical purposes or for the production of electrodes.

The disadvantage of this method is its low environmental friendliness and complexity due to the need to heat petroleum coke to high temperatures (1371-1760°C), which is associated with increased fuel consumption for heating and increased emissions of pollutants, as well as high requirements for the equipment used and reduced explosion safety.

DISCLOSURE OF THE INVENTION

The objective of the present invention is to develop an effective, environmentally friendly and economical method for oxidative desulfurization of coke, free from the above disadvantages, effective removal of thiophene sulfur from petroleum coke along with other sulfur-containing compounds.

The technical result of the present invention is to effectively remove sulfur from petroleum coke using available reagents (water, air, oxygen), as well as to facilitate the management and implementation of the desulfurization process, which leads to increased process reliability, reduced process time, increased explosion safety and reducing emissions of pollutants.

To solve the problem and achieve a technical result, a method for desulfurizing petroleum coke is proposed, which includes the following steps:

petroleum coke, crushed to sizes less than 2 mm, and water or an aqueous solution are added to the reactor,

a desulfurizing agent is supplied to the reactor, which is air oxygen or gaseous oxygen, or an oxygen-containing gas mixture,

by supplying a desulfurizing agent, an excess pressure of 1.0 to 5.0 MPa is created in the reactor,

the reactor is heated to a temperature from 150°C to 230°C, which is maintained for 0.5-8 hours, during which the water or aqueous solution is stirred.

The above conditions ensure effective mass transfer of the desulfurizing agent to the surface of the petroleum coke, while it becomes possible to carry out the oxidation of sulfur compounds not only in the structure of the petroleum coke, but also to carry out deep additional oxidation of the released sulfur compounds in the solution, combining these stages of the process locally, and an additional effect is the transfer sulfur compounds of various compositions into sulfate ions, which solves the problem of increasing the environmental safety of the method.

In the proposed process, oxygen, which is an oxidizing agent, is in the gas phase, and the organosulfur compounds to be removed are in petroleum coke, which is in the liquid aqueous phase. The gas is slightly soluble in water, the aqueous phase and petroleum coke are mutually insoluble, and when mixed, these three components form a heterophase system. As a result, the established interphase boundary makes possible the oxidation of organosulfur compounds by an oxidizing agent and subsequent reactions of these organosulfur compounds with water or oxygen. In this case, the speed and efficiency of desulfurization depend on the area of the interphase boundary and the duration of contact. Therefore, it is desirable to effectively mix the gas, petroleum coke and the aqueous phase, forming as large an interphase area as possible.

Any known method that ensures the creation of such an interphase boundary can be used to implement the proposed desulfurization process. Also, any known method can be used to separate the mixture of petroleum coke and waste working solution obtained as a result of contacting. Also, any known catalytically active additive can be introduced into the aqueous solution to accelerate reactions in the reaction system in order to implement the proposed desulfurization process.

The present invention makes it possible to achieve the desired degree of desulfurization at lower heating temperatures of petroleum coke than in the closest analogue, which leads to increased explosion safety of the method and a reduction in the emission of pollutants.

The interaction of petroleum coke with the desulfurizing agent is carried out for 0.5-8 hours, since with a time of less than 0.5 hours the completeness of the reaction is not achieved, interaction for more than 8 hours is not economically feasible.

Preferably, mixing of water or an aqueous solution is carried out by vibration mixing, carrying out mechanical vibrations of the reactor with a frequency of 1 to 5 Hz, preferably from 3 to 5 Hz. This makes it possible to improve the mass transfer of the desulfurizing agent to the surface of the petroleum coke, which further enhances the interaction of the petroleum coke with the desulfurizing agent and makes it possible to increase the degree of desulfurization.

Preferably, mixing of water or an aqueous solution can also be carried out due to the design of the reactor, for example, the reactor can be a flow-type reactor through which water or an aqueous solution is passed at a rate of 1.0-3.0 ml/min, and into which a desulfurizing agent is supplied agent at a rate of 5.0-10.0 l/h. This makes it possible to improve the mass transfer of the desulfurizing agent to the surface of the petroleum coke, which further enhances the interaction of the petroleum coke with the desulfurizing agent and makes it possible to increase the degree of desulfurization.

Preferably, an excess pressure of 3.0 to 5.0 MPa is created in the reactor, which makes it possible to further increase the degree of desulfurization of petroleum coke.

Preferably, the reactor is heated to a temperature of 180°C to 220°C, which is maintained for 3-5 hours, which further increases the degree of desulfurization of petroleum coke.

Preferably, the petroleum coke is crushed to a size of less than 0.5 mm, which further increases the degree of desulfurization of the petroleum coke.

Preferably, the content of the desulfurizing agent is selected such that the molar ratio of oxygen contained in the desulfurizing agent and sulfur contained in petroleum coke is in the range of 3 to 35.

This makes it possible to provide better conditions for the deep oxidation of sulfur-containing compounds, including organosulfur compounds, and the additional oxidation of products of incomplete oxidation of carbon-containing compounds formed during the partial defragmentation of petroleum coke.

Preferably, mixtures of oxygen with nitrogen and carbon dioxide are used as oxygen-containing gas mixtures, the mole fractions of which are: oxygen - from 20 to 60, carbon dioxide - from 0.03 to 10, nitrogen - the rest.

The use of the above mixtures makes it possible to provide the necessary excess of oxygen and compensate for fluctuations in oxidizing agent concentrations during the interaction of petroleum coke with a desulfurizing agent.

Preferably, during the interaction of the petroleum coke with the desulfurizing agent, the desulfurizing agent in the reactor is bubbling. This makes it possible to achieve effective mass transfer of the desulfurizing agent to the surface of the petroleum coke, which further accelerates the interaction of petroleum coke with the desulfurizing agent and makes it possible to increase the degree of desulfurization.

Preferably, the bubbling of the desulfurizing agent is carried out using microbubbles with sizes from 10 to 100 μm at a volumetric gas content of from 0.1 to 0.5%. In the specified ranges of microbubble sizes and gas content values, the most favorable conditions for mass and heat transfer in a multiphase environment are achieved, which ensures an increase in mass and heat transfer values from 1.5 to 3.5 times, and, accordingly, accelerates the interaction of petroleum coke with the desulfurizing agent, and the removal of reaction products from the boundary layer between the surface of petroleum coke and the liquid phase.

Preferably, water or an aqueous solution with petroleum coke in it is exposed to ultrasound with a frequency of 20 to 50 kHz at an intensity of approximately 30 to 300 W/cm ² , which also leads to the formation of cavitation microbubbles, a decrease in the thickness of the boundary layer and the intensification of heat and mass transfer processes , including mass transfer processes in the pores of petroleum coke, which further enhances the interaction of petroleum coke with the desulfurizing agent.

Preferably, catalytic additives and/or acid-base additives are introduced into water or an aqueous solution containing petroleum coke.

Preferably, the catalytic additives are selected from at least one of the compounds from the group of ruthenium, iron, cobalt in an amount of from 0.001 to 0.5 wt%. in relation to the mass of petroleum coke.

This makes it possible to increase environmental reliability, since the appearance of other pollutants is prevented, sulfur compounds undergo oxidative transformations and are removed from the reactor in the form of non-toxic compounds, and also allows for an increase in the degree of desulfurization.

Preferably, acid-base additives are added to water or an aqueous solution containing petroleum coke.

Preferably, the pH value of the aqueous solution is from 1 to 5, the pH value of the aqueous solution is regulated by acid-base additives, at the specified pH value an increase in the degree of desulfurization is observed, and the maximum degree of desulfurization is observed at pH values from 3 to 5.

Preferably, the reactor is a flow-type reactor through which water or an aqueous solution is passed at a rate of 1.0-3.0 ml/min, and into which a desulfurizing agent is supplied at a rate of 5.0-10.0 l/h.

Also, to solve the problem and achieve a technical result, petroleum coke obtained by the above method of desulfurization of petroleum coke is proposed.

IMPLEMENTATION OF THE INVENTION

Description of the proposed technical solution. Option 1.

To carry out experiments, petroleum coke is crushed in a mortar, coke is scattered on sieves, a 10 g sample of coke is taken of a given fraction (1.0-2.0, 0.5-1.0, 0.5-0.25 and less than 0.25 mm), placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 50 to 100 ml of the liquid phase is poured (water or an aqueous solution including catalytic and/or acid-base additives of known concentration), the supply of a desulfurizing agent is turned on (oxygen or air or an oxygen-containing gas mixture), setting the design pressure in the reactor (1.0-5.0 MPa), the reactor is heated to the design temperature (150-230°C), stirring is turned on (a vibration installation was used in the experiments; moment of switching on vibration installation was taken as t=0), experiments are carried out at constant gas pressure (gas mixture) for a given time.

After this, the heating of the reactor is turned off, the reactor is cooled to 80 C, after which the pressure in the system is gradually reduced to atmospheric pressure, the reactor is unloaded, and the sulfur content in the petroleum coke is analyzed by any known method.

Description of the proposed technical solution. Option 2.

To carry out experiments, petroleum coke is crushed in a mortar, coke is scattered on sieves, a 10 g sample of coke is taken of a given fraction (1.0-2.0, 0.5-1.0, 0.5-0.25 and less than 0.25 mm), is placed in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, the liquid phase is passed through it at a speed of 1.0-3.0 ml/min, and a desulfurizing agent (oxygen or air, or a gas oxygen-containing mixture) is supplied with speed of 5.0-10.0 l/h at excess pressure (1.0-5.0 MPa), the reactor is heated to the design temperature (150-230°C), experiments are carried out at constant excess gas pressure for a given time.

After this, the heating of the reactor is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the reactor is unloaded, and the sulfur content in the petroleum coke is analyzed by any known method.

The proposed method (options) is carried out for desulfurization of petroleum coke from sulfur compounds with an initial sulfur content of 1.0 to 7.0 wt%.

The advantages of the proposed method are as follows:

a high degree of desulfurization is achieved, which is confirmed by the data in the examples given;

Relatively inexpensive reagents are used - water, air, oxygen;

the process is easily controlled, simply implemented, and as a result is characterized by increased reliability;

the process time is relatively short - from 30 minutes to 8 hours;

explosion safety is easily achieved by implementing the process in a three-phase system by reducing the free volume.

An additional positive effect is that after desulfurization of petroleum coke there is no need to solve environmental problems associated with the formation of environmentally hazardous waste, which is usually required in a number of cases, thus, the environmental reliability of the purification process increases, since there is no release of pollutants, sulfurous substances undergo oxidative transformations and are removed from the reactor in the form of non-toxic compounds.

The following is a description of examples that illustrate the proposed technical solution; the results of the examples are presented in tables.

Example 1.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur is crushed in a mortar, the crushed coke is scattered on sieves, a 5 g sample of coke is taken, a fraction of 1.0-2.0 mm is placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 50 ml of distilled water is poured in, fed into oxygen reactor, setting the excess pressure in the reactor to 2.0 MPa, the reactor is heated to a temperature of 230°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 2.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. the sulfur is crushed in a mortar, the crushed coke is scattered on sieves, a 5 g sample of coke is taken, a fraction of 0.5 mm or less, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, oxygen is supplied to the reactor , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 3.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. the sulfur is crushed in a mortar, the crushed coke is scattered on sieves, a 5 g sample of coke is taken, a fraction of 0.5 mm or less, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, oxygen is supplied to the reactor , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 150°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 4.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur is crushed in a mortar, the crushed coke is scattered on sieves, a 5 g sample of coke is taken, a fraction of 1.0-2.0 mm is placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, fed into air reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 5.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.48% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve into the reactor a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:37:3, setting an excess pressure in the reactor of 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 6.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.48% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve into the reactor a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:30:10, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 7.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.48% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 10 g sample of coke with a fraction of 1.0-2.0 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, and pass water through it at a speed of 1.0 ml/min, oxygen is supplied at a rate of 5.0 l/h at an excess pressure of 5.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 180° C, experiments are carried out at constant excess gas pressure for 1.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water , dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 8.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.48% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve into the reactor a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:35:5, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 150°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 9.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.48% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve into the reactor a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions of 60:35:5, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 150°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/ ^cm2 , held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80° C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 10.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 150°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 11.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 150°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 12.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 4.0 MPa, the reactor is heated to a temperature of 160°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 13.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 160°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; hold for 1.5 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 14.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 4.0 MPa, the reactor is heated to a temperature of 160°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 1.0 h, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 15.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 4.0 MPa, the reactor is heated to a temperature of 160°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; hold for 1.5 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 16.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve air into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 160°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 17.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve air into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 18.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke of a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve air into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 19.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of 2.0 mm or less, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed into the reactor oxygen, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 20.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of 2.0 mm or less, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed into the reactor oxygen, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 21.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 22.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 23.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 0.25-0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 24.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of 2.0 mm or less, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed into the reactor oxygen, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 210°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 25.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 10 g sample of coke with a fraction of 1.0-2.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, serve oxygen into the reactor, setting the excess pressure in the reactor to 1.0 MPa, the reactor is heated to a temperature of 230°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 26.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a sample of coke 5 g of fraction 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, pour 100 ml of an aqueous solution containing catalytic additive - 15 mg/l cobalt tetrasulfophthalocyanine, oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 27.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a sample of coke 5 g of fraction 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, pour 100 ml of an aqueous solution containing catalytic additive

- 0.003 g of a mixture of iron (3+) nitrate and bromide - Fe(NO ₃ ) ₃ -FeBr ₃ in a ratio of 2:1, oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180 ° C , include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 28.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a sample of coke 5 g of fraction 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, pour 100 ml of an aqueous solution containing catalytic additive - 0.001 g of a mixture of iron (3+) and cobalt nitrates - Fe(NO ₃ ) ₃ -Co(NO ₃ ) ₂ in a ratio of 1:1, oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, reactor heated to a temperature of 180°C, turn on vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 29.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a sample of coke 5 g of fraction 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, pour 100 ml of an aqueous solution containing catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 180°C, vibration stirring is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 30.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an acidified aqueous solution hydrochloric acid and having a pH value of 3.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to temperature 180°C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 31.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, take a 5 g sample of coke with a fraction of 0.5-1.0 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an acidified aqueous solution hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to temperature 180°C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 32.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke of a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, pass water through it at a speed of 1.0 ml/min , oxygen is supplied at a rate of 5.0 l/h at an excess pressure of 5.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 3.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 33.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, and pass water through it at a speed of 3.0 ml/min , oxygen is supplied at a rate of 10.0 l/h at an excess pressure of 5.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 3.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 34.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed gas into the reactor mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:35:5, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/cm ² , held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 35.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, air is supplied to the reactor , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 36.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 3.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 37.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 38.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke of a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, pass water through it at a speed of 1.0 ml/min , oxygen is supplied at a rate of 5.0 l/h at an excess pressure of 5.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 5.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 39.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, and pass water through it at a speed of 3.0 ml/min , oxygen is supplied at a rate of 10.0 l/h at an excess pressure of 5.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 5.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 40.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, oxygen is supplied to the reactor , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/ ^cm2 , maintained for 5.0 hours, the heating of the reactor is turned off, the reactor cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 41.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed gas into the reactor mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:35:5, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/cm ² , held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 42.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured, fed into the reactor air, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 43.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 3.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 44.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 45.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke of a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, pass water through it at a speed of 1.0 ml/min , oxygen is supplied at a rate of 5.0 l/h at an excess pressure of 3.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 3.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 46.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, and pass water through it at a speed of 3.0 ml/min , oxygen is supplied at a rate of 10.0 l/h at an excess pressure of 3.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 3.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 47.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, oxygen is supplied to the reactor , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/ ^cm2 , maintained for 3.0 hours, reactor heating is turned off, reactor cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 48.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed gas into the reactor mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:35:5, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/cm ² , held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 49.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, air is supplied to the reactor , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 50.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 3.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 51.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220 ⁹ C, include vibration mixing with an oscillation frequency of 3 Hz; held for 3.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 52.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke of a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, pass water through it at a speed of 1.0 ml/min , oxygen is supplied at a rate of 5.0 l/h at an excess pressure of 3.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 5.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 53.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a flow-type metal reactor with a diameter of 10 mm, a length of 30 cm, and pass water through it at a speed of 3.0 ml/min , oxygen is supplied at a rate of 10.0 l/h at an excess pressure of 3.0 MPa, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, the reactor is heated to a design temperature of 220 ° C, experiments carried out at constant excess gas pressure for 5.0 hours. After this, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, and dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 54.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, oxygen is supplied to the reactor , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/cm ² , maintained for 5.0 hours, reactor heating is turned off, the reactor cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 55.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of distilled water, feed gas into the reactor mixture of oxygen: nitrogen: carbon dioxide in mole fractions 60:35:5, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, ultrasonic stirring is turned on with a frequency of 20 kHz at an intensity of approximately 100 W/cm ² , held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 56.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, crushed coke is scattered on sieves, a 5 g sample of coke is taken, fraction less than 0.5 mm, placed in a metal reactor with a diameter of 38 mm, a volume of 200 ml, the reactor lid is sealed, 100 ml of distilled water is poured in, air is supplied to the reactor , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, and vibration mixing is turned on with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 57.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 3.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 58.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 5.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 59.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; hold for 0.5 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 60.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, seal the reactor lid, pour in 100 ml of an aqueous solution acidified with hydrochloric acid and having a pH value of 5.0, containing a catalytic additive - 0.0005 g of ruthenium bipyridyl complex [Ru(dipy) ₃ ]Cl ₂ , oxygen is supplied to the reactor, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220° C, include vibration mixing with an oscillation frequency of 3 Hz; held for 8.0 hours, the reactor heating is turned off, the reactor is cooled to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, the coke is unloaded from the reactor, the coke is washed once with distilled water, dried at 80°C for 2 hours in air, determine the sulfur content in petroleum coke using X-ray fluorescence spectrometry.

Example 61.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured, oxygen is supplied to the reactor, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to temperature 220°C, turn on vibration mixing with an oscillation frequency of 3 Hz, hold for 3.0 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload coke from the reactor, coke once washed with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 62.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured into the reactor, a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions of 60:35:5 is fed into the reactor, bubbling the latter to form gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5% , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, vibration mixing is turned on with an oscillation frequency of 3 Hz, held for 3.0 hours, the heating of the reactor is turned off, the reactor is cooled to 80°C, after which smoothly reduce the pressure in the system to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry it at 80°C for 2 hours in air, determine the sulfur content in the petroleum coke using X-ray fluorescence spectrometry.

Example 63.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured, oxygen is supplied to the reactor, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to temperature 220°C, turn on vibration mixing with an oscillation frequency of 3 Hz, hold for 5.0 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload coke from the reactor, coke once washed with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 64.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured into the reactor, a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions of 60:35:5 is fed into the reactor, bubbling the latter to form gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5% , setting the excess pressure in the reactor to 5.0 MPa, the reactor is heated to a temperature of 220°C, vibration mixing is turned on with an oscillation frequency of 3 Hz, held for 5.0 hours, the heating of the reactor is turned off, the reactor is cooled to 80°C, after which smoothly reduce the pressure in the system to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry it at 80°C for 2 hours in air, determine the sulfur content in the petroleum coke using X-ray fluorescence spectrometry.

Example 65.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured, oxygen is supplied to the reactor, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to temperature 220°C, turn on vibration mixing with an oscillation frequency of 3 Hz, hold for 3.0 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload coke from the reactor, coke once washed with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 66.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured into the reactor, a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions of 60:35:5 is fed into the reactor, bubbling the latter to form gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5% , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, vibration mixing is turned on with an oscillation frequency of 3 Hz, held for 3.0 hours, the heating of the reactor is turned off, the reactor is cooled to 80°C, after which smoothly reduce the pressure in the system to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry it at 80°C for 2 hours in air, determine the sulfur content in the petroleum coke using X-ray fluorescence spectrometry.

Example 67.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured, oxygen is supplied to the reactor, bubbling the latter with the formation of gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5%, setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to temperature 220°C, turn on vibration mixing with an oscillation frequency of 3 Hz, hold for 5.0 hours, turn off the heating of the reactor, cool the reactor to 80°C, after which the pressure in the system is gradually reduced to atmospheric pressure, unload coke from the reactor, coke once washed with distilled water, dried at 80°C for 2 hours in air, the sulfur content in petroleum coke is determined by X-ray fluorescence spectrometry.

Example 68.

Petroleum coke subjected to the process of oxidative hydrothermal desulfurization, containing 4.36% wt. sulfur, crushed in a mortar, disperse the crushed coke on sieves, select a 5 g sample of coke with a fraction of less than 0.5 mm, place it in a metal reactor with a diameter of 38 mm, a volume of 200 ml, equipped with a gas release valve; the reactor lid is sealed, 100 ml of distilled water is poured into the reactor, a gas mixture of oxygen: nitrogen: carbon dioxide in mole fractions of 60:35:5 is fed into the reactor, bubbling the latter to form gas microbubbles with sizes from 10 to 100 μm at a volumetric gas content of 0.5% , setting the excess pressure in the reactor to 3.0 MPa, the reactor is heated to a temperature of 220°C, vibration mixing is turned on with an oscillation frequency of 3 Hz, held for 5.0 hours, the heating of the reactor is turned off, the reactor is cooled to 80°C, after which smoothly reduce the pressure in the system to atmospheric pressure, unload the coke from the reactor, wash the coke once with distilled water, dry it at 80°C for 2 hours in air, determine the sulfur content in the petroleum coke using X-ray fluorescence spectrometry.

Based on the experimental data given in the table below, it follows that the characteristics characterizing pressure, temperature, particle size and holding time together lead to a synergistic effect, significantly increasing the degree of desulfurization:

1. desulfurizing agent - oxygen-containing gas mixture: oxygen nitrogen-carbon dioxide.

At a pressure of 3.0 MPa, increasing the reactor heating temperature, reaction time, adding ultrasound and bubbling allowed to slightly increase the degree of desulfurization from 6.19 to 9.86% (examples 48, 55, 66, 68).

Increasing the pressure to 5.0 MPa made it possible to slightly increase the degree of desulfurization to 9.88% (examples 8, 9, 6, 5).

However, with a simultaneous increase in temperature to 220°C, pressure to 5.0 MPa and the use of ultrasound/bubbling, it was possible to increase the degree of desulfurization by almost 8 times: up to 51.15% (examples 34, 62, 41, 64), which does not clearly follow from the dependencies for each individual parameter and indicates the synergistic effect of all parameters.

2. desulfurizing agent - air.

At a pressure of 3.0 MPa and a reactor heating temperature of 220°C, an increase in the reaction time made it possible to slightly increase the degree of desulfurization from 5.05 to 5.96% (examples 49, 56).

At a pressure of 5.0 MPa, but a lower reactor heating temperature (160-180°C), by reducing the size of coke particles, it was possible to slightly increase the degree of desulfurization from 7.24 to 10.94% (examples 4, 16, 17, 18) .

However, with a simultaneous increase in temperature to 220°C, pressure to 5.0 MPa and a decrease in the size of coke particles to less than 0.5 mm, it was possible to increase the degree of desulfurization by almost 5 times: up to 49.08% (examples 35, 42), which is not follows clearly from the dependencies for each individual parameter and indicates the synergistic effect of all parameters.

3. desulfurizing agent - oxygen.

At a pressure of 3.0 MPa, increasing the reaction time from 0.5 to 1.5 hours, even at a lower temperature (160°C rather than 220°C), made it possible to increase the degree of desulfurization from 6.19 to 10.04% (examples 59 , 13).

At a pressure of 3.0 MPa, a further increase in the degree of desulfurization from 10.04 to 25.92% was accompanied by the use of bubbling/ultrasound/catalytic additives and an increase in reaction time (examples 65, 47, 45, 46, 67, 52, 54, 53, 51 , 50, 58, 57, 60, 44).

At a pressure of 4.0 MPa, increasing the reaction time from 1 to 3 hours with other parameters unchanged made it possible to increase the degree of desulfurization from 9.82 to 15.4% (examples 14, 15, 12).

At a pressure of 5.0 MPa, reducing the particle size of petroleum coke, increasing the temperature to 220°C, using bubbling/ultrasound/catalytic additives and increasing the reaction time to 3-5 hours made it possible to increase the degree of desulfurization by almost 8.5 times: from 7.83 to 66.05%, which does not clearly follow from the dependencies for each individual parameter and indicates a synergistic effect of all parameters (examples 7, 11, 10, 3, 21, 24, 20, 22, 19, 28, 26, 31, 27, 29, 23, 30, 2, 61, 32, 33, 63, 38, 40, 39, 37, 36, 43).

It was experimentally established that at an initial oxygen pressure of 5.0 MPa, at temperatures of 220-250°C, the degree of desulfurization turned out to be higher at lower temperatures than at high ones.

Most likely, this is due to the oxidation of the carbon framework of coke at high temperatures, as indicated by elemental analysis data, according to which the proportion of carbon in desulfurized coke decreases at high temperatures (250°C). In this case, the occurrence of surface oxidation of the granules leads to a loss of carbon mass with the formation of carbon dioxide with a loss of the total mass of the coke particle, which reduces the value of the desulfurization index. Therefore, carrying out the process at temperatures above 230°C with an initial oxygen pressure above 5.0 MPa is impractical.

Claims (18)

1. A method for desulfurizing petroleum coke, including the following steps: petroleum coke, crushed to sizes less than 2 mm, and water or an aqueous solution are added to the reactor, a desulfurizing agent is supplied to the reactor, which is air oxygen, or gaseous oxygen, or an oxygen-containing gas mixture, characterized in that by supplying a desulfurizing agent, an excess pressure of 1.0 to 5.0 MPa is created in the reactor, the reactor is heated to a temperature from 150°C to 230°C, which is maintained for 0.5-8 hours, during which the water or aqueous solution is stirred. 2. The method according to claim 1, characterized in that the mixing of water or an aqueous solution is carried out by vibration mixing, carrying out mechanical vibrations of the reactor with a frequency of 1 to 5 Hz, preferably from 3 to 5 Hz. 3. The method according to claim 1, characterized in that the reactor is a flow-type reactor through which water or an aqueous solution is passed at a rate of 1.0-3.0 ml/min, and into which a desulfurizing agent is supplied at a rate of 5.0 -10.0 l/h. 4. The method according to claim 1, characterized in that an excess pressure of 3.0 to 5.0 MPa is created in the reactor. 5. Method according to claim 1, characterized in that the reactor is heated to a temperature from 180°C to 220°C, which is maintained for 3-5 hours. 6. The method according to claim 1, characterized in that the petroleum coke is crushed to a size of less than 0.5 mm. 7. The method according to claim 1, characterized in that the content of the desulfurizing agent is selected so that the molar ratio of oxygen contained in the desulfurizing agent and sulfur contained in petroleum coke is in the range from 3 to 35. 8. The method according to claim 1, characterized in that a mixture of oxygen with nitrogen and carbon dioxide is used as an oxygen-containing gas mixture, the mole fractions of which are: oxygen - from 20 to 60, carbon dioxide - from 0.03 to 10, nitrogen - rest. 9. The method according to claim 1, characterized in that bubbling of the desulfurizing agent located in the reactor is carried out using microbubbles with sizes from 10 to 100 microns with a volumetric gas content from 0.1 to 0.5%. 10. The method according to claim 1, characterized in that water or an aqueous solution is exposed to ultrasound with a frequency of 20 to 50 kHz at an intensity of 30 to 300 W/cm ² . 11. The method according to claim 1, characterized in that the water or aqueous solution includes catalytic additives and/or acid-base additives. 12. The method according to claim 11, characterized in that the catalytic additives are selected from at least one of the compounds from the group of ruthenium, iron, cobalt in an amount of from 0.001 to 0.5 wt.%, relative to the weight of petroleum coke. 13. Method according to claim 1, characterized in that the pH value of the aqueous solution is from 1 to 5, preferably from 3 to 5.