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22SCIENTIFIC PROGRESS VOLUME 3 I ISSUE 6 I 2022 _ISSN: 2181-1601
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IMPROVING THE HYDROTREATMENT PROCESS BY SELECTION OF A MORE EFFICIENT MODERN CATALYST
Sadulla Farhod Ozoda Baxronovna Saidjon
Ghaybullayevich Kamolovich Axmedova Abdusalimovich
Toshev Davronov Gaybullaev
Bukhara engineering-technological institute
ABSTRACT
This article discusses the effects of heteroatomic compounds in petroleum products and working parameters and key factors on the process of hydrotreating petroleum products from unwanted components and the selection of a modern catalyst of a new generation, which most effectively affects the process of hydrotreating oil products.
Keywords: petroleum products, sulfur compounds, derivatives of sulfur compounds, hydrogen sulfide, mercaptan, sulfide, disulfide, hydrotreating.
INTRODUCTION
Currently, there is a steady increase in demand for motor fuels. Diesel fuel is one of the most demanded petroleum products.
The main process for upgrading the diesel fraction is the hydrotreatment process, during which sulfur-containing compounds are removed and the content of polycyclic hydrocarbons is reduced. Hydrotreatment units have been introduced and operated for a long time, so the technology and process modes have been worked out and are close to optimal.
To obtain clean diesel fuel, it is necessary to modernize the traditional diesel fraction hydrotreatment process, which will increase the catalyst service life and increase the degree of conversion of sulfur compounds. It is especially important to solve this problem in the conditions of heavy oil fractions entering refineries. One of the solutions is to supplement the unit with a diesel fuel preparation unit before the hydrotreatment process. The preparatory process can be oxidative desulfurization, which will reduce the content of sulfur-containing, nitrogen-containing and polyaromatic hydrocarbons. Hydrogen peroxide is the most popular oxidizing agent because it is cheap, non-polluting, and commercially available. The advantage of this process is the absence of hydrogen, mild mode, deep level of desulfurization, high commercial value of the resulting sulfoxides and sulfones. The process parameters are in a wide range, therefore, in order to increase the efficiency of the combined technology, it is advisable to optimize the oxidative desulfurization process.
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LITERATURE ANALYSIS AND METHODOLOGY
To search for optimal conditions for the process of oxidative desulfurization, as a preliminary stage of hydrotreating, according to the main technological parameters: temperature, contact time, molar ratio of total sulfur.
Increasing the volume of production of petroleum products, expanding their range and improving quality are the main tasks facing the oil refining industry at the present time.
The modern world market places high demands on the quality of petroleum products, as well as and for diesel fuel. Therefore, much attention is paid to reducing the content of sulfur, nitrogen and aromatic hydrocarbons. In addition, sulfur compounds present in petroleum products they greatly reduce the quality of fuels and oils, cause corrosion of equipment, reduce the activity of antiknock agents and the antioxidant stability of fuel, and increase the tendency of cracked gasolines to form gums.
Every year the world market imposes more and more stringent requirements for petroleum products, as well as tightening environmental standards and requirements for plants that produce these petroleum products. For production of diesel fuels corresponding to modern requirements, it is necessary to improve the hydrotreating process.
There are several ways to improve the process:
1. Choosing the most efficient catalyst;
2. Choosing the optimal parameters of the process;
3. The growth of requirements for raw materials;
4. Choosing the most efficient reactor and other auxiliary equipment.
Hydrotreating of petroleum distillates is the most common process, especially
when processing of sour and sour oils. The main task of hydrotreatment is to reduce the content of sulfur, nitrogen and organometallic compounds.
DISCUSSION
Many European countries are switching to fuels that meet the requirements of the standard GOST R 52368-2005 (EN 590:2009), according to which the sulfur content should not be more 0.005% wt., and polycyclic aromatic hydrocarbons not more than 8% wt. To obtain diesel fuels that meet these requirements, it is necessary to constantly improve the hydrotreating process.
Every year, about 49 million tons of diesel fuel is produced in the domestic market, 93% of it with a sulfur content of up to 0.2% wt. and only 7% - with a sulfur content of less than 0.2% wt..
Hydrotreating in modern processing has become of great importance among the secondary processes, and is part of almost any oil refinery. One of the main tasks of hydrotreatment is to organize the production of environmentally friendly fuels.
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In order for a hydrotreating plant, in fact, like any other plant, to be profitable, highly efficient, environmentally friendly and produce fuels that meet world standards, continuous improvement and modernized installations are necessary.
RESULTS
The effect of an intermediate activated carbon on an alumina support on the catalytic activity of transition metal sulfides obtained from heteropolycompounds by thiophene hydrodesulfurization, benzene hydrogenation, and hydrotreatment (including HDS and hydrogenation of polyaromatic components) in diesel fractions was studied. The carbon content on the carrier of aluminum oxide varied from 0 to 3.8 wt. %. It has been found that the structure of carbon deposited on the surface of an alumina support changes depending on the presence/absence of an active phase on the intermediate activated carbon. The total catalytic activity of catalysts for hydrodesulfurization and hydrogenation reactions was maximum for a carbon content of 1-2% and decreased for catalysts with a carbon content of 3-5%. The specific catalytic activity grew in proportion to the carbon content in the catalyst.
Experimental data showed that an increase in the reaction temperature leads to a decrease in the amount of adsorbed hydrogen, the deficiency of which limits the formation of H2S.
The results of the experiments of the prepared catalysts in the hydrotreating of diesel fuel are shown in Figure 1.
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Figure 1(a) Dependence of the HDS activity of the Co3 — Co2Mow/Cx/g — Al203 catalyst on the carbon content in it (b) Change in the HDS activity of the catalyst during the hydrogenation of polyaromatic compounds depending on the carbon content in it.
The change in the structure of carbon during the synthesis of transition metal sulfides of the catalyst deposited on alumina coated with C shows that carbon deposition is involved in the formation of the active phase.
The use of activated carbon as an intermediate carrier for the preparation of transition metal sulfide catalysts increases their HDS and HDN catalytic activity as compared to catalysts supported on Al203.
The presented results show a new approach to the deep desulphurization of diesel fuel, especially with regard to those sulfur compounds that are very difficult to remove by conventional hydrodesulfurization methods.
One way to improve a diesel hydrotreater is to choose the most efficient catalyst. This condition can be achieved in several ways:
The choice of a catalyst based on the following criteria:
1. High performance (intensity, activity);
2. High selectivity (selectivity);
3. High strength and wear resistance;
4. Long service life and regeneration period;
5. Low cost.
In world practice, aluminum-cobalt-molybdenum (ACM), aluminum-nickel-molybdenum (ANM), mixed aluminum-nickel-cobalt-molybdenum (ANKM) and aluminum-nickel-molybdenum-silicate (ANMS) catalysts are widely used in hydrogenation processes.
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Catalysts TK-578 BRIMTM and TK-570 BRIMTM were loaded into the hydrotreating reactor. The characteristics of these catalysts are presented in the following table 1.
Table 1.
Characterization of catalysts
Name of raw materials, materials, reagents, catalysts, semi-finished products, finished products Number of state or branch standard, specification, standard enterprises Quality indicators, mandatory for checks Norm according to GOST, OST, STP, TU Scope of manufactured products
Catalyst TK-570 BRIM™ by Haldor Topsoe MSDS (EU No. 1907/2006) 1. Appearance Extrudate in shape four leaf black color Catalyst for hydrotreatment and hydrodesulfurization of diesel and kerosene fractions
2. Density when loading (sleeve/dense), kg/m 3 720
3. Melting point, 0 C 795
4. Chemical composition, % w t.
- dialuminum trioxide 70...80
- cobalt oxide 3...5
- molybdenum trioxide 18.24
- diboron trioxide 1.3
5 Solubility in water Possible slight leaching of metals
Catalyst TK-578 BRIM™ by Haldor Topsoe MSDS (EU No. 1907/2006) 1. Appearance Extrudate in shape blue trefoil Catalyst for hydrotreatment and hydrodesulfurization of diesel and kerosene fractions
2. Density when loading (sleeve/dense), kg/m 3 920
3. Chemical composition, % w t
- aluminum oxide >50
- cobalt oxide 5.10
- molybdenum trioxide 20.25
- divanadium pentoxide 0,1.1
4 Solubility in water Not
Having studied the patent bases and products manufactured by world leaders in catalysis, I have chosen the following Haldor Topsoe catalysts: TK-609 HyBRIM ™ and TK-611 HyBRIM ™.
These catalysts are made using the new HyBRIM™ technology and have a significantly higher activity: the removal of sulfur and nitrogen is up to 40% higher than
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that of catalysts produced according to BRIM® technology. In addition, they provide a higher degree of aromatic hydrogenation, compounds, resulting in a higher volumetric yield. This ensures the achievement longer cycles at the same plant capacity, or the possibility of processing heavier feedstock or higher productivity at the same cycle time. Information on these catalysts is presented in the following table 2.
Table 2.
Brief information about Haldor Topsoe catalysts: TK-609 HyBRIM™ and TK-611 HyBRIM™
Catalyst brand Description
TK-609 HyBRIM™ TK-609 HyBRIM™ is a next generation high activity NiMo catalyst based on the latest HyBRIM™ technology. Catalyst TK-609 HyBRIM™ is an excellent solution for diesel hydrotreaters producing ultra low sulfur diesel (ULSD) operating at medium and high pressure. The TK-609 HyBRIM™ catalyst is suitable for both straight-run feedstocks and recycled distillates.
TK-611 HyBRIM™ TK-611 HyBRIM™ is the latest generation of high activity nickel molybdenum catalyst based on the new HyBRIM™ technology. TK-611 HyBRIM™ excellent for ultra-low sulfur diesel hydrotreaters operating at medium and high pressures. TK611 HyBRIM™ is suitable for a wide range of straight run feedstocks and cracked distillates. TK-611 HyBRIM™ is particularly suitable for aromatic saturation in high pressure applications. Aromatic saturation plays a critical role where higher cetane, low aromatics or volume expansion is required.
Returning to the beginning of the article, we recall that in order to select the most effective catalyst for diesel fuel hydrotreating unit. It must meet several requirements:
1. High performance (intensity, activity);
2. High selectivity (selectivity);
3. High strength and wear resistance;
4. Long service life and regeneration period;
5. Low cost.
As we can see, the new catalysts meet at least two of the five parameters:
1. High performance (intensity, activity);
2. Long service life and regeneration period.
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This will make the diesel fuel hydrotreater more environmentally friendly, improve product quality and increase the operating time of the unit on one catalyst.
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