CC BY
13
№ 12 (117)
A UNI
/ш. те;
UNIVERSUM:
технические науки
декабрь, 2023 г.
DOI -10.32743/UniTech.2023.117.12.16381
THE CURRENT STATE OF TECHNOLOGY DEVELOPMENT FOR GAS PURIFICATION FROM SULFUR COMPOUNDS AND ITS FUTURE PROSPECTS
Oybek Aripdjanov
Associate Professor of the Department of Chemical Technology of Oil Refining Tashkent Institute of Chemical Technology Republic of Uzbekistan, Tashkent E-mail: aripdjanov81 @gmail. com
Diora Khayrullaeva
Master's student of the Department of Chemical Technology of Oil Refining Tashkent Institute of Chemical Technology Republic of Uzbekistan, Tashkent E-mail: [email protected]
Shokhrukh Kholmatov
doctoral student of the Department of Chemical Technology of Oil Refining Tashkent Institute of Chemical Technology Republic of Uzbekistan, Tashkent E-mail: shkholmatovf@gmail. com
Jamshid Kayumov
Associate Professor
of the Department of analytical, physical and colloidal chemistry Tashkent Institute of Chemical Technology Republic of Uzbekistan, Tashkent E-mail: _ jamshid2386@mail. ru
СОВРЕМЕННОЕ СОСТОЯНИЕ РАЗВИТИЯ ТЕХНОЛОГИИ ОЧИСТКИ ГАЗОВ ОТ СОЕДИНЕНИЙ СЕРЫ И ЕЕ БУДУЩИЕ ПЕРСПЕКТИВЫ
Арипджанов Ойбек Юсупджанович
доцент
кафедры «Химическая технология переработки нефти» Ташкентский химико-технологический институт Республика Узбекистан, г. Ташкент
Хайруллаева Диора Захид кизи
магистрант
кафедры «Химическая технология переработки нефти» Ташкентский химико-технологический институт Республика Узбекистан, г. Ташкент
Холматов Шохрух Фурката угли
докторант
кафедры «Химическая технология переработки нефти» Ташкентский химико-технологический институт Республика Узбекистан, г. Ташкент
Каюмов Джамшид Сайфуллаевич
доцент
кафедры ««Аналитики, физическая и коллоидная химия» Ташкентский химико-технологический институт Республика Узбекистан, г. Ташкент
Библиографическое описание: THE CURRENT STATE OF TECHNOLOGY DEVELOPMENT FOR GAS PURIFICATION FROM SULFUR COMPOUNDS AND ITS FUTURE PROSPECTS // Universum: технические науки : электрон. научн. журн. Aripdjanov O.Yu. [и др.]. 2023. 12(117). URL: https://7universum.com/ru/tech/archive/item/16381
¿к UNIVERSUM:
№11X117}_- ^ АУКИ_декабрь. 2023 г.
ABSTRACT
In this scientific-research work, the physico-chemical properties of compositional separation of sulfur compounds formed during the processing of natural gases were studied. On the basis of experimental tests, new absorbents with high sorption capacity, selective separation of no more than 20 mg/m3, corrosion resistance to metal brands, low foam formation, MDEA+DEA+ASSEP absorbents will be developed based on experimental tests. According to the results of the research, it was found appropriate to obtain MDEA, DEA solutions in the amount of 15-20%, 5% ASSEP (nitrogen-containing water-soluble polyelectrolyte) in order to improve the efficiency of cleaning natural gas from H2S and CO2 sour additives.
АННОТАЦИЯ
В данной научно-исследовательской работе изучены физико-химические свойства композиционного абсорбента для очистки сернистых соединений, образующихся при переработке природных газов. На основе изучении различных абсорбенты выйвлены седуюшый, высокой сорбционной способностью, селективным разделением не более 20 мг/м3, коррозионной стойкостью к маркам металлов, низким пенообразованием, абсорбенты МДЭА+ДЭА+АССЭП. По результатам исследований признано целесообразным получение растворов МДЭА, ДЭА в количестве 15-20%, 5% АССЭП (азотсодержащий водорастворимый полиэлектролит) с целью повышения эффективности очистки природного газа от кислых H2S и CO2.
Keywords: adsorption, absorption, nitrogen-containing water-soluble polyelectrolytes, absorption, monodiethanolamine, amine plant, viscosity, specific gravity, foaming, sulfur.
Ключевые слова: адсорбция, абсорбция, азотсодержащие водорастворимые полиэлектролиты, абсорбция, монодиэтаноламин, аминная установка, вязкость, удельный вес, пенообразование, сера.
Introduction
In refining gases, the volume of gas production and processing has increased over the next three years; now the annual volume of these indicators in the Uzbekistan is 50.0 billion. m3. At the same time, the content of hydrogen sulfide in natural gas is also increasing, also high-sulfur gases produced in it make up a large part [1; p. 159]. In addition to hydrogen sulfide, which is considered toxic and harmful for environmental protection and corrosively active, carbon dioxide, thiols, mercaptans and alkyl sulfides remain in the composition of natural gases, and their separation is required at the initial stages of processing [2; p. 517, 3; p. 472, 4; p. 283, 112; p. 272, 5; p. 352].
Gaseous compounds of sulfur contained in raw materials are toxic and harmful, it causes a number of problems in gas extraction, storage and refining processes, including corrosion of equipment metals, poisoning catalysts and affecting their physical, mechanical and operational properties. At the same time, sulfur compounds extracted from natural gas (ethyl mercaptans, odorants for household gases, ethyl and butyl mercaptans) are important for the production of insecticides and various detergents [6; p. 279, 7; p. 270].
At the world level, currently, methyldiethanolamine (MDEA) solution, diethanolamine (DEA) solution are used in gas purification devices. The presence of sulfur compounds (COS, R-SH, R-S-R', etc.) and chlorine ions in the gas transferred to natural and secondary gas purification devices using amines, as well as from gas drying devices using zeolites, causes the formation of stable salts in MDEA and DEA solutions used in the device. Also, such technological problems accelerate the corrosion of devices and equipment, causing them to fail, and have a significant impact on environmental protection.
The processes of cleaning natural and waste gases generated in production conditions can be divided into
the following groups [8; p. 105-126, 9; p. 467-470, 10; p. 349, 11; p. 820, 12; p. 224, 13; p. 105]:
1. Chemosorption liquid processes of gas purification using absorbers with aqueous solutions of alkanolamines: monoethanamine (MEA), diethanolamine (DEA), diglycolamine (DGA), etc. These processes are based on the chemical reaction of the components with alkanolamines, which are the active, important part of the absorbent.
R
NH
R
N-R
R
where R1 - an alcohol radical, for example C2H4OH; R2 , R3 - or an alcohol, or a hydrocarbon radical, or H+ .
2. The physical method of absorption of sour components with organic solvents. It is done with propylene carbonate, dimethyl ether of polyethylene glycol, N-methylpyrrolidone and others. These processes are based on the physical absorption of acidic components.
3. Combined processes are used to purify gases from acidic components with solvents consisting of a mixture of organic solvents and aqueous solutions of alkanolamine, for example, sulfolane, methanol, etc.
4. Irreversible rotation of absorbed hydrogen of sulfide to elementary sulfur based on oxidation processes such as Giammarco-Wetrocock or Stretford.
5. Adsorption processes. Such processes are mainly used in the deep purification of natural gases from sulfur compounds. Molecular sieves-zeolites are widely used as adsorbents in this process.
6. Membrane processes. In these processes, partial separation of gas components is carried out due to the difference in their partial pressure [14; p. 24-26, 15; p. 152, 16; p. 27-31].
№ 12 (117)
Л
ДА
UNIVERSUM:
ТЕХНИЧЕСКИЕ НАУКИ
декабрь, 2023 г.
In the last 10 years worldwide, the following methods of cleaning gas hydrocarbons from various additives have been widely used [17; p. 111, 18; p. 65-88, 19; p. 64] (Fig. 1):
• physical absorption based on selective absorption of mixtures of acidic components with organic solvents (Rectisol, Purisol, Fluor, Selehol, Sepasolv-MPE);
• combined technologies for the use of absorbents, covering both chemical and physical methods of gas purification and separation;
• oxidation processes based on the irreversible transformation of compounds into elemental sulfur or other substances;
• adsorption processes based on the selective absorption of sour components on the surface of activated carbon, aluminosilicates (silicagel), zeolites and other solid substances are widely used.
In this situation, it is very convenient to use absorption and adsorption methods for cleaning methane hydrocarbons from hydrogen sulfur and mercaptans [20; p. 84-113].
Gas hydrocarbon purification methods
Microbiological
Figure 1. Purification methods of gas hydrocarbons from H2S compounds
Mono- and diethanolamine solutions with various activating additives are also widely used in the purification of acidic sulfur substances.
Adsorption methods are based on selective adsorption of sulfur compounds by solid sorbents. In practice, this adsorption process is carried out at temperature of 20-50°C and high pressure, regeneration (desorption) of the adsorbent saturated with sulfur substances is carried out at a low pressure and a temperature of 100-350°C. Any inert gases, low-sulfur natural or petroleum gas, water vapor are passed through the adsorbent layer for regeneration [21; p. 988-992].
In some cases, catalytic reactions occur simultaneously with adsorption, as a result of which sulfurous substances are converted into elemental sulfur, which is regenerated during regeneration and then used.
Molecular sieves (zeolites) of CaA and, especially, NaX are widely used as adsorbents for cleaning high-sulfur natural and petroleum gases. Their adsorption capacity largely depends on the content of H2O, CO2 and higher hydrocarbons in the gases, operating conditions and degree of purification, and it ranges from 2 to 18%.
The presence of heavy hydrocarbon vapors in the gas has a significant effect on the absorption capacity of zeolites for sulfur compounds. According to the degree of sorption in zeolites, the compounds that make up natural gas can be placed in the following order:
H2O > RSH > H2S > COS > CO2
Adsorption methods have the advantage of conducting the process at low temperatures, as well as the possibility of deep purification of gases not only from hydrogen sulfide, mercaptans, organic sulfides, but also from substances that are difficult to remove by other methods, such as thiophene and its derivatives.
This method also has a number of significant disadvantages, including the fact that almost all gases contain a certain amount of H2O, CO2 vapors, high hydrocarbons, which are well adsorbed by coal and zeolites, and it reduces the sulfur capacity of adsorbents.
Choosing the method of natural gas purification, in most cases, is carried out depending on the composition and physical parameters of the gas raw materials, the required level of purification standards, the type and amount of available energy resources, and the standard requirements of environmental protection [22; p. 48, 23; p. 77, 24; p. 16-26, 25; p. 174, 26; p. 1-7].
Analysis of studies on natural gas purification in world practice showed that the absorption purification method is highly effective [27; p. 489, 28; p. 96-103, 29; p. 777]. In conditions where the flow of gases is small or for analytical purposes of deep gas purification, it is recommended to use oxidizing and adsorption processes.
Alkanolamines easily react with sour gases H2S, CO2 and form water-soluble salts, due to which gases are purified. As a result of boiling a saturated solution of the
№ 12 (117)
UNIVERSUM:
ТЕХНИЧЕСКИЕ НАУКИ
декабрь, 2023 г.
resulting salts, they are easily decomposed and the following reactions occur:
H2S + [Amine]
[Amine • H]+ + HC- (quickly);
CO2 + 2-[Amine] ^ COO ]- (quickly);
[Amine • H]+ + [Amine
CO2 + H2S <-H2CO3 (slowly);
H2CO3 < * H+ + HCO3- (quickly);
HCO3- <-H+ + CO3 (quickly);
[Amine] + H+
[Amine • H]+ + HS"
The reaction with hydrogen sulfide and carbon dioxide in the presence of MEA is expressed as follows:
2RNH2 + H2S <-(RNH3)2 ;
(RNH3)2 + H2S
2RNH3HS;
Cleaning of gases contained carbonate anhydride in the presence of water goes by following reaction:
2RNH2 + CO?
(RNH3)2CO3 + CO2 + H2O
(RNH3)2CO3 ; —
2RNH3HCO3 ;
2RNH2 + CO2 *-RNHCOONH3R ;
where R - radical group HO-CH2 -CH2 - .
Every amines react homogeneously with H2S to form amine hydrosulfide or sulfide, and the reaction is considered to be fast reaction. Primary and secondary amines by reacting with CO2 form carbamates (car-bamine acid salts: -amine-COO- , H+), which belongs to the class of fast reactions. In addition, carbonates and bicarbonates of amines are formed with CO2 , but before that there will be a reaction of slow dissolution of H2CO3 and CO2 in water. Amine carbamates are unstable compounds. In a low-alkaline environment, they decompose slowly with the formation of bicarbonate, that is:
R2NCOOR2NH2 + H2O *- R2NH + R2NH2HCO3 ,
where, R is HOCH2CH2 .
By using amines, gas purification from hydrogen sulfide and CO2 in the initial raw materials at different working pressures and concentrations is provided to a certain degree. The solubility of hydrocarbons in these absorbents is not great, and the technological and
equipment forms of the processes differ in their simplicity and reliability.
The physical method of the absorption of sour components in the presence of organic solvents is carried out with propylene carbonate, dimethyl ether of polyethylene glycol (DMEPEG), H-methylpyrrolidone, etc. These processes are based on the physical absorption of acidic components [14; p. 24-26, 15; p. 152, 16; p. 2731, 30; p. 63, 31; p. 124, 32; p. 91-93].
The organic solvents are used to purify gas deeply from hydrogen sulfide, CO2, RSR, COS and CS2 additives under high partial pressure. These used absorbents do not foam, do not corrode devices and equipment.
The main advantages of gas purification with alkanolamines by circulation (absorption-desorption) technology are described in the literature [33; p. 392, 34; p. 349, 35; p. 20-25], regardless of the partial pressure indicators in the raw materials, the quality of extracted sulfur is improved by selective absorption of hydrogen sulfide and carbon dioxide [36; p. 59, 37; p. 58].
In addition to the aspects mentioned above, absorbents used in the cleaning process also should have:
• high absorption capacity for aggressive components of natural gas;
• high selectivity to acidic components;
• low saturated vapor pressure for minimal loss in the absorption process;
• low solubility of hydrocarbons;
• reaction inertness according to the properties of the gas to be cleaned;
• the standard level of purification (no more than 20 mg/m3 of gas);
• not corrosive activity on metal;
• inhibitors used in gas extraction and mine processing should be neutral in relation to hydrocarbons;
• required to be stable to foaming.
Natural gases extracted from different deposits differ sharply in terms of their parameters, and the absorbents used (water solutions of DEA and MDEA) often do not allow complete cleaning of aggressive acidic components.
The collected analysis of world practice in the field of natural gas treatment shows that the main processes of processing large gas streams are absorption, regenerative processes using chemical and physical absorbents and their combinations [10; p. 349, 14; p. 24-26, 15; p. 152, 27; p. 124, 38; p. 38-45, 39; p. 455-460, 40; p. 38-42]. Oxidation and adsorption processes are used to treat small amounts of gas streams.
However, alkanolamines (including DEA) also have certain disadvantages, such as high costs of thermal energy for regeneration of saturated absorbent, thermochemical degradation during operation, and corrosion problems.
The technological parameters of the cleaning process are obtained taking into account the concentration of the absorbent, its degree of saturation with H2S+CO2. Table 1.1 shows the recommended concentration of alkanolamines in the absorbent and their saturation level with H2S, CO2 [10; p. 349, 38; p. 38-45].
№ 12 (117)
A UNI
/Ш. те;
UNIVERSUM:
ТЕХНИЧЕСКИЕ НАУКИ
декабрь, 2023 г.
Table 1.1
Recommended concentration of alkanolamines and their Degree of saturation with H2S, CO2 [10; p. 349, 38; p. 38-45]
Alkanolamines Concentration of alkanolamines in solution, % mass. Proportion of H2S and CO2, mol / mol
at saturated absorbent when regenerated
MEA-monoethanolamine H2N-CH2-CH2-OH 15-20 0.30-0.35 0.10-0.15
DEA-diethanolamine HN(CH2-CH2-OH)2 25-35 0.35-0.40 0.05-0.07
MDEA-methyldiethanolamine CH3N(CH2-CH2-OH)2 30-50 0.45-0.50 0.004-0.01
DGA-diglycolamine HOCH2CH2OCH2CH2NH2 40-60 0.35-0.40 0.02-0.10
It seems that better way to improve the efficiency of the cleaning process by amine is to use new absorbents that are superior to them in all respects. Most scientific publications are devoted to the study of this direction [10; p. 349, 38; p. 38-45, 40; p. 75-79, 41; p. 107], where the main absorbents are MEA, DEA and MDEA.
Alkanolamines (aminoalcohols, hydroxamines) can be considered as derivatives of ammonia, in which one or more hydrogen atoms are exchanged with an alcohol radical or an alcohol and a hydrocarbon radical. The scheme of gas purification with aqueous solutions of alkanolamines is based on the following reaction, which occurs reversibly:
The temperature is equal to 25-40 °C, the balance of the reaction shifts to the right and forms an unstable sulfide. Also, when the temperature reaches 100-105 °C and higher, the formed sulfide decomposes and the absorbed hydrogen sulfide is released, the balance shifts to the left. In the weak alkaline environment of the absorbing solution, part of the hydrogen sulfide dissociates into HS- ions. The balance of the solution is established with respect to the undissociated hydrogen sulfide in the absorber, where the larger - the dissociated fraction of hydrogen sulfide, the higher - the absorption efficiency. The general scheme of absorption with a weak alkaline solution is as follows:
2HO(CH2)nNH2 + H2S
(HO(CH2)nNH2)2S
Alkanolamines are colorless, viscous, hygroscopic liquids, miscible with water and low molecular weight alcohols in any proportion, almost insoluble in nonpolar solvents. Anhydrous alkanolamines are usually used as an aqueous solution. The indicator of the concentration of amine in the solution can vary in wide ranges, it is selected based on the reasons for conducting experiments and corrosion of technological devices.
In recent years, methods of gas purification with solutions of alkanolamines in organic solvents have been developed [42; p. 50, 43; p. 29-31, 44; p. 7]. In addition to lower heat capacities, saturated vapor pressure and heat of vaporization, the advantage of organic solvents is that they begin to absorb CO2 under pressure (due to physical absorption), while the desorption of this part of the dissolved gas is achieved only by reducing the pressure.
Various variants of this process have been identified. MEA, DEA, DIPA are used as alkanolamine, and sulfolane ("Sulfinol" process), H-methylpyrrolidone, tetrahydrofuryl alcohol, benzyl alcohol and other products belonging to various classes of organic compounds are used as organic solvents.
Choosing the process of cleaning natural gas from sulfur compounds depends on many factors, the main of which are: the composition and parameters of the raw gas, the required level of cleaning and the areas of use
of the commodity gas, the availability of energy resources, production waste, etc. Used in industry absorbents are subject to the following requirements: non-deficiency; high absorption capacity; low vapor pressure; lower viscosity; low heat capacity; non-toxic; selectivity (in selective absorption).
In addition to H2S and CO2, the raw gas fed to processing contains COS and CS2 compounds, which irreversibly react with MEA and cause large losses, and under such conditions, it is advisable to use DEA. A methyldiethanolamine is used to selectively extract H2S in the presence of CO2 . Separation of acidic components from gas in physical processes occurs due to their physical dissolution in the absorbent used. In this case, the larger the partial vapor pressure of the components, the higher their solubility. In industry for gas purification, methanol H - methylpyrrolidone; physical absorbents such as alkyl ethers of polyethylene glycol and propylene carbonate are used.
"Sulfinol" process. By using physical and chemical absorbent mixtures, the "Sulfinol" process, developed by the "Shell Oil Company" firm, is important [45; p. 239249, 46; p. 30]. Tetrahydrothiophene dioxide (CH2)4SO2 is considered as the main absorber in this process (technical name is sulfolane). Approximate composition of absorbent consists of: 30% DIPA, 64% sulfolane
№ 12 (117)
UNIVERSUM:
ТЕХНИЧЕСКИЕ НАУКИ
декабрь, 2023 г.
and 6% water. The presence of water in the solution reduces the solidification temperature from 8-10 and to -2oC. Sulfolane gas is chemically rare gas, and affects as a physical devourer. DIPA separates sour components from gas due to chemosorbtion and is almost insensitive to changes in the partial pressure of the mixture. The combined absorbent has a high absorption capacity of sour components at low, medium and high partial pressures, and for sulfinol, depending on the gas composition and process conditions, the sour gas capacity ranges from 30 to 127 m3/m3 (MEA solution - 3-30 m3 /m3).
The high capacity of sulfinol results in its lower relative consumption, which means it requires smaller equipment and a transport system. Regeneration of saturated sulfinol requires 30-80% less energy than amine processes. Another important advantage of sulfinol is the possibility of simultaneous purification of gas not only from H2S and CO2 , but also from COS, CS2 and thiols. Unlike MEA and DIPA, it does not form a compound with the monoxide sulfide, which reduces its losses.
Sulfolane and DIPA have low saturated vapor pressures under gas stripping conditions [45; p. 239-249, 46; p. 30-38], therefore, its loss due to mixing with purified gas is not so great. In gas purification with sulfinol, the saturation of the absorbent with hydrocarbons is higher than in amine solutions. Therefore, during degassing, a large amount of gases can be released. The concentration of H2S in degassing gases is also higher than in amine plant devices.
Some difficulties arise during the operation of gas treatment plants with sulfinol, for instance, the movement of the two-phase flow causes the pipes to vibrate due to cavitation, which can lead to their destruction (if special
measures are not taken), and solution may foam, to prevent this it is necessary to add antifoaming agents.
The experience of industrial processes of cleaning hydrocarbon gases from hydrogen sulfide with ethanolamine shows that due to an increase in the concentration of alkanolamine solutions, the corrosion aggressiveness of the solutions increases sharply and the corrosion of carbon steel equipment increases [47; p. 105107, 48; p. 236, 49; p. 38-45, 50; p. 36]. With the help of absorbent-inhibitors that prevent corrosion into the working solutions, even when using simple steels, it is possible to use highly concentrated solutions of amines and to significantly increase their saturation level with sour components. Therefore, high-concentration amine solutions containing a special corrosion inhibitor are used in the following years [51; p. 200, 52; p. 58-59].
Cleaning process with GAZAMIN [53; p. 71-72, 54; p. 345], developed by NIPI gas processing company (KRAGAZ), based on the use of high-concentration ethanolamine solutions containing a passivating type corrosion inhibitor, improving the efficiency and energy of natural and associated gas refineries in gas desulfurization devices. This results in lower capital and operating costs and less equipment corrosion [55; p. 41, 56; p. 18-20]. Ethanolamine polysulfides are used as passivating type corrosion inhibitors. Technical and economic indicators of the GAZAMIN process are presented in Table 1.2.
An absorbent with inhibitors has a lower foaming rate [57; p. 539-544] and managing the process is easy and efficient. GAZAMIN technology is implemented in the devices of refineries of the Russian Federation. The real value of reducing energy consumption for cleaning up to 15-30% has been proven in practice [58; p. 74-79, 59; p. 29-31].
Table 1.2.
Technical and economic indicators of GAZAMIN process
№ Indicators The value of magnitudes
1 Cleaning gas pressure , Mpa 0.2-10.0
2 The maximum amount of acidic components in gas, % volume, as well as H2S up to 50 up to 30
3 Mass fraction of H2S in purified gas, mg/nm3 no more than 7
4 maximum mass fraction in absorbent, %: - that of monoethanolamine - that of diethanolamine 30 55
5 The amount of corrosion inhibitor in the absorption solution, g/dm 3 0.05-0.30
6 Corrosion rate of carbon steel, mm/year less than 0.1
7 Inhibitor consumption, g/1000 nm3 of purified gas 2.0-4.0
8 Reduction of energy consumption in the device, % 25-30
9 Possibility of increasing gas production capacity, % 20-25
10 Reducing economic costs of device, % 10-15
If the absorbency of the absorbent is high in relation to H2S, CO2 and other components, the less amount of ethanolamine is used for cleaning at the level of demand for the gas being cleaned. The selection of absorbent for
gas treatment processes requires a feasibility study based on alternative indicators in each specific situation.
In the gas industry of our country, absorption purification using aqueous solutions of ethanolamines
№ 12 (117)
UNIVERSUM:
ТЕХНИЧЕСКИЕ НАУКИ
декабрь, 2023 г.
is carried out in large gas processing enterprises such as Shurtanneftgaz, Muborak GR LLC and Shurtan GGhC, and their technologies were adopted from existing plants of the Russian Federation [60; p. 61, 61; p. 78]. The experience of using these devices has shown that energy consumption can be up to 30% of the cost of purified gas.
Aqueous solutions of alkanolamine are stable at temperature [62; p. 12-14, 63; p. 14-16], for example, when heated to 200oC, a 20%-MDA solution is kept stable for 120 hours, and a 58% concentrate for 70 hours. MDEA solutions are also thermally stable liquids. DEA and TEA solutions are relatively unstable, DEA changes at t>180oC, TEA at t>170oC forming tarry substances that are half-condensation products [64; p. 24-26, 65; p. 30-31].
Amino alcohols with moderate thermal resistance are oxidized by oxygen [66; p. 13-17], firstly, the terminal hydroxyl groups of alkanolamine are transferred to carboxyl groups, then the CH-group in amino acid molecules is broken and oxyacetic (glycolic) acid is formed, and then oxalic acid is formed [67; p. 13-15].
The rate of interaction of CO2 and MDEA (TEA) is slower than that of MEA and DEA, which reduces the selectivity of extracting H2S from natural gas. It is necessary to take into account the rate of reactions of alkanolamine and gases with acidic components; because this rate decreases when the pH of the medium decreases, depending on the saturation of the absorbent [68; p. 116-118, 69; p. 8-14].
During the saturation of acidic component-gases with an aqueous solution of alkanolamine, not only the rate of mutual chemical reaction declines, but also the partial pressure of the same components in the vapor phase decreases; physical solubility and concentration in the liquid phase increase under the influence of temperature, and the general quantitative description of the process becomes complicated [70; p. 60, 71; p. 53-56].
Conclusion
In order to improve the efficiency of natural gas purification technology, to reduce the corrosiveness of absorbent solutions, the formation of foam and other indicators, it is necessary to create and use composite absorbents based on DEA and MDEA using aqueous solutions of -nitrogen and amine (such as soluble polymers, NH4OH and -nitrogen and amine-containing composite absorbents). So it is advisable to use a combined cleaning method to activate and modernize the process of cleaning sulfur-containing gases (including waste gas emissions).
During the use of the absorbent created on the basis of local raw materials and industrial waste, its destruction products are formed and accumulate, as well as the absorption capacity decreases over time, and the quality of the absorbent decreases, and as a result, the efficiency of the cleaning devices is reduced. It was determined that the main drawback of the gas purification process using amines is the research and development of a comprehensive rational technology for cleaning working solutions of diethanolamine, which will improve the quality of absorbents, increase the efficiency of gas cleaning units with amine solutions. The analysis of the literature study shows that recovery of the properties of ethanolamines used in the oil and gas industry and their reuse in the process of gas purification is one of the important problems facing researchers.
Taking this into account, the processing of sour natural gases containing sulfur in the composition is a purposeful and urgent task of the gas industry of the Republic of Uzbekistan, which has a scientific and practical nature. Research aimed at introducing a combined method of gas purification, synthesis of new absorbents, and improving the efficiency of the technology of processes for purifying natural and secondary gases from sulfur compounds has not been thoroughly studied.
Reference:
1. V.I. Murin, N.N. Kislenko, Yu.V. Surkov. Gas and condensate processing technology - Vol. 2 - Moscow: LLC 'Nedra-Business Center,' - 2002. -Vol. 1 -517 p.
2. M.A. Berlin, V.G. Gorechenkov, N.P. Volkov. Processing of oil and natural gases - Moscow: - Chemistry, -1981. -472 s.
3. T.M. Bekirov. Field and factory processing of natural and petroleum gases - Moscow: - Subsoil, -1980. -283 s.
4. Tetelmin V.V., Yazev V.A. Environmental protection in the oil and gas complex // Textbook. - Dolgoprudny: Publishing House 'Intellect.' 2009. - 352 p.
5. A.M. Churakaev. Processing of oil gases - Moscow: - Nedra, 1983. -279 p.
6. A.I. Gritsenko, A.I. Galanin, L.M. Zinovieva, V.I. Murin. Purification of gases from sulfur compounds during the exploitation of gas fields - Moscow: Nedra, 1985. -270 p.
7. Gas Processes // Hydrocarbon Processing / 2006. - No. 4. -R. -105-126.
8. O. Richardson., J. Connell /Some Generalizations about Processes to adsorb Acid Gases and Mercaptans// Ind. End. Chem. Process Des. Dev-Vol. -14. -No. 4. -2022. -p. -467-470.
9. D.M. Campbell Purification and processing of natural gases - Moscow: - Subsoil. -1977. -349 pp.
10. S.A. Newman / Acid and Sour Gas Treating Processes (Latest date and methods for designing and Operating today S) // Gulft Publishing Company. - Houston. -USA. 2021. -p. -820.
11. Directory of modern gas processing processes // Oil, gas and Petrochemistry abroad -1986. -No. 7. -With. -245.
12. GOST 22387.2-97. Natural flammable gases. Methods for determining hydrogen sulfide and mercaptan sulfur -2022.
13. D. HallP / Corrosioninnibition in alkanolamine acid gas removal Plants // Report at the presentation of the Dow Chemical company - Moscow -1980. - With. -24-26.
¿k UNÍVERSUM:
№ 12 П171_ НАУК1_декабрь. 2023 г.
14. A.I. Afanasyev, V.M. Stryuchkov, N.I. Podlegaev, N.N. Kislenko and others. Natural gas - Moscow: Subsoil. 1993. -p. -152.
15. R.N. Maddox and all / Reactions of CO2 and H2S with some Alkanolamines // Ind. Eng. Chem. Res. -2020 -vol. -26. -№1 - p. -27-31.
16. V.L. Gartman Dynamics of chemisorption of sulfur by a solid absorber and its application to optimize industrial desulfurization / Dissertation for the degree of Candidate of Technical Sciences. - Moscow: -2000. -111 s.
17. A.I. Gritsenko, A.I. Galanin. Oil, gas and petrochemicals abroad. Moscow: Nedra, 1984. No. 4. With. 65-88.
18. A.A. Soghomonyan, E.K. Borisenko, G.M. Karpenko. Current state and development trends of gas processing equipment and technology. Moscow: All-Union Scientific Research Institute of Organization, Management and Economics of the Oil and Gas Industry, 1977. 64 p.
19. Lazarev V.I. Methods for purifying natural gas from hydrogen sulfide using solid sorbents // Review information; Scientific and technical aspects of environmental protection / Russian Institute for Scientific and Technical Information. 1999. No. 4. - 84-113 p.
20. Artamonov V.I., Golosman E.Z., Rubinshtein A.M., Yakerson V.I. Study of the properties and activity of zinc chemisorbents on carriers // Academy of Sciences of the USSR. Chemical series 1986. No. 5. P. 988-992.
21. F.N. Infantry, V.Yu. Nikolaev, E.N. Turevsky. Direction of intensification of processes for preparing oil and natural gas for processing. Moscow: Research Institute of Natural Gases and Gas Technologies GazProm, 1971. 48 p.
22. Kuznetsova T.O., Varavina E.P. Environmental safety in the oil and gas industry // textbook. - Kharkov. National Technical University 'Kharkiv Polytechnic Institute,' 2013. - P. 77.
23. Arzamasova G.S., Karmanov V.V. Solving complex issues of handling waste from natural gas purification from mechanical impurities. Ecology and scientific and technological progress. Urbanism. Materials of the XII-All-Russian scientific and practical conference of students, graduate students and young scientists. Perm, November 21, 2014. pp. 16-26.
24. Polozov M.B. Ecology of the oil and gas production complex // Educational manual. - Izhevsk: Udmurt University Publishing House, 2012. - 174 p.
25. Safin R.R., Ismagilova Z.F. Scheme of an environmentally friendly gas-chemical complex for processing sulfur-containing gases. Oil and Gas Business, 2010. pp. 1-7.
26. T.A. Semenova, I.L. Leites, Yu.V. Axelrod. Purification of process gases. Moscow: Chemistry, 1977. 489 p.
27. Silantiev Yu.B., Khaloshina T.O., Kananykhina O.G. Forecasting the gas market of the European Union countries using mathematical regression and cluster analysis. // Gas industry. - 2018.- No. 10(775). - P. 96-103.
28. Eder L.V., Filimonova I.V., Komarova A.V., Provornaya I.V., Shumilova S.I. Features of gas production and processing in Russia at the present stage. Gas industry, No. 11 (777), 2018.
29. Khabibullin R.R., Rogozin V.I. Vysheslavtsev Yu.F. Modern methods of gas purification from acidic components: Review. Inform. - Moscow, Russian Institute for Scientific and Technical Information. 1988. No. 3. -With. 63.
30. Purification of process gases. Semenova T.A., Leites I.L., Akselrod Yu.V. and others - Moscow: Chemistry. 1977. -p. 124.
31. Davitt G., Sundermann, Donnelly S., Ballin J. / Increasing gas purification capacity // Oil, gas and petrochemistry abroad. - No. 5. 1984. -pp. 91-93.
32. A.L. Cole, F.S. Riesenfeld. Gas purification. Text: translation from English - Vol. 2 revised and expanded Moscow: Nedra, 1968. - 392 p.
33. D.M. Campbell. Purification and processing of natural gases. Translation from English / Edited by Gudkov S.F. Moscow: Nedra, 1977. 349 p.
34. Abdallah Sofiane Berrouk, Richard Ochieng. Improved performance of the natural-gas-sweetening Benfield-HiPure process using process simulation // Fuel Processing Technology. Volume 127, November 2014, Pages 20-25.
35. Gritsenko A.I., Bekirov T.M., Stryuchkov V.M., Akopova G.S. Experience in operating gas purification plants from acidic components at the Orenburg and Mubarek State Bearing Plants. Moscow: Research Institute of Natural Gases and Gas Technologies, 1979. 59 p.
36. Tarakanov G.V., Manovyan A.K. Fundamentals of technology for processing natural gas and condensate // Textbook. Astrakhan publishing house Astrakhan State Technical University - 2010 - p. -58.
37. Dupart MS, Bacon TG, Edwards JD. / Study of the corrosion mechanism in gas purification plants using alkanolamines // Oil, Gas and Petrochemistry Abroad. -1993. No. 12 - p.38 - 45.
38. Cordi E., Bullin J. / Kinetics of CO2 and MDEA with Phosphoric Acid// A.I. Ch.E. Journal. -March 2020. - Vol. 38. No. 3. - R. 455-460.
39. Dupart M., Bacon T., Edwards / Study of the corrosion mechanism in gas purification plants with alkanolamines // Oil, gas and petrochemistry abroad. - 2003. No. 12. -With. 38-42.
40. Nasteka V.I. New technologies for purifying high-sulfur natural gases and gas condensates. - Moscow: Nedra, 1996. -p. 107.
¿k UNÎVERSUM:
№ 12 П171_¿Д ТЕХНИЧЕСКИЕ НАУКИ_декабрь. 2023 г.
41. A special composition of amines that allows you to maintain the H2S emission level below 0.001%. Oil, gas and petrochemicals abroad. Information. - 1993. No. 10. 2011. - p. 50.
42. Molchanov O.A., Shkoryapkin A.I. New adsorbents for drying and purifying natural gas. // Gas industry. - 2001. No. 6. -With. 29-31.
43. Patent 2053012, Russian Federation. A method for purifying gas from acidic components. / Adzhiev A.Yu., Astakhov V.A., Potapov V.F., Borushko Gornyak Yu.N., Rozhkova T.E., Yatsenko O.V., Tsitman A.I., Teremets N.I. -1996. -c. 7.
44. Sartori G., Savage D. / Stericaily Hindered Amines for CO2 Removal from Gases // Ind. Eng. Chem. Fundam. -2023. -v. 22. No. 2. -p. 239-249.
45. Patent Federal Republic of Germany No. 3518368, Bo1 D 53/34. Wagner E., Hetner W., Schubert F. / Verfahnen zum Entfernen von CO2, H2S aus Gasen / - 1985.
46. GOST 12.1.007-76 Harmful substances. / Classification and general safety requirements.
47. Harmful substances in industry. Directory / Edited by N.V. Lazarev and E.N. Levina. - Leningrad: Chemistry. 1958. -Vol. 236 pp.
48. Dupart M.S., Bacon T.G., Edwards D.J. / Study of the mechanism of corrosion in gas treatment plants with alkanola-mines // Oil, gas and Petrochemistry abroad. -1993 - No. 12 - p. 38-45.
49. Archakova Yu.I., Sukhotina A.M. / Corrosion resistance of chemical production equipment. Oil refining industry: -Leningrad: Chemistry. -1990. - p.36.
50. Chubar Bianca. Mechanisms of organic reactions. Moscow: Foreign Literature Publishing House -1963. - With. 200.
51. Antonov V.G., Korneev A.E., Soloviev S.A., Alekseev S.Z., Afanasyev A.I. / Mechanism of corrosion of carbon steel in the absorbent Methyldiethanolamine / Dehydroepiandrosterone sulfate // Gas industry. 2000. - No. 10. - With. 58-59.
52. Alekseev S.Z., Kislenko N.N., Stryuchkov V.M. / Gas purification with Methyldiethanolamine / Dehydroepiandrosterone sulfate absorbent at the Astrakhan State Bearing Plant // Gas industry. -2000. No. 6. -With. 71-72.
53. Berlin M.A., Gorechenkov V.G., Volkov N.P. Processing of petroleum and natural petroleum gases. - Moscow: Chemistry. -1981. -With. 345.
54. Safin R.R. Development of scientific foundations for increasing the efficiency of technologies and methods for protecting the environment when processing hydrogen sulfide-containing gases and sulfurous oils. Abstract of the dissertation for the degree of Doctor of Technical Sciences. Astrakhan State Technical University, Astrakhan, 2010, p. 41.
55. Plechev A.V., Safin P.P., Voltsov A.A., Konshenko E.V., Ismagilov F.R. Oxidative conversion of hydrogen sulfide-containing gases // Ecology and industry of Russia. - 2000. - No. 6. - P. 18-20.
56. Safin P.P. Utilization of hydrogen sulfide to produce various sulfur-containing compounds // Ecology of industrial production. - 2004.-№1.- p. 59-62.
57. Ismagilov F.R., Safin P.P., Ismagilova Z.F. Schemes for separation and purification of gases from sulfur compounds. - Ufa: Ufa State Institute of Service, 2005. - 134 p.
58. Gerasimenko M.N., Bryukhov A.V., Isaev A.V. Orenburg Gazprom. Problems and prospects for natural gas processing on the Inverse geodetic problem. // Gas industry. -2001. -No. 6. - With. 29-31.
59. Technological regulations for the production of 'Shurtanneftegaz' Administration of the President of the Russian Federation. 2005. 61 p.
60. Technological regulations for the natural gas purification line in Muborak State Commission for Mineral Reserves. 1998. 78 p.
61. Kochergina D.G., Gorelik A.A. // Corrosion and protection. Moscow: All-Union Scientific Research Institute of Organization, Management and Economics of the Oil and Gas Industry, 1972. No. 6. With. 12-14.
62. Suetin Yu.N., Dosumova E.Ya., Prokopenko V.S. // Preparation and processing of gas and gas condensate. Moscow: Research Institute of Natural Gases and Gas Technologies, 1982. No. 3. With. 14-16.
63. Vysheslavtsev Yu.F., Nazarko V.M., Latyuk V.I. // Gas Industry 1977. No. 4. With. 24-26.
64. Afanasyev A.I., Malyutin S.P., Kislenko N.N., Podlegaev N.I. // Gas Industry 1984. No. 9. With. 30-31.
65. Artyushenko G.V., Sabirov Sh.M., Mazhara L.I. // Processing of gas and gas condensate. Moscow: Research Institute of Natural Gases and Gas Technologies, 1970. No. 3. With. 13-17.
66. Nemkov V.V., Musavirov S.S., Agaev G.A. // Gas Industry, 1977. No. 12. With. 13-15.
67. Kutsher G.S., Smith P.A. // Oil and Gas J. 2019. V. 65. No. 12. R. 116-118.
68. Foreign technology. Moscow: Research Institute of Natural Gases and Gas Technologies, 1967. No. 7. With. 8-14.
69. Stryuchkov V.M., Afanasyev A.I., Shklyar R.L. Intensification of processes for purifying natural gas from acidic components // Preparation and processing of gas and gas condensate: overview information - Moscow: Research Institute of Natural Gases and Gas Technologies. - 1984. - No. 6. - 60 s.
70. Stewart E.J., Lanning R.A. Reducing reagent losses in amine treatment plants // Oil and Gas Technologies - 1995. -No. 2. - p.53-56.
71. URL: https://neftegaz.ru. O'zbekiston oil, gas va energetikasi - 2020.
