Influence of process parameters on the patterns of catalytic published by Ural Federal University eISSN 2411-1414; chimicatechnoacta.ru ARTICLE 2022, vol. 9(3), No. 20229301 DOI: 10.15826/chimtech.2022.9.3.01 1 of 8 Catalytic cracking of M-100 fuel oil: relationships between origin process parameters and conversion products Tatyana V. Shakiyeva a , Larissa R. Sassykova a* , Anastassiya A. Khamlenko a , Ulzhan N. Dzhatkambayeva a , Albina R. Sassykova b , Aigul A. Batyrbayeva a , Zhanar M. Zhaxibayeva c , Akmaral G. Ismailova a , Subramanian Sendilvelan d a: Al-Farabi Kazakh National University, Almaty 050040, Kazakhstan b: Almaty College of Economics and Law, Almaty 050004, Kazakhstan c: Abai Kazakh National Pedagogical University, Almaty 050010, Kazakhstan d: Department of Mechanical Engineering, Dr. M.G.R. Educational and Research Institute, Tamilnadu 600095, India * Corresponding author: larissa.rav@mail.ru This paper belongs to the CTFM'22 Special Issue: https://www.kaznu.kz/en/25415/page. Guest Editors: Prof. N. Uvarov and Prof. E. Aubakirov. © 2022, the Authors. This article is published in open access under the terms and conditions of the Creative Com- mons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Abstract The development of technologies for processing oil residues is rele- vant and promising for Kazakhstan, since the main oil reserves of hydrocarbons in the country are in heavy oils. This paper describes the study of the influence of technological modes on the yield and hydrocarbon composition of products formed because of cracking of commercial fuel oil and fuel oil M-100 in the presence of air in the reactor. For catalysts preparation, natural Taizhuzgen zeolite and Narynkol clay were used. It was found that the introduction of air in- to the reaction zone, in which oxygen is the initiator of the cracking process, significantly increases the yield of the middle distillate frac- tions. In the presence of air, the yield of diene and cyclodiene hydro- carbons significantly increases compared to cracking in an inert at- mosphere. According to the data of IR spectral analysis of M-100 grade oil fractions, in addition to normal alkanes, the final sample contains a significant amount of olefinic and aromatic hydrocarbons. On the optimal catalyst, owing to oxidative cracking of fuel oil, the following product compositions (in %) were established: Fuel oil M- 100: gas – 0.8, gasoline – 1.1, light gas oil – 85.7, heavy residue – 11.9, loss – 0.5 and total – 100.0%; commodity Fuel oil (M-100): gas – 3.3, gasoline – 8.4, light gas oil – 84.3, heavy residue – 4.0, loss – 0 and total – 100.0%. Keywords catalytic cracking oxidative cracking natural zeolite Taizhuzgen zeolite Narynkol clay Amangeldy GPP fuel oil M-100 Received: 12.06.22 Revised: 27.06.22 Accepted: 27.06.22 Available online: 04.07.22 1. Introduction Recently, there has been an increased interest in technolo- gies for processing oil residues due to the growing differ- ence in prices for light and heavy grades of oil. At present, the development of technologies for processing oil resi- dues is relevant and promising, which is associated with an increase in the share of hard-to-recover oil reserves: heavy and high-viscosity oils in the world. This, in turn, forces refineries to select carefully the available technolo- gies for processing oil residues and increase the share of heavy oil raw materials in the total volume of oil- processing feedstock [1–20]. 40–45% of all high-octane gasoline is produced at catalytic cracking plants with a steamer. In the classical version, the cracking process of heavy hydrocarbons occurs in the vapor phase due to con- tact with a circulating fluidized catalyst consisting of par- ticles ranging in size from 50 to 100 microns [4, 21–36]. Over the past decades, the world’s leading companies have developed a number of new catalytic cracking technologies to maximize the yield of light olefins, for example: the use of promoted catalysts or increased rigidity of the techno- logical mode; the addition of light hydrocarbon fractions to raw materials; reducing the contact time of raw materi- http://chimicatechnoacta.ru/ https://doi.org/10.15826/chimtech.2022.9.3.01 mailto:larissa.rav@mail.ru https://www.kaznu.kz/en/25415/page http://creativecommons.org/licenses/by/4.0/ https://orcid.org/0000-0002-9664-442X https://orcid.org/0000-0003-4721-9758 http://orcid.org/0000-0003-0978-510X http://orcid.org/0000-0001-8216-3206 https://orcid.org/0000-0002-1806-522X https://orcid.org/0000-0003-2280-4846 https://orcid.org/0000-0002-5751-6791 https://orcid.org/0000-0002-5555-2705 https://orcid.org/0000-0003-1743-4246 https://crossmark.crossref.org/dialog/?doi=https://doi.org/10.15826/chimtech.2022.9.3.01&domain=pdf&date_stamp=2022-7-4 Chimica Techno Acta 2022, vol. 9(3), No. 20229301 ARTICLE 2 of 8 als with the catalyst and, finally, the use of heavy fractions to ensure the thermal balance of the installation [33–49]. Fuel oil is a residual substance after a simple distilla- tion of oil, which contains mainly hydrocarbons and oil resins of large molecular weight. Fuel oil M-100 belongs to the furnace types of fuel oil and can be used as a liquid fuel for combustion in boiler furnaces of thermal power plants. The fuel oil can be further processed to produce gas oil by vacuum distillation [54, 55]. Most scientists in the field recognize that the specific properties and com- plex composition of heavy oils and oil residues do not al- low the use of classical processing methods for light oils; such schemes are ineffective or not suitable at all [1, 2, 4, 14–16]. One of the actual methods of intensification of thermal processes of refining of high-viscosity oils is wave action (ultrasonic, acoustic, ultra-frequency) [56–65]. Oxidative cracking is a process of cracking petroleum fractions carried out at atmospheric pressure in the vapor phase. A Soviet petroleum engineer, doctor of technical sciences, a specialist in the field of oil production and oil refining, one of the founders of thermal methods of oil production, A. B. Sheinman (1898–1979) with his col- leagues (among them, in particular, a famous Soviet and Hungarian scientist of Hungarian origin Carl Dubrovay (1888–1957)) created the scientific and technical founda- tions of oxidative cracking [66, 67]. The efficiency of processing raw materials with ozone to the depth of conversion of fuel oil under the conditions of its cracking process and the possibility of lowering the temperature to 425–450 °С are described [1, 2, 4, 58–75]. In the literature, studies are known of the processes of cracking vacuum distillates on a zeolite-containing cata- lyst and the reforming of gasoline fractions on a modified catalyst in the presence of atmospheric oxygen. The au- thors found that the presence of oxygen contributes to an increase in the yield of light fractions, but causes an in- crease in the yield of hydrocarbon gases and the formation of coke on the catalyst. The octane number of the obtained gasoline fraction in the presence of oxygen was higher (the increase in the number was within 1.5–2.3 units) than the octane number of the same fraction obtained in the absence of oxygen. This phenomenon can be explained by the presence of oxygen-containing hydrocarbon com- pounds in it, which was confirmed by IR spectroscopy. These results, obtained by various authors, indicate the fea- sibility of processing heavy oil fractions by oxidative crack- ing. An analysis of the data of various scientific schools al- lows us to conclude that one of the most promising ways to increase the depth of processing of heavy oil fractions is to carry out catalytic cracking in an oxidizing medium, for example, with controlled air supply to the reactor [58–75]. In this work, the influence of technological modes on the yield and hydrocarbon composition of products formed as a result of catalytic cracking of commercial fuel oil and fuel oil M-100 in the presence of air in the reactor on cata- lysts synthesized on the basis of natural raw materials of Kazakhstan fields was investigated. 2. Experimental Commercial fuel oil and fuel oil grade M-100 from the Amangeldy GPP (Kazakhstan) were used as initial prod- ucts for studying cracking. Sulfur content is 0.7% in fuel oil M-100, and 2.1% – in commercial fuel oil. For the preparation of catalytic composites, the frac- tions of 60–80 μm of natural zeolite from the Taizhuzgen deposit (Kazakhstan) and clay from the Narynkol deposit (Kazakhstan) were taken (Figure 1, Table 1). Figure 1 Study of physico-chemical properties of natural zeolite from the Taizhuzgen deposit (Kazakhstan): X-ray diffraction analysis (a), IR spectroscopy (b). The chemical composition of the original Narynkol clay is (in %): SiO2 – 38.05; CaO – 20.40; Al2O3 – 8.49; MgO – 6.15; Fe2O3 – 6.15; K2O – 1.80; Na2O – 1.10; TiO2 – 0.44; P2O5 – 0.11; MnO – 0.10. The zeolite was activated by ionic exchange of zeolite framework sodium cations for lanthanum and ammonium cations. Then, the zeolite suspension was stirred for two minutes with a suspension containing a certain amount of clay in distilled water, which was changed in each experi- ment in order to prepare composites with different con- centrations of components. (a) (b) Chimica Techno Acta 2022, vol. 9(3), No. 20229301 ARTICLE 3 of 8 Table 1 Composition of natural zeolite from the Taizhuzgen depos- it (Kazakhstan) according to X-ray diffraction analysis. No. Chemical element Concentration, % Intensity 1 Fe 49.94 739.15 2 Ca 1.71 9.16 3 Sr 0.270 1.98 4 Mn 0.130 1.82 5 Al 21.955 0.30 6 Si 23.115 0.98 7 Ti 1.902 20.86 8 K 0.975 1.97 After that, the mixture was evaporated and molded to form a 0.05–0.25 mm fraction. The resulting microspheri- cal catalyst was dried at 100 °C for 10 hours and hardened at 550 °C for 5 hours. Ion exchange for NH4+ and La3+ cati- ons was carried out at 80 °C for 3 hours in a solution of ammonium sulfate and lanthanum nitrate at a ratio of 5 g-eq. (NH4)2SO4 to 1 g-eq. Na2O and 2 wt.% lanthanum. Then the samples were heat-treated and ion exchange was repeated in a solution of a mixture of ammonium sulfate and lanthanum nitrate. The final residual sodium oxide content in the zeolite was about 0.5 wt.%. Figure 2 shows the methodology for the catalyst prepa- ration used in our study. Figure 2 The scheme of preparation of the catalyst. The procedures for selection and adjustment of process conditions were also described in more detail in our pre- vious works [21, 30, 32, 58, 59]. The process was carried out in four versions: in an in- ert atmosphere in the absence of a catalyst (thermal cracking), with air supplied to the reactor (oxidative thermal cracking), in an inert atmosphere in a 0.2 wt.% suspension of a fine catalyst (catalytic cracking), and, fi- nally, with the simultaneous supply of a catalyst suspen- sion in fuel oil and air to the reactor (oxidative catalytic cracking). Figure 3 shows a principal scheme for imple- menting the process under study. Figure 3 Schematic diagram for the implementation of catalytic processing of commercial fuel oil and fuel oil grade M-100 from the Amangeldy GPP (Kazakhstan): I – catalyst preparation sec- tion: 1 – section for mixing; 2 – sieves; 3 – temperature-controlled container with a stirrer; 4 – kiln for drying and calcining; 5 – electromagnetic homogenizer. II – section for preparation of a catalyst suspension in the feedstock (fuel oil): 1 – a thermostati- cally controlled vessel with a stirrer; 2 –reactor for electromag- netic activation of the feedstock-fuel oil. III – section for the im- plementation of the oxidative cracking process: 1 – thermostati- cally controlled flow reactor, equipped with devices and valves for dosed supply of inert gas, air, as well as a composite catalyst in the feedstock – fuel oil, 2 – flow tank with cooling for condens- ing liquid cracking products; 3 – output of the tar residue mixed with the spent catalyst; 4 – system for discharge and combustion of gaseous products formed as a result of cracking. IV – section of rectification of cracking products: 1 – evaporation column; 2 – rectification of cracking products. The analysis of gaseous cracking products was carried out on a chromatograph with a flame ionization detector: on a 2-meter column with an inner diameter of 2 mm, filled with Poralac sorbent (fraction 8.2–8.3 mm) – for the analysis of hydrocarbon gases; on a 1-meter packed col- umn filled with NaX zeolite (fraction 0.25–0.5 mm) – for the analysis of non-hydrocarbon gases. Argon was used as the carrier gas. The programmed temperature sweep was carried out for hydrocarbon gas in the range of 25–165 °C with expo- sure at 25 °C for 7 minutes; and for non-hydrocarbon – 40–100 °C, at a speed of 8°/min. Determination of the hydrocarbon composition of gasoline fractions was carried out by gas chromatography on a chromatograph with a flame ionization detector on a 50 m stainless steel capil- lary column (internal diameter 0.2 mm) filled with Squalane sorbent. The carrier gas was argon. The pro- grammed temperature sweep was carried out in the range of 40–110 °C at a speed of 2°/min. 3. Results and discussion The content of components in catalysts affects the activity of catalytic composites. The chemical composition of the starting materials and catalysts based on them was deter- mined. Two samples of catalysts were taken for compari- son; in the 1st sample the content of zeolites was less than 15%, and in the 2nd – above 15% (Table 2). The SiO2/Al2O3 ratio in the natural zeolite from the Taizhuzgen deposit is 4.5, and in the synthesized catalysts it is about 4. It should be noted that the content and ratio of silicon and alumi- num oxides in the catalysts varies in proportion to their Chimica Techno Acta 2022, vol. 9(3), No. 20229301 ARTICLE 4 of 8 concentration in the initial components and their content in the catalysts under study. When Narynkol clay is acti- vated by the ion exchange method, the sodium cations are completely replaced by lanthanum cations. The natural zeolite of the Taizhuzgen deposit has a higher ion ex- change activity compared to the used Narynkol clay. For this reason, the content of lanthanum varies. Table 2 Chemical composition of initial materials-Taizhuzgen zeolite and Narynkol clay and samples of catalysts based on them . Chemical component Activated Taizhuzgen zeolite Initial Narynkol clay Zeolite-containing composite catalysts 1 2 SiO2 67.93 38.05 40.00 47.07 CaO 1.97 20.40 19.77 15.14 Al2O3 14.28 8.49 9.97 11.51 MgO 1.39 6.15 6.27 4.72 Fe2O3 1.79 6.15 3.75 4.01 K2O 4.47 1.80 2.29 3.02 Na2O 1.11 1.10 0.30 0.55 TiO2 0.29 0.44 0.23 0.41 P2O5 0.01 0.11 0.15 0.14 MnO 0.01 0.10 0.15 0.11 Calcination losses 7.04 19.47 17.43 0.20 La 0.24 0.0 13.52 0.20 The effect of the catalyst and air on the process of cracking commercial fuel oil was studied at wsuspension = 0.1 h–1 and reaction temperature of the process is 450 °C; in the presence of 0.2 wt.% – catalyst based on Taizhuzgen zeolite and more than 80 wt.% of Narynkol clay. The ratio of the catalytic cracking products is shown in Figure 4. Figure 4 Catalytic cracking product ratio at different cracking conditions. According to the results of chromatographic analysis, the quantitative composition of the gaseous products of thermal and oxidative thermal cracking is almost identical (Table 3, Figure 5). Table 3 Composition of gaseous products (%) of M-100 fuel oil cracking (wsuspension = 1.0 h –1, T = 470 °C) Composition of gases Cracking conditions without catalyst and air without cata- lyst, wair=0.15 h –1 0.2 wt.% zeolite- containing catalyst, without air 0.2 wt.% zeo- lite- containing catalyst, wair=0.15 h –1 Hydrogen 2.8 3.4 10.7 4.3 Methane/ Ethane 16.2/15.5 20.1/18.4 68.0/4.9 21.8/20.1 Ethylene/ Butylene 25.4/9.2 25.7/6.1 11.7/0.2 29.3/2.8 Propane/ Propylene 5.6/17.6 5.6/14.0 0.1/0.1 5.6/12.2 Carbon Monoxide/ Carbon Dioxide 6.3/1.4 6.7/0 4.9/0 3.8/0.1 Figure 5 Composition of gaseous products of M-100 fuel oil cracking. The only difference is that in the presence of air slight- ly more methane is formed, and the content of propylene and butylene is reduced, i.e. the depth of destruction of gaseous hydrocarbons increases. During catalytic cracking, the yield of methane is max- imum, the resulting ethane is dehydrogenated to ethylene, and there are practically no C3–C4 hydrocarbons. Consequently, the reactions of destruction and dehy- drogenation of hydrocarbons proceed on the catalyst. The presence of the latter reaction is confirmed by the maxi- mum hydrogen concentration in the gaseous products compared to the other cracking conditions. In the presence of air additives, the yield of diene and cyclodiene hydrocarbons significantly increases compared to cracking in an inert atmosphere if the process is carried out at low volumetric feed rates to the reactor. The con- clusions obtained agree with the data that the yield of the reaction of oxidative dehydrogenation of olefins increases in the presence of air [5, 12, 22, 26]. The hydrocarbon composition of cracking gasolines depends on the condi- tions of cracking in a similar way (Table 4). Chimica Techno Acta 2022, vol. 9(3), No. 20229301 ARTICLE 5 of 8 Table 4 Influence of process conditions on the hydrocarbon com- position of gasoline cracking fuel oil M-100 (wsuspension=1.0 h –1, T = 470 °C). Composition of hydrocarbons, % Cracking conditions without catalyst and air without catalyst, wair=0.15 h –1 0.2 wt.% zeolite- containing catalyst, without air 0.2 wt.% zeolite- containing catalyst, wair=0.15 h –1 n-paraffins/ isoparaffins 23.6/46.2 24.9/45.6 7.15/5.8 17.8/40.2 Naphthenes 14.8 15.8 15.8 22.8 Olefins/ Cy- cloolefins 4.9/0 5.2/0 6.3/1.1 3.9/0 Arenes/ Dienes 10.1/0 8.2/0 12.7/0.9 15.1/0 Octane Number (RM) 71.3 70.5 76.6 76.2 In the absence of a catalyst, the ratio of hydrocarbons of different classes does not change when moving from an inert to an oxidizing atmosphere. In the presence of a cata- lyst, the process of isomerization of n-alkanes sharply in- tensifies and, to a much lesser extent, so does the dehydro- genation of the formed light hydrocarbons. The oxygen from air changes the course of catalytic cracking reactions: the proportion of naphthene and arene cyclization reactions increases and the isomerization process decreases. However, the isomerization of hydrocarbons that make up gasoline under all the conditions studied prevails over other reactions occurring during cracking. According to the data of the individual hydrocarbon composition of the obtained gasolines, their formation is most likely by the carbocation mechanism. This is evidenced by the presence of a large number of isomeric hydrocarbons with a sub- stituent at the tertiary carbon atom. The results obtained suggest the mechanism of oxida- tive cracking of fuel oil on a low-percentage suspension of an activated catalyst synthesized from natural zeolites. The catalytic destruction of hydrocarbon molecules pro- ceeds through the formation of free radicals, so the intro- duction of air into the reaction zone, in which oxygen is the initiator of this process, significantly increases the yield of the middle distillate fraction. Since the symmet- rical decomposition of heavy fraction hydrocarbon mole- cules occurs during cracking, the main product is light gas oil. The resulting less reactive light hydrocarbons are practically not cracked on the relatively weak acid sites of the natural catalyst, so the total yield of gas and gasoline fraction does not exceed 4 wt.%. According to the IR spec- tral analysis of M-100 fuel oil fractions, in their composi- tion, along with normal alkanes, a significant amount of olefinic and aromatic hydrocarbons was also noticed. The composition of the products according to the opti- mal composition of catalysts for oxidative cracking of fuel oil (in %) was as follows: fuel oil M-100: gas – 0.8; gaso- line – 1.1; light gas oil – 85.7; heavy residue – 11.9; loss – 0.5; total – 100.0%. Commodity fuel oil (M-100): gas – 3.3; gasoline – 8.4; light gas oil – 84.3; heavy residue – 4.0; loss – 0; total – 100.0%. 4. Conclusions This study showed that the introduction of air into the reac- tor during the catalytic cracking of M-100 fuel oil on natural zeolites increases the yield of the middle distillate fractions. Since cracking involves symmetrical decomposition of heavy fraction hydrocarbon molecules, the main product is light gas oil. The resulting light hydrocarbons are almost not cracked on the relatively weak acid centers of the natu- ral catalysts. The identical catalysts based on natural zeo- lites were used in this work. It is obvious that the differ- ences found in the rates of catalytic cracking can only be associated with a change in the process conditions (without air additions or in the presence of air). Supplementary materials No supplementary materials are available. Funding This research was funded by the grant provided by the Ministry of Education and Science of the Republic of Ka- zakhstan under the program: “No. AP09260687 Technolo- gy for the recovery and disposal of toxic compounds from industrial wastewater”. Acknowledgments None. Author contributions Conceptualization: T.V.S., L.R.S. Data curation: L.R.S., A.A.B. Formal Analysis: L.R.S., A.A.B., A.R.S. Funding acquisition: T.V.S. Investigation: U.N.D., A.A.K., Z.M.Z. Methodology: T.V.S., L.R.S., S. S. Project administration: T.V.S. Resources: T.V.S., L.R.S. Software: L.R.S., A. R. S., A.G. I. Supervision: T.V.S. Validation: T.V.S., L.R.S., S.S. Visualization: A.R.S., Z.M. Z., A.G.I. Writing – original draft: L.R.S., A.A.K. Writing – review & editing: L.R.S. Conflict of interest The authors declare no conflict of interest. Additional information Author IDs: Tatyana V. Shakiyeva, Scopus ID 55911739700; Larissa R. Sassykova, Scopus ID 56178673800; Anastassiya A. Khamlenko, Scopus ID 57224856359; https://www.scopus.com/authid/detail.uri?authorId=55911739700 https://www.scopus.com/authid/detail.uri?authorId=56178673800 https://www.scopus.com/authid/detail.uri?authorId=57224856359 Chimica Techno Acta 2022, vol. 9(3), No. 20229301 ARTICLE 6 of 8 Ulzhan N. Dzhatkambayeva, Scopus ID 57220106876; Albina R. Sassykova, Scopus ID 57220005479; Aigul A. Batyrbayeva, Scopus ID 57195066284; Zhanar M. Zhaxibayeva, Scopus ID 57224865951; Akmaral G. Ismailova, Scopus ID 57193336562; Sendilvelan Subramanian, Scopus ID 57207790071. Websites of Al-Farabi Kazakh National University, https://www.kaznu.kz/en; Almaty College of Economics and Law, https://www.alem-edu.kz/en; Abai Kazakh National Pedagogical University, https://www.kaznpu.kz/en; Dr. M.G.R. Educational and Research Institute, https://www.drmgrdu.ac.in. References 1. Pleshakova NA, Tyshchenko VA, Tomina NN, Pimerzin A. Hydrofining of oil fractions of naphthenoaromatic crude. 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