Technological Features of Producing High-Index Oils in the Alkylation Process

G.A. Huseynova; G.A. Gasimova; N.M. Aliyeva; S.N. Osmanova

doi:10.18321/ectj1662

Authors

G.A. Huseynova Academician Y.H. Mammadaliyev Institute of Petrochemical Processes, Baku, Azerbaijan
G.A. Gasimova Academician Y.H. Mammadaliyev Institute of Petrochemical Processes, Baku, Azerbaijan
N.M. Aliyeva Academician Y.H. Mammadaliyev Institute of Petrochemical Processes, Baku, Azerbaijan
S.N. Osmanova Khazar University, Baku, Azerbaijan

DOI:

https://doi.org/10.18321/ectj1662

Keywords:

Alkylation, Catalyst, Alkylate, Viscosity index, Dynamic light scattering

Abstract

This article presents the results of studies on key technological parameters-namely temperature and the use of modified ZSM-5 catalysts with Zr and Fe-in the alkylation process aimed at producing high-viscosity-index oils. The development of novel modified catalyst compositions exhibiting high activity in alkylation, to enhance oil viscosity indices to meet global standards, holds significant scientific and practical importance. Modified catalysts based on ZSM-5 zeolite incorporating ZrO₂ and Fe₂O₃ (ZSM-5-ZrO₂ and ZSM-5-Fe₂O₃), along with their regenerated forms after use in alkylation, were evaluated in both autoclave and pilot-scale alkylation processes. Catalyst characterization was performed using X-ray phase analysis, thermogravimetric analysis (TG), and dynamic light scattering (DLS). Alkylation of the low-viscosity-index fraction of turbine oil T-30 (initial viscosity index of 49.9) was conducted at 50 °C using catalytic cracking gases containing 56.35% olefins. The ZSM-5-ZrO₂ catalyst produced alkylates with viscosity indices of 137.0 and 121.8 in the autoclave and pilot plant, respectively. The regenerated ZSM-5-ZrO₂ catalyst yielded viscosity indices of 117.8 (autoclave) and 111.7 (pilot plant). Alkylates obtained with ZSM-5-Fe₂O₃ and its regenerated counterpart showed viscosity indices of 99.3 and 94.7, respectively. The feasibility of reusing spent and regenerated catalysts in the alkylation process was confirmed. Among the catalysts tested, ZSM-5-ZrO₂ demonstrated the highest activity and is recommended for alkylating low-viscosity-index oil fractions with catalytic cracking gases at 50 °C.

References

(1) Nafis, D.A., Detrick, K.A., Mehlberg, R.L. (2014). Alkylation in Petroleum Processing. In: Treese, S., Jones, D., Pujado, P. (eds) Handbook of Petroleum Processing. Springer, Cham. Crossref

(2) I.M. Gerzeliev, V.A. Ostroumova, M.I. Baskhanova, Enhancement of ion exchange in a FAU type zeolite during the synthesis of an active and selective catalyst for isobutane alkylation with butylenes. Pet. Chem. 58 (2018) 676–680. Crossref

(3) D. Wang, Y. Li, Y. Zhao, et al., Study on the reaction strategy of directional alkylation fulfilled by controlling the adsorption pose of benzene and methanol in space with Ru/HZSM-5, BMC Chemistry 15 (2021) 35. Crossref

(4) Y. Sekine, Y. Ichikawa, Y. Tajima, et al., Alkylation of isobutane by 1-butene over H-beta zeolite in CSTR (Part 1) Effects of zeolite-structures and synthesis methods on alkylation performance, J. Japan Petrol. Inst. 55 (2012) 299–307. Crossref

(5) A.A. Doroshenko, A.V. Utemov, K.V. Semikin, Zeolite catalysts modified with Ni for alkylation of isobutane with olefins, News St. Petersburg State Inst. Technol. (Technical Univ.) 46 (2018) 28–33.

(6) M. Pavlov, R. Basimova, O. Travkina, A promising catalyst for the alkylation of isobutane with olefins, LAP Lambert Academic Publishing, 2019. ISBN-10: 6139471702; ISBN-13, 978-6139471706 (in Russian).

(7) D. Wang, C.-M. Wang, G. Yang, et al., First-principles kinetic study on benzene alkylation with ethanol vs. ethylene in H-ZSM-5, J. Catal. 374 (2019) 1–11. Crossref

(8) S. Wang, J. Li, Q. Xu, et al., Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene, Chin. J. Chem. Eng. 67 (2024) 298–309. Crossref

(9) F. Xiong, C. Ji, S. Gan, et al., Tuning the mesoscopically structured ZSM-5 nanosheets for the alkylation between toluene and methanol, AIChE J. 69 (2023) e18054. Crossref

(10) S.I. Abasov, S.B. Agayeva, D.B. Taghiyev, et al., Effect of gaseous alkanes on conversion of straight-run naphtha in the presence of Co(Ni) (ZSM-5, MOR, Al2O3)/SO42-/ZrO2 composite catalysts, Russ. J. Appl. Chem. 94 (2021) 959–968. Crossref

(11) S.I. Abasov, S.B. Agayeva, M.T. Mamedova, et al., Conversion of Straight-Run Naphtha to C5−C6 Alkanes on Co(Ni)/HZSM–5/SO2-4–ZrO2 Composite Catalysts, Russ. J. Appl. Chem. 92 (2019) 228–234. Crossref

(12) G.A. Huseynova, F.I. Samedova, S.Yu. Rashidova, et al., A study of the products of turbine oil distillate alkylation with catalytic cracking gases, Pet. Chem. 59 (2019) 1220–1225. Crossref

(13) C.W. Chang, H.N. Pham, R. Alcala, et al., Dehydroaromatization pathway of propane on PtZn/SiO2 + ZSM-5 bifunctional catalyst, ACS Sustain. Chem. Eng. 10 (2021) 394–409. Crossref

(14) C.K. Russell, A. Saxena, J.T. Miller, Influence of bifunctional PtZn/SiO2 and H-ZSM-5 catalyst on the rates and selectivity of propene aromatization, Catal. Res. 3 (2023). Crossref

(15) X. Su, Y. Fang, P. Gao, et al., In-situ microwave synthesis of nano-ZSM-5 bifunctional catalysts with controllable location of active GaO+ species for olefins aromatization, Microporous Mesoporous Mater. 306 (2020) 110388. Crossref

(16) O. Klepel, A. Loubentsov, W. Böhlmann, H. Papp, Oligomerization as an important step and side reaction for skeletal isomerization of linear butenes on H-ZSM-5, Appl. Catal. A Gen. 255 (2003) 349–354. Crossref

(17) V.F. Tretyakov, Y.I. Makarf, R.M. Talyshinsky, et al., Catalytic conversion of ethanol to hydrocarbons, Fine Chemical Technologies 5 (2010) 77–86. (In Russ.). URL

(18) L.M. Velichkina, Y.A. Barbashin, E.Y. Gerasimov, A.V. Vosmerikov. Influence of iron-containing additives on the physicochemical properties of zeolite catalysts and the coke deposits formed during the refining of straight-run gasoline, News of Universities. Chemistry and Chemical Technology 66 (2023) 67–75. Crossref

(19) Z. Song, A. Takahashi, N. Mimura, T. Fujitani Production of propylene from ethanol over ZSM-5 zeolites, Catal. Lett. 131 (2009) 364–369. Crossref

(20) V.V. Lunin, V.F. Tretyakov, R.I. Kuzmina, A.Y. Pilipenko, Ethanol conversion over zirconium-containing ZSM-5 zeolite, Moscow Univ. Chem. Bull. 70 (2015) 203–206. Crossref

(21) N.M. Aliyeva, U.A. Karimova, A.A. Aliyeva, et al., Study of nanoparticles by dynamic light scattering method, Azerbaijan Oil Industry Journal, 2024, 45–50. Crossref

(22) S. Li, J. Cao, X. Feng, et al., Insights into the confinement effect on isobutane alkylation with C₄ olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study, Chin. J. Chem. Eng. 47 (2021) 174–184. Crossref

(23) B.T. Tuktin, A.M. Temirova, G.T. Saidilda, A.A. Omarova. Conversion of propane-propylene fraction into aromatic hydrocarbons on modified zeolite catalysts, News of the National Academy of Sciences of the Republic of Kazakhstan. Series of Chemistry and Technology Sciences 2020 (1) 64–71. URL

(24) L.M. Velichkina, L.N. Vosmerikova, D.A. Kanashevich, A.V. Vosmerikov. Effect of silicate modulus and modifying with metals on the acidic and catalytic properties of ZSM-5 type zeolite in the isomerization of n-octane, Chemistry for Sustainable Development 22 (2014) 237–245. URL

(25) G.A. Huseynova, G.A. Gasimova, A.D. Quliyev, et al. Study of the ZSM-5 catalyst, modified with ZrO₂, for use in the process of alkylation of T-30 oil with catalytic cracking gases. World of Petroleum Products 1 (2025) 14–20 (in Russian). DOI: 10.32758/2782-3040-2025-0-1-14-20