Feasibility study on the conversion of dimethyl disulfide produced in the petrochemical industry into methyl phenyl sulfide
Subject Areas : شیمی آلی
1 -
Keywords: H2S, Dimethyl disulfide (DMDS), Methyl phenyl sulfide (MPS), Fe3O4,
Abstract :
The conversion of H2S into new products is of great economic and environmental importance in the petrochemical, oil and gas industries. In this regard, one of the products from H2S in the petrochemical industry is dimethyl disulfide (DMDS), which can be used as a starting material for the synthesis of organic compounds (such as biological heterocycles, sulfide derivatives and sulfoxide derivatives). H2S is a toxic gas and its reactions require advanced chemical reactors and special equipment, but DMDS is a non-volatile liquid that can be converted into new products under laboratory conditions with general equipment. Therefore, in this research, a recoverable and reusable magnetic nanocatalyst consisting of a copper complex immobilized on magnetic Fe3O4 nanoparticles was designed and synthesized, which was defined as Fe3O4@PDBOA-Cu. The nanocatalyst was characterized using X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray spectroscopy (EDS), wavelength dispersive X-ray spectroscopy (WDS), thermal gravimetric analysis (TGA)/differential thermal analysis (DTA), and vibrating sample magnetometry (VSM). Then, methyl phenyl sulfide (MPS) was successfully synthesized in the presence of Fe3O4@PDBOA-Cu nanocatalyst from DMDS. MPS was synthesized in 2 hours with 93% yield in the presence of Fe3O4@PDBOA-Cu in PEG-400 solvent using DMDS and iodobenzene. Due to the magnetic nature of Fe3O4@PDBOA-Cu nanocatalyst, this nanocatalyst was easily recycled at a very low cost, which firstly led to high purity of the products, and secondly, it could be easily reused for multiple times, which was both economically viable and significantly reduces the process costs. This catalyst was recycled and reused for 4 consecutive steps.
[1] Mustakim D, Ramadhan GA, Husin Z, Zulfikar AJ. Hydrogen sulfide (H₂S) leak risk management in gas plant facilities: A review article. TEKNOSAINS: Jurnal Sains, Teknologi dan Informatika. 2025;12(2):329-37. doi: org/10.37373/tekno.v12i2.1597
[2] Nguyen-tiêt AM, Letelier-Gordo CO, Aalto SL. Rapid H2S production in layers of freshwater and marine fish organic waste from recirculating aquaculture systems. Aquacultural Engineering. 2025;111:102578. doi: org/10.1016/j.aquaeng.2025.102578
[3] Viveka N, Poornimadevi C, Kala CP, Thiruvadigal DJ. DFT Insights into the gas sensing properties of light platinum group metal (Ru, Rh & Pd) doped MoSe2 monolayer. Surfaces and Interfaces. 2025;66:106579. doi: org/10.1016/j.surfin.2025.106579
[4] Rafique M, Shuai Y, Ghorbal A, Hussain D, Awan S, Ahmed Z, et al. Toxic gas sensing of copper (Cu)-functionalized BC6N monolayers under ambient and elevated conditions; Ab-initio and MD study. Surfaces and Interfaces. 2025;56:105724. doi: org/10.1016/j.surfin.2024.105724
[5] Mohammadbagherlou S, Samari E, Sagharyan M, Zargar M, Chen M, Ghorbani A. Hydrogen sulfide mechanism of action in plants; from interaction with regulatory molecules to persulfidation of proteins. Nitric Oxide. 2025;156:27-41. doi: org/10.1016/j.niox.2025.02.001
[6] Su S, Zhang Z, Chen J, Chen Y, Cao X, Yan S, et al. Portable on-site colorimetric kit using stable gold nanorod powder for tracing hydrogen sulfide in typical environmental samples. Journal of hazardous materials. 2025;493:138389. doi: org/10.1016/j.jhazmat.2025.138389
[7] Katayama T, Nagata M. Photocatalytic gas-phase hydrogen sulfide removal using Mo cocatalyst: Implementation of counter-poisoning photocycle. ACS Omega. 2025;10(5):4670–4678. doi: org/10.1021/acsomega.4c09395
[8] Benchoam D, Cuevasanta E, Möller MN, Alvarez B. Hydrogen sulfide and persulfides oxidation by biologically relevant oxidizing species. Antioxidants. 2019;8(2):48. doi: org/10.3390/antiox8020048
[9] Kohansal M. Advances in green chemistry: Sustainable approaches in organic synthesis. International Journal of New Chemistry. 2025;12(4):726-37. doi: org/10.22034/ijnc.2025.719174
[10] Kate A, Sahu LK, Pandey J, Mishra M, Sharma PK. Green catalysis for chemical transformation: The need for the sustainable development. Current Research in Green and Sustainable Chemistry. 2022;5:100248. doi: org/10.1016/j.crgsc.2021.100248
[11] Andraos J, Matlack AS. Introduction to green chemistry. 2ed. Boca Raton: CRC press; 2022. doi: org/10.1201/9781439882115
[12] Polshettiwar V, Varma RS. Green chemistry by nano-catalysis. Green Chemistry. 2010;12(5):743-54. doi: org/10.1039/B921171C
[13] Sheldon RA. Engineering a more sustainable world through catalysis and green chemistry. Journal of The Royal Society Interface. 2016;13(116):20160087. doi: org/10.1098/rsif.2016.0087
[14] Anastas PT, Kirchhoff MM, Williamson TC. Catalysis as a foundational pillar of green chemistry. Applied Catalysis A: General. 2001;221(1-2):3-13. doi: org/10.1016/S0926-860X(01)00793-1
[15] Tahmasbi B, Moradi P, Darabi M. A new neodymium complex on renewable magnetic biochar nanoparticles as an environmentally friendly, recyclable and efficient nanocatalyst in the homoselective synthesis of tetrazoles. Nanoscale Advances. 2024;6(7):1932-44. doi: org/10.1039/D3NA01087B
[16] Emad-Abbas N, Naji J, Moradi P, Kikhavani T. 3-(Sulfamic acid)-propyltriethoxysilane on biochar nanoparticles as a practical, biocompatible, recyclable and chemoselective nanocatalyst in organic reactions. RSC advances. 2024;14(31):22147-58. doi: org/10.1039/D4RA02265C
[17] Sheikhveisi M, Hazeri N, Lashkari M, Faroughi Niya H, Fatahpour M. Application of Fe3O4@ THAM CH2CH2 SCH2CO2H magnetic nanoparticles as an acidic, recyclable and green catalyst for the synthesis of hexahydroacridine-1, 8-diones, hexahydroquinolines, and 2-Amino-3-cyanopyridines. Organic Preparations and Procedures International. 2025;57(4):322-34. doi: org/10.1080/00304948.2025.2453802
[18] Liu L, Lu J, Yang Y, Ruettinger W, Gao X, Wang M, et al. Dealuminated beta zeolite reverses ostwald ripening for durable copper nanoparticle catalysts. Science. 2024;383(6678):94-101. doi: org/10.1126/science.adj1962
[19] Leybo D, Etim UJ, Monai M, Bare SR, Zhong Z, Vogt C. Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis. Chemical Society Reviews. 2024;53(21):10450-90. doi: org/10.1039/D4CS00527A
[20] Li Y, Zhang J, Cheng D, Guo W, Liu H, Guo A, et al. Magnetic biochar serves as adsorbents and catalyst supports for the removal of antibiotics from wastewater: A review. Journal of Environmental Management. 2024;366:121872. doi: org/10.1016/j.jenvman.2024.121872
[21] Tan M, Zhang W, Liu H, Zhang J, Guo Z, Ma Q, et al. Revolutionizing high-temperature polymer electrolyte membrane fuel cells: Unleashing superior performance with vertically aligned TiO2 nanorods supporting ordered catalyst layer featuring Pt nanowires. Fuel. 2024;357:130084. doi: org/10.1016/j.fuel.2023.130084
[22] Tahmasbi B, Darabi M, Nikoorazm M. A new Schiff‐base complex of palladium nanoparticles on modified boehmite with di(pyridin‐2‐yl)methanone as a robust, reusable, and selective nanocatalyst in the C‐C coupling reaction. Applied Organometallic Chemistry. 2024;38(3):e7348. doi: org/10.1002/aoc.7348
[23] Xie C, Jiang Z, Pang Y, Xiao C, Song J. Carbon-based catalytic materials for aerobic oxidative transformation of 5-hydroxymethylfurfural: Advancements, challenges, and opportunities. Green Chemistry. 2024;26(12):6886-99. doi: org/10.1039/D4GC01621A
[24] Trueba M, Trasatti SP. γ‐Alumina as a support for catalysts: a review of fundamental aspects. European journal of inorganic chemistry. 2005;2005(17):3393-403. doi: org/10.1002/ejic.200500348
[25] Julkapli NM, Bagheri S. Graphene supported heterogeneous catalysts: An overview. International Journal of Hydrogen Energy. 2015;40(2):948-79. doi: org/10.1016/j.ijhydene.2014.10.129
[26] Kikhavani T, Moradi P, Mashari‐Karir M, Naji J. A new copper Schiff‐base complex of 3, 4‐diaminobenzophenone stabilized on magnetic MCM‐41 as a homoselective and reusable catalyst in the synthesis of tetrazoles and pyranopyrazoles. Applied Organometallic Chemistry. 2022;36(12):e6895. doi: org/10.1002/aoc.6895
[27] Moradi P, Hajjami M. Magnetization of graphene oxide nanosheets using nickel magnetic nanoparticles as a novel support for the fabrication of copper as a practical, selective, and reusable nanocatalyst in C–C and C–O coupling reactions. RSC Advances. 2021;11(42):25867-79.
[28] Moradi P, Hajjami M, Tahmasbi B. Fabricated copper catalyst on biochar nanoparticles for the synthesis of tetrazoles as antimicrobial agents. Polyhedron. 2020;175:114169. doi: org/10.1016/j.poly.2019.114169
[29] Tahmasbi B, Darabi M, Moradi P, Tyula YA, Nikoorazm M. Gadolinium Schiff-base complex on nanocomposite of graphene oxide magnetic nanoparticles as a robust, reusable and chemoselective nanocatalyst in the C–C coupling reactions. Polyhedron. 2024;258:117038. doi: org/10.1016/j.poly.2024.117038
[30] Tyula YA, Moradi P, Nikoorazm M. A new neodymium complex on boehmite nanoparticles with
1,3-Bis(pyridine‐3‐ylmethyl)thiourea as a practical and reusable nanocatalyst for the chemoselective synthesis of tetrazoles. ChemistrySelect. 2023;8(24):e202301674. doi: org/10.1002/slct.202301674
[31] Ghobadi M, Kargar Razi M, Javahershenas R, Kazemi M. Nanomagnetic reusable catalysts in organic synthesis. Synthetic Communications. 2021;51(5):647-69. doi: org/10.1080/00397911.2020.1819328
[32] Polshettiwar V, Luque R, Fihri A, Zhu H, Bouhrara M, Basset J-M. Magnetically recoverable nanocatalysts. Chemical reviews. 2011;111(5):3036-75. doi: org/10.1021/cr100230z
[33] Norouzi M, Moradi P. A new copper complex on functionalized magnetic biochar nano-sized materials as sustainable heterogeneous catalysts for C–O bond formation in the natural deep eutectic solvent. Biomass Conversion and Biorefinery. 2025;15:2465–77. doi: org/10.1007/s13399-023-05163-z
[34] Mrówczyński R, Nan A, Liebscher J. Magnetic nanoparticle-supported organocatalysts–an efficient way of recycling and reuse. Rsc Advances. 2014;4(12):5927-52. doi: org/10.1039/C3RA46984K
[35] Gawande MB, Branco PS, Varma RS. Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of sustainable methodologies. Chemical Society Reviews. 2013;42(8): 3371-93. doi: org/10.1039/C3CS35480F
[36] Wang D, Deraedt C, Ruiz J, Astruc D. Magnetic and dendritic catalysts. Accounts of chemical research. 2015;48(7):1871-80. doi: org/10.1021/acs.accounts.5b00039
[37] Kazemi M. Reusable nanomagnetic catalysts in synthesis of imidazole scaffolds. Synthetic Communications. 2020;50(14):2095-113. doi: org/10.1080/00397911.2020.1728334
[38] Dalpozzo R. Magnetic nanoparticle supports for asymmetric catalysts. Green Chemistry. 2015;17(7):3671-86. doi: org/10.1039/C5GC00386E
[39] Tahmasbi B, Moradi P, Darabi M. A new neodymium complex on renewable magnetic biochar nanoparticles as an environmentally friendly, recyclable and efficient nanocatalyst in the homoselective synthesis of tetrazoles. Nanoscale Advances. 2024;6(7):1932-44 .doi: org/10.1039/D3NA01087B
[40] Tahmasbi B, Ghorbani-Choghamarani A. Magnetic MCM-41 nanoparticles as a support for the immobilization of a palladium organometallic catalyst and its application in C–C coupling reactions. New Journal of Chemistry. 2019;43:14485-14501. doi: org/10.1039/c9nj02727k
[41] Ghorbani-Choghamarani A, Tahmasbi B, Noori N, Ghafouri-nejad R. A new palladium complex supported on magnetic nanoparticles and applied as an catalyst in amination of aryl halides, Heck and Suzuki reactions. Journal of the Iranian Chemical Society. 2017;14:681-93. doi: org/10.1007/s13738-016-1020-x
[42] Wang Y-y, Wu X-m, Yang M-h. Copper-catalyzed methylthiolation of aryl iodides and bromides with dimethyl disulfide in water. Synlett. 2020;31(12):1226-30. doi: org/10.1055/s-0040-1707131
[43] Baldovino-Pantaleon O, Hernandez-Ortega S, Morales-Morales D. Alkyl- and arylthiolation of aryl halides catalyzed by fluorinated bis-imino-nickel NNN pincer complexes [NiCl2{C5H3N-2,6-(CHNArf)2}], advanced synthesis & catalysis, 2006;348(1-2):236–42. doi: org/10.1002/adsc.200505207
