Title Science and Technology Indonesia e-ISSN:2580-4391 p-ISSN:2580-4405 Vol. 7, No. 3, July 2022 Research Paper Catalytic Oxidative Desulfurization of Dibenzothiophene by Composites Based Ni/Al-Oxide Nur Ahmad1, Alfan Wijaya2, Amri2, Erni Salasia Fitri2, Fitri Suryani Arsyad3, Risfidian Mohadi1,2, Aldes Lesbani1,2* 1Graduate School of Mathematics and Natural Sciences, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Palembang, 30662, Indonesia2Research Center of Inorganic Materials and Coordination Complexes, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Palembang, 30662, Indonesia3Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sriwijaya, Palembang, 30662, Indonesia *Corresponding author: aldeslesbani@pps.unsri.ac.id AbstractIn the present study, composite layer double hydroxide-metal oxide (Ni/Al-TiO2 and Ni/Al-ZnO) was successfully prepared andused as catalyst of oxidative desulfurization of dibenzothiophene. Characterization of catalyst was used XRD, FTIR, and SEM-EDS.The structure of Ni/Al-LDH, TiO2, and ZnO in composite Ni/Al-TiO2 and Ni/Al-ZnO was consistent, which also indicated that thepreparation of composite did not change the form of precursors. FTIR spectra of Ni/Al-TiO2 and Ni/Al-ZnO absorption band at 3398,1639, 1339, 832, 731, and 682 cm−1. The catalysts have an irregular structure, TiO2 and ZnO adhere to the surface of Ni/Al-LDH.The percent mass of Ti and Zn on the composite at 29.3% and 18.2%, respectively. The acidity of Ni/Al-LDH increased after beingcomposited with TiO2 and ZnO. The optimum reaction time, dosage catalyst, and temperature were 30 min, 0.25 g, and 50°C,respectively, and n-hexane as a solvent. The percentage conversion of dibenzothiophene on Ni/Al-LDH, TiO2, ZnO, Ni/Al-TiO2, andNi/Al-ZnO were 99.44%, 91.92%, 95.36%, 99.88%, and 99.90%, respectively. The catalysts are heterogeneous system and theadvantage is that can be used for reusability. After 3 times catalytic reactions, the conversion of dibenzothiophene still retains morethan 80%, even Ni/Al-TiO2 and Ni/Al-ZnO composites still 97.79% and 98.99%, respectively. KeywordsDesulfurization, Dibenzothiophene, Layered Double Hydroxide, Composite Received: 11 April 2022, Accepted: 15 July 2022 https://doi.org/10.26554/sti.2022.7.3.385-391 1. INTRODUCTION Fuel oil is an energy source that has a vital role in the global economy (Zeng et al., 2017). The fuel is oil from exploration on the earth, known as petroleum. Although the availability of petroleum continues to run low, its supply is still sucient for the needs of human life on earth. However, the intensive use of petroleum, especially in transportation, causes gas emissions to be produced, namely SOx (Mahmoudi et al., 2021). SOx signicantly contributes to air pollution, acid rain, and damage to the gas emission section of vehicles (Abedini et al., 2021; Kang et al., 2018; Mousavi-Kamazani et al., 2020). The specications issued by Japan and European Com- mission show that the sulfur content in the oil is constantly changing and revising due to the eects caused when the sulfur content is found in large quantities in fuel oil. In 2005, the sulfur content in fuel oil allowed in Europe was 10 ppm (Ren et al., 2016). The same thing happened in America, which revised the permissible sulfur content in fuel oil to 15 ppm in 2006 (Bazyari et al., 2016). The current trend shows that the sulfur content in fuel oil is a maximum of 10 ppm (Luna et al., 2022). Sulfur compounds in fuel oil are organosulfur such as dibenzothiophene(DBT) andderivatives (Mujahidetal.,2020; Ye et al., 2020). The chemical structure of dibenzothiophene is shown in Figure 1. Figure 1. Chemical Structure of Dibenzothiophene Reducing sulfur content in dibenzothiophene is known as the desulfurization process using the catalytic principle of ox- idation. The success of the desulfurization process is highly dependent on the catalyst used, considering the process applied in catalytic oxidation. Malani et al. (2021) used microorgan- isms in the desulfurization process known as biodesulfurization. However, this method has diculties in controlling the use https://crossmark.crossref.org/dialog/?doi=10.26554/sti.2022.7.3.385-391&domain=pdf https://doi.org/10.26554/sti.2022.7.3.385-391 Ahmad et. al. Science and Technology Indonesia, 7 (2022) 385-391 of microorganisms and in the treatment of microorganisms, so chemical methods with the principle of catalytic oxidation continue to be developed until now. Several desulfurization technologies for dibenzothiophene compounds have been car- ried out such as photocatalytic desulfurization (Mgidlana et al., 2021), adsorptive desulfurization (Subhan et al., 2019), and oxidative desulfurization (ODS) (Li et al., 2020). In addition, in petroleum which is explored together with gas containing sulfur, the desulfurization process is carried out using a separa- tor column and the extractive desulfurization process (EDS) (Rezaee et al., 2021). Until now, the desulfurization process is still beingresearched to nd eective materials to convert sulfur by chemical processes, especially with the principle of catalytic oxidation reactions using synthesized catalysts. Catalysts have been reported for desulfurization of DBT, including montmo- rillonite (Kang et al., 2018), Fe promoted Ni/Co-Mo/Al2O3 (Muhammad et al., 2018), silica (Teimouri et al., 2018), and layered double hydroxide (Masoumi and Hosseini, 2020; Wu et al., 2018). The potential catalyst to be used is Layered Double Hy- droxide (LDH). LDH can be made easily, with low cost, and has a high-eciency level (Taher et al., 2021). LDH is de- rived from the mineral clay brucite, whose general formula is Mg(OH)2. In the catalytic process, LDH has been used for water remediation (Karim et al., 2022), n-heptane hydrocon- version (Zhu et al., 2019), and biodiesel production (Gabriel et al., 2021). LDH is interested in catalysis due to its large surface area and homogeneous distribution of various essential components (Zhu et al., 2019). The disadvantage of LDH is easily exfoliated, so the reusability of LDH is less attractive. Therefore, LDH is composited with metal oxide. LDH is easily made into composites with metal oxides by calcining at high temperatures to remove organic pollutants (Dang et al., 2021). In the experiment part, Ni/Al-TiO2 and Ni/Al-ZnO were prepared as catalysts and DBT was the sulfur compound. Char- acterization of catalysts used XRD, FTIR, and SEM-EDS to know the successful preparation of the catalysts. The process of optimizing the oxidative desulfurization of DBT was car- ried out with variations in time, UV-Vis spectrum, the dosage of catalyst, temperature, solvent (n-pentane, n-hexane, and n-heptane), acidity test, heterogeneous test, and reusability. 2. EXPERIMENTAL SECTION 2.1 Chemicals and Instrumentation Dibenzothiophene (DBT) was obtained from Sigma-Aldrich and directly used as received. Other chemicals such as hydro- genperoxide(H2O2), acetonitrile (CH3CN),pyridine(C5H5N), n-pentane (C5H12), n-hexane (C6H14), n-heptane (C7H16), nickel (II) nitrate hexahydrate (Ni(NO3)2.6H2O), aluminum nitratenonahydrate (Al(NO3)2.9H2O),sodiumcarbonate (Na2 CO3), and sodium hydroxide (NaOH), titanium(IV) oxide (TiO2), and zinc(II) oxide (ZnO) were also directly used with- out further purication. Water was supplied from the Research Center of Inorganic Materials and Complexes FMIPA Uni- versitas Sriwijaya after several cycles of water purication us- ing Puriter. Instrumentation such as X-Ray Diractometer (XRD) type Rigaku Miniex-6000, EMC-18PC-UV Spec- trophotometer, Fourier Transfer Infra-Red (FTIR) type Shi- madzu Prestige-21, and Scanning Electron Microscope Energy Dispersive Spectrometer (SEM-EDS) Quanta 650. 2.2 Synthesis and Preparation of Catalyst and Characteriza- tion Synthesis of Ni/Al-LDH was conducted according to Lesbani et al. (2021) as follows: 0.75 M (Ni(NO3)2.6H2O) and 0.25 M (Al(NO3)2.9H2O) dissolved in 100 mL of distilled water, stirred for 2 h. Then slowly added the mixture of NaOH and Na2CO3 (ratio 2:1) to pH 10. The mixture was stirred for 17 h at 70°C, then ltered and dried. Preparation Ni/Al-Oxide was conducted 0.75 M (Ni(NO3) 2.6H2O) and 0.25 M (Al(NO3)2.9H2O) dissolved in 100 mL distilled water, stirred for 2 h. Then slowly added the mixture of NaOH and Na2CO3 (ratio 2:1) to pH 10. The mixture was stirred for 17 h at 70°C then added TiO2/ZnO (ratio 1:1), shakenfor3h. Themixturewasadded150mL0.37MNaOH, shaken for 17 h at 70°C, ltered, dried, and then calcinated at 300°C for 7 h. 2.3 Oxidative Desulfurization of Dibenzothiophene Dibenzothiophene with the concentration of 500 ppm was pre- pared in n-hexane and transferred to a two-pronged catalytic reaction ask. The ask is connected to a condenser to prevent evaporation of n-hexane. 0.25 g Catalysts (Ni/Al-Oxide) fol- lowed byadding1 mLof 30% hydrogen peroxide. The reaction was observed per 10 minutes time interval through extraction with acetonitrile followed by measuring using a UV-Visible spectrophotometer at 235 nm. The percentage conversion of DBT followed the equation: %conversion of DBT = (C0,DBT − Cf,DBT) C0,DBT × 100 Where, C0,DBT and Cf,DBT are the initial and nal concentra- tions of DBT, respectively. The process of optimizing the oxidative desulfurization of DBT was carried out with variations in time (10-60 min), UV-Vis spectrum (220-250 nm), the dosage of catalyst (0.05-1 g), temperature (30-50°C), solvent (n-pentane, n-hexane, and n-heptane), acidity test, heterogeneous test, and reusability. Reusability of catalyst is carried out by centrifugation of the reaction mixture after 1 h to recover the Ni/Al-oxide catalyst. The catalyst was washed with n-hexane several times, dried, and reused in the desulfurization of DBT. 3. RESULTS AND DISCUSSION XRD powder diraction of Ni/Al-LDH, TiO2, ZnO, Ni/Al- TiO2, and Ni/Al-ZnO is shown in Figure 2. XRD peaks of Ni/Al-LDH were analyzed from the JCPDS No. 15-0087 (Chen et al., 2022). Ni/Al-LDH peaks were detected at 2\= 11.48°(003), 23.30°(002), 35.03°(311), and 61.40°(013) (see © 2022 The Authors. Page 386 of 391 Ahmad et. al. Science and Technology Indonesia, 7 (2022) 385-391 Figure 2a). The diraction peaks at 2\= 11.48°(003) and 61.40°(013) indicate crystal planes of Ni/Al-LDH (Xie et al., 2021). Figure2bshowndiractionofTiO2 at2\=25.59°(101), 37.09°(004),48.16°(200),54.03°(211),55.26°(105), and62.29° (204). Figure 2c shown diraction of ZnO at 2\= 31.75°(100), 34.41°(002),36.24°(101),47.52°(002),56.56°(110), and62.84° (103). TiO2 and ZnO followed JCPDS No. 73-1764 and 36-1451, respectively (Basnet et al., 2019). The structure of Ni/Al-LDH, TiO2, and ZnO in composite Ni/Al-TiO2 and Ni/Al-ZnO was consistent, which also indicated that the prepa- ration of composite did not change the form of precursors (see Figures 2d and 2e). Figure 2. XRD Powder Diraction of Ni/Al-LDH (a), TiO2 (b), ZnO (c), Ni/Al-TiO2 (d), and Ni/Al-ZnO (e) FTIR spectra of Ni/Al-TiO2 and Ni/Al-ZnO absorption band at 3398, 1639, 1339, 832, 731, and 682 cm−1 (see Fig- ures 3d and 3e). An absorption band at 3398 cm−1 was the O-H stretching vibrations in the hydroxyl layer (Normah et al., 2021; Palapa et al., 2021). 1639 and 1339 cm−1 as H-O-H and NO3− stretching from Ni/Al-LDH (Lv et al., 2022). The peaks at 832, 731, and 682 cm−1 can be assigned metal oxide in Ni/Al-LDH, TiO2, and ZnO (Intachai et al., 2021). Table 1. EDS of Catalysts Element Ni/Al-LDH (%wt) Ni/Al-TiO2 (%wt) Ni/Al-ZnO (%wt) Ni 33.9 20.7 15.6 Al 5.2 3.1 13.9 Ti - 29.3 - Zn - - 18.2 O 43.2 34.8 27.2 Figure 4 shows the SEM Image and EDS of Ni/Al-LDH, Ni/Al-TiO2, and Ni/Al-ZnO. SEM image investigated the morphology of catalysts at 2500 times magnication. The catalysts have an irregular structure, TiO2 and ZnO adhere Figure 3. FTIR spectrum of Ni/Al LDH (a), TiO2 (b), ZnO (c), Ni/Al-TiO2 (d), and Ni/Al-ZnO (e) to the surface of Ni/Al-LDH. EDS analysis in Table 1 shows the Ni, Al, Ti, Zn, and O atom percentages. Ti and Zn atoms appearaftercomposited intoNi/Al-TiO2 andNi/Al-ZnO.The percent mass of Ti and Zn at 29.3% and 18.2%, respectively. Thus, preparation of Ni/Al-TiO2 and Ni/Al-ZnO has been a success. Figure 4. SEM Image and EDS of Ni/Al-LDH (a), Ni/Al- TiO2 (b), and Ni/Al-ZnO (c) The acidity test was carried out using the gravimetric met- hod with pyridine as the adsorbate base. Pyridine has a large size causing bonding to occur only on the surface. The results of the determination of the acid site for each catalyst are shown in Table 2. Ni/Al-LDH increased after being composited with TiO2 and ZnO. the acidity of Ni/Al-LDH, TiO2, ZnO, Ni/Al- TiO2, and Ni/Al-ZnO were 0.148, 0.298, 0.782, 0.714, 0.184 © 2022 The Authors. Page 387 of 391 Ahmad et. al. Science and Technology Indonesia, 7 (2022) 385-391 mmol/gram, respectively. The increase in the acidity of Ni/Al- LDH, because it has been reduced, will lack electrons so that it has a higher ability to absorb pyridine. Acid sites of catalysts are polyacid to convert DBT into DBT-sulfone (Trisunaryanti et al., 2021). Table 2. Acidity of Catalyst Catalyst Acidity (mmol/g) Ni/Al-LDH 0.148 TiO2 0.298 ZnO 0.782 Ni/Al-TiO2 0.714 Ni/Al-ZnO 0.184 Figure 5. Prole of Desulfurization by Time Over Composite Catalysts The catalytic oxidative desulfurization of DBT is strongly inuenced by time. The eect of the desulfurization time of DBT is displayed in Figure 5. The catalytic data showed a long reaction time was directly proportional to the high %conversion of DBT (Muhammad et al., 2018). The optimum reaction time was 30 min and the percentage conversion of DBT on Ni/Al-LDH, TiO2, ZnO, Ni/Al-TiO2, and Ni/Al-ZnO were 99.44%, 91.92%, 95.36%, 99.88%, and 99.90%, respectively. The composite increases the ability of the catalyst in the desul- furization of DBT. In this study, Ni/Al-ZnO is better than Ni/Al-TiO2 in conversion of DBT. The DBT that appeared in the acetonitrile phase was rapidly oxidized and converted to DBT-sulfone after extraction. UV-Vis spectrum of oxidative desulfurization dibenzoth- iophene by composite catalysts is shown in Figure 6. UV-vis spectrum used wavelength 220-250 nm. The Absorbance of DBTat 235 nm decreased with increasing desulfurization time. The decrease in absorbance gradually indicates the concentra- tion of DBT is decreasing. At 30 min, %conversion of DBT Figure 6. UV-Vis Spectrum of Oxidative Desulfurization Di- benzothiophene by Composite Catalysts >90% with the most signicant reduction indicated by Ni/Al- ZnO catalyst. The eect of the dosage of catalyst is presented in Fig- ure 7. Generally, a higher catalyst dosage will provide more opportunities for interaction between the active site of the cat- alyst and the DBT (Ye et al., 2020). However, in contrast to this study, the optimum dosage for all catalysts was 0.25 g. A higher catalyst dosage will increase the active site of the catalyst while competing with oxidant molecules (Subhan et al., 2019). Therefore, increasing the catalyst dosage can reduce the %con- version of DBT. Percentage of Desulfurization order of DBT: Ni/Al-ZnO > Ni/Al-TiO2 > Ni/Al-LDH > ZnO > TiO2. Figure 7. Eect of Catalyst Dosage on Desulfurization of Di- benzothiophene Figure 8 shows the eect of temperature catalytic oxidative desulfurization of DBT. The catalytic data shows that high temperature is directly proportional to the high %conversion of DBT. Desulfurization of DBT using H2O2 is better at high temperatures by converting DBT to DBT-sulfone (Fraile et al., 2016; Lesbani et al., 2015). Desulfurization of DBT at 50°C is better than at 30°C and 40°C. Percentage of Desulfurization © 2022 The Authors. Page 388 of 391 Ahmad et. al. Science and Technology Indonesia, 7 (2022) 385-391 orderof DBT: Ni/Al-ZnO > Ni/Al-TiO2 > Ni/Al-LDH > ZnO > TiO2. The fuel oil is operated at 60-70°C to overcome dierent oxidant dissociation energies. Therefore, this study is superior because the temperature is lower with the same eciency. The eect of solvent was carried out to determine the best solvent in the oxidative desulfurization of DBT. n-pentane, n-hexane, and n-heptane were used as DBT solvents. The solvent eect shows that n-hexane is better at desulfurizing DBT than n-pentane and n-heptane. The results are compiled in Figure 9 showing the desulfurization of DBTon Ni/Al-ZnO > Ni/Al-TiO2 > Ni/Al-LDH > ZnO > TiO2. Figure 8. Eect of Various Temperatures on Desulfurization of Dibenzothiophene Using Composite Catalysts Figure 9. Eect of Solvent on Desulfurization of Dibenzothio- phene by Composite Catalysts Figure 10 shows the heterogeneous test of catalyst. Het- erogeneous test the catalyst to determine whether the catalyst is homogeneous or heterogeneous. Homogeneous catalysts are soluble in the reactants/products of the reaction, while het- erogeneous catalysts are insoluble. The Heterogeneous test was carried out by desulfurization of DBT at 50°C for 10 min, the catalyst and DBT solution were separated. DBT solution continued with desulfurization process for 20-30 min. The un- changed DBT concentration indicates that Ni/Al-LDH, TiO2, ZnO, Ni/Al-TiO2, and Ni/Al-ZnO are truly heterogeneous system. The advantage of heterogeneous catalysts is that can be used for reusability (Vallés-García et al., 2020). Figure 10. Heterogeneous Test of Catalyst Reusability of catalysts is very inuential for the industry to save operating costs (Song et al., 2021). Reusability is suitable for Ni/Al-LDH, TiO2, ZnO, Ni/Al-TiO2, and Ni/Al-ZnO catalysts because they are heterogeneous. Figure 11 shows the good reusability of catalyst. After 3 times catalytic reactions, the conversion of DBT still retains more than 80%, even Ni/Al- TiO2 and Ni/Al-ZnO composites still 97.79% and 98.99%, re- spectively. FTIR analysis was carried out to investigate changes in the structure of the catalyst after the reusability process. The new peak appearing at 1200 cm−1 is sulfone. Figure 12 shows that the FTIR Ni/Al-TiO2 has undergone structural changes, while Ni/Al-ZnO is stable in reusability process. Figure 11. Reusability of Catalyst © 2022 The Authors. Page 389 of 391 Ahmad et. al. Science and Technology Indonesia, 7 (2022) 385-391 Figure 12. FTIR Spectrum of Composites Ni/Al-TiO2 (a), Ni/Al-ZnO (b) Before and After Desulfurization of Third Cycle 4. CONCLUSIONS In the present study, composite layer double hydroxide-metal oxide (Ni/Al-TiO2 and Ni/Al-ZnO) was successfully prepared and used as catalyst of oxidative desulfurization of dibenzoth- iophene. The acidity of Ni/Al-LDH increased after being composited with TiO2 and ZnO. The optimum reaction time, dosage catalyst, and temperature were 30 min, 0.25 g, and 50°C, respectively, and n-hexane as a solvent. The percentage conversion of dibenzothiophene on Ni/Al-LDH, TiO2, ZnO, Ni/Al-TiO2, and Ni/Al-ZnO were 99.44%, 91.92%, 95.36%, 99.88%, and 99.90%, respectively. The catalysts are heteroge- neous system and the advantage is that can be used for reusabil- ity. After 3 times catalytic reactions, the conversion of diben- zothiophene still retains more than 80%, even Ni/Al-TiO2 and Ni/Al-ZnO composites still 97.79% and 98.99%, respectively. 5. ACKNOWLEDGEMENT Authors thank Universitas Sriwijaya for funding this research through DIPA of Public Service Agency of Universitas Sri- wijaya, Hibah Profesi SIP DIPA-023.17.2.677515/2022 on December 12, 2021 in accordance with the Rector degree number 0111/UN9.3.1/SK/2022 on April 28, 2022. 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Macroporous 3D Carbon-Nitrogen (CN) Conned MoOx Catalyst for Enhanced Oxidative Desulfurization of Dibenzothiophene. Chinese Chemical Let- ters, 31(10); 2819–2824 Zeng, X., X. Xiao, Y. Li, J. Chen, and H. Wang (2017). Deep Desulfurization of Liquid Fuels with Molecular Oxygen Through Graphene Photocatalytic Oxidation. Applied Catal- ysis B: Environmental, 209; 98–109 Zhu, X., C. Chen, Q. Wang, Y. Shi, D. O’Hare, and N. Cai (2019). Roles for K2CO3 Doping on Elevated Temperature CO2 Adsorption of Potassium Promoted Layered Double Oxides. Chemical Engineering Journal, 366; 181–191 © 2022 The Authors. Page 391 of 391 INTRODUCTION EXPERIMENTAL SECTION Chemicals and Instrumentation Synthesis and Preparation of Catalyst and Characterization Oxidative Desulfurization of Dibenzothiophene RESULTS AND DISCUSSION CONCLUSIONS ACKNOWLEDGEMENT