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Innovative Catalysts for the Oxidative Desulfurization Process – Catalysis
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<main class="site-main" id="main"> <article id="post-105" class="post-105 post type-post status-publish format-standard has-post-thumbnail hentry category-oxidative-desulfurization tag-clean-fuels tag-fuel-desulfurization tag-ionic-liquids tag-metal-modified-catalysts tag-oxidative-desulfurization tag-polyoxometalate tag-sustainable-catalysts" itemtype="https://schema.org/CreativeWork" itemscope> <div class="inside-article"> <div class="featured-image page-header-image-single "> <img width="1200" height="628" src="https://catalysis.blog/archive/wp-content/uploads/2024/09/image-_34_-scaled-e1727176227541.jpg" class="attachment-full size-full" alt="" itemprop="image" decoding="async" fetchpriority="high" /> </div> <header class="entry-header"> <h1 class="entry-title" itemprop="headline">Innovative Catalysts for the Oxidative Desulfurization Process</h1> <div class="entry-meta"> <span class="posted-on"><time class="entry-date published" datetime="2024-09-24T16:40:34+05:30" itemprop="datePublished">September 24, 2024</time></span> <span class="byline">by <span class="author vcard" itemprop="author" itemtype="https://schema.org/Person" itemscope><a class="url fn n" href="https://catalysis.blog/archive/author/catalysis/" title="View all posts by catalysis" rel="author" itemprop="url"><span class="author-name" itemprop="name">catalysis</span></a></span></span> </div> </header> <div class="entry-content" itemprop="text"> <p><span style="font-weight: 400;">There has been an increase in the demand for cleaner fuels recently due to strict environmental legislation that helps minimize sulfur emissions because the sulfur compounds in fuels have become key contributors to air pollution. The traditional industrial process of hydrodesulfurization has difficulties in removing refractory sulfur compounds under mild conditions that is , the development of alternative methods is imperative. Among them, oxidative desulfurization appears very promising due to its ability to operate under mild conditions and effectively target refractory sulfur compounds. The key to ODS’s success is the generation of creative catalysts that are likely to increase the efficiency and selectivity of the desulfurization process. Thus, the article seeks to offer a comprehensive review of the state of the art in catalysts for the oxidative desulfurization process, highlighting design, performance, and prospects for industrial applications.</span></p> <h3><b>The Importance of Oxidative Desulfurization</b></h3> <p><span style="font-weight: 400;">Oxidative desulfurization is a developing process that is either complementary or alternative to HDS, as it has lower operational temperatures and pressures that will in turn reduce the operation costs and energy consumption. In the ODS process, oxidation of the sulfur compounds into sulfoxides or sulfones takes place first. These are formed to be highly polar products, which can be easily removed through extraction or adsorption. The effectiveness of the process is very dependent on the catalyst utilized because it should facilitate the reaction of oxidation while maintaining high selectivity and stability. Through the years, a good number of catalysts have been designed and optimized, and each of them presents some unique advantages and highlights some particular problems in the desulfurization process.</span></p> <h3><b>Polyoxometalate-Based Catalysts</b></h3> <p><span style="font-weight: 400;">Among the various catalysts investigated for the process of oxidative desulfurization, polyoxometalates have emerged as one of the most efficient ones. These metal-oxygen clusters have demonstrated excellent catalytic properties, including high thermal stability, strong power in oxidation, and redox potentials that are tunable. In recent developments, POMs are modified and immobilized in various supports in order to enhance catalytic activity and facilitate their reutilization. For example, tethered tri lacunary polyoxometalate Na12[α-P2W15O56]·24H2O on alumina is reported to enhance mass transfer, hence resulting in ultrafast desulfurization of diesel fuels. This modification significantly improves catalytic performance and problems related to catalyst recovery and reusability hence, POM-based catalysts are very suitable for industrial applications.</span></p> <p><span style="font-weight: 400;">Other development strategies in POM-based catalysts include the use of composite materials. For instance, polyoxometalate was successfully loaded onto carbonized cellulose nanofibers to form a composite that exhibited high efficiency in removing DBT and other sulfur compounds from model oil. This approach allows for the catalytic power of POMs with the structural benefits provided by nanofibers to achieve a powerful and green catalyst.</span></p> <p></div></div> <div style="background: #f7f7f7;border: 1px solid rgba(0, 0, 0, 0.07);"> <div style="padding: 30px;"><div class="Adblock-main"> <div class="Adblock-head"> <h2>Yearwise Publication Trend on <b>“<a href="https://catalysis.blog/publication-trends/index/oxidative desulfurization" target="_blank" title="oxidative desulfurization - yearwise publication trends">oxidative desulfurization</a>”</b></h2> </div> </div><div class="results-container"><div class="chart-block" style="padding:15px;"> <div class="left"> <div id="results" class="results"></div> </div> <div class="right"> <div class="chart-container"><canvas id="publicationChart"></canvas></div> </div> <div class="keywordsdiv"> <div style="text-align:center;"><b>Find publication trends on relevant topics</b> </div> <span class="gp-icon icon-tags"><svg viewBox="0 0 512 512" aria-hidden="true" xmlns="http://www.w3.org/2000/svg" width="1em" height="1em"><path d="M20 39.5c-8.836 0-16 7.163-16 16v176c0 4.243 1.686 8.313 4.687 11.314l224 224c6.248 6.248 16.378 6.248 22.626 0l176-176c6.244-6.244 6.25-16.364.013-22.615l-223.5-224A15.999 15.999 0 00196.5 39.5H20zm56 96c0-13.255 10.745-24 24-24s24 10.745 24 24-10.745 24-24 24-24-10.745-24-24z"></path><path d="M259.515 43.015c4.686-4.687 12.284-4.687 16.97 0l228 228c4.686 4.686 4.686 12.284 0 16.97l-180 180c-4.686 4.687-12.284 4.687-16.97 0-4.686-4.686-4.686-12.284 0-16.97L479.029 279.5 259.515 59.985c-4.686-4.686-4.686-12.284 0-16.97z"></path></svg></span> <span id="keyword-stats"></span> </div> </div></div></div><div class="inside-article"><style> table { margin: 0 0 1.5em; 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The most relevant are low volatility, high thermal stability, and the ability to dissolve a wide variety of compounds. Especially metal-based ionic liquids have recently shown very good prospects both as catalysts and solvents in an ODS process. By modifying the metal center and the ionic structure, MILs can be functionalized to possess catalytic properties that allow a high degree of tailoring depending on the targeted sulfur compounds.</span></p> <p><span style="font-weight: 400;">One of the critical advantages of MILs is that, due to their dual function as both an oxidizing agent and an extractant, for example, imidazole-based polyoxometalate dicationic ionic liquids showed very outstanding performance in the ECODS process of fuel oil. These MILs not only facilitate the oxidation of sulfur compounds but also increase their extraction from the oil phase, resulting in a highly efficient desulfurization process. Besides, this feature of MILs being regenerated and re-used without much loss in activity further makes them an industrially very viable option for sustainable industrial processes.</span></p> <h3><b>Metal-modified catalysts</b></h3> <p><span style="font-weight: 400;">An effective approach toward enhancing the performance of an oxidative desulfurization process is by incorporating metals into catalyst structures. Metal-modified catalysts have been surveyed with respect to promoting the oxidation of refractory sulfur compounds under very mild conditions, including molybdenum- and vanadium-based catalysts. For instance, acidic SBA-15 modified by molybdenum oxide has been synthesized to realize deep oxidative desulfurization of model fuels. This catalyst comes out very active and selective, hence finding applications in processes that require stringent sulfur removal.</span></p> <p><span style="font-weight: 400;">Vanadium-based catalysts have also shown a number of great potentials in ODS processes. A series of vanadium catalysts used in pyridinium phosphate ionic liquids showed high catalytic activity, especially when coupled with some oxidizing agents like nitric and sulfuric acids. Under optimized conditions, they are capable of achieving sulfur removal rates of up to 98.9% in diesel fuels. The synergy between vanadium and the ionic liquid matrix would enlarge the power of the catalyst during oxidation, hence being a prospective choice for deep desulfurization applications.</span></p> <h3><b>Challenges and Future Directions</b></h3> <p><span style="font-weight: 400;">Although great development has been made in catalysts for oxidative desulfurization, there are still difficulties and challenges. First of all, that concerns the scale-up of these catalysts with respect to their industrial applications. Whereas a great number of pioneering catalysts exhibited very good performance on a laboratory scale, large-scale production of such catalysts and how to combine them with existing industrial processes need further optimization. Besides, the long-term stability and recyclability of these catalysts should be carefully studied for continuous operation.</span></p> <p><span style="font-weight: 400;">Another challenge lies in the selective removal of a number of specific sulfur compounds from complex matrices in fuels. The presence in fuel of a number of other entities, among which are aromatic and aliphatic hydrocarbons, further interferes with desulfurization, thus decreasing the efficiency of catalysts. Future research should be focused on the development of catalysts with improved selectivity toward refractory sulfur compounds and minimizing the impact of other components in the fuel matrix.</span></p> <p><span style="font-weight: 400;">Moreover, a view into the environment has to account for the production of catalysts and their subsequent disposal. Sustainable materials and green chemistry in the design of the catalysts become important, especially in reducing the environmental impact from oxidative desulfurization processes. One crucial step in the extension of the application of ODS to become a standard technique of desulfurization is the development of recyclable and environmentally benign catalysts.</span></p> <p></div></div> <div style="background: #f7f7f7;border: 1px solid rgba(0, 0, 0, 0.07);"> <div style="padding: 30px;"><div class="Adblock-main"> <div class="Adblock-head"> <h2>Recent Publications on <b>“<a href="https://catalysis.blog/recent-publications/index/oxidative desulfurization" target="_blank" rel="noopener" title="oxidative desulfurization - yearwise publication list">oxidative desulfurization</a>”</b></h2> </div> </div> <div class="pb-main"><div class="article-scroll"><div id="results_recent" class="results"></div></div><div class="keywordsdiv" style="margin: 0px 15px;margin-top:20px;"> <div style="text-align:center;"><b>Find publications on relevant topics</b> </div> <span class="gp-icon icon-tags"><svg viewBox="0 0 512 512" aria-hidden="true" xmlns="http://www.w3.org/2000/svg" width="1em" height="1em"><path d="M20 39.5c-8.836 0-16 7.163-16 16v176c0 4.243 1.686 8.313 4.687 11.314l224 224c6.248 6.248 16.378 6.248 22.626 0l176-176c6.244-6.244 6.25-16.364.013-22.615l-223.5-224A15.999 15.999 0 00196.5 39.5H20zm56 96c0-13.255 10.745-24 24-24s24 10.745 24 24-10.745 24-24 24-24-10.745-24-24z"></path><path d="M259.515 43.015c4.686-4.687 12.284-4.687 16.97 0l228 228c4.686 4.686 4.686 12.284 0 16.97l-180 180c-4.686 4.687-12.284 4.687-16.97 0-4.686-4.686-4.686-12.284 0-16.97L479.029 279.5 259.515 59.985c-4.686-4.686-4.686-12.284 0-16.97z"></path></svg></span> <span id="keyword-papers"></span> </div></div></div><div class="inside-article"> <style> .pb-main{ border: solid 1px #ccc; border-top: none; margin-bottom: 20px; padding-bottom: 25px; background:#fff; } .author-main { border: solid 1px #ccc; border-top: none; margin-bottom: 20px; padding-bottom: 25px; background:#fff; } .publication-block { padding: 10px; margin-bottom: 10px; background-color: #f9f9f9; text-align: 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20px; text-align: center; } </style> <script> function decodeString(str) { str = str.replace(/\\'/g, "'"); str = str.replace(/\\'/g, "'"); str = str.replace(/\\'/g, "'"); return str; } function displayResults_recent(papers) { var resultsContainer = document.getElementById('results_recent'); if (!papers || papers.length === 0) { resultsContainer.innerHTML = '<p>No recent publications found.</p>'; return; } papers.forEach(paper => { var publicationBlock = document.createElement('div'); publicationBlock.className = 'publication-block'; var title_de = decodeString(paper.title); var publicationHTML = ` <div style="margin-bottom: 10px;line-height: 24px;"><a href="${paper.url}" target="_blank" title="${title_de}">${title_de}</a></div> <p><strong>Issue Release:</strong> ${paper.publishedDate}</p> `; publicationBlock.innerHTML = publicationHTML; resultsContainer.appendChild(publicationBlock); }); } function displayKeywordPapers(keywords) { var resultsContainer = document.getElementById('keyword-papers'); resultsContainer.innerHTML = ''; if (!keywords || keywords.length === 0) { resultsContainer.innerHTML = '<p>No data found.</p>'; return; } var keywordHTML = ''; keywords.forEach((key, index) => { let key_replace = key.replace(/ /g, '-'); key_replace = key_replace.toLowerCase(); keywordHTML += `<a href="https://catalysis.blog/recent-publications/index/${key_replace}" target="_blank" title="${key} - publication list">${key}</a>`; if (index < keywords.length - 1) { keywordHTML += ', '; } }); resultsContainer.innerHTML = keywordHTML; } // Call the function with the PHP data var recent_papers = [ { "title": "Deep Oxidative Desulfurization of Planar Compounds Over Functionalized Metal-Organic Framework UiO-66(Zr): An Optimization Study.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38854503", "publishedDate": "2024" }, { "title": "Oxidative and Extractive Desulfurization of Fuel Oils Catalyzed by -Carboxymethyl Pyridinium Acetate and -Carboxyethyl Pyridinium Acetate Acidic Ionic Liquids: Experimental and Computational DFT Study.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38854558", "publishedDate": "2024" }, { "title": "Controllable Synthesis of Titanium Silicon Molecular Zeolite Nanosheet with Short b-Axis Thickness and Application in Oxidative Desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38869578", "publishedDate": "2024" }, { "title": "Functional characterization of Helicoverpa assulta CYP6B6 in insecticide metabolism.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38685236", "publishedDate": "2024" }, { "title": "Unusual Photochemistry in Aromatic Dithioimides: Quantitative Thione Reduction Promoted by Ether Solvents.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38748890", "publishedDate": "2024" }, { "title": "Mechanism and kinetic of piezo-catalytic desulfurization of model and actual fuel samples over CeO\/SrO nanocomposite at room temperature.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38304796", "publishedDate": "2024" }, { "title": "Room Temperature Ultrafast Oxidative Desulfurization with Sodium Hypochlorite in the Presence of Silica-Supported Catalysts.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38560000", "publishedDate": "2024" }, { "title": "Oxidative desulfurization of fuels using alcohol-based DESs.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38584233", "publishedDate": "2024" }, { "title": "One-Pot Preparation of Nitro-Functionalized Bimetallic UiO-66(Zr-Hf) with Hierarchical Porosity for Oxidative Desulfurization Performance.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39163172", "publishedDate": "2024" }, { "title": "The Utilization of Rice Husk as Both the Silicon Source and Mesoporous Template for the Green Preparation of Mesoporous TiO\/SiO and Its Excellent Catalytic Performance in Oxidative Desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39202935", "publishedDate": "2024" }, { "title": "Engineering surface framework TiO single sites for unprecedented deep oxidative desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38577670", "publishedDate": "2024" }, { "title": "In Situ Generation of HO over MoO Decorated on CuO@CuO Core-Shell Particle Nanoarchitectonics for Boosting Photocatalytic Oxidative Desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38285625", "publishedDate": "2024" }, { "title": "The single metal atom (Ni, Pd, Pt) anchored on defective hexagonal boron nitride for oxidative desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38170798", "publishedDate": "2024" }, { "title": "Aerobic Oxidative Desulfurization by Supported Polyoxometalate Ionic Liquid Hybrid Materials via Facile Ball Milling.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38611826", "publishedDate": "2024" }, { "title": "A linker selective retention strategy to construct hierarchical porous metal-organic frameworks with high catalytic activity for oxidative desulfurization.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38488126", "publishedDate": "2024" }, { "title": "Efficient and promising oxidative desulfurization of fuel using Fenton like deep eutectic solvent.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/38824177", "publishedDate": "2024" }, { "title": "Two High-Nuclear Wheel-Hub-Shaped Transition-Metal-Doped Polyoxovanadates.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39037868", "publishedDate": "2024" }, { "title": "Self-assembly of Dawson-type HPWO@[CuO(TZI)(HO)] for high-performance aerobic oxidation desulfurization of fuel.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39010721", "publishedDate": "2024" }, { "title": "Ionic Liquids as Green and Efficient Desulfurization Media Aiming at Clean Fuel.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39063490", "publishedDate": "2024" }, { "title": "Robust interaction of ZnO and TiO nanoparticles with layered graphitic carbon nitride for enhanced photocatalytic oxidative desulfurization of fuel oil: mechanism, performance and stability.", "url": "https:\/\/pubmed.ncbi.nlm.nih.gov\/39144369", "publishedDate": "2024" } ]; var keywordsArray = ["Oxidative desulfurization","Polyoxometalate","Ionic liquids","Metal-modified catalysts","Fuel desulfurization","Sustainable catalysts","Clean fuels"]; displayResults_recent(recent_papers); displayKeywordPapers(keywordsArray); // function stripslashes(str) { // if (typeof str === 'string') { // return str.replace(/\/g, ''); // } // } </script></p> <h3><b>Conclusion</b></h3> <p><span style="font-weight: 400;">Oxidative desulfurization has proved to be an excellent alternative process to hydrodesulfurization because it has many operational advantages with respect to conditions and efficiency of sulfur removal. One of the factors contributing to making ODS processes efficient has been innovative catalyst development, including that based on polyoxometalate-based materials, metal-modified catalysts, and metal-based ionic liquids. These catalysts not only improve the efficiency of oxidation of sulfur compounds but also lead to a possible route for their sustainable and industrially scalable applications.</span></p> <p><span style="font-weight: 400;">Advanced desulfurization techniques are increasingly becoming important as demand for cleaner fuels rises. In fact, it is continued research and development in the design of catalysts that can best suit the stringent sulfur regulations set for producing environmentally friendly fuels. A bright future does await oxidative desulfurization, with new catalysts paving the way forward in processing cleaner and more efficient production technologies for fuels.</span></p> <p></p> <h3><b>References</b></h3> <ol> <li>Akopyan, A.V., Shlenova, A.O., Cherednichenko, K.A. and Polikarpova, P.D., 2021. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.1c00172">Immobilized multifunctional ionic liquids for highly efficient oxidation of sulfur-containing compounds in model fuels.</a> <i>Energy & Fuels</i>, <i>35</i>(8), pp.6755-6764.</li> <li>Li, J., Guo, Y., Tan, J. and Hu, B., 2021. <a href="https://www.mdpi.com/2073-4344/11/3/356">Polyoxometalate dicationic ionic liquids as catalyst for extractive coupled catalytic oxidative desulfurization.</a> <i>Catalysts</i>, <i>11</i>(3), p.356.</li> <li>Liu, Y., Chu, J., Lian, L., Chen, X., An, S., Hong, L., Wang, D. and Chen, W., 2021. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.0c03673">Ultrafast oxidative desulfurization of diesel fuels by mass transfer enhancement of polyoxometalate modified alumina catalysts.</a> <i>Energy & Fuels</i>, <i>35</i>(3), pp.2110-2120.</li> <li>Liu, F., Yu, J., Qazi, A.B., Zhang, L. and Liu, X., 2021. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.est.0c05855">Metal-based ionic liquids in oxidative desulfurization: a critical review.</a> <i>Environmental Science & Technology</i>, <i>55</i>(3), pp.1419-1435.</li> <li>Akopyan, A., Polikarpova, P., Gul, O., Anisimov, A. and Karakhanov, E., 2020. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.0c02008">Catalysts based on acidic SBA-15 for deep oxidative desulfurization of model fuels.</a> <i>Energy & Fuels</i>, <i>34</i>(11), pp.14611-14619.</li> <li>Benmabrouka, H., Mesdour, S., Boufades, D., Moussiden, A., Berrabia, N., Tliba, L. and Hamada, B., 2019. <a href="https://www.tandfonline.com/doi/abs/10.1080/10916466.2018.1563611">Vanadium-catalyzed extractive oxidesulfurization of commercial diesel in ionic liquid with combined oxidizing agents.</a> <i>Petroleum Science and Technology</i>, <i>37</i>(6), pp.662-670.</li> <li>Tanimu, A. and Alhooshani, K., 2019. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.9b00354">Advanced hydrodesulfurization catalysts: a review of design and synthesis.</a> <i>Energy & Fuels</i>, <i>33</i>(4), pp.2810-2838.</li> <li>Gan, M., Yang, G., Wang, Z., Sui, X. and Hou, Y., 2019. <a href="https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.9b03712">Highly efficient oxidative desulfurization catalyzed by a polyoxometalate/carbonized cellulose nanofiber composite.</a> <i>Energy & Fuels</i>, <i>34</i>(1), pp.778-786.</li> </ol> <p></div></div> <div style="background: #f7f7f7;border: 1px solid rgba(0, 0, 0, 0.07);"> <div style="padding: 30px;"><div class="Adblock-main"> <div class="Adblock-head"> <h2>Top Experts on “<b style="color:#000;font-size:22px;">oxidative desulfurization</b>“</h2> </div> </div><div class="author-main"><div id="results_author"></div><div style="text-align: center;"><a class="register-button" href="https://catalysis.blog/expert-search" target="_blank" rel="noopener">Find experts on any field</a></div></div><div class="inside-article" style="background: none;border: none;box-shadow: none;margin-top: -70px;"> <style> .author-block { padding: 15px; 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", "email": "htgomes@ipb.pt", "slug_tail": "h-gomes" } }; //console.log(authors_data); displayResults_author(authors_data); var keywordsArray = ["Oxidative desulfurization","Polyoxometalate","Ionic liquids","Metal-modified catalysts","Fuel desulfurization","Sustainable catalysts","Clean fuels"]; displayKeywordAuthors(keywordsArray); </script></p> <p> </p> </div> <footer class="entry-meta" aria-label="Entry meta"> <span class="cat-links"><span class="gp-icon icon-categories"><svg viewBox="0 0 512 512" aria-hidden="true" xmlns="http://www.w3.org/2000/svg" width="1em" height="1em"><path d="M0 112c0-26.51 21.49-48 48-48h110.014a48 48 0 0143.592 27.907l12.349 26.791A16 16 0 00228.486 128H464c26.51 0 48 21.49 48 48v224c0 26.51-21.49 48-48 48H48c-26.51 0-48-21.49-48-48V112z" /></svg></span><span class="screen-reader-text">Categories </span><a href="https://catalysis.blog/archive/category/oxidative-desulfurization/" rel="category tag">Oxidative Desulfurization</a></span> <span 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