Mesoporous zirconium–silica nanocomposite modified with heteropoly tungstophosphoric acid catalyst for ultra-deep oxidative desulfurization

An adsorbent catalyst was proposed to reduce the leaching of active species of the catalyst and enhance the kinetics of the oxidative desulfurization (ODS) reaction of dibenzothiophene (DBT) from model diesel fuel. By loading phosphotungstic acid (HPW) species onto a zirconium-modified hexagonal mesoporous silica (Zr-HMS), a novel catalyst was synthesized and utilized for the ODS process. An ultrafast ODS kinetics was specifically identified using 20%HPW/Zr-HMS as catalyst. Within 30 min, more than 95% of the 350 ppm DBT content of the model fuel was oxidized by H₂O₂. The synthesized catalyst retained its sulfur removal ability even after five subsequent ODS reactions and the leaching of HPW species was found to be suppressed successfully. Overall, this new reusable catalyst provided an alternative for highly efficient ultra-deep desulfurization process.     

柴油在超声波/Cu2+/H2O2中的氧化脱硫

为了实现生产低硫柴油和超低硫柴油的目标,以超声波为外加能源,构筑超声波/类Fenton试剂的柴油氧化脱硫反应体系,考察了水相pH值和超声功率这两个参数对柴油氧化脱硫效果的影响。实验结果表明,当类Fenton试剂的水相pH值为2.00左右时,其脱硫效果较好;无超声波下H2O2、类Fenton试剂、超声波/H2O2及超声波/类Fenton试剂的柴油氧化脱硫反应符合表观一级反应动力学规律。超声波功率的提高对氧化脱硫有明显的促进作用,这主要是由于功率的增加,有助于加速空穴的形成与内爆,从而促进反应的进行。     

柴油催化氧化脱硫新技术

柴油催化氧化脱硫技术不需高温高压、不耗费氢气、设备投资少等优点,是一项很有前景的脱硫技术。本文介绍了柴油氧化脱硫的机理,重点概述了近年来国内外柴油催化氧化脱硫技术所取的最新成果,并分析了各种氧化脱硫体系的最佳工艺条件和各自的优缺点。     

Macroporous 3D carbon-nitrogen (CN) confined MoOx catalyst for enhanced oxidative desulfurization of dibenzothiophene

Macroporous 3D carbon doped with nitrogen confined Mo catalyst (MoO_x@CN) had been prepared by a facile one-step pyrolysis technique using silica as a template and was employed for oxidative desulfurization (ODS) of dibenzothiophene (DBT) in model fuel with H₂O₂ as oxidant. The effect of different operating conditions (i.e., reaction temperature and time, catalyst dosage, H₂O₂/DBT (O/S) molar ratio) were also systematic investigated. Under the optimal reaction condition, MoO_x@CN catalyst exhibited highly excellent ODS performance toward DBT, the highest sulfur removal efficiency can be up to 99.9% and sulfur content was wiped out from 800 ppm to 10 ppm. Due to the robust 3D structure promoting rapid transfer, in addition to the increased number of active sites induced by the Mo vacancies, the catalyst, prepared using chitosan and ammonium heptamolybdate in a mass ratio of 1:0.5, displayed rapid kinetics and low activation energy in the oxidation of dibenzothiophene. Moreover, it exhibited excellent recyclability after five cycles without any obvious decrease in catalytic activity for the oxidative desulfurization reaction.     

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre-catalyst

Regulations on the permissible levels of sulfur in transportation fuels are becoming ever more strict, with a global shift towards “zero sulfur” fuels, and the revamp of existing hydrodesulfurization (HDS) facilities to meet these lower caps is cost-prohibitive. Metal-catalyzed sulfoxidation chemistry is viewed as an economically viable desulfurization strategy that could complement conventional HDS technology. In the present work, the complex [η⁵-IndMo(CO)₃Me] ( 1 ) (Ind = indenyl) was employed in the catalytic oxidative desulfurization (CODS) of model and real liquid fuels, using aqueous hydrogen peroxide (H₂O₂) as oxidant. After optimization of the CODS reaction parameters (diesel/H₂O₂ ratio, catalyst amount, temperature), a high-sulfur (2000 ppm) model diesel containing benzothiophene, dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene could be completely desulfurized within 2 hr under solvent-free conditions or in the presence of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆) as extraction solvent. The catalyst formed under solvent-free conditions could be recycled without a significant decrease in desulfurization activity. The high performance of the CODS system was verified in the sulfur removal from a commercial untreated diesel fuel with a sulfur content of 2300 ppm, and a jet fuel with a sulfur content of 1100 ppm. Solvent-free CODS in combination with initial/final extraction gave desulfurization efficiencies of 70% for the diesel fuel and 55% for the jet fuel. CODS with [BMIM]PF₆ in combination with initial/final extraction led to a sulfur removal of 95.9% for the diesel fuel, which is one of the best results yet reported for ODS of commercial diesels.     

燃料油氧化脱硫技术中氧化剂的研究进展

随着世界硫含量燃料标准的提高,降低燃料油的硫含量成为全球研究热点。氧化脱硫技术因其操作条件温和、成本低,近十几年研究较多。在氧化脱硫技术中,氧化剂的选择是其关键。本文就十几年来,氧化脱硫技术中氧化剂的研究进行了综述,并提出今出氧化剂的发展方向。     

Oxidative desulfurization of model diesel oil over Ti-containing molecular sieves using hydrogen peroxide

Three Ti-containing molecular sieves were studied in the oxidative desulfurization (ODS) of model diesel oil with hydrogen peroxide. Under optimal conditions, dibenzothiophene (DBT) conversion up to 80.6% and 42.6% could be obtained with Ti-HMS and Ti-MSU as catalysts, respectively. However, there is no activity in the sulfoxidation of DBT over TS-1. Effects of the TiO₂/SiO₂ ratio in Ti-HMS and reaction conditions, such as the reaction temperature, reaction time, n(H₂O₂)/n(S) on the sulfur removal were investigated.     

燃油深度脱硫用离子液体研究进展

综述了离子液体萃取脱硫、萃取氧化脱硫以及催化氧化脱硫技术的国内外研究进展;阐述了离子液体在不同脱硫体系中的作用及再生问题;论述了离子液体催化氧化脱硫技术的优点,如:反应条件温和,脱硫效率高,操作简单,最有发展前景,可以作为加氢脱硫的补充,实现燃油的深度脱硫;并分析了离子液体脱硫技术存在的问题及其工业化应用前景.     

氧化-萃取脱除柴油中噻吩类硫化物研究进展

近年来针对柴油中噻吩类硫化物的脱除问题国内外进行了多种非加氢脱硫技术研究,其中氧化脱硫、萃取脱硫、氧化-萃取脱硫技术是研究较多、具有应用前景的脱硫方法。本文从柴油氧化-萃取脱除噻吩类硫化物的反应机理出发,重点概述了有机酸、酸酐催化体系、离子液体催化体系及分子筛催化体系氧化-萃取脱除噻吩类硫化物获得低硫柴油的最新研究成果,并提出了目前存在的问题及该领域未来的研究方向。     

乳液催化剂存在下空气辅助甲酸氧化法使油品脱硫(英文)

Catalytic oxidative desulfurization(ODS) of model oil and commercial oil samples was investigated using an air-assisted performic acid oxidation system with a phase transfer or emulsion catalyst comprising a quaternary ammonium salt-based heteropolyoxometalate.Different emulsion catalysts with a Keggin type heteroployoxometalate anion(containing W,Mo,and V) and cetyltrimethylammonium bromide cation were prepared and characterized by X-ray fluorescence,Fourier transform infrared spectroscopy,and scanning electron microscopy.[C16H33N(CH3)3]3[PW9Mo3O40] was the most effective catalyst in the current oxidation system,which reduced the sulfur content of the model oil from 1275 μg/g to 57 μg/g.The reactivity order of different model sulfur compounds was thiophene < dibenzothiophene < 4,6-dimethyldibenzothiophene. The ODS of model sulfur compounds followed first order kinetics with apparent activation energy from 29 to 27 kJ/mol.The catalysts also performed efficiently in the ODS of the industrial oil samples,including untreated naphtha,light gas oil,heavy gas oil,and Athabasca oil sands derived bitumen,for which sulfur removal rates were 83%,85%,68% and 64%,respectively.     

Facile synthesis of inorganic–organic Fe2W18Fe4@NiO@CTS hybrid nanocatalyst induced efficient performance in oxidative desulfurization of real fuel

In this work, a new nanocatalyst, Fe₂W₁₈Fe₄@NiO@CTS, was synthesized by the reaction of sandwich‐type polyoxometalate (Fe₂W₁₈Fe₄), nickel oxide (NiO), and chitosan (CTS) via sol–gel method. The assembled nanocatalyst was systematically characterized by FT‐IR, UV–vis, XRD, SEM, and EDX analysis. The catalytic activity of Fe₂W₁₈Fe₄@NiO@CTS was tested on oxidative desulfurization (ODS) of real gasoline and model fuels. The experimental results revealed that the levels of sulfur content and mercaptan compounds of gasoline were lowered with 97% efficiency. Also, the Fe₂W₁₈Fe₄@NiO@CTS nanocatalyst demonstrated an outstanding catalytic performance for the oxidation of dibenzothiophene (DBT) in the model fuel. The major factors that influence the desulfurization efficiency and the kinetic study of the ODS reactions were fully detailed and discussed. The probable ODS pathway was proposed via the electrophilic mechanism on the basis of the electrophilic characteristic of the metal‐oxo‐peroxo intermediates. The prepared nanocatalyst could be reused for 5 successive runs without any appreciable loss in its catalytic activity. As a result, the current study suggested the potential application of the Fe₂W₁₈Fe₄@NiO@CTS hybrid nanocatalyst as an ideal candidate for removal of sulfur compounds from fuel.     

Keggin结构多阴阳离子构筑高活性多酸基氧化脱硫催化剂

设计开发高活性超深度氧化脱硫催化剂是解决未来石化工业适应日益严格要求的清洁燃油标准的重要出路之一。本文合成了Keggin结构多聚铝阳离子烷基硫酸盐Al_13-SDS和磷钨酸(HPW)多阴离子构筑的催化剂HPW-Al_13-SDS(SDS=十二烷基硫酸钠),采用傅里叶红外光谱(FT-IR)、紫外可见光谱(UV-Vis)、热重分析(TG)、X射线衍射(XRD)和Brunauer-Emmett-Teller(BET)等测试手段对催化剂的结构进行表征。FT-IR和UV-Vis的表征结果表明,焙烧后的催化剂中多聚铝阳离子和HPW同时保持Keggin骨架结构。以有机硫二苯并噻吩(DBT)的正己烷溶液为模拟油品的氧化脱硫为探针反应,在选定的条件下,DBT有机硫的脱除率达到99.5%。反应后HPW-Al_13-SDS催化剂的FT-IR和XRD的表征证实产生过氧化多钨酸化合物。催化剂能够循环使用,易分离,循环使用后活性未见明显降低,是理想的模型有机硫化物氧化脱除用催化剂。     

Deep Desulfurization by Amphiphilic Lanthanide‐Containing Polyoxometalates in Ionic‐Liquid Emulsion Systems under Mild Conditions

Amphiphilic lanthanide‐containing polyoxometalates (POMs) were prepared by surfactant encapsulation. Investigation of these lanthanide‐containing POMs in oxidative desulfurization (ODS) showed that highly efficient deep desulfurization could be achieved in only 14 min with 100 % conversion of dibenzothiophene under mild conditions by using (DDA)₉LaW₁₀/[omim]PF₆ (DDA=dimethyldioctadecylammonium, omim=1‐octyl‐3‐methyl‐imidazolium) in the presence of H₂O₂. Furthermore, deep desulfurization proceeds smoothly in model oil with an S content as low as 50 ppm. A scaled‐up experiment in which the volume of model oil was increased from 5 to 1000 mL with S content of 1000 ppm indicated that about 99 % sulfur removal can be achieved in 40 mins in an ionic‐liquid emulsion system. To the best of our knowledge, the (DDA)₉LaW₁₀/[omim]PF₆ catalyst system with H₂O₂ as oxidant is one of the most efficient desulfurization systems reported so far.     

Efficient catalytic performance of tetra-alkyl orthotitanates for the oxidative desulfurization of dibenzothiophene at room temperature

Desulfurization of fuel oil is of great importance for producing clean energy. In this study, we report that tetra-alkyl orthotitanates exhibited efficient catalytic performance in the oxidative desulfurization of dibenzothiophene. The sulfur content in model oil (1000 ppmw) could be reduced to less than 10 ppmw within 10 min at room temperature and ambient pressure. In addition, the formed sulfones can be easily separated from the oil phase without extraction process. This work will provide a basis for the design of novel oxidative desulfurization catalysts with high desulfurization efficiency.     

Unusual Regenerable Porous Metal–Organic Framework Based on a New Triple Helical Molecular Necklace for Separating Organosulfur Compounds

Desulfurization of fuels is receiving more and more attention all over the world due to the increase of stringent environmental regulations and fuel specifications. The metal–organic framework (MOF) is a new class of crystalline materials, and high porosity, one of the most important properties of MOFs, plays a central role in the functional properties. However, the investigation of MOFs, being employed as sorbents for adsorptive desulfurization, is still scarce. In this regard, we have constructed a new 3D porous compound 1 by using rigidly designed carboxylate ligands, which, for the first time, exhibit an unusual triple molecular necklace‐like helix. The N₂ sorption isotherms of 1 show that it has a large Brunauer–Emmett–Teller (BET) surface area and pore volume. With the stable pore structure and appropriate pore sizes, compound 1 has been used as a sorbent for adsorptive desulfurization. The results indicate that compound 1 shows an excellent adsorption property and, more importantly, displays excellent stability, repeatability, and regenerability. Thus, the design and synthesis of targeted MOFs with appropriate pore size and increased interactions between organosulfur compounds and ligands/metals from MOFs is crucial for adsorptive desulfurization, which might be an effective guide to find an efficient and green adsorbent for desulfurization.     

Effective Heterogeneous Oxidative Desulfurization Catalyzed by H3PMo9W3O40@rht-MOF-1

With the increasingly strict standard for sulfur content in fuel, it is necessary to develop high-efficiency catalyst for extractive and catalytic oxidative desulfurization systems (ECODS). Herein, a series of three remarkable complexes H₃PMo_(12-n)W_nO₄₀@rht-MOF-1 ( 1 a , n=1; 2 a , n=2; 3 a , n=3) have been designed and prepared. Complexes 1 a , 2 a and 3 a were characterized by single-crystal X-ray diffraction and FT-IR, PXRD, SEM, N₂ adsorption-desorption isotherms, etc. Upon complex 3 a was applied as catalyst, it exhibited remarkably high catalytic activity in the ECODS reactions of aromatic sulfur compounds under optimal conditions. On the basis of its excellent heterogeneity, the catalyst could be recycled for nine consecutive cycles without significant losing of activity centers. Then, the reaction kinetics and mechanism were investigated and the activation energy have been calculated and discussed. Further, the complex 3 a is employed to catalyze the ODS of commercial diesel oil. As a result, the desulfurization efficiency reached 90%. These results provided important structure data for study the structure-property relationship and potential heterogeneous catalyst applied in ODS in industry.     

模拟轻质油品的氧化脱硫

以正庚烷为溶剂，苯并噻吩（BT）、二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）作为模型含硫化合物组成模拟轻质油品，在H2O2-HCOOH氧化体系中对模拟轻质油品氧化脱硫进行了研究。考察了氧化剂用量、氧化温度、氧化时间及芳烃、烯烃、含氮化合物的存在等因素对BT、DBT脱除的影响。实验结果表明：在反应温度60 ℃，H2O2∶S＝7∶1（mol/mol）,H2O2∶HCOOH＝1∶1（v/v）,反应时间在40 min的条件下，4,6-DMDBT能全部脱除, DBT、BT的脱除率分别为96% 、58%。向油品中添加芳烃、烯烃、含氮化合物等对BT、DBT的脱除均有不同程度的影响。     

常温常压D072树脂氧化吸附油品脱硫的研究

采用ODS方法,讨论了以D072树脂为催化剂,双氧水为氧化剂脱除汽油中含硫化合物的实验规律。实验采用14 mL汽油,5 g处理后的树脂,一定量H₂O₂,0.1 g Span 60充分搅拌,每30 min监测油品中硫含量,反应2 h后用NMP(N-甲基吡咯烷酮),剂油比为1/2萃取。主要考察反应温度(室温、40 ℃、60 ℃、80 ℃),氧化剂用量(O/S=0、O/S=17、O/S=34)对脱硫效果的影响。结果表明,常温常压下O/S为17时脱硫率最佳,达到75%。     

Clean fuel-oriented investigation of thiophene oxidation by hydrogen peroxide using polyoxometalate as catalyst

After catalyst screening for oxidative desulfurization of fuel oil within several polyoxometalates, H₃PW₆Mo₆O₄₀ was confirmed for the first time to be an effective and recoverable catalyst for the oxidative removal of thiophene, being also effective for the desulfurization of real diesel and gasoline.     

Extractive desulfurization of fuel oil with metal-based ionic liquids

Several metal-based ionic liquids (ILs) were synthesized and used as extractants for the desulfurization of dibenzothiophene (DBT) in simulated fuel oil. The effects of several anion and metal ions, n(ILs)/n(metal) as mole ratio, V_IL/V_oil and extractive times on the removal ratio of DBT were investigated in detail. The results showed that [BMIM]HSO₄/FeCl₃(BMIM was short for 1-butyl-3-methyl imidazole) was superior to the other ILs for the extractive desulfurization. A total of 100% of DBT was removed at room temperature in 5 min with V_[BMIM]HSO₄=FeCl₃=V_oil=1:1. The extractive activity of [BMIM]HSO₄/FeCl₃ IL did not change almost after five runs. Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined. The removal ratios of the sulfur compounds as the reaction substrates were all over 90% and the sulfur content of commercial diesel oil decreased to 120 ppm from 12,400 ppm.