Oxidative desulfurization of simulated light fuel oil and untreated kerosene

An experimental investigation was conducted on the oxidative desulfurization of model sulfur compounds such as dibenzothiophene and benzothiophene in toluene as a simulated light fuel oil with a mixture of hydrogen peroxide as the oxidant and various acids as the catalyst. The influences of various parameters including reaction temperature (T), acid to sulfur molar ratio (Acid/S), oxidant to sulfur molar ratio (O/S), type of acid, and the presence of sodium tungstate and commercial activated carbon as a co-catalyst on the fractional conversion of the model sulfur compounds were investigated. The experimental data obtained were used to determine the reaction rate constant of the model sulfur compounds and the corresponding activation energy. Moreover, the adsorption of model sulfur compounds on the commercial activated carbons supplied by Jacobi Co. (Sweden, AquaSorb 101) was studied and the effects of different parameters such as temperature, and various chemical treatments on the adsorption of the sulfur compounds were investigated. Furthermore, the oxidative desulfurization of untreated kerosene with the total sulfur content of 1700 ppmw produced by an Iranian refining company (Isfahan refinery) was successfully investigated. These experiments were performed using formic acid as the catalyst and hydrogen peroxide as the oxidant at the mild operating conditions of T = 50 °C, O/S = 5, and the Acid/S = 10. It was realized that about 87% of the total sulfur content of untreated kerosene could be removed after 30 min oxidation followed by liquid–liquid extraction.     

Ultra-deep oxidative desulfurization of diesel fuel by the Mo/Al2O3-H2O2 system: The effect of system parameters on catalytic activity

This work presents the results obtained in the development of Mo/γ-Al₂O₃ catalysts and their evaluation in the oxidative desulfurization (OD) process of diesel fuel using hydrogen peroxide as the oxidizing reagent. The catalysts were prepared by equilibrium adsorption using several molybdenum precursors and aluminas with different acidity values. They were characterized by Raman spectroscopy. The effect of the reaction time, reaction temperature, nature of solvent, concentration of solvent and hydrogen peroxide, content of molybdenum and phosphate in the catalysts were investigated. The results showed that the activity for sulfur elimination depends mainly on the presence of hepta- and octamolybdates species on the catalyst support and the use of a polar aprotic solvent. Likewise, the presence of phosphate markedly increases the sulfur elimination. In this way, it is possible to reduce sulfur level in diesel fuel from about 320 to less than 10 ppmw at 333 K and atmospheric pressure. Additionally, on the basis of the results obtained a mechanistic proposal for this reaction is described, as an oxidation mechanism by nucleophilic attack of the sulfur atom on peroxo species of hepta- and octamolybdates, but a mechanism involving the singlet oxygen presence can be discarded.     

Oxidative Desulfurization of Hydrocarbon Fuels

New requirements for very low sulfur content (10 ppm) in liquid motor fuels demand novel approaches for ultra-deep desulfurization. For production of near-zero-sulfur diesel and low-sulfur fuel oil, removal of refractory sulfur compounds, like 4,6-dimethyldibenzothiophene and other alkyl-substituted thiophene derivatives, is necessary. Elimination of these compounds by hydrodesulfurization (HDS) requires high hydrogen consumption, high pressure equipment, and new catalysts. Various oxidative desulfurization processes, including recent advances in this field for diesel fuels, and the drawbacks of this technology in comparison with HDS are examined and discussed. It is shown that the oxidation of sulfur compounds to sulfones with hydrogen peroxide allows for production of diesel fuels with a sulfur content of 10 ppmw or lower at atmospheric pressure and room temperature. The gas phase oxidative desulfurization of sulfur compounds with air or oxygen is feasible at atmospheric pressure and higher temperatures: 90–300 °С and offers better economic solutions and incentives.     

Sulfur removal in coal tar pitch by oxidation with hydrogen peroxide catalyzed by trichloroacetic acid and ultrasonic waves

A procedure for the desulfurization of coal tar pitch (CTP) by oxidation with hydrogen peroxide (H₂O₂) was developed, in which trichloroacetic acid (TCA) was used as a catalyst combined with ultrasonic waves. For comparison, the effects of H₂O₂ combined with different catalysts on sulfur removal were also investigated. The oxidative system composed of H₂O₂ and TCA is highly effective for sulfur removal from CTP. The reaction conditions such as type of solvent used, temperature, and CTP-to-TCA ratio considerably influence sulfur removal when the same oxidant is used. The desulfurization efficiency for CTP with 0.9 wt.% sulfur content reaches 91.1 wt.% at a xylene-to-CTP volume ratio of 2.5, a CTP-to-TCA mass ratio of 0.5, an ultrasonic treatment duration of 60 min, a reaction temperature of 70 °C, and with an extraction liquid containing methanol and sodium hydroxyl. The experiment confirms that the addition of surface active agent has no beneficial effect on sulfur removal.     

Deep Desulfurization of Gasoline Fuel using FeCl3-Containing Lewis-Acidic Ionic Liquids

The FeCl₃-containing Lewis-acidic ionic liquids (ILs) [C₆mim]Cl/FeCl₃(1:1.5), [C₆mim]Cl/FeCl₃(1:2), [C₈mim]Cl/FeCl₃(1:1.5), and [C₈mim]Cl/FeCl₃(1:2) were used as extractants for desulfurization of model fuel and gasoline fuel, respectively. The results demonstrate that these ILs are effective for the removal of sulfur compounds from model fuel under different mass ratio of IL to model fuel (1:1, 1:3, 1:5, 1:10) at 25°C. The extractive performance of ILs increased as the molar ratio of FeCl₃ to [C_nmim]Cl(n = 6, 8) varied from 1:1 to 1:2. The selectivity of sulfur compounds by extraction process followed the order of dibenzothiophene (DBT)>benzothiophene (BT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT). The sulfur removal of gasoline fuel containing sulfur content of 440.3 ppmw could be up to 85.8%; that is to say that the sulfur content of gasoline fuel varied from 440.3 ppmw to 62.4 ppmw after one extraction stage. Moreover, the [C₆mim]Cl/FeCl₃(1:2) can be recycled for at least 4 times with a little decrease in the desulfurization activity.     

Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 °C and 700 °C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 °C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H₂O₂/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 °C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed.     

Peroxide-Assisted Oxidative Desulfurization of Nonhydrotreated Vacuum Gas Oil

The possibility of using a catalyst system based on hydrogen peroxide and formic acid for the oxidative desulfurization of nonhydrotreated vacuum gas oil has been explored. Conditions for the effective extraction of oxidized sulfur compounds from nonhydrotreated vacuum gas oil have been selected. The effect of oxidation and thermolysis conditions on the oxidative desulfurization process has been studied, and a 44% decrease in the total sulfur content in nonhydrotreated vacuum gas oil has been achieved.

     

Hydrodesulfurization and hydroconversion of heavy FCC gasoline on PtPd/H-USY zeolite

In the search for catalysts suitable for upgrading fractions of FCC gasoline, PtPd/USY zeolite was investigated. The objectives of the work were to reduce simultaneously the sulfur, nitrogen and aromatic contents of heavy FCC gasoline having various sulfur (30–203 ppmw) and 28 ppmw nitrogen contents. The process conditions were the following: temperature: 200–300 °C; pressure: 30 bar; liquid hourly space velocity: 1.0–3.0 h⁻¹; H₂/hydrocarbon ratio: 500 m³/m³. The results indicated that PtPd/H-USY zeolite catalyst can be applied for the desulfurization of heavy FCC gasoline up to 203 ppm sulfur content. When a base heavy FCC gasoline fraction of 30 ppmw sulfur content was used the catalyst was able to reduce the aromatic content by 14 abs.% as well as sulfur and nitrogen contents to <1 ppmw in one step. Blending calculations were made to evaluate the quality of a full range FCC gasoline obtained by mixing the desulfurized heavy FCC gasoline and the untreated light cut.     

Deep extractive desulfurization of oil over 12-molibdophosphoric acid encapsulated in metal-organic frameworks

A desulfurization process for model oil and real oil was investigated based on the chemical oxidation of mixed sulfur containing compounds in the presence of nitrogen compounds (indole and quinoline) using hydrogen peroxide as oxidizing agent and dodecamolibdophosphoric acid (H₃PMo₁₂O₄₀) encapsulated in a kind of metal-organic framework (HKUST-1) as PMo@HKUST-1. The effect of isopropanol, ethanol and acetonitrile as extractive solvent and 1-ring (toluene, xylene and mesitylene) and 2-ring (naphthalene) aromatic hydrocarbons in desulfurization of model oil was studied. The desulfurization of sulfur-containing compounds was accelerated in the presence of aromatic hydrocarbons. In fact, a higher desulfurization efficiency of the heterogeneous catalyst could be achieved with system containing a polar solvent in contact with an aromatic hydrocarbon. Quinoline had no effect on oxidative desulfurization (ODS) reaction, whereas indole had a slightly negative effect. Presence of aromatic compounds had slightly positive effect on ODS reaction.     

Microwave-assisted extractive catalytic-oxidative desulfurization of diesel fuel via a VO(acac)2/ionic liquid system with H2O2 and H2SO4 as oxidizing agents

The removal of sulfur compounds from transportation fuel is an important aspect for protecting environment and for fuel cell applications. On the other hand, an innovative way to remove the sulfur is necessary because clean low-sulfur diesel is more widely used in the world today. In this work, we studied the effect of microwave irradiation power and time on the extractive catalytic oxidative desulfurization (ECODS) process of diesel fuel model (40 mL with initial S-content of 450 ppm), using vanadyl acetylacetonate (VO(acac)₂) as a catalyst and N-carboxymethylpyridine hydrosulphate ionic liquid ([CH₂COOHPy][HSO₄] IL) as an extractant, and hydrogen peroxide (H₂O₂) as an oxidant agent. The optimal microwave-assisted extractive catalytic – oxidative desulfurization (MECODS) experimental conditions were as follows: microwave irradiation power?=?500?W, microwave irradiation time?=?90?s, IL/diesel volume ratio?=?1:10, VO(acaca)₂/diesel mass ratio?=?0.5?wt%, and H₂O₂ volume?=?1 mL. Under these conditions, the sulfur content in commercial diesel fuel was reduced from 450 to 60?ppm (sulfur removal efficiency of 86.67%), which was superior to that of the simple oxidation with no IL (22.6%) or oxidation with not including catalyst (11.3%), and without affecting the physicochemical properties of diesel fuel. The catalytic system VO(acac)₂/IL can be recycled 5 times with merely a negligible loss in activity. Based on these experimental results, a MECODS mechanism was proposed. Ultra-deep desulfurization with 99.1% of sulfur removal efficiency was reached, using MECODS reaction under optimum conditions by adding 3?mL of H₂SO₄ (0.1?N) to the main reaction. This highest sulfur removal efficiency can be attributed to the synergetic effect between microwave activation heating energy and the additional protonation, which multiplied the sulfones’ (BTO₂s and DBTO₂s) formation pathways and thus accelerated the desulfurization reactions.     

用过氧化氢和乙酸对未经氢化处理的煤油进行直接氧化脱硫

The oxidative desulfurization of a real refinery feedstock (i.e., non-hydrotreated kerosene with total sulfur mass content of 0.16%) with a mixture of hydrogen peroxide and acetic acid was studied. The influences of various operating parameters including reaction temperature (T), acid to sulfur molar ratio (nacid/nS), and oxidant to sulfur molar ratio (nO/nS) on the sulfur removal of kerosene were investigated. The results revealed that an increase in the reaction temperature (T) and nacid/nS enhances the sulfur removal. Moreover, there is an optimum nO/nS related to the reaction temperature and the best sulfur removal could be obtained at nO/nS 8 and 23 for the reaction temperatures of 25 and 60&#61616;C, respectively. The maximum observed sulfur removal in the present oxidative desulfurization system was 83.3%.     

An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide–acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe²⁺/H₂O₂ 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 μg/g to 9.50 μg/g.     

Deep oxidative–extractive desulfurization of fuels using benzyl‐based ionic liquid

Four benzyl‐based ionic liquids (ILs) were synthetized and used for deep desulfurization of model oil and real diesel fuel. The removal efficiencies of benzothiophene (BT) and dibenzothiophene (DBT) with [Bzmim][NTf₂] and [Bzmim][SCN] as extractants are higher than that with [Bzmp][NTf₂] and [Bzmp][SCN] as extractants. The desulfurization capability follows the Nernst's Law. A reactive extraction mathematical model for desulfurization was established. An oxidative‐extractive two‐step deep desulfurization method was developed. DBT was first oxidized by H₂O₂ with CH₃COOH as catalyst and then the unoxidized DBT and uncrystallized dibenzothiophene sulfoxide (DBTO₂) in model oil were extracted by [Bzmim][NTf₂], and finally the removal efficiency was 98.4% after one‐stage extraction. Besides, the removal efficiency of 4,6‐DMDBT was 96.4% after oxidation and one‐stage extraction processes. Moreover, the oxidative‐extractive two‐step deep desulfurization method was also effective for desulfurization of diesel fuel. The removal efficiency of sulfur reached up to 96% after oxidation and three‐stage cross‐current extraction processes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4023–4034, 2016     

Oxidative desulfurization of tire pyrolysis naphtha in formic acid/H2O2/pyrolysis char system

Waste tires are one potential source of alternative energy because of their long chain hydrocarbon with a high calorific heating value. However, the pyrolysis oil that is derived from waste tires is not appropriate for direct use in a combustion process due to its high sulfur content. Therefore, the oxidative desulfurization (ODS) process was evaluated for its ability to reduce the sulfur content of the naphtha fraction distillated from light oil derived from waste tire pyrolysis. The addition of formic acid to pH of 4.0 in the presence of 25 vol.% hydrogen peroxide (H₂O₂) and tire pyrolysis char enhanced the level of sulfur removal to ca. 70% due to the simultaneous adsorption and oxidation of sulfurous compounds on the surface of the pyrolysis char. The chemical treatment to form surface-modified char promoted the benefit for ODS process in the presence of formic acid (pH 4) and H₂O₂ (25 vol.%) by increasing the sulfur reduction in the pyrolysis naphtha up to 75%.     

Sulfur removal of gas oil using ultrasound-assisted catalytic oxidative process and study of its optimum conditions

Ultrasound-assisted oxidative desulfurization process (UAOD) was applied to reduce sulfur compounds of gas oil containing various types of sulfur content. The environmental regulation requires a very deep desulfurization to eliminate the sulfur compounds. UAOD is a promising technology with lower operating cost and higher safety and environmental protection. For the first time the typical phase transfer agent (tetraoctyl-ammonium-bromide) was replaced with isobutanol because using isobutanol is much more economical than TOAB, imposing no contamination. The reaction was carried out at optimal point with various temperatures, in single-, two- and three step-procedures, investigating the effect of gradual increase of H₂O₂ and TOAB being used instead of isobutanol. Total sulfur concentration in oil phase was analyzed by ASTM-D3120 method. The highest removal of about 90% for gas oil containing 9,500 mg/kg of sulfur was achieved in three-steps during 17 minutes of process at 62±2 °C when 180.3 mmol of H₂O₂ was used and extraction carried out by methanol.     

Highly Efficient Oxidative Desulfurization of Fuels by Lewis Acidic Ionic Liquids Based on Iron Chloride

Acidic ionic liquids (ILs) have been employed as extractant and catalyst in the oxidative desulfurization (ODS) process of fuels in recent years. Several Lewis acidic ionic liquids [C₆³MPy]Cl/nFeCl₃ (molar fraction n = 0.5, 1, 2, 3) and [C₆MIM]Cl/FeCl₃ were prepared and used to remove the aromatic sulfur compounds dibenzothiophene and benzothiophene from fuels. In the ODS process, the used ILs acted as both extractant and catalyst with 30 wt % hydrogen peroxide aqueous solution as oxidant. The effects of Lewis acidity of ILs, IL's cation structure, molar ratio of O/S, reaction temperature, and different sulfur compounds on the sulfur removal of model oil were investigated. The results indicated that the sulfur removal for dibenzothiophene was affected by Lewis acidity of ILs and nearly reached 100 % by [C₆³MPy]Cl/FeCl₃ at conditions of 298 K, IL/oil mass ratio of 1/3, O/S molar ratio of 4/1, in 20 min. The sulfur removal of real gasoline reached 99.7 % after seven ODS runs in the [C₆³MPy]Cl/FeCl₃‐H₂O₂ system.     

焦化柴油过氧化环己酮氧化脱硫工艺研究

为了满足日趋严格的环保标准及市场对低硫柴油的巨大需求,柴油氧化脱硫技术显得日益重要。实验采用氧化萃取相结合的方法对焦化柴油进行了氧化脱硫实验。以自制过氧化环己酮为脱硫氧化剂,分别考察了氧化剂用量、氧化温度、氧化时间、萃取剂用量和二次萃取对焦化柴油硫含量的影响。结果表明,反应温度为100℃,反应时间3h,氧化剂与柴油的体积比0．04,萃取剂氮一甲基吡咯烷酮与柴油的剂油比为0．5,一级萃取可以脱除焦化柴油中93％的硫化物,柴油回收率达99％。二级萃取,可以脱除焦化柴油中95％的硫化物,柴油回收率为94．5％,硫含量可达到43．6μg·g^-1,小于50μg·g^-1,满足欧Ⅳ标准。     

Desulfurization of high-sulfur jet fuel by mesoporous π-complexation adsorbents

Desulfurization of JP-5 jet fuel (1172 ppmw S) was investigated by π-complexation adsorption with AgNO₃ supported on mesoporous silica SBA-15 and MCM-41. The average pore sizes of AgNO₃/SBA-15 and AgNO₃/MCM-41 were 48.8 and 19.1 Å, respectively. The results of JP-5 desulfurization showed that significant sulfur breakthrough occurred at ∼10.0 and ∼15.0 mL/g by AgNO₃/SBA-15 and AgNO₃/MCM-41, respectively, at a space velocity of 1.25 h⁻¹. The spent AgNO₃/MCM-41 was regenerated by a simple process (heating in air at 200 °C) and ∼50% of the sulfur capacity was recovered after the first cycle. Molecular orbital calculations show that Cu⁺ (as that in CuY zeolite) formed stronger π-complexation bonding with the thiophenic compounds than Ag⁺ (in AgNO₃), as evidenced by experimental heats of adsorption. However, pore diffusion limitation of the large sulfur molecules (alkylated benzothiophenes) became an important factor for desulfurization of high sulfur jet fuels such that the AgNO₃-supported mesoporous sorbents yielded substantially better results than Cu(I)Y, although Cu(I)Y was better for a model fuel that contained only small sulfur molecules. Among all sorbents that have been investigated, the AgNO₃/MCM-41 sorbent showed the best desulfurization performance for high sulfur jet fuels.     

酸性离子液体和Na2WO4·2H2O催化

以酸性离子液体和Na₂WO₄·2H₂O组成的体系为催化剂，过氧化氢为氧化剂，将催化柴油中的噻吩硫氧化为砜类物质，并通过NMP将其萃取出来，同时考察了反应温度、反应时间和催化剂用量等因素对氧化脱硫反应的影响，得出最佳反应条件为：3 mL油样（含硫200 μg·g^_-1），1 g离子液体，0.021 g 钨酸钠（Na₂WO₄·2H₂O）， 0.7 mL过氧化氢，反应温度323 K，反应时间3 h，萃取剂与柴油体积比为1∶1，此时样品中的硫可降低到23 μg·g^-1。反应结束后，可以通过简单的倾倒将油样和催化剂分离，催化剂重复使用5次，催化活性基本不变。     

Supported silver adsorbents for selective removal of sulfur species from hydrocarbon fuels

Dispersed silver oxides on supports such as TiO₂, γ-Al₂O₃ and SiO₂ were observed to be effective desulfurizing agents for refined fuels at ambient conditions. TiO₂ was determined to be the most stable support for silver oxide. Ag (4 wt%)/TiO₂ demonstrated a saturation sulfur capacity of 6.3 mgS/g for JP5 fuel containing 1172 ppmw sulfur. This high affinity for sulfur translated to one sulfur heterocycle associated with every two surface Ag atoms in the sorbent even in the presence of a 160-fold excess of other aromatics found in the fuel. A unique attribute of these sorbents was that they were thermally regenerable at 450 °C using air as a stripping medium over multiple cycles. Desulfurization characteristics also varied with fuel composition. Variation in desulfurization performance between JP5, JP8 and a light fraction JP5 were established and associated with the differences in sulfur composition of these fuels. The effects of surface area, porosity and crystal structure of the sorbent on sulfur capacity are also presented.