Sulfur removal from hydrotreated petroleum fractions using ultrasound-assisted oxidative desulfurization process

Ultrasound-assisted oxidative desulfurization (UAOD) process was applied to diesel oil and petroleum product feedstock containing model sulfur compounds (benzothiophene, dibenzothiophene and dimethyldibenzothiophene). The influence of oxidant amount, volume of solvent for the extraction step and time and temperature of ultrasound treatment (20 kHz, 750 W, operating at 40%) was investigated. Using the optimized conditions for UAOD, sulfur removal up to 99% was achieved for model compounds in petroleum product feedstock using a molar proportion for H₂O₂:acetic acid:sulfur of 64:300:1, after 9 min of ultrasound treatment at 90 °C, followed by extraction with methanol (optimized solvent and oil ratio of 0.36). Using the same reagent amount and 9 min of ultrasound the removal of sulfur was higher than 75% for diesel oil samples. Sulfur removal without ultrasound using the same conditions was lower than 82% for model compounds and 55% for diesel oil samples showing that ultrasound improved the efficiency of oxidative desulfurization. In comparison to conventional hydrodesulfurization, the proposed UAOD process can be performed under relatively mild conditions (atmospheric pressure and 90 °C, without using metallic catalysts).     

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.     

Diesel fuel desulfurization with hydrogen peroxide promoted by formic acid and catalyzed by activated carbon

Desulfurization of diesel fuels with hydrogen peroxide was studied using activated carbons as the catalysts. Adsorption and catalytic properties of activated carbons for dibenzothiophene (DBT) were investigated. The higher the adsorption capacity of the carbons is, the better the catalytic performance in the oxidation of DBT is. The effect of aqueous pH on the catalytic activities of the activated carbons was also investigated. Oxidation of DBT is enhanced when the aqueous pH is less than 2, and addition of formic acid can promote the oxidation. The effect of carbon surface chemistry on DBT adsorption and catalytic activity was also investigated. Adsorption of DBT shows a strong dependence on carboxylic group content. The oxidative removal of DBT increases as the surface carbonyl group content increases. Oxidative desulfurization of a commercial diesel fuel (sulfur content, 800 wt. ppm) with hydrogen peroxide was investigated in the presence of activated carbon and formic acid. Much lower residual sulfur content (142 wt. ppm) was found in the oxidized oil after the oxidation by using the hydrogen peroxide-activated carbon-formic acid system, compared with a hydrogen peroxide-formic acid system. The resulting oil contained 16 wt. ppm of sulfur after activated carbon adsorption without any negative effects in the fuel quality, and 98% of sulfur could be removed from the diesel oil with 96.5% of oil recovery. Activated carbon has high catalytic activity and can be repeatedly used following simple water washing, with little change in catalytic performance after three regeneration cycles.     

Transesterification of palm oil and esterification of palm fatty acid in near- and super-critical methanol with SO4-ZrO2 catalysts

Sulfated zirconia (SO₄-ZrO₂) catalysts, prepared with three different sulfur loading contents (0.75%, 1.8% and 2.5%) at two calcination temperatures (500 °C and 700 °C), were tested for use in the transesterification of purified palm oil (PPO) and the esterification of palm fatty acid (PFA) in near-critical and super-critical methanol. Techniques including BET, XRD, NH₃- and CO₂-TPD revealed that the sulfur content and calcination temperature strongly affects the catalyst base-acid site, specific surface area, average pore size, phase structure, and thus the catalytic reactivity. The most suitable sulfur loading content was found to be 1.8% and the optimum calcination temperature 500 °C. The results show that the use of SO₄-ZrO₂ reduces esterification reaction times, the amount of methanol necessary and the required reaction temperature. The reactions at 250 °C in the presence of the SO₄-ZrO₂ catalyst at 0.5 w/w% catalyst to PPO or PFA were found to give the highest FAMEs conversions. Under these conditions, 90% and 75% conversions were achieved within 10 and 1 min from PPO (at 25:1 MeOH:PPO molar ratio) and PFA (at 6:1 MeOH:PFA molar ratio), respectively.     

Catalytic oxidative desulfurization of benzothiophene with hydrogen peroxide over Fe/AC in a biphasic model diesel-acetonitrile system

Catalytic oxidative desulfurization (Cat-ODS) of benzothiophene (BT) in n-octane has been investigated with hydrogen peroxide (H₂O₂) over catalysts of activated carbon (AC) supported iron oxide under mild conditions. The catalyst was characterized by N₂ adsorption, XRD, SEM/EDS, TPR and XPS. Under the best operating condition for the catalytic oxidative desulfurization—temperature 60 °C, atmospheric pressure, 0.15 g Fe/AC, 18 molar ratio of hydrogen peroxide to sulfur, using acetonitrile as extraction solvent for double extraction—the sulfur content in model diesel fuel (MDF) was reduced from 700 ppmw to 30 ppmw with 95.66% of total sulfur was removed.     

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.     

Influence of fuel sulfur on the characterization of PM10 from a diesel engine

To study the effects of fuel sulfur content on the characteristics of diesel particle emitted from a typical engine used in China, two types of diesel fuel with sulfur content of 30 ppm and 500 ppm were used in this engine dynamometer test under six operation conditions corresponding to 20%, 50% and 80% load at 1400 rpm and 2300 rpm engine speeds, respectively. Gaseous pollutants and particulate matter (PM) emissions were sampled with AVL AMA4000 and Model 130 High-Flow Impactor (MSP Corp), respectively. More specifically, the PM mass, total carbon (TC), organic carbon (OC), elemental carbon (EC) and water-soluble ion distribution were also measured. Compared with high sulfur diesel, the application of low sulfur diesel can lower fuel-based PM emissions by 9.2-56.6%. At 1400 rpm, the low sulfur diesel decreased both OC and EC by 5-34% and about 20%; while at 2300 rpm, the low sulfur fuel decreased OC by 33-57% and increased EC emission, resulting in a lower OC/EC ratio. The evidence implicating that OC oxidation was promoted by low sulfur diesel, but the effect on EC oxidation was dependent on engine speed. The linear regression has been conducted between TC and PM₁₀, and the slopes were 0.88 and 0.80 for low sulfur diesel and high sulfur one, respectively. Higher sulfate content was detected in the 0.13 μm particles when using the high sulfur diesel, but the percentage of sulfate was 0.9% for PM₁₀ from both diesel fuels. Comparing with that of 500 ppm, EC increased sharply to a maximum of 114% in particles of 0.13 μm when using 30 ppm sulfur diesel at 2300 rpm.     

Sulfur removal from model diesel fuel using granular activated carbon from dates’ stones activated by ZnCl2

Samples of granular activated carbon (GAC) were produced from dates’ stones by chemical activation using ZnCl₂ as an activator. Textural characteristics of GAC were determined by nitrogen adsorption at 77 K along with application of BET equation (Brunauer, Emmett and Teller) for determination of surface area. Pore size distribution and pore volumes were computed from N₂ adsorption data by applying the nonlinear density function theory (NLDFT). FT-IR spectra of GAC samples were also obtained to determine the functional groups present on the surface. GAC samples were used in desulfurization of a model diesel fuel composed of n-C₁₀H₃₄ and dibenzothiophene (DBT) as sulfur containing compound. More than 86% of DBT is adsorbed in the first 3 h which gradually increases to 92.6% in 48 h and no more sulfur is removed thereafter. The adsorption data were fitted to both Freundlich and Langmuir equations to estimate the adsorption parameters. The optimum operating conditions for GAC preparation based on high adsorption capacity are T_carb = 700 °C, θ_carb = 3.0 h and R = 0.5. Moreover, the efficiency of sulfur removal by GAC is reduced when applied to commercial diesel fuel. Finally, linear regression of experimental data was able to predict the critical pore diameter for DBT adsorption (0.8 nm) and validating the reported impact of average pore diameter of activated carbon on the adsorption capacity.     

Oxidation desulfurization of fuel using pyridinium-based ionic liquids as phase-transfer catalysts

In this work, several ionic liquids based on pyridinium cations are prepared. The ionic liquids are employed as phase-transfer catalysts (PTCs) for phase-transfer catalytic oxidation of dibenzothiophene (DBT) dissolved in n-octane. The partition coefficients of DBT between ionic liquids and n-octane are investigated. Then H₂O₂-formic acid is used as an oxidant and ionic liquids are used as PTCs. The reaction turns to be heterogeneous and desulfurization rate of DBT increased apparently. When IL ([BPy]HSO₄) is used as PTC, and the condition are: temperature is 60 °C, time is 60 min, H₂O₂/sulfur molar ratio (O/S) is 4, the desulfurization rate reaches the maximum (93.3%), and the desulfurization of the real gasoline is also investigated, 87.7% of sulfur contents are removed under optima reaction conditions. The PTC [BPy]HSO₄ can be recycled for five times without significant decrease in activity.     

Polyoxometalate-based ionic liquids as catalysts for deep desulfurization of fuels

In order to obtain the ultra low-sulfur diesel, deep desulfurization of diesel oil has become a vital subject of environmental catalysis studies. Extraction and catalytic oxidation desulfurization (ECODS) system is one of the most promising desulfurization processes. A series of Keggin-type POM-based ionic liquids hybrid materials [MIMPS]₃PW₁₂O₄₀·2H₂O (1-(3-sulfonic group) propyl-3-methyl imidazolium phosphotungstate), [Bmim]₃PW₁₂O₄₀ (1-butyl 3-methyl imidazolium phosphotungstate), [Bmim]₃PMo₁₂O₄₀ (1-butyl 3-methyl imidazolium phosphomolybdate) and [Bmim]₄SiW₁₂O₄₀ (1-butyl-3-methyl imidazolium silicotungstate) have been developed in this study, and the reaction has performed using the POM-ILs materials as catalysts, H₂O₂ as oxidant, and ionic liquid (IL) as solvent. Through experimental evaluations, [MIMPS]₃PW₁₂O₄₀·2H₂O was found to be the best catalyst, with an S-removal of 100% at 30 °C for 1 h. The main factors affecting the process including temperature, catalyst dosage, and O/S (H₂O₂/DBT) molar ratio were investigated in detail. Under the optimal conditions, DBT (dibenzothiophene) and 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) could achieve high desulfurization efficiency. Moreover, the reaction system also exhibited high activity in actual diesel oil, which could be reduced from 1113 ppm to 198 ppm. The reaction system could recycle 8-times with a slight decrease in activity.     

Production of microporous palm shell based activated carbon for methane adsorption: Modeling and optimization using response surface methodology

In this study, the optimization of the palm shell based activated carbon production using combination of chemical and physical activation for methane adsorption is investigated. response surface methodology (RSM) in combination with central composite design (CCD) was used to optimize the operating parameters of the production process. Physical activation temperature, chemical impregnation ratio and physical activation time were chosen as the main process variables and the amount of methane adsorption was selected as the investigated response. Phosphoric acid and carbon dioxide were used as chemical and physical agents, respectively. The optimum reaction conditions were found to be a physical activation temperature of 855 °C, H₃PO₄ impregnation ratio of 9.42 g of phosphorous per gram palm shell and physical activation time of 135 min. The results exhibited significant increase in methane adsorption after physio-chemical activation.     

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO_x) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol.     

活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性

研究了活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性。采用气相色谱-硫化学发光检测器（GC-SCD）分析了汽油和柴油中噻吩类硫化物的分布及浓度;以活性炭作为催化剂,以30％过氧化氢溶液为氧化剂,在甲酸存在条件下考察了汽油和柴油中噻吩类硫化物催化氧化脱除的选择性,讨论了硫化物中硫原子电子密度对硫化物氧化选择性的影响。结果表明：汽油中噻吩类硫化物主要有噻吩（T）及其烷基衍生物（T alkylated derivatives）和苯并噻吩（BT）;而柴油中噻吩类硫化物主要分布有苯并噻吩(BT)及其烷基衍生物(BT alkylated derivatives)和二苯并噻吩（DBT）及其烷基衍生物（DBT alkylated derivatives）;硫原子电子密度大于5.716的含3个C烷基噻吩（C3-T）、BT、BT alkylated derivatives、DBT 和DBT alkylated derivatives 能被催化氧化脱除,硫原子的电子密度越大,其被氧化的速率越快,被脱除的选择性也越大;被脱除选择性顺序为：DBT alkylated derivatives > DBT > BT alkylated derivatives> BT> C3-T;然而硫原子电子密度小于5.716的T,含1个烷基噻吩（C1-T）和含2个C烷基噻吩（C2-T）则不能被氧化脱除。采用此方法,能将初始硫浓度为1200 μg•g^-1的柴油降低至小于10 μg•g^-1,可将初始硫浓度为320 μg•g^-1的汽油降低至155 μg•g^-1。     

Energy-efficient ultra-deep desulfurization of kerosene based on selective photooxidation and adsorption

Selective photooxidation and adsorptive desulfurization of kerosene was investigated for fuel cell applications. Photooxidation was conducted using a 5 W low-pressure mercury lamp at 25 °C in the presence of O₂. It was found for the first time that the rates of photooxidation of dominant sulfur compounds remaining in commercial kerosene after hydrogenation were at least 100 times higher than those of benzothiophenes (BTs) and dibenzothiophenes (DBTs), although their molecular forms were not clarified. The photooxidation of these highly reactive sulfur compounds was completed within 30 min and made them removable by adsorbents such as molecular sieves. On the other hand, non-reactive sulfur compounds such as DBTs were removed by adsorbents such as activated carbon. Using this proposed method, which combines selective photooxidation of highly reactive sulfur compounds and adsorptive desulfurization of reactive and non-reactive sulfur compounds, the total sulfur content in kerosene can be efficiently reduced to less than 0.1 μg g⁻¹ (ppm) under mild conditions.     

Hydrogen production from bioethanol reforming in supercritical water

Hydrogen production by reforming and oxidative reforming of ethanol in supercritical water (SCW) at the intermediate temperature range of 500-600 °C and pressure of 25 MPa were investigated at different ethanol concentrations or water to ethanol ratios (3, 20 and 30), with the absence and the presence of oxygen (oxygen to ethanol ratio between 0 and 0.156). Hydrogen was the main product accompanied with relatively low amounts of carbon dioxide, methane and carbon monoxide. Some liquid products, such as acetaldehyde and, occasionally, methanol were present. The ethanol conversion and hydrogen yield and selectivity increased substantially as the water to ethanol ratio and the reaction temperature increased. Ethanol was almost completely reformed and mainly converted to hydrogen giving a H₂/CO ratio of 2.6 at 550 °C and water to ethanol ratio of 30 without carbon formation. Coke deposition was favored at low water to ethanol ratio, especially at high temperatures (≥550 °C). The hydrogen yield improved as the ethanol was partially oxidized by the oxygen added into the feed at oxygen to ethanol ratios <0.071. It was evidenced that the metal components in Inconel 625 reactor wall reduced by a hydrogen stream acted as a catalyst promoting hydrocarbon reforming as well as water-gas-shift reactions while dehydrogenation of ethanol forming acetaldehyde can proceed homogeneously under the SCW condition. However, at high oxygen to ethanol ratio, the reactor wall was gradually deactivated after being exposed to the oxidant in the feed. The loss of the catalytic activity of the reactor surface was mainly due to the metal oxide formation resulting in reduction of catalytic activity of the reactor wall and reforming of carbon species was no longer promoted.     

Dry catalytic partial oxidation of diesel-fuel distillates into syngas

Volatile compounds distilled below 205 °C from diesel fuel are reformed into synthesis gas by dry catalytic partial oxidation using porous membrane reactors, eliminating complex liquid-fuel injectors and fuel-air mixers, greatly simplifying reformers for applications with solid-oxide fuel cells and NO_x traps. For distillates utilizing 20 wt% of the diesel fuel, 88 mol% of the carbon is converted into CO and 75 mol% of the hydrogen into H₂. Rationale is as follows: Long-chain n-alkanes such as n-hexadecane, with normal boiling point, 286.5 °C, but autoignition temperature, 205 °C, are the least thermally stable hydrocarbons in diesel fuel. If attempts are made to vaporize diesel fuel under oxygen-lean conditions without precautions, long-chain n-alkanes crack at autoignition temperatures forming radicals that initiate polymerization. By eliminating more troublesome compounds by distillation, and by effusing cooler air through porous ceramic membranes to react radicals with oxygen, carbon deposition is largely suppressed. A perovskite catalyst, fed pre-heated air at >900 °C, provides a reservoir of mobile lattice oxygen to react with adsorbed carbon. In continuous runs of 72 h, carbon deposition was negligible in the reactor, on the catalyst, and in the exhaust, except for minor graphite deposited onto walls near the catalytic hot zone.     

Carbon infiltration of carbon-fiber preforms by catalytic CVI

Experimental studies were conducted to assess catalytic chemical vapor infiltration processing for preparing carbon/carbon composites as a potential improvement to conventional one. The catalyst was introduced into the carbon fiber preforms by wet impregnation. Using C₃H₆/Ar/H₂ as the original gas, catalytic carbon was formed at 500-1000 °C for 1-3 h. It was found that carbon filaments were formed as the preparing temperatures were 500-700 °C, and carbon particles could be obtained at 800-1000 °C. The increasing rate of density was up to 0.916 g/ml/h when the sample was formed at 600 °C for 1 h with the catalytic of 0.7 wt.% Ni, and the carbon yield arrived to 90 wt.% . According to the micrographs of catalytic carbon, the forming mechanism of carbon filaments agreed with that of carbon filaments due to a metal catalyst. The weighted average interlayer spacing of C/C composites with catalytic carbon decreased to 0.341.     

Selective adsorption of organic sulfur in coal extract by using metal-loaded carbon

The objective of this study was to develop an efficient cleaning process for hydrocarbon resources. We investigated the removal of organic sulfur from coal extract by using metal-loaded carbons. Tetralin and tetralin/phenol mixture were used for thermal extraction of Illinois No. 6 coal at 375 °C with a holding time of 1 h, and we examined the effects of temperature on product yield and sulfur-removal behavior using metal-loaded carbons. A decrease in the n-hexane insoluble fraction was observed at a temperature range from 200 °C to 250 °C in the extracts of tetralin and tetralin/phenol mixture. The organic sulfur content in the n-hexane insoluble fraction drastically decreased with increasing temperature. The organic sulfur in the n-hexane insoluble fraction was reduced above 200 °C, while the sulfur content reached 30-35% at 375 °C for both tetralin and tetralin/phenol mixture extracts. We investigated the effect of holding time on the extent of the coal extract desulfurization using Ni-loaded carbon. The sulfur content in the coal extract decreased as the holding time increased. The rate of coal extract desulfurization using tetralin/phenol was slower than that obtained using tetralin. The coal extract obtained using the tetralin/phenol mixture contained a heavier polar fraction, which may have impeded the adsorption. All organic sulfur in the coal extract could be successfully removed Ni-loaded carbon at a treatment temperature of 350 °C and a holding time of 8 h. No appreciable changes were observed in the content of carbon, hydrogen, or nitrogen at any temperature or holding time in the ultimate analysis of the n-hexane insoluble fraction treated with Ni-loaded carbon. The results demonstrated that Ni-loaded carbon was much effective in removing organic sulfurs from the coal extract.     

Ultra-deep desulfurization of coker and straight-run gas oils: Effect of lowering feedstock 95% boiling point

Production of diesel fuels with ultra-low-sulfur levels by deep desulfurization of gas oil feeds has received considerable importance in the petroleum refineries in recent years. The type of the gas oil feed and its distillation temperature play a key role in the deep desulfurization process. In the present research project, the effect of lowering the 95% distillation temperature (T₉₅) of two gas oil feeds, namely, straight-run gas oil (SRGO) and coker gas oil (CGO), on deep desulfurization to ultra-low-sulfur levels was investigated. The results showed that for both types of feeds a higher degree of desulfurization was achieved with reduction of T₉₅ from > 360 °C to < 340 °C. The refractory alkyl dibenzothiophenes boiling above 320 °C were present in very low concentrations in the low-boiling cuts and deep HDS to ultra-low-sulfur levels (< 50 ppm) was achieved at low severity operating conditions. Among the two feeds, the CGO that contained high nitrogen content, high concentrations of sterically hindered alkyl DBTs and high aromatics content (low feed saturation) was more difficult to desulfurize than SRGO.     

Deep desulfurization of fuels catalyzed by surfactant-type decatungstates using H2O2 as oxidant

Oxidation of dibenzothiphene (DBT) in model oil with H₂O₂ using surfactant-type decatungstates Q₄W₁₀O₃₂ (Q = (CH₃)₃NC₁₆H₃₃, (CH₃)₃NC₁₄H₂₉, (CH₃)₃NC₁₂H₂₅ and (CH₃)₃NC₁₀H₂₁) as catalysts was studied. The surfactant-type decatungstates were synthesized and characterized. The suitable reaction condition of deep desulfurization was suggested: n(DBT):n(catalyst):n(H₂O₂) = 1:0.01:3, 60 °C for 0.5 h, under which the DBT conversion can reach 99.6% with [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ as catalyst. The length of carbon chains of quaternary ammonium cations played a vital role in the catalytic activity of surfactant-type decatungstates, that is, the longer the carbon chain of quaternary ammonium cation of a catalyst was, the better the activity of this catalyst showed. [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ exhibited the best catalytic performance and can be recycled for six times without significant decrease in catalytic activity. Using benzothiphene (BT) and 4,6-dimethyldibenzothiphene (4,6-DMDBT) as substrates in model oil, surfactant-type decatungstates also showed high catalytic activity. During desulfurization process, BT conversion can reach 99.6% at 3.25 h, while 99.4% of 4,6-DMDBT conversion reached at 1.25 h, with the temperature of 60 °C under atmospheric pressure. The sulfone can be separated from the oil using N,N-dimethylformamide (DMF) as an extractant, and the sulfur content can be lowered from 1000 to 4 ppm. For real diesel, the sulfur removal can reach 93.5% after five times extraction.