Oxidation Desulfurization of Model Sulfur Compound in the Presence of the Catalyst of Sodium Tungstate and Sodium Hydrogen Sulfate

Abstract

An oxidation desulfurization process for model sulfur compound has been investigated using sodium tungstate and sodium hydrogen sulfate as the catalyst and 30% aqueous hydrogen peroxide as the oxidizing agent. The effect of the reaction time, the reaction temperature, the amount of the oxidizing agent and the catalyst on the removal of dibenzothiophene (DBT) were investigated. The sulfur compound was extracted with the solvent after oxidization. The higher removal of DBT was up to nearly 80%.     

硫酸亚铁/异丁醛/甲酸/过氧化氢体系FCC汽油深度氧化脱硫

 采用硫酸亚铁/异丁醛/甲酸/过氧化氢体系对催化裂化(FCC)汽油进行了深度氧化脱硫研究。考察了该氧化体系中双氧水用量、硫酸亚铁用量、异丁醛用量、甲酸用量、反应温度和反应时间对FCC汽油氧化脱硫的影响。结果表明,采用该氧化体系可以增强FCC汽油氧化脱硫效果,氧化50mL FCC汽油的最佳操作条件为反应温度60℃、异丁醛1 mL、硫酸亚铁0.05g、双氧水5mL、甲酸5mL、乙腈萃取剂、乙腈/汽油体积比为1。在该条件下,30min内FCC汽油的脱硫率可达92.39%。     

Oxidative Desulfurization of Fuel Oil with Hydrogen Peroxide Catalyzed by Keggin-type Polyoxotungstate in a DC Magnetic Field

Abstract

The oxidation of sulfur-containing compounds was conducted in a DC magnetic field-assisted system, composed of model compound or diesel, 30 wt% hydrogen peroxide, and an iron mono-substituted Keggin-type heteropolytungstate [(C₄H₉)₄N]₄ [PW₁₁Fe(H₂O)O₃₉] catalyst. By combining oxidative desulfurization (ODS) in a magnetic field and acetonitrile extraction, when magnetic field intensity was at 17.3 mT, the removal efficiency of the model compound dibenzothiophene (DBT) in petroleum ether with 1,000 ppm S can reach 98% at 70°C within 30 min with O/S ratio = 3 and catalyst dosage 5%, with 2% increase over that without magnetic field assistance. Under the same reaction conditions, the sulfur level of diesel oil was reduced from 5,647 to 508 ppm. This shows that the DC magnetic field facilitates the oxidation of sulfur-bearing compounds, which allowed greater sulfur removal efficiency under milder reaction conditions.     

钨酸铋的制备及其催化氧化脱硫性能

催化氧化脱硫法因反应条件温和、可高效深度脱除燃料油中二苯并噻吩(DBT)类硫化物,是一种有潜力的非加氢脱硫方法。以钨酸钠和五水合硝酸铋为原料,采用直接沉淀法和水热法制备钨酸铋(Bi₂WO₆)。采用傅里叶变换红外光谱(FT-IR)、X-射线衍射(XRD)、电子扫描显微图像(SEM)、能量色散X射线光谱(EDS)和N₂等温吸附-脱附等分析方法对其结构、组成、表面形貌和比表面积进行表征。分别以DBT、苯并噻吩(BT)、4-甲基-二苯并噻吩(4-MDBT)和4,6-二甲二苯并塞吩(4,6-DMDBT)为代表性硫化物,以正癸烷为溶剂、十四烷为内标物配制含硫模拟油,以制备的Bi₂WO₆为催化剂、过氧化氢(H₂O₂)为氧化剂、乙腈(CH₃CN)为萃取剂构建催化氧化脱硫体系,系统地考察了其催化氧化脱硫性能。结果表明,水热法制备的Bi₂WO₆(BWO-2)表现出较优的脱硫性能。在反应温度...     

Oxidative Desulfurization of Diesel Fuel with Hydrogen Peroxide Using Na_2WO_4 as Catalyst

Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions (atmospheric pressure and temperature range of 293—343 K). Different organic compounds including benzothiophene (BT), dibenzothiophene (DBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) were used to investigate the reactivity of this catalyst, and the effect of various parameters, such as temperature, solvents and the amount of oxidant reagent used in oxidative desul...     

Deep Oxidative Desulfurization of Dibenzothiophene in Simulated Diesel with Tungstate and H2O2 in Ionic Liquids

Abstract

A green extraction and catalytic oxidative desulfurization (ECODS) system composed of simple tungsten-containing catalyst, 30 wt% H₂O₂, and ionic liquids was discovered suitable for the deep removal of dibenzothiophene (DBT) in simulated diesel. In the case of the system comprising Na₂WO₄ · 2H₂O, 30 wt% H₂O₂ and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄), the removal of DBT could reach 99.7% at 60°C for 3 hr, which was superior to mere solvent extraction with ionic liquid or catalytic oxidation without ionic liquid. This desulfurization system could be recycled five times with a small decrease in activity.     

Dawson结构杂多磷钨酸钠催化氧化噻吩脱硫

以钨酸、磷酸二氢钠为原料,通过水热法合成了 Dawson 结构杂多磷钨酸钠(P_2W_(18))。以 P_2W_(18)为催化剂、无水乙醇为助催化剂、质量分数30%的过氧化氢水溶液为氧化剂,在温和条件下将模拟燃油中的噻吩氧化为砜类:亚砜类等极性较强的物质,并以 N,N-二甲基甲酰胺为萃取剂将其萃取出来,考察了反应温度、反应时间、过氧化氢水溶液用量、萃取剂用量和萃取级数对脱硫率的影响。在模拟燃油(硫含量500 mg/L)20 mL、P_2W_(18)0.030 g、无水乙醇1.2 mL、过氧化氢水溶液0.12 mL、反应温度310 K、反应时间60 min、萃取剂与油相的体积比1.0、萃取3次的优化条件下,脱硫率达96.7%。反应结束后,可通过简单的倾倒将模拟燃油与催化剂分离,催化剂可重复使用5次,稳定性较好。     

Zinc-Substituted Polyoxometalate for Oxidative Desulfurization of Dibenzothiophene

Abstract

An oxidative desulfurization process for model compound has been studied using Na₁₂[WZn₃(H₂O)₂(ZnW₉O₃₄)₂] · 46H₂O as catalyst and 30 wt% aqueous hydrogen peroxide as the oxidizing agent. The effects of the reaction time, the reaction temperature, the amount of the oxidizing agent and the catalyst on the removal of dibenzothiophene (DBT) were investigated. The oxidated resultant was removed by extraction with polar solvent to reduce the sulfur level in the model compound. The maximum removal of DBT was up to 70%.     

用于FCC柴油氧化萃取脱硫的负载型磷钨酸催化剂和复合萃取剂

采用浸渍法制备磷钨酸(HPW)质量分数不同的半焦负载型催化剂HPW/Sc,利用扫描电镜、紫外漫反射吸收光谱和 N₂吸附-脱附分析方法表征了所制备 HPW/Sc 催化剂的结构,并在FCC 柴油的氧化萃取脱硫过程中将其作为氧化催化剂,考察了HPW 的负载量和萃取剂种类对氧化萃取脱硫率的影响。结果表明,半焦是 HPW 的良好载体,HPW 负载到半焦后保持了原有的Keggin 结构;在最优氧化反应和萃取条件下,FCC 柴油中的硫质量分数由1100 μg/g 降至89.1 μg/g, 脱硫率达到91.9%;评选出了柴油氧化萃取脱硫的专用复合萃取剂,用氢键理论和位阻效应解释了复合萃取剂可以提高回收率的原因。     

磷钼酸为催化剂的高铁酸钾氧化脱硫的研究

In this work, the removal of thiophene from simulated oil has been studied by using the adsorption, extraction and oxidation/adsorption methods, respectively. In the adsorptive desulfurization process, different commercial adsorbents were used to eliminate thiophene at ambient pressure and mild temperature, and the results showed that carbon powder had the best adsorption ability. In the extractive desulfurization process, the best desulfurization result was obtained when DMF is used. In the oxidative/adsorptive desulfurization procedure using synthesized potassium ferrate as the oxidant and phosphomolybdic acid solution as the catalyst, thiophene was oxidized and removed from hydrocarbons in combination with active carbon adsorption, and the residual sulfur content of simulated oil could be reduced to 15.3mg/L from the original level of 200mg/L, with the desulfurization rate reaching 92.3%.     

油品氧化脱硫技术中氧化剂的研究进展

综述了近年来氧化脱硫技术中氧化剂的研究进展,其中氧化剂包括过氧化氢、高锰酸钾、有机过氧化物、分子氧等;并提出氧化剂的发展方向。     

活性氢物质存在时丁硫醚在HZSM催化剂上的催化脱硫转化反应研究

1. Introduction The negative effects, which accompanied with the high-speed development of the petroleum and automobile industries in the last century, show that the sulfur compounds are usually the harmful component in oil products, and affect the proper…     

几种汽油脱硫工艺中含硫化合物类型变化规律

采用气相色谱-原子发射光谱联用(GC—AED)技术,研究了几种不同的脱硫工艺(加氢脱硫、吸附脱硫和抽提脱硫)中各种含硫化合物的变化。加氢脱硫工艺中含硫化合物的脱除效果最好,硫脱除率可达98％以上,硫醇、硫醚最易脱除,仅有少量的烷基取代噻吩不易被脱除,加氢脱硫条件的选择应以汽油中噻吩类化合物的含量而定;吸附脱硫工艺中,硫醇、硫醚、四氢噻吩类化合物最易脱除,受空间位阻的影响,取代噻吩比噻吩难脱除;在抽提脱硫工艺中,因苯并噻吩与所用抽提剂结构相近,最易被脱除,而空间位阻较大的三甲基噻吩和四甲基噻吩不能被脱除。采用GC—AED技术,可根据汽油馏分中含硫化合物的分布来选择合适的脱硫工艺。     

The Research of Ultra-deep Desulfurization in Diesel via Ultrasonic Irradiation Under the Catalytic System of H2O2-CH3COOH-FeSO4

Abstract

In recent years, many countries have drawn up strict laws regarding the sulfur-containing compounds of fossil fuels, especially the gasoline and diese. Ultra-deep desulfurization of fuel is a main component of fossil fuel development. The experiment imposes the photochemistry field on the catalytic oxidation system in order to broaden the newly desulfurization technology. The sulfur-containing compounds, such as dibenzothiophene (DBT) and its derivatives, in diesel fuel are oxidized to corresponding sulfones using H₂O₂-CH₃COOH-FeSO₄ oxidation systems via ultrasonic irradiation. Later, the oxidized sulfur compounds (sulfones) are extracted by a suitable polar solvent. The influences of the catalytic system, reaction time, and ultrasonic source (frequency, intensity) are tested on desulfurization efficiency. Experimental results show that the removal efficiency of the sulfur compound could amount to 97.5%, and the recovery of oil is above 92% under the catalytic system of H₂O₂-CH₃COOH-FeSO₄ by the assistance of ultrasound.     

Oxidative Desulfurization of Fuel Catalyzed by Amphiphilic Peroxomolybdate

Abstract

The oxidation of sulfur-containing compounds (benzothiophene [BT], dibenzothiophene [DBT], and 4,6-dimethyldibenzothiophene [4,6-DMDBT]) was studied in an emulsion system composed of model oil, hydrogen peroxide, and an amphiphilic catalyst [C₇H₇C₁₂H₂₅(CH₃)₂N]₂Mo₂O₃(O₂)₄. The most suitable conditions were suggested: n (DBT): n (catalyst): n (H₂O₂) = 1:0.1:10, at 60°C for 2 hr. Under optimized experimental conditions, the removal of DBT, BT, and 4,6-DMDBT could reach 98.0, 94.0, and 62.7%, respectively. The oxidation product sulfones could be readily separated by extraction. The catalyst could be recycled five times without a significant decrease in catalytic activity.     

Ionic Liquid-based Extraction of Sulfur Compounds From Gasoline as a Complementary Process to Oxidative Desulfurization

The extractive desulfurization of a model and several real gasoline samples was investigated using imidazolium-based ionic liquids (ILs). Factorial design of experiments indicated that, among several process variables, the number of extraction steps and the IL/gasoline volume ratio were statistically highly significant. The results showed a desulfurization efficiency of 95.2% under the optimal conditions. The following order was observed for the extraction of thiophenic compounds: benzothiophene>thiophene>3-methylthiophene>2-methylthiophene, with 96.1% removal efficiency for the first one. The IL extraction was applied as a complementary process for the oxidative desulfurization by hydrogen peroxide and formic acid, which provided high efficiency and selectivity for desulfurization of gasoline.     

Oxidation Desulfurization of Thiophene Using Phase Transfer Catalyst/H2O2 Systems

Abstract

In our study, an effective phosphomolybdic acid/hexadecyltrimethyl-ammonium bromide catalyst for oxidative desulfurization of thiophene in a model compound was formed. The oxidation activities of thiophene for a series of heteropoly acids were estimated. The results show that the oxidation activity of thiophene increased with increasing oxidation time, oxidation temperature, and the volume of 30% H₂ O₂ oxidant. The optimal values are 150 min, 40°C, and 3 mL, and sulfur removal attained 96.3% when phosphotungstic acid/hexadecyltrimethylammonium bromide was used as a catalyst.     

Oxidative Desulfurization of Diesel Fuel Using Ultrasound

Abstract

Catalytic oxizdation is a non-HDS technology to remove sulfur compounds from diesel fuel, and ultrasound irradiation was introduced to provide energy for this reaction. The effects of reaction temperature, time, and the ratio of oxidant and oil were investigated. The results show that under certain conditions, the optimal conditions were as follows: volume ratio of oxidant to oil was 1:10, reaction temperature was 50°C, and oxidation time was 10 min.     

杂多酸在油品氧化脱硫中的应用进展

氧化脱硫技术是一种很有前景的脱硫技术。综述了单体杂多酸、杂多酸盐、杂多酸相转移催化剂以及负载型杂多酸催化剂在油品氧化脱硫过程中的作用机理及应用进展,指出了杂多酸催化剂应用于油品氧化脱硫过程中有待解决的问题及今后发展方向。