Oxidative Desulfurization of Fuel Oil: Modeling Based on Artificial Neural Network

Abstract

Oxidative desulfurization of fuel oil was investigated using a process consisting of oxidation and distillation steps. In the oxidation step, various organic carboxylic acid/H₂ O₂ systems, especially acetic acid/H₂ O₂, were used as oxidant. They oxidize both easy and refractory sulfur compounds and convert them into oxidized sulfur compounds. The oxidized sulfur compounds are finally removed from fuel oil by distillation in the presence of water. The sulfur content of fuel oil was decreased to levels as low as 20 ppm (up to 90%) in a short contact time, ambient temperature, and atmospheric pressure. The results showed that applying this process did not have any deleterious influence on the distillation characteristic, composition, and content of fuel oil that was examined. An artificial neural network, using back propagation (BP), was also utilized for modeling oxidative desulfuration process of fuel oil. The comparison between the output of ANN modeling and the experimental data showed satisfactory agreement.     

燃料油氧化脱硫技术进展

综述了氧化脱硫技术中氧化剂和催化剂的研究进展。其中氧化剂包括高锰酸钾、氮化物（NO2和硝酸）、分子氧（臭氧、氧气和空气）、双氧水、有机过氧化物（过氧化叔丁醇、过氧化叔戊醇及过氧化环己酮）。催化剂主要介绍与双氧水相匹配的催化剂,分为液相催化剂和固相催化剂,液相催化剂包括甲酸、乙酸、乙酸酐或杂多酸磷钨酸;固相催化剂包括以金属氧化物为载体的固体催化剂,即WOx／ZrO2,负载在TiO2上的V2O5催化剂;以分子筛为载体的固体催化剂,即钛硅分子筛催化剂。并提出今后氧化脱硫醇技术的发展方向。     

Mo/γ-Al2O3催化剂制备及催化氧化船用燃料油脱硫

以γ-Al2O3为载体,采用浸渍法制备了负载型催化剂Mo/γ-Al2O3。利用X-射线衍射仪(XRD)、N2-吸附脱附、H2程序升温还原(H2-TPR)等手段对催化剂进行了表征。分别以二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)、苯并噻吩(BT)和噻吩(Th)的正辛烷溶液作为模拟燃料油,异丙苯过氧化氢(CHP)为氧化剂,评价了Mo/γ-Al2O3的催化氧化脱硫(ODS)活性;并将Mo/γ-Al2O3催化剂应用于馏分型船用燃料油氧化脱硫。结果表明：Mo/γ-Al2O3催化剂对不同结构的含硫化合物的催化脱硫活性由大到小的顺序为DBT、4,6-DMDBT、BT、Th;Mo/γ-Al2O3上的Al2(MoO4)3为主要活性中心;在反应温度80 ℃、氧/硫原子比5、催化剂用量1.0 g时,硫质量分数为1.6%的船用燃料油的脱硫率可达到82.6%,硫质量分数可以降至0.3%,达到了最新船用燃料油标准硫质量分数低于0.5%的规定。催化剂重复使用10次后,催化剂活性没有明显的降低。     

汽柴油氧化-萃取脱硫技术中萃取过程研究进展

简要介绍了汽柴油氧化一萃取脱硫原理及常用萃取剂。重点介绍了萃取工艺条件对汽柴油氧化一萃取脱硫效果的影响,其中包括采用的催化氧化体系、萃取温度、萃取剂的筛选、剂油比及萃取时间等。萃取工艺条件中萃取剂的选择是萃取脱硫过程的关键,选择的萃取剂必须与催化氧化体系匹配;萃取温度通常为室温,剂油比1：1,在较佳的萃取脱硫工艺条件下,可有效降低汽柴油硫含量,达到深度脱硫目的。     

Application of Artificial Neural Network in the Residual Oil Hydrotreatment Process

Abstract

Based on the industrial measured data of the residual oil hydrotreatment process, the artificial neural network (ANN) model was developed to determine metal, sulfur, nitrogen, and carbon residue content of hydrogenated residual oil. The established ANN model has seven input variables, four output variables, and 1 hidden layer with 15 neurons. The training results show that the agreement between predicted and industrial measured values is good. The mean relative errors of the testing data for the four output variables are less than 6%. It indicated that the developed ANN model has good predictive precision and extrapolative features. The model can provide reference for the further processing of hydrogenated residual oil. This kind of application can be easily developed in any other hydrotreatment process with available adequate historical data.     

燃料油选择性吸附脱硫研究进展

依据燃料油中硫化物与吸附剂表面活性点相互作用的类型,综述了π络合吸附、S—M配位吸附、酸性位吸附和多活性位吸附等选择性吸附脱硫方式的研究进展。认为通过结合多种选择性吸附原理,制备具有多种活性位的吸附剂,达到深度脱硫过程中高选择性和高吸附容量的目的,是燃料油深度脱硫吸附剂研究和开发的主要方向。     

Study on the Deep Oxidative Desulfurization of Oil

Desulfurization efficiencies were studied in this article using H₂O₂, H₂O₂-CH₃COOOH, Fe²⁺-H₂O₂-CH₃COOOH, and KMnO₄-CH₃COOOH as oxidants. The experimental result indicated that the desulfurization rate was higher than 88.2% when the volume content of oxidant to oil was 9% at 40°C for 30 min when KMnO₄-CH₃COOOH was used as the oxidant.     

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.     

离子液体在燃料油脱硫中的应用进展

离子液体用于燃料油脱硫是一种环境友好的新技术。综述了离子液体用于燃料油脱硫的几种方法,包括直接萃取法、氧化-萃取法、络合萃取法和烷基化法,介绍了离子液体的几种再生方法,并进行了对比。     

Kinetics of Oxidative Desulfurization of Sulfur Compounds in Diesel Fuel

Abstract

The oxidation of diesel fuel sample was carried out using tertiary butyl hydroperoxide oxidant in the presence of two commercially available Ni-Mo catalysts. The studies were carried out by changing reaction conditions such as treat ratios (oxidant/sulfur molar ratio), WHSV, temperature, etc., to achieve product diesel with sulfur content of <20 ppm. The results of the study on diesel were compared by carrying out similar experiments on model compound, namely, dibenzothiophene dissolved in sulfur-free liquid paraffin oil. GC-PFPD instrument was used to identify and group different sulfur compounds present in diesel and the kinetics of desulfurization was studied.     

电场作用下原油氧化脱硫研究

Oxidative desulfurization (ODS) of Azeri crude oil was studied under the electric field.By means of orthogonal experiments,the optimum conditions for desulfurization of crude oil were identified,while the effect of oxidative desulfurization under the electric field was compared with that of the single oxidative desulfurization method.The test results showed that the desulfurization reaction taking place under the electric field would be better than the traditional method.The desulfurization rate of crude oil could reach up to 77.06% at 115 ℃ at a distilled water amount of 10 m%,a desulfurizer dosage of 200 μg/g,and a demulsifier dosage of 50 μg/g.     

燃料油氧化脱硫的研究进展

综述了氧化法脱除燃料油中有机硫的研究进展,介绍了过氧化物、臭氧、氧气、生物氧化等脱硫方法。重点介绍了以过氧化氢水溶液为氧化剂,采用不同的催化剂、助剂、与超声波或光催化相结合的脱硫效果,比较了不同方法的优缺点。过氧化氢氧化脱硫方法的脱硫率可达90%以上,具有很好的发展前景。并从清洁生产的角度出发,对氧化脱硫的前景进行了展望。     

活性炭用于燃油吸附脱硫研究进展

从活性炭吸附剂的制备和修饰改性综述了这一领域的最新进展;对重要的研究结果进行了总结,并讨论了影响活性炭吸附性能的主要因素;对活性炭吸附剂的进一步开发提出了建议.     

活性炭吸附法在燃料油脱硫中的应用研究进展

活性炭由于具有较大的比表面积和丰富的孔道结构,成为广泛使用的催化剂载体和吸附剂,广泛应用于化学和石化工业中,其中应用于燃料油脱硫是近几年研究的热点。综述了活性炭吸附法在燃料油脱硫中的研究进展,介绍了失活活性炭的再生方法,指出了活性炭吸附法脱硫的未来研究方向,认为活性炭吸附法在燃料油脱硫中有着广泛的应用前景。     

离子液体萃取耦合过氧钒配合物催化氧化燃油脱硫

<正>燃油中的硫化物燃烧后产生的SOx严重威胁着人类的健康。目前,工业上的脱硫技术主要为加氢脱硫(HDS)技术,但对于二苯并噻吩(DBT)及其衍生物,HDS技术很难将它们除去。萃取耦合氧化脱硫法被认为是一种具有很好应用前景的深度脱     

离子液体用于燃料油深度脱硫的研究进展

首先介绍了加氢催化脱硫和其他脱硫技术的特点,综述了近年来国内外利用离子液体在萃取脱硫、萃取脱硫与氧化脱硫耦合、萃取脱硫与生物脱硫耦合等方面的研究。认为离子液体萃取脱硫具有操作简便、可循环使用、无需氢气、环境友好、能深度脱硫等特点,是一项具有广阔发展前景的技术。若要实现该技术的工业化应用,还需进一步加强离子液体在合成工艺、脱硫选择性及回收再生等方面的研究。     

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。     

车用燃料油络合脱硫技术的研究进展

车用燃料油络合脱硫相对于现有的其他脱硫技术,具有操作条件缓和、能有效脱除噻吩类硫化物、脱硫率和油品收率高等优势。综述了国内外车用燃料油络合脱硫技术的研究进展,包括π络合吸附脱硫、离子液体脱硫和络合萃取脱硫的作用原理、特点与研究现状,指出了目前各种络合脱硫技术存在的问题,最后提出了车用燃料油络合脱硫技术领域今后研究的方向。     

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.     

MoO3/Al2O3介孔催化剂在柴油氧化脱硫中的应用

 通过溶胶-凝胶法,以硝酸铝为铝源、蔗糖为模板剂、氨水为沉淀剂,制备了介孔 Al₂O₃,并以其为载体,等体积浸渍法制备了MoO₃/Al₂O₃介孔催化剂。采用 N₂吸附-脱附及X射线衍射对介孔 Al₂O₃和 MoO₃/Al₂O₃催化剂进行了表征。将 MoO₃/Al₂O₃催化剂用于柴油催化氧化脱硫,以 H₂O₂为氧化剂,探讨了 MoO₃负载量以及 H₂O₂用量对其催化柴油氧化脱硫的影响。结果表明,自制的 Al₂O₃载体为具有介孔结构的 γ-Al₂O₃,其比表面积、孔容、平均孔径分别为304.3 m²/g、 0.467 cm³/g 和6.14 nm。MoO₃负载量为20%(质量分数)、H₂O₂与柴油中硫的摩尔比为12、氧化温度为60℃时,柴油的氧化脱硫效果较佳,脱硫率为68.4%。