微生物脱硫过程中的产物分析

ｌ 引 言微生物脱除矿物燃料中的杂环有机硫分为微生物降解脱硫和微生物催化脱硫，前一途径中菌株通过断裂有机化合物的Ｃ－Ｃ键，降解模型化合物二苯并噻吩（ＤＢＴ）生成含硫水溶性产物从燃料中脱除，破坏了碳氢化合物的碳骨架，引起燃烧值的降低。后一途径中微生物或它们的酶催化氧化ＤＢＴ的杂环硫原子，生成二苯并噻吩砜（ＤＢＴＯ２）及终产物 ２－羟基联苯（ＨＢＰ）和硫酸盐（‘４Ｓ’途径），保留了整个碳氢化合物的骨架。本研究用ＤＢＴ作为唯一硫源筛选不同菌种，通过液相色谱（ＨＰＬＣ）和液相色谱／质叙质谱联用（ＬＣ／ＭＳ…     

活性炭及甲酸催化过氧化氢氧化噻吩脱硫研究

以噻吩代表汽油中的有机硫化合物，将其溶解于正辛烷配制成反应原料，考察了活性炭对噻吩的吸附脱硫情况，研究了质量分数为30％的过氧化氢水溶液为氧化剂，在活性炭和甲酸的催化作用下，反应原料中噻吩氧化脱硫。考察了活性炭的催化性能及反应条件对其催化性能的影响。实验结果表明，30％H2O2-HCOOH-AC（活性炭）三元体系产生的过氧甲酸和羟基自由基能将模型有机硫化合物氧化，噻吩的氧化脱硫率可达到85％以上；活性炭和甲酸的催化氧化性能明显优于单纯使用甲酸催化性能。甲酸浓度、活性炭加入量、过氧化氢初始浓度及温度对噻吩硫的氧化脱除均有影响。     

相转移催化应用于催化裂化汽油氧化脱硫的研究

随着人们环境保护意识的增强及原油硫含量的增大, 生产满足环境保护要求的清洁燃料是全球炼油工业的发展趋势, 燃料油脱硫显得越来越重要. 在众多的脱硫方法中, 选择性氧化脱硫技术以其工艺条件温和, 脱硫效果明显等特点, 受到了炼油行业的极大关注[1~3], 但脱硫率偏低(30％), 其关键是水相氧化剂与含硫化合物的有效混合. 本文将相转移催化应用于催化裂化(FCC)汽油的氧化脱硫中, 并对脱硫的工艺和机理进行了研究.     

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。     

TS-1/H2O2催化模拟汽油中噻吩的选择氧化研究

随着环境法规的日益严格,世界各国对于燃料中硫质量分数做了新的规定,要求车用燃料的硫控制在10×10-6~50×10-6,燃料电池硫的质量分数控制为(1×10-6。要达到这样高的脱硫深度,传统的脱硫方法面临着极大的挑战[1]。因此,其他非HDS脱硫方法受到研究者关注,其中氧化萃取深度脱硫     

载铜5A分子筛在汽油模拟体系中脱硫性能的研究

近年,美国环保局计划将汽油中硫的质量分数从当前的300×10-6降到2006年的30×10-6,欧盟也已经通过了新的汽油硫质量分数标准为30×10-6~50×10-6,德国甚至提出计划使用无硫汽油[1]。中国汽油硫的质量分数高达800×10-6以上,与世界汽油品质距离甚远。因此汽油中硫化物的脱除成为当务之急。目前,脱硫技术主要有催化裂化脱硫、催化加氢脱硫、水蒸气脱硫、生物催化脱硫、吸附精制脱硫、氧化脱硫等[2~5]。吸附精制法具有净化度高、能耗低、易于操作等优点,高效的脱硫吸附剂制备是过程开发的关键。负载金属离子的活性纤维是脱除汽油中硫醇的一种…     

溴化钠水溶液体系中煤的电化学脱硫

煤炭脱硫技术包括:物理洗选、化学脱硫、生物脱硫、超声波脱硫和微波脱硫等[1～3]。物理洗选法脱硫最经济,但只能脱无机硫。生物、化学法脱硫不仅能脱无机硫,也能脱有机硫,但生产成本昂贵,距工业应用尚有一定距离。20世纪80年代出现的电化学脱硫技术是一种既能克服物理、化学等法的缺点,又能达到较好脱硫效果的洁净、温和的脱硫方法[4,5]。本文对电化学氧化脱硫进行了研究,探讨了电化学氧化法脱除煤中硫的适宜体系和条件。1　实验部分1 1　原料和试剂　实验采用山西平朔煤(Pingsucoal)为原料,煤样粒径小于0 125mm。对煤样进行硫分析,其…     

光催化脱硫及组合技术研究进展

光催化技术因其选择性好、操作条件温和、收率高等特点而在环境保护领域显示出极大优势。综述了光催化技术在天然气、轻质油、煤等燃料能源脱硫领域的研究和应用,分析了光催化技术与超声波、微波、微生物等技术组合的反应机理和应用现状,并对光催化组合技术在燃料脱硫领域的研究进行了展望。     

多酸基共价有机骨架材料的合成与氧化脱硫性能研究在实验教学中的设计与探究

化石燃料燃烧带来的硫排放将导致酸雨的产生,因而实现燃油深度脱硫显得至关重要。多酸（POM）基共价有机骨架材料具有氧化还原性、可调的亲疏水性、可循环再生等特点,被认为是燃油氧化脱硫的一种优异催化材料。本实验在科研成果的基础上创新设计了一个综合实验。通过离子交换法将强氧化型多酸分子（NH₄）₅H₆PMo₄V₈O₄₀ （简写为PMo₄V₈）引入共价有机骨架（COF）,合成了一种多酸基共价有机骨架材料（POM@EB-COF,EB代表溴化乙啶）。利用X射线衍射、红外光谱、元素分析等表征手段对材料结构进行解析。以含有二苯并噻吩的十氢萘作为模型燃油,体系中通入氧气,在PMo₄V₈@EB-COF固体材料表面进行二苯并噻吩的氧化反应,考察其氧化脱硫性能。研究结果表明,以PMo₄V₈@EB-COF作为氧化脱硫催化剂,反应温度为100°C,反应时间...     

紫外光催化氧化在环境水质分析中的应用

紫外光催化氧化是近年来环境水质分析中采用的一种样品预处理新技术,目前在国内环境监测领域还应用得不多。本文结合笔者近期的工作,介绍了紫外光催化氧化的原理、特点、设备及其在环境水质分析中的应用,并简介了微波辅助紫外光催化氧化和超声波-紫外光氧化两种最新技术。     

近红外光谱法测定喷气燃料的总硫含量

采用ZX440型近红外多组分油料分析仪建立了喷气燃料总硫含量的校正模型,对校正模型的准确性进行了验证,实际分析结果表明,近红外光谱分析可以实现对喷气燃料总硫含量的快速、准确测定。     

Determination of polycyclic aromatic sulfur heterocycles in diesel particulate matter and diesel fuel by gas chromatography with atomic emission detection

The sulfur content of diesel fuel is of environmental concern because sulfur can facilitate the formation of diesel particulate matter (DPM) and sulfur dioxide (SO2) in the exhaust can poison catalytic converters. The US Environmental Protection Agency (EPA) has established more stringent regulations to reduce the sulfur content of diesel fuels in the near future. In this study, various types of organosulfur compounds in DPM extracts and the corresponding fuels have been determined by gas chromatography with atomic emission detection. The diesel fuels used have sulfur contents of 2284 and 433 ppm, respectively, and are labeled as high-sulfur and low-sulfur diesel fuels. The compounds identified are mainly polycyclic aromatic sulfur heterocycles (PASHs). In the fuels tested, trimethylbenzothiophenes (TMBTs), dibenzothiophenes (DBTs), and 4-methyldibenzothiophene (4-MDBT) were the most abundant sulfur compounds, while larger PASH compounds were more abundant in DPM extracts. The high-sulfur diesel fuel contained a larger proportion of PASHs with one or two rings (lighter PASHs). In DPM, the concentrations of total organic sulfur and individual PASHs are higher for the high-sulfur diesel fuel, and the relative percentage of one or two-ring PASHs is higher as well. The influence of engine load on the DPM composition was also examined. With increasing load, the PASH concentration in DPM decreased for lighter PASHs, increased for heavier PASHs, and had a bell-shaped distribution for PASHs in between.     

Desulfurization using the 1,2-dimethylimidazolium ionic liquid as an adsorbent

The aim of this study is to investigate the possible use of a 1,2-dimethylimidazolium ionic liquid,2,2-bis((1,2-dimethylimidazolium)methyl)propane-1,3-diol hexafluorophosphate(1),as an adsorbent to selectively remove aromatic heterocyclic sulfur compounds from model fuels.The result indicates that adsorbent 1 is insoluble in model fuels.The spent IL saturated sulfur compounds could be regenerated by a water dilution process.The influence of extraction time or temperature as well as the molar ratio of 1 to aromatic heterocyclic sulfur compound was also studied.     

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.     

Direct oxidation of sulfur-containing fuels in a solid oxide fuel cell

Solid-oxide fuel cells with Cu-ceria anodes are shown to provide stable power generation through the direct oxidation of hydrocarbon fuels having sulfur levels similar to that in gasoline and can be regenerated by steam after being poisoned with higher sulfur levels.     

Rapid determination of total sulfur in fuels using gas chromatography with atomic emission detection

The purpose of this study is to determine whether gas chromatography (GC)-atomic emission detection (AED) can be used in a low-resolution mode for rapid, accurate determinations of total sulfur in fuels at trace levels to complement other popular methods of total sulfur analysis. A method for the rapid determination of total sulfur in fuels (called "fast GC-AED") is developed. The method is tested on gasoline, jet fuel, kerosene, and diesel fuel with sulfur concentrations ranging from 125 mg/L down to 2.5 mg/L. Fast GC-AED shows better performance than traditional GC-AED for total sulfur determinations, especially for complex mixtures containing many different sulfur-containing compounds at trace levels. This method also shows that GC-AED can be used for both rapid determinations of total sulfur and traditional determinations of speciated sulfur without requiring equipment changes. Fast GC-AED is competitive with other popular methods for sulfur analysis. The 5-min program that is developed for fast GC-AED is comparable with the time scale of other methods, such as wavelength dispersive X-ray fluorescence and UV-fluorescence (2 to 5 min). Fast GC-AED also compares favorably with UV-fluorescence for trace sulfur determinations, demonstrating accuracy down to 2.5-mg/L sulfur.     

Capillary electrophoretic separation of polycyclic aromatic sulfur heterocycles

Capillary electrophoresis (CE) was used to separate polycyclic aromatic sulfur heterocycles (PASHs), a class of compounds that occurs in fossil fuels and refined products of petroleum. An electric charge was introduced into the compounds through methylation or phenylation of the sulfur atom. Separations of standard PASHs that are expected to be present in industrially desulfurized fuels showed that CE possessed a higher resolution than reversed phase liquid chromatography. The CE method can separate all the monomethylbenzothiophenes; this is not achieved in capillary gas chromatography. A linear relationship was found between migration time and the calculated volume of the compounds. The PASHs in deeply desulfurized diesel were separated after preconcentration, and the electropherogram was compared with the chromatograms from GC and HPLC. Finally, derivatized PASHs are often enantiomeric and the enantiomers can be separated if a suitable cyclodextrin is added to the running buffer.     

渣油超临界萃取馏分中硫化物的分离富集研究

采用选择性氧化与色谱结合的方法分离渣油中的硫醚硫化物和噻吩硫化物，该法是基于不同类型硫的选择性氧化、氧化组分与未氧化组分间极性的差异实现的。首先用高碘酸四丁铵在不氧化噻吩硫的情况下将硫醚硫选择性氧化为高极性的亚砜，经色谱柱分离富集后，利用红外色谱和硫元素分析仪，研究了馏分中硫化物的类型分布。结果表明,在俄罗斯渣油中噻吩硫和硫醚硫的质量分数随组分变重均呈增长趋势，噻吩硫相对质量分数(指硫醚硫+噻吩硫)随馏分变重呈下降趋势，相对质量分数在70%以上，噻吩硫是俄罗斯渣油中硫的主要存在形态。     

Electrochemical Determination of Organic Compounds in Automotive Fuels

This article critically reviews the electroanalytical methods devoted for the determination of organic compounds in automotive fuels that can range from contaminants to additives typically introduced into liquid biofuels and liquid fossil fuels. Contaminants such as aldehydes and ketones in bioethanol, free fatty acids and glycerol in biodiesel, and sulfur and nitrogen organic compounds in gasoline and diesel fuel, and additives such as colour markers and antioxidants added to fuels were determined by electroanalytical methods. Special focus is given to electrodes, electrochemical techniques, and sample preparation strategies. Future directions of research on electroanalysis of liquid fuels are presented.