选择性反应结合气相色谱进行汽油硫化物分析

通过3个分别针对硫醇、硫醚和含α-H噻吩的官能团选择性反应,结合连有脉冲火焰光度检测器的毛细管气相色谱对汽油中各类硫化物进行区分,实现了汽油中不同类型有机硫化物的快速分析.经过化学反应处理的汽油样品谱图逐步简化,方便了对不同类型硫化物的归属,也在一定程度上解决了叠合峰的辨别和归属问题.对汽油样品的实际分析研究表明,其中的有机硫化物主要以噻吩及其衍生物的形式存在,也含有一部分硫醚,硫醇最少.     

汽油馏分的硫化物形态分布研究

采用气相色谱和硫化学发光检测(GC-SCD)技术,经过对色谱条件的优化,建立了汽油馏分中硫化物形态分布的测定方法。用标准物质的保留时间辅以化学法脱除硫醇、硫醚的方法对107个硫化物进行了定性;标准硫化物保留时间重复测定结果的相对标准偏差(RSD)≤0.25%。用内标法对主要的硫化物和总硫含量进行了定量,方法的加标回收率为96%~115%;同一样品重复测定5次,含硫大于7 mg/kg的硫化物组分重复测定结果的RSD≤8.9%。所建立的方法可用于不同装置的汽油馏分的硫化物形态分布规律的研究。     

预富集分子吸收光谱法测定硫化物

研究了用分子吸收光谱法测定硫化物。以镁空心阴极灯（ＨＣＬ）为辐射光源，测定了２０２．６ｎｍ处Ｈ２Ｓ的分子吸收。采用蠕动泵预富集和气动雾化预富集两种富集方法，考察了两种不同进样方式时实验参数的影响，这两种富集方法测定了Ｓ＾２－的检出限均为０．０２μｇ／ｍＬ。并测定了钢样中硫的含量。     

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。     

气相色谱法测定催化裂化汽油中的硫化物

采用气相色谱-脉冲火焰光度检测器(PFPD),以甲基聚硅氧烷(PONA)石英毛细柱作为分析柱,建立了催化裂化汽油(FCC)中硫化物的分析方法.样品的RSD值均小于2%.     

催化裂化汽油中硫化物的气相色谱-原子发射光谱分析方法及应用

采用气相色谱-原子发射光谱联用(GC-AED)技术，建立了催化裂化汽油中各种硫化物类型分布的分析方法。考察了色谱条件对催化汽油中各种硫化物分离的影响，定性了催化汽油中的60余种硫化物，首次计算了程序升温条件下汽油馏分中各种硫化物的保留指数，为不同实验室的定性比较提供了依据。该方法可应用于不同来源汽油中各种硫化物类型分布的研究。     

催化裂化汽油中硫化物类型分布的气相色谱-硫化学发光检测的方法研究

采用气相色谱-硫化学发光检测器(GC-SCD),建立了催化裂化汽油(FCC汽油)中各种硫化物类型分布的分析方法。考察了色谱条件对催化裂化汽油中各种硫化物分离的影响,定性了某催化裂化汽油中的58个硫化物。采用该方法,硫化物中的硫在其质量浓度为0.5~800.0 mg/L时,其峰面积与质量浓度呈较好的线性关系,相关系数达0.999,其响应与硫化物的类型无关。FCC汽油中几种主要硫化物(噻吩、正丁硫醇、2-甲基噻吩、3-甲基噻吩、2,4-二甲基噻吩)的浓度测定值的相对标准偏差(RSD)均小于5.0%。当信噪     

焦化汽油中硫化物类型分布的气相色谱-硫化学发光检测方法

建立了焦化汽油中硫化物类型分布的气相色谱-硫化学发光检测分析方法。考察了色谱条件对焦化汽油中各种硫化物分离的影响,定性了某焦化汽油中的74个硫化物。以硫化氢、乙硫醇、正丙硫醇、噻吩、2-甲基噻吩、2-乙基噻吩、2-丙基噻吩、碳四噻吩(tR=40.28 min)、苯并噻吩、甲基苯并噻吩(tR=58.13 min)的保留时间为尺度,计算了焦化汽油中各种硫化物的保留指数,并可推广到其他类型的汽油馏分中各种硫化物保留指数的计算,为仅能提供硫化物信息的仪器提供了可靠的定性依据。焦化汽油中几种主要硫化物(异丙硫醇、正丙硫醇、正丁硫醇、2-甲基噻吩、3-甲基噻吩、2,4-二甲基噻吩、2,3,4-三甲基噻吩)含量测定值的相对标准偏差均小于5%。当信噪比为3时,测得硫的检测限为0.05 mg/L。研究发现:同其他类型的汽油相比,焦化汽油的硫含量较高且所含硫醇比例明显偏高,2-甲基噻吩和3-甲基噻吩的含量差别较大。该法可为加氢脱硫催化剂和工艺的研究提供数据。     

水介质对有机硫化物形成影响的模拟实验

利用高压釜反应装置在高温高压下开展了汽油-硫酸镁化学还原反应含水和无水体系的模拟实验,通过气相色谱仪、微库仑仪、毛细管气相色谱/脉冲火焰光度检测器、红外光谱仪及X射线衍射仪对气、油、固三相产物分别进行了分析并对动力学进行了解析,表明主要生成氧化镁、硫、焦炭、硫化氢、二氧化碳以及硫醇、硫醚和噻吩类等有机硫化物;随反应温度升高,反应体系中无机硫转化为有机硫的趋势增强,并主要生成热稳定性高的噻吩硫。 动力学解析表明,含水和无水条件硫酸镁转化反应的活化能分别为68.9和78.5 kJ/mol,证明水存在有利于无机硫向有机硫转化。     

催化裂化汽油中类型硫含量分布

利用催化裂化汽油中各类硫化物的系统分析方法,对催化裂化(FCC)汽油和重油催化裂化(RFCC)汽油中各类型硫进行了分析测定,碱洗后FCC汽油和RFCC汽油中类型硫的布规律为:硫醇硫和二硫化物硫的含量较少,硫醚硫含量中等,而噻吩类硫的含量最多,占总硫含量的60%以上.     

Fast analysis of oxygen and sulfur compounds in gasoline by GC-AED

This paper describes a method for determining both the total sulfur content and the concentration of oxygenated additives in gasoline by gas chromatography with atomic emission detection (GC-AED). The AED provides selective detection of oxygen and sulfur compounds. Because the response factors for sulfur and oxygen are largely independent of the type of compound, calibration and determination of total element content are simplified. The use of a 0.1 mm i.d. capillary column enables complete elution of the components of the gasoline in under 10 minutes.     

Additives for the reduction of sulfur in FCC gasoline

Sulfur reduction ability of alumina supported zinc, gallium and zinc-gallium additives for fluid catalytic cracking catalysts was evaluated in a micro-activity test unit (MAT). Gallium/alumina showed the highest sulfur reduction of 31%, but the cracking activity of the catalyst was decreased. Zinc-gallium/alumina reduced sulfur in 24 wt.% without decreasing the base catalyst activity.     

固体碱对油品中有机硫化物的脱除性能及分析

预碱洗（电精制）是轻质油品精制中的重要环节,通过氢氧化钠水溶液预碱洗可除去油品中的硫化氢、低分子硫醇等酸性物质,但大量含硫废碱液的排放给环保造成很大压力。以固体碱代替液体碱预碱洗,是减少甚至消除废碱液产生和排放的最有效措施。近十几年来,许多学者致力于固体碱对轻质油品中硫醇、硫化氢的脱除研究。     

New methodologies in trace analysis of volatile organic compounds

Two methods for sampling and concentration of volatile organic compounds are reported. In the first method, traps coated with a very thick film (ca. 100 μm) of cross-linked silicone stationary phase are employed. Such thick films can be prepared with a modified dynamic coating procedure, which is briefly described. The low phase ratio traps can be utilized for enrichment of volatiles from gaseous as well as aqueous matrices. The second technique is based on chromatographic evaporation of a solvent in a capillary tube, where the process is sustained by a repeated sample injection and a cyclic flow reversal. In this way, large solvent volumes can be handled by a small volume system. Under optimal conditions, when using a solvent barrier, quantitative recovery is possible even for compounds of comparatively high volatility. Another important application of the technique is extraction of trace components from gases such as headspace samples, polluted air, etc.     

Catalytic transformations of sulfur dioxide into organic sulfur compounds

The applications of catalytic transformations of SO₂ into sulfur-containing organic compounds, reported in the literature, are briefly reviewed. The authors' studies in this field of chemistry,viz., the hydrosulfination of alkenes, the synthesis of γ-oxo sulfonesvia hydrosulfination, and the synthesis of aromatic sulfinic acids from diazonium salts, are summarized. Current results on the synthesis of the new sulfinato complex [Pd(SO₂Ph)(Cl)dppp] and its hydrogenation to PhSO₂H are presented, and a mechanism for the catalytic synthesis of sulfinic acids is proposed. The structure of ([Pd(μ-Cl)(dppp)l₂ ²⁺(SO₄)^2?·4SO₂ salt is studied by X-ray diffraction analysis.     

催化裂化催化剂有机硫氮转化机理量子化学分析

国家环保法规的日益严格使得对催化裂化（FCC）再生烟气提出了更高的管控要求,再生烟气中污染物组成复杂且转化机制尚不清楚,迫切需要深入理解FCC待生催化剂中污染物的转化机理。对待生催化剂中有机硫和有机氮进行合理简化,选取合适的模型化合物,采用Gassian09软件,在B3LYP/def2-TZVP级别下,对模型化合物进行几何优化得到最稳定构型,并进行振动分析。利用Multiwfn多功能波函数分析仪对优化后模型化合物进行Laplacian键级分析（LBO）,通过LBO键级计算结果,得到自由基在再生过程中的详细转化机理。结果表明,含氮化合物中C—N键和含硫化合物中C—S键与C—C键相比均较弱,在催化剂再生过程中会优先发生断裂,生成不同的含氮（NH3、HCN）、含硫（H2S、COS）中间体,随后进一步与氧气反应生成相应的NOx、SOx。     

F改性Hβ对Mo-Ni/F-Hβ催化剂的FCC汽油硫转移反应催化性能的影响

通过添加不同含量的F对Hβ分子筛进行改性,制备Mo-Ni/F-Hβ催化剂,采用N₂吸附-脱附、NH₃-TPD、XRD、Py-FTIR和SEM等方法对该催化剂进行了表征,研究了F改性对该Mo-Ni/F-Hβ催化剂在FCC汽油中硫醇醚化和噻吩烷基化等硫转移反应中催化性能的影响。结果表明,以0.5%含量F修饰的β分子筛制备的催化剂对硫醚化反应和噻吩烷基化反应具有明显的促进作用,并能提高对二烯烃选择性加氢的选择性。F的引入可增强Hβ分子筛的中强酸量,降低强酸量,并提高了L/B酸中心比例,这些变化对催化性能改善起到重要作用。     

微波辅助脱除煤中有机硫的机理研究

为阐明微波场联合过氧乙酸(PAA)脱除煤中有机硫的机理,选取山西临汾(LF)、宁夏宁东(ND)、山西灵石(LS)和河南洛阳(LY)脱矿物质煤及三种含硫模型化合物苄硫醇(Benzyl mercaptan, BM)、苯并(b)噻吩(Benzo (b) thiophene, BT)和二苯基亚砜(Diphenyl sulfoxide, DS)作为研究对象。微波功率为100 W,并联合PAA,辐照1-5 min,通过X射线光电子能谱仪(X-ray photoelectron spectroscopy, XPS)分析固相中硫形态的变化;通过离子色谱仪(Ion chromatography, IC)分析脱硫后液相中SO_4~(2-)的浓度;通过气相色谱-质谱联用仪(Gas chromatography/mass spectrometry, GC/MS)分析萃取物中硫形态的变化。结果表明,有机硫化物硫的含量高,脱硫率大,LY和LS最大脱硫率分别高达55.06%和45.78%,ND和LF最大脱硫率分别为31.24%和28.21%,煤中的硫醇比噻吩和亚砜更易脱除,且脱硫过程中硫形态逐渐向高价态转化,含硫键在微波场中断裂,最终可被PAA氧化为SO_4~(2-)。     

Preparation of cerium-loaded Y-zeolites for removal of organic sulfur compounds from hydrodesulfurizated gasoline and diesel oil

Ce(IV)-loaded Y-zeolites (CeY) were prepared for selective removal of the trace amount of organic sulfur compounds from hydrodesulfurization (HDS)-treated diesel oil. The CeY samples can be obtained from NH4-Y-zeolite (NH4Y) using liquid-phase ion-exchange and solid-state ion-exchange methods. The ion-exchange reactions, structures, and selective adsorptions of organic sulfur compounds of the CeY samples were investigated using XRD, IR, XPS, TEM, and GC sulfur analyzer. The organic sulfur compound uptakes strongly depend on the amount and the valency of Ce in the zeolite structure. Ce(IV) shows much higher adsorptive ability than Ce(III). A CeY-S sample prepared by solid-state ion-exchange reaction of NH4Y and Ce(NO3)3 with Ce/NH4 mole ratio of 0.63 at 250 degrees C showed a maximum sulfur uptake from a model solution of HDS-treated gasoline containing thiophene [S = 5 ppm (ppm = mg/L)]. A desulfurization from a HDS-treated diesel oil containing organic sulfur compounds (S = 1.87 ppm) and H2S (S = 0.73 ppm) was investigated with a combination of the CeY-S and a CuO adsorbent for removal of H2S by a batch method. The sulfur content was reduced to below 0.01 ppm for the first time. This method provides a promising desulfurization process to prepare a clean fuel for fuel cells.