固相萃取法/全二维气相色谱-飞行时间质谱测定柴油及其加氢产品中的含硫化合物

开发了两种PdCl2-Al2O3固相萃取法,用于分离高硫柴油及加氢柴油中的硫化物,并建立了全二维气相色谱-飞行时间质谱（GC×GC-TOF MS）定性分析柴油中硫化物的方法。该方法不仅能够有效去除柴油中其他组分对硫化物的干扰,清晰展现硫化物分布,还能够准确提供不同工艺生产的柴油及加氢前后柴油中硫化物类型及碳数分布信息。结果表明：高硫柴油及加氢柴油中近90%硫化物集中在分离出的含硫组分中,而且该组分中芳烃含量极少;直馏柴油和催化裂化柴油中分别归类并定性出8类757种硫化物和4类179种硫化物,在相应加氢产品中分别鉴定出4类98种硫化物和3类81种硫化物;加氢柴油中90%以上硫化物为二苯并噻吩类化合物,侧链碳数集中在低碳数段。     

风城超稠原油减压渣油及其窄馏分焦化柴油的烃及非烃组成

采用GC,GC-MS,GC-SCD,GC-NCD方法对风城减压渣油及其萃取窄馏分焦化柴油的烃类及硫、氮化合物组成与分布进行分析。结果表明：原料性质直接影响产品烃类及硫、氮化合物的组成和分布;随馏分变重,硫、氮含量增加,烃类及硫、氮化合物种类越来越复杂;焦化柴油中饱和烃含量高于芳烃,环烷烃含量高于链烷烃;随馏分变重,对应的焦化柴油中的芳烃含量增加,饱和烃含量降低;柴油中的硫化物主要为苯并噻吩类和二苯并噻吩类,而氮化物主要为碱性的喹啉类和苯并喹啉类化合物及非碱性的吲哚类和咔唑类化合物。     

FCC柴油中硫、氮化合物的馏分和类型分布

分别对石油大学胜华炼油厂和齐鲁石化公司胜利炼油厂的FCC柴油进行了实沸点切割,采用硫、氮分析仪和GC—PFPD、GC—MS测定了各窄馏分的硫、氮含量,同时测定了齐鲁FCC柴油中各窄馏分的硫、氮化合物的类型分布。结果表明,FCC柴油中的硫、氮含量主要集中在240℃以上的馏分中。其氮化物的类型分布为：在小于200℃的馏分中主要是砒啶类和胺类氮化物,占总氮含量的3．2％;在200～300℃的馏分中主要是吲哚及其衍生物,占总氮含量的26．6％;300℃以上的馏分中主要以咔唑及其衍生物为主,占总氮含量的70．2％。其硫化物的类型分布为：在小于200℃的馏分中主要是硫醇和噻吩类硫化物,占总硫含量的3．2％;在200～300℃的馏分中主要是苯并噻吩类硫化物,占总硫含量的49．5％;300℃以上的馏分中主要以二苯并噻吩类硫化物为主,占总硫含量的47．3％。     

氧化还原法分离和鉴定柴油中的硫化物

用氧化还原法分离柴油中的硫化物。详细考察了氧化剂TBAPI和MCPBA的氧化条件及硅胶柱分离条件 ,并选择还原剂LiAlH4对各自的氧化物进行了还原。对分离所得硫化物的基本结构和类型进行了红外和质谱鉴定 ,结果表明 :柴油中硫醚硫主要是环戊硫醚类硫化物 ,噻吩硫主要是烷基噻吩、苯并噻吩、二苯并噻吩及其同系物     

减压馏分油（VGO）中噻吩类硫化物的沸点分布

将噻吩类硫化物母环已有的沸点数据与经验公式相结合,得到减压馏分油（VGO）中各类硫化物在不同碳数下的沸点数据,经验公式计算得到的沸点数据与已知的沸点数据基本吻合。采用傅里叶变换离子回旋共振质谱(FT ICR MS)测得了大庆、胜利、辽河、塔河4种原油的直馏VGO馏分中噻吩类硫化物的详细碳数和类型分布。结合FT ICR MS质谱数据和各类硫化物的沸点数据,可以得到硫化物的沸点分布。使用气相色谱 硫化学发光检测器(GC SCD)对FT ICR MS所得到的硫化物沸点分布结果进行校正,得到了与实际蒸馏温度相一致的硫化物沸点分布。由于FT ICR MS可以区分不同类型的硫化物,因此进一步给出了这4种VGO中噻吩类、苯并噻吩类、二苯并噻吩类以及苯并萘并噻吩类硫化物的沸点分布,可以为重油脱硫工艺的开发和改进提供依据。     

柴油加氢与微生物脱硫过程中硫化物类型变化规律研究

采用气相色谱-原子发射光谱联用(GC-AED)技术,研究了柴油馏分加氢前后各种硫化物的变化。在加氢脱硫过程中,二苯并噻吩类化合物中的硫最难脱除,催化剂的类型及各操作参数的选择应以柴油中二苯并噻吩类化合物含量来确定。研究了某加氢柴油进行微生物脱硫处理后各种硫化物的变化,并研究了硫含量不同的柴油馏分进行微生物脱硫处理后各种硫化物的分布。可选取在加氢脱硫过程中将柴油中的硫含量降到多大时,再进行生物脱硫技术处理的最佳方案。     

汽油馏分中硫含量及硫形态分布方法的研究

采用气相色谱和硫化学发光检测器（GC—SCD），建立了汽油馏分中各种硫化物类型分布的分析方法。考察了色谱条件对汽油馏分中各种硫化物分离的影响，定性了汽油馏分中的107个硫化物，测定出当硫化物中的硫含量在0．2—200ng／ul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，响应与硫化物的类型无关。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）浓度测定值重现性的相对标准偏差（RSD）均小于5．0％。当信噪比（S／N）为3时，测得2一甲基噻吩的检测限为0．1ng／ul。本研究所建立的方法可用于分析不同装置的汽油馏分的硫化物形态分布规律。     

中东VGO硫形态分布研究

考察了中东VGO及其9个馏分的各类型硫化物分布规律,对比了加氢前后VGO中硫形态的分布变化。采用四丁基高碘酸铵选择性氧化法、柱分离-X射线荧光光谱法,并利用傅里叶变换离子回旋共振质谱仪（FT-ICR MS）分析了中东VGO不同馏分段的硫醚硫、噻吩硫、二苯并噻吩及更复杂的苯并噻吩类硫化物的分布规律。结果表明：中东VGO中硫醚硫约占总硫的13.6%,其它均为噻吩类硫化物;随着馏分沸点升高,各馏分总硫含量、硫醚硫含量、噻吩硫含量均呈增加趋势,硫醚硫在各馏分总硫中的比例逐渐升高;在噻吩硫中,烷基噻吩类硫含量下降,且主要集中在蜡油低沸点馏分中,烷基苯并噻吩类硫含量逐渐下降,其它更复杂含硫化合物硫含量随着馏分沸点的升高而增加;加氢处理后总硫含量大幅度降低,硫醚硫、苯并噻吩类硫含量的比例降低,其它更复杂含硫化合物硫含量的比例增加;随着加氢深度增加,硫醚硫、烷基噻吩硫含量的比例逐渐降低,其它更复杂含硫化合物硫含量的比例逐渐增加。     

全二维气相色谱-飞行时间质谱鉴定柴油馏分中烯烃化合物

采用Ag-SiO2固相萃取法分离出二次加工柴油馏分中的烯烃,再采用全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)对烯烃组分进行详细表征。通过谱库检索、标准化合物保留时间、沸点与结构关系及全二维谱图特点对各类烯烃化合物进行鉴别,采用归一化法计算各种烯烃化合物的相对含量,并对比了焦化柴油馏分和催化裂化柴油馏分中烯烃类型及碳数分布。在焦化柴油馏分中共鉴定出1168个烯烃化合物,催化裂化柴油馏分中共鉴定出515个烯烃化合物。采用固相萃取法与全二维气相色谱-飞行时间质谱法相结合的技术分析柴油馏分中烯烃的组成,能有效降低柴油馏分中其他组分对烯烃定性定量的干扰,而且全二维谱图可以简单、清晰展现烯烃样品中各种烯烃化合物的分布,能直接分析目标单体化合物,快速准确得到类型和碳数分布信息。     

FCC柴油中硫、氮化合物的类型及分布

对三种烃类组成不同的FCC柴油中含硫、含氮化合物的类型及分布进行了研究。结果表明：三种FCC柴油中含硫化合物、含氮化合物的类型分布及含量不同,FCC柴油中含硫化合物的类型主要是苯并噻吩类硫化物和二苯并噻吩类硫化物。苯并噻吩及其衍生物主要分布在200℃～300℃馏分中,而二苯并噻吩及其衍生物主要存在于大于300℃的馏分中。含氮化合物主要为碱性氮化物和非碱性氮化物,其中碱性氮化物主要是苯胺及其衍生物,主要分布在小于230℃的馏分中;非碱性氮化物主要包括吲哚及其衍生物,主要分布在200℃-300℃的馏分中,咔唑及其衍生物主要分布在大于300℃的馏分中。     

全二维气相色谱-飞行时间质谱分析直馏柴油馏分中硫化物的分子组成

The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compoundsin straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with a sulfur chemiluminescencedetector to harvest a satisfactory result. The identification of the structure of sulfur compounds by comprehensivetwo-dimensional gas chromatography coupled with the time-of-flight mass spectrometry indicated that cyclo-sulfides,benzothiophenes, dibenzothiophenes, dihydro-benzothiophenes and tetrahydro-dibenzothiophenes were included in straightrundiesel obtained from the Arab medium crude （AM）. A total of 259 individual compounds were detected and their molecularstructures were identified. The analytical method was approved as an effective way to characterize the composition ofsulfur compounds, which reduced the interference of other compounds, facilitated the data presentation and provided moredetailed information about molecular composition of sulfur compounds.     

DATABASE FOR ORGANIC SULFUR COMPOUNDS USING GC-SCD METHOD. DETERMINATION OF SULFUR CONTAINING COMPOUNDS IN STRAIGHT RUN GAS OBLS (SRGO)

Sulfur standards were studied on a high resolution gas chromatograph (GC) “HP 5890 series II plus ”. Retention times were determined for each individual compound, A sample of straight run gas-oil (SRGO) was analyzed by coulomax method for total sulfur and by GC equipped with sulfur chemiluminescence detector (SCD) for individual sulfur identification, A database for about 165 sulfur compounds was established. Using relationship between total sulfur contents determined by coulomax method and sura of individual sulfur compounds determined by GC-SCD the quantity of different sulfur compounds in SRGO was determined     

液化气中硫化物形态分布的研究

采用气相色谱和硫化学发光检测器(GC-SCD)技术，通过对色谱条件进行优化，建立了液化气中硫化物形态分布的测定方法。用定性混合气体标样中20个标准物质的保留时间，并结合文献确定了液化气中14个硫化物物种。采用外标曲线法定量测定了分离的硫化物和总硫质量浓度。该方法的加标回收率在90．0％～120．3％；将脱臭后液化气中硫化物样品中硫的质量浓度重复测定5次，除了乙硫醇和二甲基二硫醚这两种不稳定硫化物的测定结果有较大的波动以外，其余组分中硫质量浓度测定结果的相对标准偏差小于等于7．2％，说明该方法对于液化气中硫化物组分测定的重复性能够满足要求，可用于实际测定液化气中硫化物的形态分布。     

硫化学发光检测器型气相色谱仪校准方法探讨

硫化学发光检测器(SCD)因其线性范围宽、高灵敏度等特性,在国内已经大量应用,但目前对硫化学发光检测器型气相色谱仪(GC-SCD)的检定/校准尚属空白。依据JJG 700-2016《气相色谱仪》,结合GC-SCD使用的实际情况,提出了评价GC-SCD计量性能的5项重要校准项目:柱箱温度稳定性、基线噪声、基线漂移、检测限以及定量重复性,并通过评价实例,验证了5项校准项目的可行性和适用性,以期为GC-SCD检定规程或校准规范的制定提供参考。     

Fluid Catalytic Cracking Feed Hydrotreatment and its Impact on Distribution of Sulfur and Nitrogen Compounds in FCC Diesel

The sulfides and nitrogen compounds in FCC diesel were analyzed by gas chromatography equipped with a pulsed flame photometric detector(GC-PFPD) and gas chromatography coupled with nitrogen chemiluminescence detection(GC-NCD). And the variation of sulfides and nitrogen compounds in FCC diesel produced from gas oil feed hydrotreated at different temperatures was investigated. The test results showed that two main types of sulfur compounds, i.e. benzothiophenes(BTs) and dibenzothiophenes(DBTs) were found in diesel. Nitrogen compounds are mainly composed of non-basic nitrogen compounds, and indoles and carbazoles account for about 98% of the total nitrogen contents. The sulfides in FCC diesel obtained from hydrotreated feed are mainly BTs with a small amount of 4-MDBT and 4,6-DMDBT. With the increase in FCC feed hydrotreating temperature, indoles content in FCC diesel increases, while carbazoles content decreases.     

SULFUR COMPOUND TYPE DISTRIBUTION IN NAPHTHA AND GAS OIL FRACTIONS OF KUWAITI CRUDE

ABSTRACT

The need for detailed information on the types of sulfur compounds present in various petroleum cuts has been well recognized by refiners and environmentalists worldwide. This need is growing in recent years in view of the current environmental regulations that limit the sulfur content of transportation fuels to very low levels. In the present work we have studied the distribution of different kinds of sulfur compounds present in light and middle distillates of Kuwait crude oil. A representative sample of Kuwait crude oil was fractionated into naphtha (15-160°C) and 10-15°C cuts in the gas oil boiling range (210-340°C) using an 80L capacity autodistillation unit “AUTODEST-800” according to ASTM 2892. The distribution of various types of sulfur compounds in each of these cuts was quantitatively estimated by capillary gas chromatography equipped with a sulfur chemiluminescence detector. Thiophene and its alkyl derivatives constituted about 60% of the total sulfur compounds in the naphtha fraction. The remaining 40% was composed of mercaptanes and alkyl sulfides. In the gas oil boiling range (210-340) two groups of sulfur compounds, namely, alkyl benzothiophenes and alkyl dibenzothiophenes were present. A major portion of the alkyl benzothiophenes was found in the fraction boiling in the narrow range 235-257°C. Among the alkyl dibenzothiophenes, the concentration of C, and C₂ DBTs decreased while that of higher alkyl DBTs (< C₃-DBTs) increased with increasing temperature. The C₁ and C₂ alkyl DBTs were highly concentrated in a fraction boiling between 280-325°C and these sulfur compounds were absent in the fraction boiling above 330°C. The industrial implications of these results are discussed.     

CHARACTERIZATION AND DEPOSIT FROMING TENDENCY OF POLAR COMPOUNDS IN CRACKED COMPONENTS OF GASOLINE IDENTIFICATION OF PHENOLS AND AROMATICSULFUR COMPOUNDS

Acidic compounds in cracked components of gasoline, isolated by extraction with aqueous solutions of sodium bicarbonate and sodium hydroxide, were identified as phenol and its mono- di - tri- and tetramethyl- derivatives. Aromatic sulfur compounds seDarated as the hexanc and benzene fractions by chromatography on an alumina column were identified as thiophenc, its mono- di - and trimethyl- derivatives, ethylihiophenc, benzolhiophene and methylbenzoihiophene. The identification of the phenolic compounds was achieved by IR, hydrogen-1 and carbon-13 NMR spectroscopy and GC - MS. Additionally, for complete identification of sulfur compounds a GC equipped with a selective sulfur detector was used. ISD Induction System Deposit (ISD) tests showed a decreased deposit-forming tendency for phenol compounds and no significant deposit formation for aromatic sulfur compounds or other fractions isolated.     

Comparison Study for the Distribution of Organo-Sulfur Containing Compounds of Two Kuwaiti Crude Oil Distillates

Abstract

This paper deals with the comparison, analysis, and characterization of two Kuwaiti crude oil samples received from different origins. (Burgan and Al-Wafra oil fields). Systematic analysis was conducted for API gravity, sulfur content, metal content, and viscosity. The representative samples of the two Kuwaiti crude oils were fractionated into naphtha (IBP–170^○C), kerosene (170–265^○C), medium gas oil (265–355^○C), and heavy gas oil (355–550^○C) using an 80 L capacity autodistillation unit “AUTODEST-800” according to ASTM D2892 and ASTM D5236. Particular attention was paid to study the distribution of various types of sulfur compounds in each of these wide cuts, which was qualitatively and quantitatively estimated by capillary gas chromatography equipped with a sulfur chemiluminescence detector, which is suitable for a wide range of sulfur systems. The fingerprinting obtained from the analysis of GC-SCD showed different families of organo-sulfur compounds in crudes, including mercaptans, sulfides, thiophenes, benzothiophenes, dibenzothiophene, benzonaphtothiophene, and their alkyl derivatives. From the analyses the behavior and distribution of the refractory and unrefractory sulfur compounds in the two Kuwaiti crude oils can now be easily followed.     

炼油厂恶臭污染源综合监测与评价 Ⅰ.污染源监测

 建立了炼油厂各类贮罐呼吸气、污水处理场逸散气及氧化脱硫醇尾气等恶臭无组织排放源的采样与分析成套技术,监测项目基本涵盖石油炼制特征恶臭污染物和油气组分。废气样品用双连球和聚四氟乙烯采样袋采集。废气中特征恶臭污染物的组成及烃类碳数分布用气相色谱/质谱法定性和半定量分析,挥发性硫化物含量用新型的硫化学发光检测/宽口径毛细管气相色谱法分析,总烃含量用总烃分析仪法分析,C1~C3烃类含量用火焰离子化检测/气相色谱法分析,苯系物和氨气含量参照国家标准方法分析。监测了多家炼油厂的典型恶臭污染源,较为全面和系统地获取了炼油厂恶臭污染源排放特征。