重油中金属卟啉化合物对催化裂化性能的影响

从仪长管输油渣油和委内瑞拉380重油中分离出镍、钒卟啉化合物,并按不同比例掺入原料油中,在固定流化床反应器上考察金属卟啉化合物含量对重油催化裂化产物分布和催化剂性能的影响。结果表明：随着原料油中镍、钒卟啉含量的增多,催化裂化产物中汽油和柴油的收率降低,气体和焦炭的产率增加,催化剂对轻油的选择性变差,镍卟啉化合物对反应选择性的影响更大;镍、钒卟啉可使催化剂的相对结晶度下降,且钒卟啉对结晶度的影响大于镍卟啉;镍卟啉对再生催化剂的活性影响不大,而钒卟啉对再生催化剂的活性有一定程度的影响。     

原油的厌氧细菌降解作用及其产物特征

原油的厌氧细菌降解作用和喜氧降解作用一样普遍存在,但它不仅仅只具破坏作用,而且能再生某些新的烃类,并能形成新的油气藏。我国许多所谓的浅层过渡气实际上是原油厌氧细菌降解作用的结果。原油厌氧细菌降解作用的产物具有甲烷碳同位素轻(δ¹³C₁<-5.5%)、乙烷碳同位素特别轻(δ¹³C₂<-4.0%)和单烃化合物碳同位素为负值异常(δ¹³C_n-3.7%～-5.3%)的特点。塔中地区的天然气至少混有20%以上的菌解甲烷。     

费-托合成反应产物的气相色谱法全分析

 采用2个温度不同的收集阱将费-托合成反应产物按照沸点的不同分为尾气、热气和蜡相3个部分,建立了各部分产物的气相色谱分析方法。在尾气和热气分析中,采用了 PLOT Q色谱柱分析干气,采用13X 分子筛填充柱分离并分析 He 及 H₂,采用100 m HP-1柱分析热气组分(C₁~C₃₀),实现了气体产物的分离。采用阀切换的多维色谱法,以达到节约分析时间的目的。在蜡相分析中,采用了中心切割技术（Dean-switch）对组分进行分离和分析,可得到 C₄₀以下的详细产物分布。各组分测定结果的相对标准偏差均小于3%。对 Co 基催化剂催化费-托合成反应的产物进行气相色谱全分析的结果表明,产物遵循经典的 ASF 分布,从 C₃开始即表现出良好的线性关系。实测得到的质量平衡为101.2%,碳、氢、氧平衡分别为98.7%、 98.9%和98.3%。     

仪长管输油中镍及钒卟啉化合物的分布及赋存状态

采用2次柱色谱分离工艺和紫外可见光分光光度法分析了仪长（江苏仪征-湖南岳阳长岭）管输渣油中镍、钒卟啉化合物的分布,还采用质谱法表征了镍、钒卟啉化合物的结构。结果表明,仪长管输油渣油中的金属镍、钒主要存在于胶质和沥青质中;钒卟啉化合物主要分布于硬胶质和沥青质中,镍卟啉化合物主要分布在软胶质和硬胶质中;含量最丰富的卟啉化合物是C34-ETIO型钒卟啉和C35-ETIO型镍卟啉;仪长管输油是较成熟的陆相沉积原油。     

塔里木盆地石炭系烃源岩热模拟实验研究——Ⅱ.生物标志化合物的组成和演化

塔里木盆地群井巴楚组(C₁b)的泥岩和灰岩中,生物标志化合物可分为两大类:(1)正构烷烃和类异戊二烯烷烃类;(2)三环和五环萜类.不同的模拟温度点具有不同的生物标志化合物组合,与以往的其他模拟实验结果类似.生物标志化合物的不同组合除源于生油岩中生物标志化合物不同外,还取决于无机元素的催化作用.不同的生油岩中,生物标志化合物先质存在差异,并且在不同的热演化阶段,释放出不同强度的生物标志化合物.因此,可以根据生物标志化合物的组成特征进行油源对比.塔里木盆地石炭系生油岩生成的原油,其三环萜烷C₂₁/C₂₃比值一般大于1,明显区别于寒武-奥陶系生油岩生成的原油(C₂₁/C₂₃<1),由此判断曲1井原油可能来自石炭系泥岩生油岩.     

东营凹陷沙四段原油裂解热模拟实验及产物特征

对东营凹陷沙四段成熟阶段早期的原油样品(按比例与水、砂混合封入金管) ,采用高压釜封闭连续加热方式进行热压模拟实验。根据11个模拟温度点的烃类裂解气产率分析,原油裂解气累计产率为650～660 m³/t_TOC。原油裂解气R_O值在1.3%～1.5%和2.3%～2.7%区间存在2个明显的高峰。原油裂解气中甲烷含量和C₂/C₃值随模拟温度升高而明显增加,但C₁/C₂值变化较小。原油裂解气碳同位素在成熟阶段相对较轻,高—过成熟阶段不断变重,并且甲烷与乙烷、乙烷与丙烷的碳同位素差值具有逐渐增加的趋势。     

石油中部分“非卟啉”钒化合物的形态分析

采用溶剂萃取法获得了委内瑞拉原油的“非卟啉”富集组分;以甲酸铵为促电离剂,利用傅里叶变换离子回旋共振质谱(FT-ICR MS)对“非卟啉”富集组分进行分析;将“非卟啉”富集组分进行逐级萃取分离,利用高温气相色谱 原子发射检测器联用仪(HT GC-AED)和FT-ICR MS分析分离后的各亚组分。结果表明：“非卟啉”富集组分中含有成系列的钒卟啉类化合物,说明部分“非卟啉”分子仍然含有卟啉结构单元;“非卟啉”结构与卟啉结构存在明显差异,但其中一部分“非卟啉”化合物是卟啉分子与其他化合物的结合体。     

酸解烃的Al

用Al₂O₃填充玻璃毛细柱来分离分析岩屑酸解烃,分析速度快,可反映C₁～C₉的烃类物质信息。丰富的烃类信息可弥补Porapak-Q分离分析技术的不足。     

塔里木盆地海相腐泥型天然气的成因判识

腐泥型天然气既可来自腐泥型于酪根的裂解,也可以来自腐泥型原油的裂解.于酪根直接裂解形成的天然气的C₂/C₃比值基本不变,原油裂解的天然气逐渐增大,乙烷和丙烷的碳同位素差（δ¹³C₂-δ¹³C₃）表现出与上述比值相反的变化规律.据此判断,塔北地区吉拉克、桑塔木、解放渠的天然气来自腐泥型于酪根的裂解,而轮南地区、英买力地区的天然气来自原油的裂解.     

连续重整装置生产优化

目的提高苯、甲苯和二甲苯(“三苯”)产品的质量与收率,降低装置能耗。 方法采用PETRO-SIM流程模拟软件,对不同初馏点下的重整原料进行模拟计算;采用Aspen软件模拟优化二甲苯塔操作参数。 结果重整进料较为理想的初馏点为82 ℃,通过调整预分馏塔操作条件,重整进料中C₅组分质量分数下降了0.79个百分点;通过实施重整反应温度分段控制,重整生成油中甲基环戊烷质量分数下降了0.16个百分点,C₆～C₈芳烃质量分数提高了2.28个百分点;利用近红外在线分析技术,实时分析数据并动态调整操作,二甲苯收率由22.27%提高至28.50%;Aspen软件模拟结果表明,二甲苯塔的3 ℃异构级二甲苯收率由23.20%提高至25.60%。 结论通过生产优化,实现了装置自控水平提升、“三苯”等芳烃产品收率和质量双提升及能耗降低的“三升一降”增效目标,对同类装置芳烃产品的生产具有借鉴意义。      

Distribution of vanadium and vanadyl porphyrins during fractionation of resins of heavy sulfurous oils

Features of the content and distribution of vanadium and vanadyl porphyrins in the fractions of resins, which were obtained by separation using column chromatography on silica, have been studied on heavy sulfurous oils of various deposits of the Volga–Ural basin (Russia). The difference of the vanadium and vanadyl porphyrin contents in the fractions of oils of various production complexes has been shown. Features of structural–group composition and predominant types of vanadyl porphyrins in the fractions of resins have been determined.     

Features of the composition of vanadyl porphyrins in the crude extract of asphaltenes of heavy oil with high vanadium content

Features of changes in the content of nickel and vanadium in heavy oils and their asphaltenes are shown for various fields of Volga-Ural region (Russia). The change in the content of vanadyl complexes in the studied asphaltenes upon increase of vanadium content was demonstrated. Several polar solvents (acetone, N,N-dimethylformamide, isopropanol, acetonitrile) are compared as extractants to obtain crude extracts of vanadyl porphyrins from asphaltenes with vanadium content of 0.44 wt%. The opportunity of more efficient extraction of vanadyl porphyrins from asphaltenes is shown by deposition extraction method, particularly when using N,N-dimethylformamide. Absorption spectra and matrix-assisted laser desorption/ionization (MALDI) mass spectra of the extracts obtained were analyzed. For extracts with maximum content of vanadyl porphyrins, the presence of mainly etio- and deoxophylloerythroetioporphyrins was revealed. It was shown that proportion of etio-type vanadyl porphyrins does not exceed 75% of the amount of porphyrins of DPEP-type. A maximum of molecular weight distribution in both types falls on a homologue of vanadyl porphyrin C₃₁ containing nine carbon atoms in the alkyl substituents.     

Conversion of nickel and vanadium porphyrins under catalytic cracking conditions

The conversion of nickel and vanadium porphyrins under conditions of catalytic cracking has been studied. Samples of porphyrins and their mechanical mixtures with a cracking catalyst have been investigated by thermogravimetric analysis. As a result of the cracking of porphyrins, a significant amount of gaseous and liquid products are formed. The liquid products are mainly represented by polycyclic compounds. A possible mechanism of nickel and vanadium porphyrin conversions has been suggested.     

基于密度泛函理论的量子化学方法研究仪长管输油渣油中金属卟啉化合物

基于密度泛函理论(DFT)的量子化学计算方法,对仪长管输油渣油中几种含量最丰富的金属卟啉化合物进行分子模拟,并对其空间分子结构进行结构优化及计算,得到键参数、偶极矩以及电子吸收光谱等信息。通过分子的键参数和偶极矩发现,镍卟啉化合物的极性小于钒卟啉化合物,DPEP型卟啉分子的极性略大于ETIO型卟啉分子。计算了4种典型金属卟啉分子紫外吸收光谱的Soret吸收带和Q吸收带特征吸收峰,并得到4种卟啉化合物的稳定性由强到弱的顺序为ETIO型镍卟啉C₃₅-(ETIO-Ni)、DPEP型镍卟啉C₃₅-(DPEP-Ni)、ETIO型钒卟啉C₃₄-(ETIO-VO)、DPEP型钒卟啉C₃₁-(DPEP-VO)。     

METALLOPETROPORPHYRINS AS PROCESS INDICATORS: SEPARATION OF PETROPORPHYRINS IN GREEN RIVER OIL SHALE PYROLYSIS PRODUCTS

Product oils from the LLNL Hot-Recycled-Solids (HRS) retorting process were separated to isolate and concentrate the metallopetropor-phyrins. A modified column chromatography procedure developed previously for heavy crude oils and tar sand bitumens was used. The fractions were then examined by UV-vis spectroscopy to determine categories of porphyrins and other related metal-containing species.

No porphyrins were found in the hexane fraction (least polar fraction); Ni porphyrins were found in the methylene chloride fraction (moderate polar fraction); and a free-base porphyrin-like species was found in the methanol fraction (the most polar fraction) of some of the oils. The CH₂Cl₂ fractions were further examined to quantify the amount of porphyrins detected. In the whole oil samples examined, ∼ 40 wt % of the Ni was found as Ni petroporphyrins. The vacuum residua of two product oils had ∼ 20 wt % of the Ni bound as Ni por-phyrins indicating that the vacuum distillation process destroys porphyrins.     

Sulfuric Acid Assisted Extraction and Fractionation of Porphyrins From Heavy Petroleum Residuals With a High Content of Vanadium and Nickel

Primary porphyrin extracts were obtained from carbon tetrarchloride solutions of different heavy oil residuals with assistance of sulfuric acid. According to data of chromatographic separation of extracts porphyrinic fractions appear in amount of 13.0–24.2%. Based on UV/visible absorption spectroscopy the presence of porphyrins of etio and phyllo types mostly with rhodo and deoxophylloerythroetioporphyrins in lower amount was established. The content of porphyrins in obtained fractions was determined at the level of 15.3–44.8% of the total weight. It was shown that a higher concentration of porphyrins in sulfuric acid extracts occurs for the case of the high vanadium and nickel content and low amounts relation of asphaltenes to resins.     

我国一些原油中镍卟啉化合物初步研究

中国大多数原油中金属含量都是镍高钒低.用液体色谱,紫外-可见光吸收光谱、质谱和原子吸收光谱分析鉴定,可以把原油中的镍有机化合物分成三族,即弱极性的镍化合物、卟啉镍化合物和强极性镍化合物.木文对高升羊三木、胜利等五个原油作了测定,并用质谱鉴定出高升油中脱氧叶红初卟啉、初卟啉、二环脱氧叶红初卟啉、玫红型初卟啉等系列化合物.     

Mass Spectrometry of Metalloporphyrins in Egyptian Oil Shales from Red Sea Area

Abstract

Metalloporphyrins, extracted from asphaltene and maltene fractions of some Egyptian oil shales (Abu-Shegeili, El-Beida, El-Nakheil, and Abu-Tundub in the Red Sea area) by means of adsorption column chromatography and TLC, were subjected to mass spectrometry in order to elucidate the structure of different types of VO, Ni, or Fe porphyrins. Metalloporphyrins were not detected in maltene or asphaltene fractions of Abu-Shegeili oil shale. The mass spectra appeared as a truncated series of mass numbers, which is characteristic of geo-porphyrins in sediments or oil shales. The data indicated that the five types of porphyrins (Etio, DPEP, BEtio, BDPEP, and THBD) with carbon numbers ranging from C₂₀ to C₅₀ were present in considerable detection levels. Based on mass spectrometric data, the major components of metalloporphyrins (VO, Ni, or Fe) were identified and their chemical structures were suggested. The occurrence and distribution of VO, Ni, and Fe porphyrins were interpreted from a geochemical point of view, particularly maturation levels and oil-gas potentials of kerogens.