色谱-质谱联用对催化裂化轻柴油中双环芳烃、多环芳烃和极性馏份的分析

用 GC、GC-MS 法分析催化裂化轻柴油中双环芳烃(Fr.2)、多环芳烃馏份(Fr.3)的组成和含量,并借助 DI-MS 和 Fr-IR 法研究极性物馏份(Fr.4)中的主要化合物类型的归属。分析结果表明:催化裂化轻柴油中约90%为芳烃物质,其中3%为单环芳烃,31%为双芳烃,51%为多环芳烃,3%为极性的多环稠合芳烃。双环芳烃主要由 C_1—C_6烷基萘、C_1—C_4烷基联苯组成。多环芳烃馏份主要由 C_1—C_4烷基蒽菲及烷基笏组成。极性物馏份则主要由烷基咔唑、烷基二苯并呋喃系列及酚类和芳酮构成。     

高压液相色谱法分离减压柴油的族组成

本文提出以硅胶、氧化铝为吸附剂,正已烷和三氯甲烷为载液,梯度淋洗分离重油族组成的高速液相色谱方法。确定了分离条件,并求出山东和任丘300—500℃馏份油的饱和烃、单环芳烃和双环芳烃的校正因子。分析速度较快,重复性较好。     

由裂解制乙烯副产轻焦油中用二甲亚砜萃取芳烃的中间试验

前言石油馏份裂解制乙烯副产轻焦油中(C_6—C_8馏份)含有丰富的苯、甲苯、二甲苯等芳烃,一般石油馏份裂解装置的裂解轻焦油产率为裂解原料的10—15%,芳烃产率为裂解原料的5—8%。乙烯是石油化工的基本原料。随着石油化工的发展,乙烯的产量将增加,装置将大型化,因此裂解焦油的综合利用,轻焦油中芳烃     

C_4烃类在ZSM-5分子筛催化剂上的芳构化(Ⅰ)

本文为综合利用C_4烃类以扩大芳烃来源探索了新的途径。研究了HZSM-5分子筛催化剂的制备条件对C_4烃类芳构化催化活性的影响,以及反应条件对反应产物分布的效应,并对C_4烃类在HZSM-5分子筛催化剂上的芳构化过程作了初步探讨。试验结果表明:分离掉丁二烯后的混合C_4烃类可用作制备芳烃的原料,在反应温度530—550℃,重量空速1.7小时~(-1)左右,以及常压不临氢条件下连续反应8小时,总芳烃平均收率为49—55％(重),C_6—C_8芳烃平均收率为46—53％(重)。液态烃中芳烃含量达96—98％(重),尾气主要由H_2,CH_4,C_2H_6,C_2H_4,C_3H_8所组成。     

裂解汽油低温加氢Pd-Cr/Al_2O_3双壳层催化剂的研制

前言 在高温裂解生产各种烯烃的同时,总是副产一些C_5以上的液态烃。其中C_5～C_9馏份中,含有不同程度不饱和烃,如双烯烃及烷烯基芳烃,这些化合物容易聚合生成胶质,使裂解汽油不能直接应用。为了抽提其中芳烃,发展了裂解汽油两段加氢过程。低温加氢主要是除掉双烯烃及烷烯基芳烃,加氢产品可直接作为车用汽油或再进行二段加氢。用于低温加氢过程的催化剂有Pd/Al_3O_3、Ni/Al_2O_3、Fd-Cr/Al_2O_3、     

高压液体色谱测定焦油族组成及毛细管色谱测定焦油主要组分

前言为了便于开展对乙烯装置裂解产物焦油综合利用的研究工作,我们用高压液体色谱法测定其族组成,并用毛细管色谱法对其主要组分进行了分析,取得了裂解焦油组成的基础性数据。用5μ硅胶[φ4(内径)×250mm]及无定型硅胶—氨基(φ4(内径)×250mm]作高压液体色谱柱,已烷作流动相,给出了饱和烃、单环芳烃、双环芳烃及胶质的族组成定量分析结果,相对误差3％。与柱色谱     

变压器油的化学组成及油品性质与台架评定结果相关性研究

本文考察了变压器油的化学组成(饱和烃、单环芳烃、双环芳烃、多环芳烃、胶质和总芳烃)与油品性质(如比色散、氧化安定性、介质损耗因数和界面张力)的相关性,以及变压器油性质(如密度、酸值、抗氧剂量、界面张力、氧化安定性)与台架评定结果之间的相关性,并藉助于统计的方法建立了有关的数学模型。结果表明,变压器油的比色散与双环、多环芳烃及胶质有关;氧化安定性与饱和烃有关;介质损耗因数与单环芳烃有关;界面张力与胶质有关。     

饱和烃和芳烃的高压液相色谱法精细分离

该文介绍了用高压液相色谱对族组分中的饱和烃、单环芳烃、二环芳烃及三环以上芳烃的精细分离方法。用二级活度的氧化铝除去非烃和沥青质,用正己烷和二氯甲烷依次淋洗出(硅胶)色谱柱上的饱和烃、单环芳烃、二环芳烃及三环以上芳烃。该方法同国外方法相比具有快速、节省试剂的优点,色质谱图显示各组分有较高的分离度。      

从裂解制乙烯副产轻焦油中用二甲亚砜萃取芳烃

前言苯、甲苯、二甲苯等芳烃是发展石油化工的基本原料。随着我国石油化工的发展,乙烯产量的增长,开展由石油馏份裂解制乙烯副产轻焦油中回收芳烃的研究,是一项具有现实意义的工作。通常,从复杂的C_(?)—C_8馏份中分离芳烃,是采用一种对芳烃溶解性、选择性好的极性溶剂,进行液—液萃取得以实现,已     

催化裂化柴油中多环芳烃选择性加氢饱和工艺研究

采用Ni-Mo-W/γ-Al2O3加氢精制催化剂,在中型加氢试验装置上考察了加氢工艺参数对催化裂化柴油中多环芳烃选择性加氢饱和反应规律的影响。结果表明,不同工艺条件对多环芳烃转化为单环芳烃、单环芳烃进一步加氢生成饱和烃的各步反应影响效果不同,在反应温度为330℃、氢分压为6.4 MPa、体积空速为1.2h-1、氢油体积比为800的条件下,多环芳烃饱和率可达80.1%,总芳烃饱和率16.4%,单环芳烃产率42.6%,可实现高的多环芳烃饱和率下单环芳烃的产率最大化。     

Removing of resins from crude oils

Crude oil contains four chemical group classes, namely saturates, aromatics, resins, and asphaltenes (SARA fractions). Resins fraction of crude oil comprises polar molecules often containing heteroatoms such as nitrogen, oxygen, or sulfur. Resin is a heavier fraction than aromatics and saturates. Resins are composed of fused aromatic rings with branched paraffin and polar compounds. The resin fraction is soluble in light alkanes such as pentane and heptane, but insoluble in liquid propane. The resins are adsorbed on a solid such as alumina, clay, or silica, and subsequently recovered by use of a more polar solvent and the oils (aromatics and saturates) remain in solution. The resins often coprecipitate with the asphaltenes in controlled propane deasphalting procedures. The composition of the resins can vary considerably and is dependent on the kind of precipitating liquid and on the temperature of the liquid system. The resins are adsorbed on a solid such as alumina, clay, or silica, and subsequently recovered by use of a more polar solvent and the oils (aromatics and saturates) remain in solution.     

Linkage of Aromatic Ring Structures in Saturates,Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

The linkage of aromatic ring structures in vacuum residues was important for the refining process. The Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with collision-induced dissociation(CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions(SARA), and each fraction was characterized by CID technology. According to the experimental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.     

Group Type Analysis of Asphalt by Column Liquid Chromatography

An improved analysis method for characterization of asphalt was established. The method is based on column chromatography technique. The asphalts were separated into four groups: saturates, aromatics, resins, and asphaltenes, quantitatively. About 0.1 g of sample was required in each analysis. About 20 mL of n-heptanes was used to separate out saturates first. Then about 35 mL of n-heptanes/dichloromethane (1/2.5, v/v) mixture was used to separate out aromatics. About 30 mL of dichloromethane/tetrahydrofuran (1/3, v/v) mixture was used to separate out resin. The quality of the separation was confirmed by infrared spectra (IR) and ¹H NMR analysis. The model compounds, tetracosan for saturates, dibenz(ah)anthracen for aromatics, and acetanilide for resins were used for verification. The IR and ¹H NMR analysis of the prepared fractions from the column liquid chromatography were in good agreement that of pure reagents.     

Group Type Analysis of Asphalt by Column Liquid Chromatography

An improved analysis method for characterization of asphalt was established. The method is based on column chromatography technique. The asphalts were separated into four groups: saturates, aromatics, resins, and asphaltenes, quantitatively. About 0.1 g of sample was required in each analysis. About 20 mL of n-heptanes was used to separate out saturates first. Then about 35 mL of n-heptanes/dichloromethane (1/2.5, v/v) mixture was used to separate out aromatics. About 30 mL of dichloromethane/tetrahydrofuran (1/3, v/v) mixture was used to separate out resin. The quality of the separation was confirmed by infrared spectra (IR) and ¹H NMR analysis. The model compounds, tetracosan for saturates, dibenz(ah)anthracen for aromatics, and acetanilide for resins were used for verification. The IR and ¹H NMR analysis of the prepared fractions from the column liquid chromatography were in good agreement that of pure reagents.     

减压渣油及其四组分在接触剂上的裂化反应规律

以减压渣油为原料,采用热解色谱和热重-质谱,考察了减压渣油及其四组分(饱和分、芳香分、胶质和沥青质)在惰性接触剂LHBK和酸性接触剂C上的裂化反应。结果表明：四组分在有孔无酸剂LHBK上裂化程度由强到弱的顺序为胶质、沥青质、芳香分、饱和分,在有孔有酸剂C上裂化程度由强到弱的顺序为饱和分、芳香分、胶质≈沥青质。四组分在2种接触剂上缩合反应生成的积炭均比减压渣油在接触剂上缩合反应生成的积炭具有更低的H/C摩尔比;接触剂的酸性明显促进了四组分的裂化,C_20-馏分产率明显增加;且增加了减压渣油裂化反应的生焦率,增加部分主要来自芳香分和胶质的催化裂化生焦。说明接触剂的酸性能促进饱和分C—C键、芳香分侧链C—C键断裂以及胶质和沥青质中键能较低的键断裂。     

碰撞诱导解离技术研究减压渣油四组分中芳环结构的连接方式

The linkage of aromatic ring structures in vacuum residues was important for the refining process. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with collision-induced dissociation (CID) was a powerful method to characterize the molecular structures. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions (SARA), and each fraction was characterized by CID technology. According to the experiment results, the aromatic rings in saturates and aromatics fractions were mainly island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.     

可逆性吸脱附材料用于气相色谱法测定喷气燃料中芳烃含量

为提高喷气燃料中芳烃含量测定的准确性、精密度和分析速率,解决荧光指示剂吸附法面临的荧光指示剂供应问题,提出采用气相色谱(GC)快速测定喷气燃料中芳烃总量的方法。通过制备芳烃可逆性吸脱附材料,并将其用于气相色谱柱固定相,实现了喷气燃料中饱和烃与芳烃的气相色谱分离。该气相色谱法的芳烃测定结果与芳烃配制结果相关系数达到0.9999,加标回收率100%±5%,定量结果准确,重复性标准偏差为0.21%,重复性良好。为确定该气相色谱方法的准确性和可靠性,测定了加氢裂化和直馏两种工艺来源的喷气燃料样品,讨论了喷气燃料饱和烃和芳烃相对密度对喷气燃料中芳烃质量分数和体积分数换算结果的影响,并与GB/T 11132—2008荧光指示剂吸附法(FIA法)和NB/SH/T 0939—2016示差折光检测器高效液相色谱法(HPLC)的测定结果进行了比较,分析结果具有较好的一致性。此外,采用核磁共振(NMR)分析方法对加氢裂化和直馏两种工艺来源的喷气燃料样品中可能存在的烯烃进行了鉴别,结果表明,加氢裂化和直馏两种工艺来源的喷气燃料样品中烯烃最大质量分数不超过1%,不会对芳烃含量的测定产生较大的影响。     

重馏分油烃类碳数分布的气相色谱-场电离飞行时间质谱测定

 采用固相萃取技术将重馏分油分离为饱和烃和芳烃组分,并通过气相色谱-场电离飞行时间质谱联用仪（GC-FI TOF MS）分别进行分析。根据分子离子峰的精确相对分子质量可实现化合物的定性分析,根据分子离子峰强度进行定量分析,从而得到重馏分油饱和烃和芳烃的碳数分布信息。与现有的ASTM D 2786和D 3239烃类组成分析方法相比,本方法可提供更加详细的重馏分油烃类组成信息。     

减压渣油微观相结构特性的分子模拟

选用4种模型化合物代表减压渣油四组分(SARA),采用分子动力学模拟了减压渣油微观相结构,发现不同结构分子间相互作用的差异是减压渣油微观非均匀分布的本质原因,并通过电子分布特性分析了不同结构分子间相互作用差异的本质原因。沥青质分子间强相互作用使得沥青质分子自缔合形成聚集体;而多个胶质分子与沥青质分子的强相互作用封闭了沥青质分子自身进一步发生相互作用的活性位;同时,与胶质分子、饱和烃分子具有强相互作用的芳香烃分子将沥青质 胶质分子形成的聚集体分散在由芳香烃 饱和烃分子构成的连续相内,其中芳香烃分子更靠近胶质分子。因此,增加沥青质、饱和烃分子的含量会促进沥青质聚集,降低减压渣油稳定性;增加胶质、芳香烃分子的含量会阻碍沥青质聚集,提高减压渣油稳定性。     

塔河常压渣油及其亚组分的非等温热转化反应性能研究

采用热重分析法对塔河常压渣油(THAR)及其亚组分的热转化反应性能进行了考察;在Sharp微分法基础上,采用分段动力学拟合,获得了渣油及其亚组分热转化速率峰值、速率峰值处的反应温度、转化率和剧烈裂解温度区间等动力学基本数据以及各亚组分的生焦性能。结果表明：各亚组分生焦率由低到高依次为饱和分＜芳香分＜胶质＜沥青质,沥青质是焦炭的主要来源;四组分按组成加权后的生焦率较THAR生焦率高4.21百分点,表明THAR亚组分混合物共焦化有利于抑制各亚组分的生焦;饱和分可促进其它亚组分生焦,而芳香分和胶质可抑制沥青质生焦,且芳香分的抑焦性能更强;在热转化反应过程中,裂化反应活性由高到低的顺序为饱和分＞芳香分＞胶质＞沥青质,各亚组分在低温段和高温段的活化能由低到高的顺序均为饱和分＜芳香分＜胶质＜沥青质,表明胶质和沥青质大分子的热转化过程需要提供较多的能量。