沥青质含量对渣油加氢转化残渣油收率和性质的影响

以塔河常渣脱沥青油掺兑不同含量的沥青质为原料,于高压釜反应器内进行加氢转化反应实验,考察沥青质含量对渣油加氢转化残渣油收率和性质的影响。研究结果表明,随原料中沥青质含量的增加,加氢残渣油的收率逐渐降低,加氢残渣油中的沥青质和焦炭产量之和与原料中沥青质含量的比值逐渐减小,在实验选定的条件下,高沥青质含量时沥青质更倾向于发生氢解反应生成小分子组分。与原料相比,反应后所得>350 ℃残渣油的平均相对分子质量、H/C摩尔比减小,密度增大,硫含量降低,氮含量增加,饱和分和沥青质含量增加,芳香分及胶质含量降低。随渣油中沥青质含量的增加,硫、氮脱除率先增加后降低。     

渣油在加氢处理中的性质和结构变化规律研究

利用渣油加氢处理中试装置,获得了经过脱金属催化剂、脱硫催化剂和脱氮催化剂的系列渣油加氢处理产物,分析了各产物的性质。随加氢深度增加,硫、氮、残炭、镍和钒在渣油加氢产物中的的质量分数降低,总脱除率分别为84.9%、51.3%、62.8%、84.8%和94.0%。各产物的组分分布发生变化,饱和分组分增加,芳香分、胶质、沥青质组分减少,重组分胶质和沥青质组分的转化分别达到了57.5%和73.3%。以核磁共振为基础计算了渣油加氢产物组分的平均结构参数。结果表明,芳香分和胶质组分单元结构芳香环数和环烷环数减少,芳香碳分率fA、环烷碳分率fN和烷基碳分率fP变化不明显;而沥青质分子fA增加,fN和fP降低。从平均结构参数还可以看出,不同加氢产物同一种组分在结构上有其共性,但不同组分有明显区别。     

反应温度对加氢残渣油四组分含量和结构的影响

以沙轻减渣为原料,在高压釜内研究了不同反应温度下加氢反应前后渣油的四组分含量及其结构组成变化。结果表明,加氢残渣油中的饱和分含量明显增加,而芳香分和胶质的含量均降低,四组分含量随反应温度的升高均呈现规律性变化。加氢后四组分的H/C摩尔比和平均相对分子质量均降低,芳碳分率增加。随反应温度升高,四组分的H/C摩尔比和平均相对分子质量降低,烷基碳分率降低;芳香分、胶质和沥青质的芳碳分率增加;胶质和沥青质的总环数和芳环数均降低。渣油加氢过程中四组分都发生了明显的氢解和脱烷基反应。加氢反应中,胶质和沥青质结构单元间的各种桥键可发生明显地断裂,导致其结构单元数减少,且结构单元数随反应温度的升高而减少。     

钌离子催化氧化法研究大港减压渣油组分化学结构

利用钌离子催化氧化方法对大港减压渣油芳香分、胶质和庚烷沥青质进行了选择性降解，通过GC、GC-MS等分析手段对降解反应产物中一元正构脂肪酸、α,ω-二元正构脂肪酸和苯二～六元羧酸的含量和分布分别进行了定量分析。结果表明，芳香分、胶质和庚烷沥青质中的芳香结构上都存在大量烷基取代基和桥接不同芳碳的聚亚甲基桥。烷基取代基碳数最大约为33，聚亚甲基桥最大碳数约为24，而且这两种结构单元的含量均随碳数的增加而减少，并呈现出了偶碳优势。庚烷沥青质C12以下侧链相对较多而C16＋较少，与芳香分的分布相反；正构烷基侧链的浓度按庚烷沥青质、胶质和芳香分的顺序递减。降解产物中都检测到了苯二甲酸到苯六甲酸等一系列的苯多酸，表明三个组分中都存在稠环芳香结构。庚烷沥青质中缩合程度较高的迫位缩合结构含量最高，芳香分渺位缩合结构最多，胶质介于两者之间。     

供氢剂与分散型催化剂协同作用的研究

以辽河渣油为原料,四氢萘为供氢剂,二烷基二硫代氨基甲酸钼为油溶性催化剂在高压釜中进行裂化反应,比较了临氢裂化,临氢供氢裂化,催化加氢裂化以及供氢剂与分散型催化剂共同存在下的加氢裂化,在同样生焦量的情况下,渣油裂化转化率的顺序为：临氢催化供氢过程＞临氢催化过程＞临氢供氢过程＞临氢过程,同时发现供氢剂与分散型催化剂在渣油加氢裂化过程中具有协同作用,与单独使用分散型催化剂的改质反应相比,供氢剂的协同作用不但可以在低转化率下延迟生焦诱导期,提高渣油生焦前的最大转化率,而且在高转化率下对渣油的缩合反应有更大的抑制作用。由420－440℃四集总表观动力学模型计算出的动力学速率常数和活化能表明,供氢剂与分散型催化剂产生的协同作用提高了沥青质和焦生成的活化能,极大地抑制了沥青质和焦生成 速率,而对可溶质生成馏分油的裂化反应的抑制作用很小。     

废轮胎热解油重质馏分制备的道路沥青老化性能研究

针对废轮胎热解油重质馏分(＞350℃)组成上具有蜡含量低,芳香分、胶质和沥青质含量高的特点,研究了废轮胎热解油重质馏分采用蒸馏法生产道路沥青的可行性。结果表明,废轮胎热解油中＞420℃、＞430℃、＞440℃三种渣油的性质可以满足不同牌号道路石油沥青老化实验前的技术指标,特别是延展性能优异,但是抗老化性能较差。渣油老化前后的族组成、官能团、氢分布及分子量分布变化表明,渣油在老化过程中存在氧化反应以及脱氢缩合反应,使渣油的化学组成发生变化,即芳香分、胶质含量减少,沥青质含量明显增加,使得沥青胶体体系中分散相明显增多而分散介质相对减少,造成热解油的渣油抗老化性能较差。     

超声波处理对渣油加氢过程的影响

对四种减压渣油的超声波处理前后渣油加氢反应产物分布研究表明,超声波处理后渣油加氢反应的焦炭和>500℃残渣油收率降低,气体、汽油、柴油和VGO收率提高,轻油产率提高6~10个百分点,渣油转化率增大,轻质化性能明显增强;不同渣油经超声波处理后的加氢反应性能改变不同;利用超声波处理后渣油加氢的虹吸作用模型,从宏观层次解释了超声波改善渣油加氢效果的原因;超声波处理后杂原子的脱除效果均有不同程度的提高,尤其是对金属钒的脱除影响最为明显。超声波处理后加氢残渣油的饱和分和沥青质含量增加,芳香分和胶质的含量减少。     

在分散型催化剂下渣油中饱和分和芳香分临氢热反应行为的研

在微型高压釜中研究了克拉玛依常压渣油（KLAR）和辽河减压渣油（LHVR）的饱和分、芳香分在分散型催化剂作用下的临氢热反应行为并计算其动力学参数。结果表明，饱和分与芳香分主要发生裂化反应，生成石脑油与柴油馏分，不会生成甲苯不溶物，极少量的芳香分缩合生成沥青质。在相同的反应苛刻度下，KLAR与LHVR饱和分裂化和缩合产物产率没有明显的差别，而KLAR芳香分的裂化产物产率略高于LHVR芳香分，而其缩合产物产率略低于LHVR饱和分。     

胜利褐煤液化沥青烯光谱表征

以胜利褐煤为原料,通过不同条件下加氢液化制备了相应的沥青烯,利用元素分析、红外光谱、紫外可见光谱和荧光光谱等分析技术对所制备的沥青烯进行了结构表征,探讨了氢气初压和液化温度对沥青烯结构的影响。结果表明,胜利褐煤液化活性高,沥青烯和前沥青烯等重质中间物收率较低。胜利褐煤沥青烯中芳香体系主要以2~3环缩合芳环及联苯类芳香结构为主。提高氢气初始压力,可以促进煤的加氢裂解及AS脱羟基。高温、高氢压有利于AS中芳环取代基的加氢裂解。相对而言,荧光光谱是沥青烯芳香结构的有效表征手段,其荧光光谱特征结果与元素分析、H/C原子比间存在明显的相关性。     

供氢(氘)剂在减压渣油四组分裂化中的作用及其同位素效应

研究了辽河减渣四组分在微型高压釜内中临氮热裂化、临氢热裂化和临氢催化加氢反应,考察了供氢剂或供氘剂对上述反应的影响。结果表明,临氮热裂化时沥青质是大量生焦的物种,胶质的生焦能力不显著,芳香分、饱和分不生焦;临氢热裂化沥青质生焦量减少,胶质很少生焦,芳香分和饱和分不生焦;临氢催化加氢时,辽河减渣四组分在临氢反应基础之上,生焦量进一步降低。辽河减渣四组分在临氮热裂化、临氢热裂化和临氢催化加氢过程中添加供氢剂或供氘剂后,生焦反应得到显著抑制,相比之下供氢剂的作用更为明显。三种氢源都具有抑制渣油四组分缩合或缩聚反应的作用。渣油四组分从供氢剂或供氘剂中获得氢（氘）的能力不同,沥青质>胶质>芳香分≈饱和分。就同一组分而言,供氢剂或供氘剂的表观供氢（氘）率随反应条件不同而不同,临氮热裂化> 临氢热裂化>临氢催化加氢过程。供氢剂与供氘剂在所有的过程中都存在明显的动力学效应,并且这个动力学效应随加工环境的不同而变化,在临氮热裂化过程中动力学同位素效应明显。在临氢热裂化过程,尤其是催化加氢裂化过程中动力学效应逐渐变得不明显。2H-NMR分析表明,氘代四氢萘的环烷环中的α位比β位的脱氢选择性高,氘代四氢萘脱氢选择性大小的顺序为：临氮热裂化>临氢热裂化>临氢催化加氢过程。     

煤焦油重组分沥青质性质分析及对加氢裂化生焦影响的推测

从中/低温煤焦油中切取重组分,提取了重组分C7-沥青质,并以此重组分为原料进行了高压釜加氢实验,通过1H-NMR、XRD、FT-IR、SEM、元素分析和相对分子量测定等手段对重组分沥青质结构参数、官能团、表观形态等方面进行了分析,并将其与加氢过程中生焦情况进行了关联。结果表明,C7-沥青质基本结构单元以稠环芳烃为中心,周围分布少而短的侧链,侧链以小于3个碳的短直链正构烷基为主,相对分子量小,芳香片层没有堆积结构。O是该沥青质中氢键主要来源,大多分布在环氧烷烃和醚类结构中,外围的O数量低,分子间氢键更难形成,结构单元之间缔合性弱,沉积聚合慢而均匀。沥青质中短侧链不易断裂,在反应过程中产生的稠环芳烃自由基少,缩合能力小,使该馏分油生焦能力低,具有较高的加氢潜质。     

Investigation of catalytic degradation of high-density polyethylene by hydrocarbon group type analysis

Catalytic degradation of waste high-density polyethylene (HDPE) to hydrocarbons by ZSM-5, zeolite-Y, mordenite and amorphous silica–alumina were carried out in a batch reactor to investigate the cracking efficiency of catalysts by analyzing the oily products including paraffins, olefins, naphthenes and aromatics with gas chromatography/mass spectrometry (GC/MS). Catalytic degradation of HDPE with zeolite-Y, mordenite and amorphous silica–alumina yielded 71–82 wt.% oil fraction, which mostly consisted of C₆–C₁₂ hydrocarbons, whereas ZSM-5 yielded much lower 35% oil fraction, which mostly consisted of C₆–C₁₂ hydrocarbons. Both all zeolites and silica–alumina increased olefin content in oil products, and ZSM-5 and zeolite-Y particularly enhanced the formation of aromatics and branched hydrocarbons. ZSM-5 among zeolites showed the greatest catalytic activity on cracking waste HDPE to light hydrocarbons, whereas mordenite produced the greatest amount of coke. Amorphous silica–alumina also showed a great activity on cracking HDPE to lighter olefins in high yield, but no activity on aromatic formation.     

格尔木渣油加氢反应及生焦行为的研究

选用超低沥青质含量的格尔木渣油（沥青质质量分数：0.32%）作为加氢原料,考察反应条件对加氢反应样品组分性质、胶体稳定性参数（CSP）、生焦性能的影响。结果表明,随着加氢反应温度的升高和反应时间的延长,沥青质和饱和分的含量增加,胶质和芳香分的含量减少;胶体稳定性参数降低,生焦率不断增加;胶质与沥青质的缩合度增加,芳碳率f_A不断增大;金属与杂原子在加氢过程中不断得到脱除,V比Ni更容易脱除、S比N更容易脱除;催化剂表面形成了类似石墨有序结构的炭基物质,使得催化剂的孔结构参数不断减小。在所研究的反应中,当反应温度和时间分别为420℃和5 h时,催化剂的孔结构损害最为严重,出现了较大的微孔分布。     

Influence of residence time and catalyst regeneration on the pyrolysis–zeolite catalysis of oil shale

Oil shale from the Kark region of Pakistan has been pyrolysed in a fixed bed batch reactor and the properties of the derived shale oil determined. The reactor system was then modified to incorporate a second reactor where the derived vapours from oil shale pyrolysis were passed directly to the second reactor containing zeolite ZSM-5 catalyst. The influence of the process parameters of vapour residence time (VRT) over the catalyst and the regeneration of the catalyst were examined. The yield and composition of the derived gases before and after catalysis were determined. In addition, the yield and composition of the derived oil in terms of total nitrogen and sulphur content and the content of aromatic hydrocarbons in the oils was investigated. The results showed that the yield of oil after catalysis was reduced with a consequent higher yield of gases and formation of coke on the catalyst. The main gases from the pyrolysis of oil shales were CO₂, CO, H₂, CH₄, C₂H₄, C₂H₆ and C₃H₆, C₃H₈ and minor concentrations of other hydrocarbon gases. The main role of catalysis was to convert the long chain alkanes and alkenes in the oil to lower molecular weight, short chain, alkyl substituted and iso species and high concentrations of aromatic hydrocarbons. Total nitrogen and sulphur contents in the oils were markedly reduced after catalysis. This reduction was reflected in the reduced concentration of nitrogen and sulphur containing aromatic hydrocarbons. The influence of longer VRTs was to increase the formation of aromatic hydrocarbons, reduce the nitrogen, and sulphur compounds in the oils. The influence of catalyst regeneration, involving five regenerations was not significant on the yield and composition of the derived catalytically upgraded oils.     

乙烯在煤焦及石英砂床层上裂解实验研究

以石油炼制过程中产生的炼厂气与煤共转化利用为背景,采用小型石英管固定床反应装置,在850℃～1000℃下,对乙烯在空床、彬县煤焦以及石英砂床层上的裂解反应进行了研究。结果表明,乙烯裂解产物包括氢气、甲烷、乙烷及裂解炭,反应温度越高,裂解越彻底,生成的氢气越多;850℃～950℃时,乙烯在彬县焦上初始转化率最高,随着反应的进行逐渐降低到一个较低的平衡值,并且与在石英砂上裂解结果接近。这说明新鲜彬县煤焦对乙烯裂解呈现良好的催化作用,但随着反应进行其催化活性由于裂解生成的炭沉积在煤焦表面而逐渐丧失。1000℃时乙烯在石英砂上和空床裂解转化率均可达到94％,即在此温度下乙烯无需催化剂通过热作用即可接近完全裂解。     

含有酰胺基或酯基的可降解阳离子Gemini表面活性剂在水溶液中的聚集行为

In the last thirty years, Gemini surfactants with various structures have been designed, synthesized, and demonstrated to show superior physicochemical properties. However, the utilization of non-degradable surfactants, including these Gemini surfactants, poses a threat to the environment; hence, degradable Gemini surfactants are desirable. Herein, biodegradable cationic Gemini surfactants with amide or ester groups in the hydrophobic chains or the spacer were synthesized. A monomeric surfactant containing an amide group and a Gemini surfactant with amide groups both in the hydrophobic chains and the spacer were synthesized for comparison. The effects of amide group location on the aggregation behavior of Gemini surfactants were studied systematically. The differences between the Gemini surfactants with amide groups and Gemini surfactants with ester groups were evaluated by comparing their aggregation behavior and hydrogen bonding formation. The Gemini surfactants with amide groups (C₁₂A-C_n-AC₁₂) in the chains showed much larger exothermic ΔH_mic and more negative ΔG_mic values than those of the corresponding monomeric surfactant C₁₂A; besides, their critical micelle concentration (cmc) was more than one order of magnitude lower than that of C₁₂A. The amide groups located in the hydrophobic alkyl chains promoted hydrogen bonding formation and self-assembly of the Gemini surfactants C₁₂A-C_n-AC₁₂. Moreover, ¹H NMR spectra revealed that the co-effect of a short spacer and hydrogen bonding leads to slow exchange of the C₁₂A-C₂-AC₁₂ molecules between the monomer and the aggregate. For the Gemini surfactant series C₁₂-AC_nA-C₁₂, the amide groups notably increased the spacer length, and largest cmc value and smallest exothermic ΔH_mic value were observed for C₁₂-AC₂A-C₁₂ instead of C₁₂-AC₆A-C₁₂. In C₁₂-AC₁₂A-C₁₂, the spacer was long and sufficiently flexible to adopt a "U"-shaped conformation above the cmc, and it acted as the hydrophobic part of the surfactant, as confirmed by ¹H NMR spectra. Among the Gemini surfactant with amide groups in both the spacer and the hydrophobic alkyl chains, C₁₂A-AC₆A-AC₁₂ had a smaller cmc and I₁/I₃ ratio as well as more exothermic ΔH_mic values than those of C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂. ¹H NMR spectra indicated that an ester-alcohol structural equilibrium exists during aggregation for the Gemini surfactants with ester groups. In addition, the Gemini surfactants with ester groups formed water-mediated hydrogen bonds in the aggregates. This water-mediated hydrogen bonding between ester groups was weaker than the direct hydrogen bonding between amide groups. Therefore, the Gemini surfactants with ester groups, C₁₂E-C₆-EC₁₂ and C₁₂-EC₆E-C₁₂, exhibited lower surface activity, a larger micelle ionization degree, higher micropolarity, and smaller exothermic ΔH_mic and less negative ΔG_mic values than their counterparts with amide groups, C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂.     

沙特减压渣油临氮热反应过程中沥青质聚集体尺寸变化研究

将沙特轻质原油的减压渣油在395℃临氮条件下进行热反应,利用在线取样装置得到不同热反应时间的样品,借助小角X射线散射(SAXS)技术,测定了各液相残渣油中沥青质聚集体尺寸。结果表明,热反应生焦诱导期的初期沥青质聚集体的尺寸逐渐减小,为29~21 nm;在生焦诱导期后期,其尺寸急剧增大,在热反应进行到150 min时达到43 nm;达到生焦诱导期后,沥青质聚集体尺寸变化较小,在46~42 nm变化。在渣油热反应过程中沥青质聚集体的尺寸受沥青质热裂解、沥青质解缔和缔合等过程的共同影响,与沥青质含量无明显关系。     

压力对塔里木原油四组分热解性能的影响

压力对深层油藏原油热化学过程的影响尚存在较大争议,为研究其在油藏原油热解成气过程中的作用机理,我们在450℃、5~40 MPa压力下对塔里木原油四组分(饱和分、芳香分、胶质和沥青质)进行了封闭体系的热解实验,通过气相色谱(GC)和气相色谱/质谱(GC/MS)分别对原油四组分热解反应的气体产物及饱和分热解过程的液态产物进行了分析。结果表明,在450℃、24 h及不同压力下,沥青质热解产气率高于胶质、芳香分和饱和分;四组分的气相热解产物中,C1的产率明显高于C2~C5组分。增大压力抑制沥青质、胶质及芳香分的热解产气过程而促进饱和分的热解产气过程。随压力的增大,饱和分热解的液态产物的主峰组分碳数先减小,再增大。压力低于20 MPa时,饱和分热解过程中以裂解反应为主;高于30 MPa时,增大压力有利于缩合反应。研究结果可为认识深层油藏原油的稳定程度及天然气的成因提供一定的理论参考。