Hydrocracking Gudao Residual Oil Using Supercritical Water-Syngas as Hydrogen Source in Suspension Bed. Part III: Water-Gas Shift Reaction

Abstract

The catalytic hydroconversion of Gudao residue in supercritical water-syngas system is a heavy oil upgrading technology. The hydrogen derived from water-gas shift reaction can be used for residue hydrocracking, so, it is important for studying the water-gas shift reaction that takes place in the hydrocracking system. Here, the water-gas shift reaction in the supercritical water-syngas system was investigated. The results showed that the water-gas shift reaction could be effectively increased with dispersed catalysts, and more than 80% CO was conversed in the initial processes.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source. Part II: The Comparison of Residue Hydrocracking in Different Hydrogen Sources

Different catalytical hydrogen sources were compared with molecular hydrogen gas in the hydrocracking of Gudao residue in the presence of catalysts (PMA). The results showed that alternative hydrogen sources were effective in catalytic hydroconversion of heavy oil. The hydroconversion of residue in supercritical water-syngas system showed similar results when performed with molecular hydrogen.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source

Heavy oil upgrading is a very important process in the petroleum industry, but is very difficult because it has a high impurity content. A variety of heavy oil upgrading technologies have been developed in the world, including the catalytic hydrocracking process, which can process various heavy oils with a high yield of liquid products. Although this technology is one of the most widely used methods for upgrading heavy oil, the use of expensive molecular hydrogen is costly. The heavy oil upgrading technology with alternative hydrogen is very important. The catalytic hydroconversion of Gudao residue with different catalysts using water-syngas as an alternative hydrogen was investigated in this study. Hydrogen is provided in-situ for hydrocracking through the water-gas shift reaction (WGSR). The experimental results show that catalysts play a very important role in catalytic hydroconversion of Gudao residue using water-syngas as an alternative hydrogen. Addition of catalysts to residue was found to improve the distribution or properties of cracking products and inhibit the asphaltene or TI formation.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source. Part II: The Comparison of Residue Hydrocracking in Different Hydrogen Sources

Abstract

Different catalytical hydrogen sources were compared with molecular hydrogen gas in the hydrocracking of Gudao residue in the presence of catalysts (PMA). The results showed that alternative hydrogen sources were effective in catalytic hydroconversion of heavy oil. The hydroconversion of residue in supercritical water-syngas system showed similar results when performed with molecular hydrogen.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source

Abstract:

Heavy oil upgrading is a very important process in the petroleum industry, but is very difficult because it has a high impurity content. A variety of heavy oil upgrading technologies have been developed in the world, including the catalytic hydrocracking process, which can process various heavy oils with a high yield of liquid products. Although this technology is one of the most widely used methods for upgrading heavy oil, the use of expensive molecular hydrogen is costly. The heavy oil upgrading technology with alternative hydrogen is very important. The catalytic hydroconversion of Gudao residue with different catalysts using water-syngas as an alternative hydrogen was investigated in this study. Hydrogen is provided in-situ for hydrocracking through the water-gas shift reaction (WGSR). The experimental results show that catalysts play a very important role in catalytic hydroconversion of Gudao residue using water-syngas as an alternative hydrogen. Addition of catalysts to residue was found to improve the distribution or properties of cracking products and inhibit the asphaltene or TI formation.     

页岩储层超临界CO2增透规律实验

为研究超临界CO2对页岩储层的增透效果,利用自主研制的岩石三轴渗流实验装置,开展超临界CO2注入页岩储层增透规律研究.研究结果表明:页岩储层CH4渗透率随孔隙压力增加呈负指数变化,页岩样品注入超临界CO2后增透效果显著,CH4渗透率最大可提高103.98％(3号样品);恒温条件下,注入压力为9.0 MPa时超临界CO2...     

超临界CO2压裂裂缝特征研究现状与展望

为加强对超临界CO2压裂裂缝特征的认识,指导超临界CO2压裂技术的发展,总结了前人对超临界CO2起裂、扩展和导流能力特征的研究.结果表明:超临界CO2压裂裂缝起裂压力比液态和清水压裂低,其主导原因是超临界CO2的低黏度和高扩散性使孔隙压力增大起裂压力降低;超临界CO2压裂裂缝扩展影响因素复杂,主要受CO2相变、岩石弱面...     

重力分异和非均质性对天然气藏CO2埋存的影响——以中国南方ＸＣ气藏为例

在含CO₂的天然气藏中实施CO₂长期稳定埋存并提高天然气采收率,实现CO₂的规模化综合利用,具有重大的现实意义。为此,以一个真实的含CO₂浅层废弃气藏为埋存靶场,运用数值模拟方法,设计了纵向非均质气藏剖面模型,用于研究气藏储层在正韵律、反韵律以及复合韵律条件下气体运移对超临界CO₂稳定埋存的影响,并重点研究了重力分异和地层非均质性条件下的流体运移规律。结果表明：不同韵律剖面模型在注超临界CO₂埋存及开采剩余天然气过程中,作为反韵律的目标气藏注超临界CO₂埋存过程在生产井突破最晚,吸入的超临界CO₂量最大,天然气累计采出量最多,其超临界CO₂埋存潜力相对最大;重力分异可引起超临界CO₂与天然气之间产生非平衡态相的分离,天然气向气藏高部位运移,CO₂最终趋向于形成“超临界CO₂垫气”,可以很稳定地沉积在气藏下部形成“垫气”埋存。该成果为实现CO₂减排、降低CO₂捕集与埋存技术（ＣＣＳ）成本提供了技术支撑。     

泄漏柴油对杀菌剂生物黏泥控制效果的影响

在油品泄漏情况下,循环水水质发生变化,常规的杀菌剂投加模式将不能满足循环水系统生物黏泥控制要求。利用现场循环冷却水中的微生物,在挂片上培养出稳定附着期的生物黏泥后,以柴油为泄漏介质,考察了不同质量浓度泄漏柴油对氧化型杀菌剂ClO₂和非氧化型杀菌剂1427生物黏泥控制效果的影响。结果表明,随着柴油添加质量浓度从100 mg/L增大到900 mg/L,无论是在ClO₂还是在1427作用下,溶液COD均呈现上升趋势,生物黏泥脂磷浓度和细菌数量呈现先快速下降后平稳趋势,杀菌率呈现先快速上升后平稳趋势。相对于1427来说,柴油质量浓度的变化对ClO₂的杀菌作用影响更大。     

MOF-199固载过氧化磷钨酸盐催化剂的制备及其在柴油脱硫中的应用

采用简易的原位合成法合成了过氧化磷钨酸盐(TBA)₃PW₄封装于MOF-199孔道内的固载型催化剂(TBA)₃PW₄@MOF-199,借助电感耦合等离子体(ICP)、傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TG)、场发射扫描电子显微镜(SEM)及N₂吸附-脱附等温曲线(BET)等分析手段对催化剂样品(TBA)₃PW₄@MOF-199的组成、稳定性及形貌进行了表征。采用含苯并噻吩(BT)、二苯并噻吩(DBT)、4-甲基二苯并噻吩(4-MDBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT) 4种硫源的多组分模拟柴油与萃取剂组成的液-液双相系统,以双氧水为氧化剂,对催化剂的脱硫活性进行了探究,并探讨了催化剂用量、氧化剂用量及反应温度对脱硫效率的影响。结果表明：在最佳反应条件(反应温度70 ℃、催化剂(TBA)₃PW₄@MOF-199用量40 mg、H₂O₂用量0.26 mmol、模拟柴油体积0.75 mL及萃取剂［Bmim］PF₆体积0.75 mL)下,催化剂(TBA)₃PW₄@MOF-199的脱硫效率可以在80 min内达到99.9%,同时重复使用8次,脱硫效率仍保持在91%以上。该催化剂优异的催化脱硫活性及稳定性使其在工业应用上具有一定的前景。     

超临界二氧化碳射流冲击压力参数影响规律

为了探明超临界CO_2射流对岩石冲击压力及其参数影响规律,利用计算流体力学模拟了超临界CO_2射流冲击的三维流场,对比了超临界CO_2射流和水射流的冲击压力,进行了参数影响规律研究。结果表明:在相同条件下,超临界CO_2射流能产生比水射流更强的冲击效果;超临界CO_2射流冲击压力随着喷嘴压降和喷嘴直径的增大而增大;随着喷距的增大,超临界CO_2射流的冲击压力降低,冲击范围扩大;围压和流体温度的变化对超临界CO_2射流冲击压力的强度和范围的影响极小,在工程应用中可以忽略。研究结果证实了超临界CO_2射流的冲击效果,探明了超临界CO_2射流冲击压力的参数影响规律,为超临界CO_2射流在钻完井工程中的应用提供了指导。     

柴油超深度加氢脱硫催化剂RS-2100的工业应用

在中国石油辽阳石化公司200万t/a加氢精制装置上进行了柴油超深度加氢脱硫催化剂RS-2100的工业应用,对应用初期的运行结果进行了标定。结果表明:使用催化剂RS-2100后,装置运转正常,催化剂各项指标满足生产要求;在反应器入口温度为322℃,高压分离器压力为6.0 MPa,氢油体积比为288,体积空速为1.62 h~(-1)的条件下,精制柴油产品含硫量为4μg/g,脱硫率可达99.8%,可满足国Ⅵ柴油标准要求。     

页岩注入超临界CO2渗流及增透实验

以四川省长宁县双河镇燕子村龙马溪组页岩为研究对象,采用自行研制的三轴渗流装置,开展了考虑注入压力和体积应力影响的页岩中超临界CO₂渗流及增透规律实验研究。结果表明：页岩中超临界CO₂渗透率随着孔隙压力增大呈现先减小后增大趋势,当孔隙压力较小时存在Klinkenberg效应;随体积应力的增大渗透率逐渐减小,曲线基本呈现负指数变化规律。开展不同增透条件下页岩中CH₄渗流实验,宏观量化分析超临界CO₂注入压力对于页岩增透效果的影响,可以得出随着超临界CO₂注入压力的增加,CH₄渗透率呈现上升趋势,但增长幅度先上升后下降,即超临界CO₂注入压力为9.5MPa时增透效果最为明显。通过微观分析页岩元素含量得出超临界CO₂可以萃取和溶解页岩中的O、Ca、Mg等矿物元素,有效促进页岩内部微孔隙的发育,致使页岩渗透能力增强。     

柴油与硫酸镁反应体系模拟实验研究

利用高压釜反应装置,在高温高压含水条件下对柴油与硫酸镁热化学还原反应体系进行了模拟实验研究。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,并进行了动力学研究。结果表明,该体系在温度450～550℃内可以发生热化学还原反应,主要生成氧化镁、硫、焦炭、硫化氢、二氧化碳以及硫醇、硫醚和噻吩类等一系列有机硫化物,反应活化能为58.6kJ/mol。     

不同催化剂对催化裂化柴油加氢裂化产品影响及预测

采用中国石油化工股份有限公司大连(抚顺)石油化工研究院研制的三种酸性依次提高,比表面积依次增大,加氢功能金属含量依次减少的催化剂,以芳烃含量较高的催化裂化柴油为原料进行了中试试验,在工艺条件相同的情况下,研究了上述三种不同类型催化剂对催化裂化柴油加氢裂化的产品分布、液体收率、氢耗和产品性质的影响规律.结果表明:在适宜的...     

氢油体积比对柴油加氢烃类碳数分布的影响

以不同氢油体积比下加氢前后的柴油为研究对象,在对其进行烃类组成分析的基础上,借助气相色谱-场电离飞行时间质谱(GC-FI TOF MS),对加氢反应前后的柴油进行烃类碳数分布组成分析。结果表明:烃类组成分析可以反映柴油加氢前后1环、2环等环烷烃,以及烷基苯等芳烃的组成变化;氢油体积比超过500∶1后,精制柴油的烃类组成无明显变化,可用于指导工艺条件的初步优化;而GC-FI TOF MS的分析结果可以定量化地反映不同氢油体积比对柴油加氢精制过程中烃类碳数分布组成的影响,如氢油体积比由500∶1继续提高时,精制柴油中不同碳数下单环芳烃等烃类组成的变化趋于平缓;集中分布的低碳数多环芳烃通过逐环的加氢反应,转化为低碳数的单环芳烃、2环和3环环烷烃,如原料柴油中C_(10)~C_(15)萘类加氢转化为精制柴油中C_(10)~C_(15)茚满/四氢萘和C_(11)~C_(15)2环环烷烃等反应。     

Performance-focused Catalyst Design to Meet Diesel Quality Improvements—Part II

In this work, we present an experimental evaluation concerning the catalytic hydrocracking of gas oil (GO) feedstock. The study was carried out using five types of supported NiMo-based catalysts (100A, 100AP, 100AB, 100H-DY, and 30H-DY). Screening tests of the performance of these sulfided catalysts were carried out in a high-pressure batch autoclave at temperatures of 350°C-425°C, reaction time of 1-3 hr, catalyst/feed ratios of 5-10%, and initial hydrogen pressure of 6.0 MPa. This study clearly shows that the incorporation of H-DY zolite into aluminum borate (AB) matrix led to a greatly improved hydrocracking catalyst for production of lighter products, in addition to depressing the pour point of the diesel fuel product. In all experiments, the yield of gasoline and gaseous products increased dramatically by increasing the severity of the process variables. A high-pressure test unit was used to study the effect of different process variables as pressure (3.0-6.0 MPa), liquid hourly space velocity (1.5-3 hr^-1), hydrogen/ GO volumetric ratio (400 vol./vol.), and temperatures of 375°C, on the GO conversion to various products using 30H-DY catalyst, and to correlate the impact of process conditions on the yield and quality of diesel fuel and gasoline products to optimize the process     

CoMo/Al2O3催化剂柴油加氢脱芳烃集总反应动力学模型

为满足生产国六标准车用柴油的需要,采用等温高通量反应器,对加氢精制催化剂CoMo/Al2O3上的柴油加氢脱芳烃(HDA)动力学进行了研究。考察了反应温度、氢分压、氢/油体积比、空速等因素对柴油加氢脱芳烃反应的影响。根据芳烃加氢反应机理将柴油中的芳烃化合物按所含芳环个数分成了三集总。在此基础上,建立了考虑竞争吸附影响的集总反应动力学模型,并采用鲍威尔优化算法确定了模型参数。结果表明,所得动力学模型与实验结果吻合良好。进一步的验证结果表明,所建动力学模型能够很好地预测柴油加氢脱芳烃过程,所得模型可为柴油加氢脱芳烃反应的操作优化提供技术支撑。     

高含水后CO2驱油机理的探讨

针对高含水油藏水驱效率低,不流动区域无法波及等问题,利用微观可视模型,研究了CO₂超越水的驱油机理、油膜运移特征以及CO₂与原油间传质过程,并提出了CO₂驱替不连通区域的驱替机制。实验结果表明,在CO₂驱油过程中,原油中的蜡不断在孔喉处沉积并堵塞孔喉,CO₂可以超越孔道中水的阻碍进一步驱替残余油,通过柱面流和柱状流两种流动方式将其中的原油驱替出来,且由于CO₂中分子聚集现象的存在,使其具有较强的溶解原油的能力,可从原油中萃取轻烃组分,对原油中重质组分具有一定的溶解能力。     

EFFECTS OF HYDROTREATING COKER LIGHT GAS OIL ON FUEL QUALITY

Coker light gas oil (LGO) derived from Athabasca bitumen was hydrotreated in a fixed bed reactor using two commercial NiO-MoO₃/Al₂0₃ catalysts. The effect of temperature on product quality was investigated in a pilot plant between 330 and 390 °C at 12.4 MPa, space velocity of 0.5 Ir1 and 700 liter of hydrogen per liter of coker LGO (L/L). The product quality was monitored by ^I3C NMR spectroscopy, elemental analysis, density and distillation techniques.

The data showed that coker LGO can be hydrotreated using nickel-molybdenum catalysts at 350 °C, 0.5 h¹, 12.4 MPa and 700 L/L to meet the diesel product specifications, namely, 0.5 wt % sulfur, 20% aromatics and cetane index of 40. The cetane index improvement and aromatic saturation, which are affected by thermodynamic equilibrium at temperature higher than 370 °C, could reach 29 and 86% respectively. The cetane improvement was attributed to aromatic saturation and hydrocracking with hydrogen consumption ranging from 215-340 L/L. The Ketjenfine KF-840 catalyst was found slightly better performance than Procatalyse HR-348 catalyst.