金属纳米晶催化稠油原位裂解加氢降黏改质

实验制备了单金属Ni、Fe及双金属Ni-Fe合金纳米晶催化剂,并以水合肼(N_2H_4·H_2O)为供氢剂,对旅大32-2脱水原油进行催化裂解加氢改质研究。采用TEM,XRD对所制备的催化剂进行表征;通过正交实验确定了最佳反应条件,并采用GC-MS,FTIR,TG-DSC等测试手段对原油及改质油样进行分析。表征结果显示,金属纳米晶催化剂平均粒径约为5.0～6.0 nm,且分布均匀。实验结果表明,金属纳米晶具有催化稠油大分子裂解并使供氢剂分解析氢双重功能,其中Ni-Fe合金/N_2H_4·H_2O体系共催化作用对稠油的降黏效果最佳,改质后油样中轻质组分含量为89.20%(w),上升了26.86百分点,黏度降至72 mPa·s,降黏率达95.6%;稠油经催化裂解加氢后重质组分结构被破坏,黏度发生不可逆的降低,稠油品质提高。     

纳米铜催化裂解超稠油改质降黏实验研究

以纳米铜和供氢剂为主要裂解剂,对辽河油田超稠油开展催化裂解改质降黏实验,在纳米铜质量分数为0.05％、供氢剂质量分数为0.1％、反应温度为180～270℃的条件下反应24 h,超稠油的黏度(50℃)从1.55×105 mPa·s降为2122～6684 mPa·s,降黏率达到95.69％～98.63％.原油的族组分分析表...     

油酸改性Fe2(MoO4)3用于稠油水热催化降黏的研究

利用自制油酸改性Fe2(MoO4)3催化剂，将其用于新疆克拉玛依稠油水热催化降黏的研究，考察了催化剂加入量、反应温度、反应时间对稠油水热催化改质降黏的影响，得到最佳工艺条件为：催化剂添加量（w）0.4%，反应温度240 ℃，反应时间36 h，此时降黏率为61.21 %。稠油族组成分析结果表明有13.2%（w）的稠油重组分裂解成轻组分，这是稠油黏度降低的主要原因。通过进一步对反应前后稠油重组分进行元素分析、FT-IR、1H NMR谱图分析，发现稠油重组分在反应过程中存在脱硫、脱氮、加氢开环、支链断裂等反应。     

磺化型有机金属催化剂在稠油降黏改质中的应用

制备了3种磺化型有机酸金属催化剂,用高温高压反应釜进行了稠油的催化降黏实验,筛选出了最佳催化剂和最佳降黏条件。结果表明,磺化型有机酸铁催化剂的降黏效果最佳,当稠油量为250g时,加入1g该催化剂,加入油层水量为m(油层水)∶m(稠油)=30%,在220℃反应24h,辽河稠油黏度从81 400mPa·s降至3 000mPa·s,降黏率达96.31%。检测了催化降黏前后稠油四组分及不凝气体产物:饱和分含量提高7.5%、芳香分含量提高3.2%,胶质含量降低8.2%,沥青质含量降低2.5%;检测出不凝气相产物含有甲烷、烯烃和二氧化碳等气体,符合稠油水热裂解降黏规律,证明由于催化改质降低了稠油的黏度。     

埕北稠油近临界水改质降黏的研究

通过对埕北稠油进行近临界水改质模拟实验,优选了最佳反应条件,分析了稠油改质前后的烃族组成和结构,对比了普通水热改质、近临界水改质与近临界水催化改质的降黏效果。实验结果表明:由于水在近临界条件下具有近临界流体、溶剂化和催化供氢等效应,在油水质量比8∶2、反应温度260℃、反应压力6 MPa和反应时间24 h的条件下,稠油近临界水改质降黏率达到21.40%,稠油沥青质含量下降56.46%,红外光谱图显示改质前后稠油发生明显的C—S键断裂。将反应压力降至3 MPa,在非近临界条件下对稠油进行普通改质,稠油黏度下降7.98%;加入0.1%的催化剂,对稠油进行近临界水催化改质,稠油黏度下降51.27%。从降黏效果比较,近临界水催化改质近临界水改质普通改质。     

超稠油水热催化裂解反应前后性质变化

为了更好地应用水热催化裂解技术对稠油进行开采,明确稠油性质变化的本质,对胜利油田超稠油进行微乳液纳米镍催化降黏剂水热催化裂解实验研究。实验结果表明,水热催化裂解反应后,稠油黏度大幅度降低,稠油中胶质、沥青质的含量下降,硫含量大幅降低,氮含量略减少。稠油氢碳原子比增加,平均分子质量减小。族组分中沥青质的平均分子质量减小幅度最大,说明沥青质裂解对稠油黏度的降低和平均分子质量的减小起到了关键作用。该研究为日后稠油水热催化裂解降黏技术的推广提供了技术参考。     

超稠油裂解改质降黏实验

稠油的改质降黏是指在非催化裂解的反应条件下,稠油烃类可以进行分解、异构化、芳构化、氢转移、叠合和烃化等多种反应,其中最主要的反应是分解反应(如断侧链、断环、脱氢等裂解反应)。改质降黏过程中裂化转化率与反应温度、反应时间相关。改质稠油的黏度的变化主要与裂化转化率有关,也就是说,在不同温度下,只要裂化转化率接近,减黏稠油的黏度基本接近,减黏稠油的黏度随裂化转化率的提高而降低。在实验条件下,200～350℃馏分的生成速率最大,对于一般的20%左右的裂化转化率而言,490℃以下时轻质馏分显著增多,490℃以上时轻质馏分显著降低。在裂化转化率低于25%,甲苯不溶物含量小于0.2%,满足一般减黏过程对缩合反应的控制要求。     

井下裂解提高稠油油藏蒸汽吞吐采收率

开展了井下裂解就地改质稠油,提高稠油油藏蒸汽吞吐采收率的室内模拟实验和矿场应用试验。研究表明,油藏矿物可催化稠油水热裂解反应,其中黏土矿物的催化效果优于其他矿物,可使稠油黏度降低30%以上,黏土矿物含量越高,越有利于水热裂解反应;注入催化剂硫酸镍和供氢剂四氢萘溶液段塞后,蒸汽吞吐最终采收率大幅度提高,比单纯蒸汽吞吐提高8.8%,产出油降黏率增加51.7%,饱和烃、芳香烃含量分别增加38.0 mg/g 和26.3 mg/g,胶质、沥青质含量分别降低41.9 mg/g 和41.1 mg/g. 矿场试验结果表明,井下裂解就地改质稠油技术可延长蒸汽吞吐周期生产时间、提高日产油量、提高油汽比和回采水率,较大程度地改善蒸汽吞吐开发效果。     

大庆外围稠油水热裂解地质协同催化降黏研究

为更好地实现稠油就地水热裂解降黏,以油藏矿物、催化剂和供氢剂为催化体系,检测其对大庆外围稠油水热裂解反应的催化作用.实验结果表明,油藏矿物可以催化稠油水热裂解反应,并可与催化剂协同催化稠油水热裂解,矿物与油溶性催化剂的协同催化效果好于水溶性催化剂;供氢剂的加入可进一步强化稠油水热裂解反应,与不添加供氢剂相比,反应后胶质...     

化学生热催化裂解体系对稠油降黏实验研究

为了更好地提高稠油油藏开发效果,采取化学生热与催化裂解方式来降低稠油黏度、提高地下稠油的流动能力非常必要。选择NaNO₂和NH₄Cl溶液作为化学生热剂,通过正交实验优选出生热剂最佳反应条件为:4 mol/L NaNO₂,4mol/L NH₄Cl,体系pH值为2。该条件下,反应温度和压力在短时间内迅速上升,分别达到峰值204℃和13.6 MPa,达到峰值的时间为6 min,反应基液温度升高149℃。油酸镍催化降黏体系最佳配方为:以反应原油的质量为基准,羧酸盐型油酸镍催化剂0.3%,供氢剂甲酸7%,助剂尿素7%,乳化剂十二烷基苯磺酸钠0.13%。该催化体系的最佳反应温度为280℃。油酸镍催化后,原油黏度由213.8 mPa·s降至74.2 mPa·s,降黏率为65.3%。当化学生热剂与催化裂解剂共同作用时,降黏率可达66.5%,饱和烃和芳烃含量增加,胶质和沥青质含量减小,催化降解效果较好。     

孤岛减压渣油在CO-SCW体系中催化加氢

对孤岛减压渣油在CO -SCW体系中加氢改质研究表明 ,利用CO与SCW发生的水 -气变换反应获得加氢所需氢源是可行的。在适宜的条件下 ,渣油在CO -SCW体系中改质可达到在H2 -SCW体系中改质同样的效果     

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

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.     

地下水热催化裂化降粘开采稠油新技术研究

针对辽河油田的3种稠油,筛选陋一种合适的水热裂解催化剂（过渡金属盐）,确定了水热裂解的最佳条件,在0．2％该催化剂顾在下,3种稠油样在240℃经水热裂解反应24h后,50℃粘度分别下降89．9％－77．7％,饱和烃和芳香烃含量大幅上升,胶质,沥青质含量下降,烃碳数分布移向低碳数方向,产生大量气体和少量固体,在辽河油田曙光采油3口蒸汽吞吐井进行的地下稠油催化剂水热裂解降粘开采现场试验获得成功,采出的稠油粘度大同度降低。     

加氢裂化尾油临氢降凝催化剂及工艺研究

以ZSM-5分子筛为载体制备了Ni/Ca/ZSM-5临氢降凝催化剂,研究了催化剂中Ni、Ca改性对润滑油基础油凝点、收率和黏度指数的影响。结果表明,Ni、Ca改性后,催化剂的裂化活性降低,润滑油基础油的收率和黏度指数升高。以加氢裂化尾油为原料,对Ni-Ca/ZSM-5催化剂进行加氢工艺考察,最佳反应条件为：反应温度310 ℃、体积空速3.0 h-1、反应压力15 MPa、氢油体积比500,在此条件下,润滑油基础油凝点为－17 ℃,黏度指数为93,收率为72%。     

Investigation of the fluid catalytic cracking of different H-Oil vacuum gas oils and their blends with hydrotreated vacuum gas oil

H-Oil vacuum gas oils obtained during hydrocracking of vacuum residual oils originated from the crudes Russian Export Blend, Basrah light, and Heavy Kazakh were cracked in a mixture with a hydrotreated vacuum gas oil in the LUKOIL Neftohim Burgas commercial fluid catalytic cracking (FCC) unit. Some of the H-Oil vacuum gas oils were also cracked in a laboratory FCC (ACE) unit. The results from the commercial and the laboratory tests showed that the laboratory FCC experiments in an ACE unit can be used to evaluate the effect of feed quality on the commercial FCC unit performance. The assumption that the conversion of a vacuum gas oil (VGO) blend in the fluid catalytic cracking could be considered as a linear combination of the conversion of the individual components made by other researchers was also confirmed in this study. The higher the hydrogen content in the vacuum residual oil of a crude is the higher the FCC conversion of the H-Oil VGO, obtained during hydrocracking of that high saturate vacuum residual oil, will be expected.     

Effect of reaction temperature and hydrogen donor on the Ni0@graphene-catalyzed viscosity reduction of extra heavy crude oil

Ni⁰@graphene nanocomposites were prepared via a solvothermal method and used as the catalysts for the viscosity reduction of extra heavy crude oil. Higher graphene content in Ni⁰@graphene nanocomposite has an adverse effect on its catalytic activity. The addition of tetralin and higher reaction temperature can obviously promote the catalytic activity. The catalyst accompanied by hydrogen donor can attain a viscosity reduction rate of 84.3% after the catalytic reaction under 280°C for 24 h and reduce the viscosity of crude oil from 174,219 to 27,352 mPa s (measured at 50°C).     

Study of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor

We have studied the effect of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor (formic acid) on the viscosity of Liaohe extra-heavy oil. The paraffinic/naphthenic and aromatic hydrocarbon content of the oil as well as the H:C ratio of the oil increase after aquathermolysis in the presence of a hydrogen donor, while the sulfur, resin, and asphaltene content decreases dramatically. We use the thermogravimetric method to show that with aquathermolysis in the presence of formic acid, a substantial portion of the asphaltenes in the heavy oil is converted to paraffins. Accelerating the aquathermolysis reaction results in a synergistic effect between the catalyst and the hydrogen donor.     

河南油田超稠油复合催化降粘体系效果评价

河南油田创新地进行了稠油热采地下复合催化降粘技术研究。本实验考察了无水体系、含水体系、水热催化裂解体系、乳化降粘体系、乳化水热催化裂解复合体系（即复合催化降粘体系）对特超稠油作用后物理化学性质的变化以及对特超稠油的降粘效果,探讨了乳化水热催化裂解降粘的作用机理。结果表明,在催化剂作用下,特超稠油中重质组分发生部分裂解,原油物化性能得到明显改善,乳化水热催化裂解复合体系对河南油田超稠油的降粘率达98.7%。     

MILD HYDROCRACKING OF VACUUM GAS OILS TO IMPROVE FCC PERFORMANCE AND MAXIMIZE DISTILLATE YIELDS

A pilot plant study was conducted on mild hydrocracking of heavy vacuum gas oils derived from two different crude sources over a commercially available catalyst to determine the possibility of utilizing mild hydrocracker bottoms as fluidized catalytic cracking feedstock along with improved middle distillate yields. The mild hydrocracking experiments were conducted at 390°C, 60 kg/cm², 1.0/h liquid hourly space velocity and H₂/oil ratio of 390 l/l in a pilot plant trickle bed reactor using two catalyst beds for pretreatment and mild hydrocracking reactions. The experimental results showed that mild hydrocracking would result in valuable middle distillates with low sulphur and nitrogen content. With research octane number of 78, the naphtha obtained from mild hydrocracking was found to be a good blending stock for gasoline pool. The middle distillate fraction (140-370°C) obtained from mild hydrocracking product was found to have cetane number in the range of 48-54. The bottom product from mild hydrocracking of heavy vacuum gas oils was found to be a good feedstock for fluidized catalytic cracking unit because of its low sulphur, nitrogen and aromatic contents. The data obtained from pilot plant studies showed that the processing of mild cracker bottom in FCC unit would result in better quality fuels.