Study on the in situ desulfurization and viscosity reduction of heavy oil over MoO_(3)–ZrO_(2)/HZSM-5 catalyst

Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.

Commercial Application of Novel Heavy Oil Catalytic Cracking Catalyst HSC

The commercial application of a novel RFCC catalyst HSC used in an 1.4 Mt/a RFCC unit at a refinery A was introduced. The application results show that in comparison with the base catalyst, the yield of dry gas and slurry was reduced, while the total liquid yield, gasoline yield and LPG yield increased by 1.34, 5.05 and 1.43 percentage points,respectively. The properties of the products showed no significant change while the anti-abrasion strength of the catalyst was relatively high. Based on the mid-term calibration test, the summary calibration test and the daily statistics of long term industrial application practice, the HSC catalyst features a strong conversion ability of heavy oil, a high gasoline yield, a satisfactory product distribution and a good selectivity.

Research and Development of Novel Heavy Oil Catalytic Cracking Catalyst RCC-1

A novel heavy oil catalytic cracking catalyst RCC-1 was developed by using the ultra-stable zeolite, which was hydrothermally treated and modified through cleaning its pores to serve as the active component. The chemical composition and physicochemical properties of RCC-1 catalyst were studied by XRF, BET, pore volume analysis, attrition index analysis, and particle size distribution determination methods, and its catalytic cracking performance was also evaluated by a microreactor for light oil cracking and the ACE device. The test results showed that the new type of heavy oil catalytic cracking catalyst RCC-1 had good physicochemical properties and heavy oil cracking ability, strong anti-metallic contamination capability, good product distribution, good coke selectivity and gasoline selectivity, and excellent reduction of gasoline olefin content characteristics.

Aquathermolysis of heavy crude oil with ferric oleate catalyst

Oil-soluble catalysts could be of special significance for reducing the viscosity of heavy crude oil, because of their good dispersion in crude oil and high catalytic efficiency toward aquathermolysis. Ferric oleate was synthesized and applied as catalyst in the aquathermolysis reaction of Shengli heavy oil. It was found that ferric oleate was more efficient for heavy oil cracking than Co and Ni oleates. Besides, it was superior to oleic acid and inorganic ferric nitrate and achieved the highest viscosity reduction rate of up to 86.1%. In addition, the changes in the components of Shengli heavy oil before and after aquathermolysis were investigated by elemental analysis, Fourier transform infrared spectrometry, and ^1H nuclear magnetic resonance spectroscopy. Results indicated that ferric oleate contributed to a significant increase in the content of light components and decrease in the content of resin, N and S. The as-prepared ferric oleate showed good activity for reducing the viscosity and improving the quality of the heavy crude oil, showing promising application potential in aquathermolysis of heavy crude oil.

Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO_(2)at Low Temperatures in Tahe Heavy Oil

MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.

Upgrading of Heavy Crude Oil with W-Zr Catalyst

The main problem of new crude oil reserves is the incipient increase of heavy crude oils in the American continent, i.e. USA, Mexico, Canada and Venezuela. These types of crude oils require several treatments before refining. One of these treatments can be hydrocracking. In this petroleum refining process, it is possible to modify the heavy crude oils to light crude oils. In this paper, we try to use hydrocracking to improve the quality of raw heavy crude oil, through some chemical transformations C-H binding rupture using a catalyst containing active metals such as tungsten and zirconium (W-Zr). After the crude oil was hydrocracked in presence of this novel bimetallic catalyst, the hydrocracked products showed lower content of asphaltenes, resins, sulfur and nitrogen. Also positive changes in the viscosity of crude oil measured as a decreasing of this value were observed. The American Petroleum Institute (API) gravity was significantly increased 6 units. Consequently, all these changes confirmed that the upgrading of the heavy crude oil was successful.

Synthesis of La-Modified Ultra Stable Zeolite L and Its Application to Catalytic Cracking Catalyst

A new type of zeolite La-USL （ultra stable zeolite L （zeolite USL） modified by La）, which has superior activity, stability and selectivity in catalytic cracking of hydrocarbons and thus can be used as an active catalyst component, is reported in this paper. The zeolite L with relative crystallinity of above 90% was synthesized by the hydrothermal crystallization method under optimum conditions and characterized by means of XRD, NH3-TPD and isotherm adsorption techniques. The in-situ synthesized zeolite L with a SiO2/Al2O3 mole ratio of 5-6 was modified by cation ion exchange, hydrothermal dealumination and chemical modifications with La in order to prepare La-containing USL with a higher framework SiO2/Al2O3 mole ratio of 15-30. The modified zeolite La-USL was used as an active additive component of fluid catalytic cracking （FCC） catalyst and the resulting catalysts were evaluated by microactivity test （MAT） and fixed-fluidized bed （FFB） experiments using heavy oil as feedstock. The influence of La content in La- USL on cracking product distribution, gasoline group composition and research octane number （RON） was investigated. The results showed that when La content in La-USL was 0.8 wt%, the addition of the corresponding La-USL could result in a FCC catalyst that produced significant improvement in product distribution and gasoline quality.

Novel magnetic carbon supported molybdenum disulfide catalyst and its application in residue upgrading

A novel hybrid material consisted of carbon covered Fe_(3)O_(4)nanoparticles and MoS_(2)nanoflower(FCM)was designed and prepared by micelle-assisted hydrothermal methods.Multiple techniques,including X-Ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM)and X-ray photoelectron spectroscopy(XPS)were employed to characterize it.The results show that FCM has a flower-like morphology with a 330 nm Fe_(3)O_(4)core as well as 70 nm highly crystalline MoS_(2)shell.FCM is superparamagnetic with a saturation magnetization of 35 emu g-1.Then hydrocracking of Canadian bitumen residue(CBR)was applied to estimate its catalytic activity.The results show that FCM exhibits superior catalytic hydrocracking activity compared to bulk MoS_(2)and commercial oil-dispersed Mo(CO)6 by the same Mo loading.Further measurement by elemental analysis,XPS and XRD reveals that the MoS_(2)nanoflower with abundant catalytic active sites and covered carbon layer with anti-coke ability donate to the superior upgrading performance.Besides,the catalysts can be easily recovered by the external magnetic field.This work provides a novel kind magnetic nanocatalyst which is potential for slurry-phase hydrocracking applications.■2020,Institute of Process Engineering,Chinese Academy of Sciences.Publishing services by Elsevier B.V.on behalf of KeAi Communications Co.,Ltd.This is an open access article under the CC BY-NC-ND license(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Application of the Endurance Catalyst in RFCCU Unit

In order to improve the capability of the RFCC unit for heavy oil conversion, reduce the yields of coke and oil slurry, and increase the economic benefits of the unit, starting August 2007 the SINOPEC Luoyang Branch Company began to apply in its No. 2 RFCC unit the Endurance catalyst featuring strong heavy oil conversion ability, low yields of coke and oil slurry, and high total light liquid yield. The results on calibration of the Endurance catalyst conducted in November 2007 indi-cated that under the circumstances of using deteriorating feedstock quality and lower unit consump-tion of catalyst, the yields of coke, oil slurry and gas decreased by 0.28 %, 1.24 % and 0.35 %, respectively. The light distillate yield and total light liquid yield increased by 0.8 % and 1.88%, respectively.

Commercial Application of X-62 Catalyst for Reducing Olefins in Gasoline

In order to reduce the coke yield and increase the economic benefits of FCC unit under the prerequisites of securing the olefin content of gasoline in compliance with the requirement, SINOPEC Luoyang Branch Company applied in the period from July through October 2004 the new generation X-62 catalyst (FlexTec-LOL1) developed by the Engelhard Corporation of USA to improve the heavy oil conversion and to reduce coke make. The result of tests has shown that indicators on reducing the unit catalyst consumption,amplitude on reduction of non-ideal products (coke+oil slurry+dry gas) yield, and amplitude on reduction of coke yield were comparatively satisfactory.

PHT-01/PHC-05组合催化剂在加氢裂化装置的工业应用

在中国石油辽阳石化公司110万t/a加氢裂化装置中,以俄罗斯原油的二次油(减压蜡油和催化柴油的混合油,二者质量比10∶1)为原料,采用中国石油自主开发的PHT-01加氢精制催化剂、PHC-05加氢裂化催化剂及PHT系列加氢保护剂,为最大限度生产重石脑油进行了工业应用,考察了催化剂应用情况、产品性质及其分布。结果表明:催化剂运行中,可同时进行湿法硫化与钝化操作,精制反应器、裂化反应器的平均反应温度分别为367,363℃,比设计值分别低5,15℃,温升比设计值分别低3,4℃;目标产品重石脑油的含硫(氮)量均小于0.5μg/g、溴指数0.755 mg/g、芳潜质量分数47.3%、初馏点73℃、收率51.56%,精制油含氮量为7~9μg/g,主要产品收率为94.04%,满足下游重整装置进料要求。

蜜勒胺负载二氧化锰的合成及其稠油低温催化氧化性能

以三聚氰胺在354℃下热聚的蜜勒胺(Melem)为含有碳、氮元素的载体,以KMnO_(4)为锰源,通过水热法成功合成了MnO_(2)/Melem复合材料。采用SEM、TEM、XRD和XPS等方法进行结构表征。并以MnO_(2)/Melem为催化剂,通过调控催化剂用量、氧化剂用量对塔河稠油的催化氧化性能进行考察。结果表明:合成的β-MnO_(2)纳米颗粒成功负载于Melem表面上;通过对稠油催化反应前后的氧化油分别进行族组成分析、FT-IR、GC-MS和黏度测试,确定了催化氧化体系中催化剂用量为1.0%(质量分数),氧化剂选用过氧化氢叔丁醇(TBHP),TBHP用量为0.5%(质量分数);且催化改质后实现了稠油中轻质组分的增加,降黏率可达67.06%。

基于氮化物结构与加氢行为关系设计重油加氢脱氮催化剂

氮化物分子的结构随着油品馏程增加呈规律性变化,氮化物结构与加氢行为之间的关系是重油加氢脱氮催化剂设计的重要指导理论。本文采用量子化学理论计算的方法研究碱性氮化物和非碱性氮化物的理化性质与反应行为随氮化物结构的变化规律。研究发现,随着氮化物中共轭芳环数目的增加:氮化物吸附能力增强,且吸附过程中电荷转移能力也随之增强,氮化物的平躺吸附逐渐占优势;C—N键通过低活化能的消去路径断裂的难度增加,只能通过高活化能的取代反应路径实现断裂,这就要求与氮化物相邻芳环在C—N键断裂前必须充分得到加氢饱和。高氢解能力催化剂加氢产物中剩余氮化物以含有多环芳烃的氮化物为主,而高加氢饱和能力催化剂加氢产物剩余氮化物中含有更多的双环氮化物,加氢实验结果说明了具有高氢解能力的加氢催化剂更有利于轻质油品中氮化物的脱除,而具有高加氢饱和能力的催化剂更有利于重质油品中氮化物的加氢脱除。

“双碳”政策下重油催化裂解技术研究进展

从重油催化裂解反应机理的研究概况、重油催化裂解分子筛催化材料的分析对比、不同重油催化裂解工艺的技术特点和工业应用情况等三个方面进行了总结,综述了国内外重油催化裂解技术的研究进展。改性分子筛催化剂材料、小晶粒分子筛、多级孔分子筛等成为目前研究和应用的热点,以强化重油催化裂解的催化剂的水热稳定性、晶内扩散和重油大分子在梯级孔内的分级裂化,基于催化裂解反应正碳离子机理和自由基机理等研究,DCC、CPP、HCC、RTC和HSFCC等重油催化裂解技术的反应苛刻度不断提高,为匹配不同进料所需最优反应环境的差异,新型反应器或多反应器组合技术成为工艺技术研发的主要方向,已达到提高低碳烯烃产率和选择性的目的。

水杨醛双席夫碱-镍配合物的合成及其催化稠油改质研究

针对特超稠油油藏黏度大、常规开发效果不理想等问题,合成水杨醛双席夫碱镍配合物催化剂。催化剂晶体为内部具有多孔介孔结构的金属有机框架材料,有利于稠油中的胶质、沥青质分子或聚集体进入介孔孔道,增大催化活性中心与重组分之间的接触效率。同时,材料表面呈弱亲水强亲油性,易于分散在水中并能够自发向油水界面迁移,有效提高镍催化中心的运载效率。材料的耐温性能良好,在600℃下质量保留率为65.14%。使用高温高压反应釜评价了催化剂对稠油的降黏性能和黏度反弹率,分析催化改质前后稠油的碳数分布特征。通过高温高压模拟驱替实验,研究催化剂对驱油效率的影响。在胜利油田进行现场试验,并对催化改质效果进行跟踪分析。结果表明,合成的席夫碱-镍催化剂在250℃、反应时间10 h、质量分数为1.5%时,对胜利稠油的降黏率可达87.6%。放置30 d后,黏度反弹率仅为3.9%。反应后的稠油显著轻质化,碳数大于41的组分含量明显减少,碳数小于26的组分含量明显增加。室内驱替实验表明:先进行2 PV蒸汽驱,再伴注席夫碱-镍催化剂,驱油效率比纯蒸汽驱提高了10.5%。现场试验结果表明:催化改质措施后,油井日产液和日产油均明显增加,含水下降,累计增油315 t。措施后沥青质和胶质含量下降,饱和分和芳香分含量升高,可以实现稠油黏度的不可逆降低。

重质油催化裂化用催化剂的研制及性能评价

催化裂化是提高重质油资源利用效率的一种常用加工技术,为了提高重质油资源催化裂化的效率,以Ni(NO_(3))_(2)、FeCl_(3)和脂肪酸为主要原料,制备出一种适用于重质油催化裂化的新型油溶性催化剂FN-1,并采用小型固定流化床装置考察了不同因素对重质油催化裂化反应的影响。实验结果表明,随反应温度的升高,重质油转化率逐渐增大,生成的汽油成分中烯烃和芳烃含量逐渐增大;随剂油质量比的逐渐增大,重质油转化率逐渐增大,汽油中异构烷烃和烯烃的含量逐渐减小,芳烃含量逐渐增大;随质量空速的逐渐增大,重质油转化率逐渐减小,汽油中异构烷烃和烯烃的含量逐渐增大,芳烃含量逐渐减小,但变化的幅度比较小。当重质油催化裂化的反应温度为520℃、剂油质量比为6、质量空速为15h-1时,重质油的转化率可以达到95.38%,催化裂化效果较好。

MIP-CGP工艺加工俄罗斯原油重油总结

中国石油辽阳石化分公司2.2 Mt/a俄罗斯原油重油催化裂化装置采用MIP-CGP技术(增产丙烯、多产异构烷烃的清洁汽油生产技术)进行改造,使用专用催化剂CGP-LY。标定结果表明:在100%生产负荷条件下,与改造前的催化裂化技术相比,采用MIP-CGP技术改造后,液化石油气产率基本不变;丙烯产率提高了0.3百分点;汽油产率提高了5.47百分点,研究法辛烷值为92.23,提高了1.18单位,抗爆性提高,烯烃质量分数降至30%以下,降低了16.78百分点,有效减少了油品对大气环境的污染;焦炭产率提高了3.73百分点;原料油转化率提高了8.71百分点。上述结果说明MIP-CGP技术具有良好的降低汽油烯烃含量的能力,在改善汽油性质的同时,能显著提高产品产率,满足生产清洁型汽油、降低汽油烯烃含量、提高汽油辛烷值、提高丙烯产率的市场需求。

胜利稠油水热裂解过程中沥青质结构特征的变化分析

为了阐明在双亲性催化剂的条件下,在250℃和280℃下稠油水热裂解反应对稠油沥青质分子结构及稠油黏度的影响,以胜利稠油为研究对象,使用C_(12)BSNi为催化剂,通过使用FT-IR和~1HNMR等手段分析水热裂解反应前后沥青质分子结构的变化。研究结果表明,稠油在250℃下发生水热裂解反应后,黏度大幅降低,降黏率可达到60.4%,但随着反应温度升高到280℃时,反应后的降黏率降至53.8%。随水热裂解反应温度从250℃升高到280℃,稠油沥青质分子平均侧链长度逐渐减小,然而芳香度不断增加,芳环数量增多,说明沥青质分子发生了自由基缩合反应,沥青质平均分子结构变大,导致降黏率相对减小;此外,沥青质分子在反应过程中发生一系列的断键反应,导致其空间位阻减小,且沥青质分子单元片层越小越容易发生堆积。通过SEM观察到,随温度升高,沥青质的孔道逐渐变大并且更加密集,但表面聚集颗粒变大。本文研究对稠油水热裂解反应操作条件的优化有重要的指导意义。

基于γ-Al_(2)O_(3)载体的高孔隙率Ni-Mo催化剂制备及催化特超稠油降黏效果评价

塔河油田特超稠油在井筒掺稀降黏开采过程中掺稀比高、频繁上返异常,难以实现经济有效开采。针对塔河特超稠油高沥青质含量的特点,以1,3-丙二醇、仲钼酸铵和硝酸镍为原料,研发了一种基于γ-Al_(2)O_(3)载体的高孔隙度Ni-Mo催化剂,评价了其地面改质降黏效果。结果表明,三叶形γ-Al_(2)O_(3)催化剂载体具有圆柱形孔隙结构,孔隙直径以5~11 nm为主。Ni-Mo催化剂可以将特超稠油的黏度(50℃)从28 200 mPa·s降至298 mPa·s,降黏率为98.94%,密度从1.0070 g/mL降至0.8724 g/mL;同时,饱和烃的含量显著增加,胶质和沥青质的含量大幅降低。地面催化改质降黏与改质稀油回掺相结合的开采技术能有效降低特超稠油黏度,地面催化改质效果良好,可有效节约掺稀油用量,提升开采效果。