FCC重循环油选择性加氢改质-催化裂化多产高附加值产品

面对国内柴油产量过剩,汽油需求低迷新形势,降低柴汽比以及增产化工原料产品成为炼厂优选转型路线。催化裂化重循环油中含有大量多环芳烃,难以催化加工利用,成为炼厂转型升级的结构性难题。本研究从分子结构出发,提出先将重循环油进行选择性加氢,使重循环油中难以转化的多环芳烃转化为可裂化结构,然后再进行催化裂化,并根据市场需求,灵活调节装置以多产轻质油或化工原料等高附加值产品。研究表明,重循环油选择性加氢后,催化裂化转化率最高可提升至60.14%（质量分数）;与加氢前相比,汽油和柴油收率分别增加了19.16%（质量分数）和6.50%（质量分数）;汽油辛烷值最高可达95.6,此时汽油中总芳烃含量为56.8%（质量分数）,其中三苯含量为21.3%（质量分数）,约占总芳烃含量的37%;同时重油和焦炭产率大幅降低。     

减压渣油超临界萃取分离与结构研究

减压渣油结构复杂,其合理利用应以充分了解其结构为基础。采用超临界流体萃取分馏技术,将伊朗和沙轻减压渣油混合油分离成6个窄馏分和1个萃余残渣,测定各窄馏分的性质和组成,为沸腾床加氢原料的结构表征提供重要基础数据。结果表明,随着窄馏分产率的增加,残炭值、S和N及金属元素含量逐渐增加,饱和分质量分数减小,胶质质量分数增大,芳香分质量分数逐渐增大,各窄馏分中基本不含沥青质。用改进的Brown-Ladner法计算了各个原料和窄馏分的结构参数,对窄馏分的二次加工性能进行了预测。     

劣质催化裂化柴油综合利用技术研究进展

催化裂化柴油硫含量高,芳烃含量高,十六烷值低,是较为劣质的柴油组分。通过加氢方法一般可以实现催化裂化柴油的大幅改质,但芳烃加氢饱和对提高中间馏分油的十六烷值有限。催化裂化柴油已成为限制企业柴油质量升级的关键。针对国内外车用柴油质量升级趋势,以劣质催化裂化柴油高值化和清洁化利用为出发点,综述劣质催化裂化柴油综合利用技术的研究进展,分析劣质催化裂化柴油加氢改质后调和柴油的劣势,重点介绍由劣质催化裂化柴油生产低碳芳烃或高辛烷值汽油的工艺技术,提出利用催化裂化柴油富含芳烃的特点,加氢后生产高辛烷值汽油或轻质芳烃是最具竞争力的加工路线。下一步的工作重点是进一步提高现有技术芳烃加氢饱和与侧链断裂选择性,提高低碳芳烃产率,减少低值副产物,使经济效益最大化。     

地层原油及其族组分的氧化反应特性研究

为了考察油藏注空气过程中地层原油的氧化反应规律,采用柱层析方法将地层原油组分分离为饱和烃、芳香烃、胶质和沥青质。采用热重和差示扫描量热仪,研究了原油和其不同族组分的氧化反应特性。结果表明,中原油田该区块原油差示扫描量热曲线第一放热区间峰值热流高于第二放热区间峰值热流,饱和烃和芳香烃的第一放热区间的峰值高于第二放热区间峰值,胶质和沥青质的第二放热区间峰值高于第一放热区间峰值,原油中饱和烃和芳香烃的含量较高时,有利于轻质油藏注空气过程中原油自燃现象的发生。原油的族组成对原油的氧化特性有决定性影响。     

Separation and characterization of bitumen from Athabasca oil sand

Separation and chemical analysis was investigated using bitumen samples from Athabasca oil sand in Alberta. Fractionation according to solubility and polarity has been used to separate bitumen into its fractions. The solvent de-asphaltening was performed by n-pentane solvent (solubility fractionation), and the polarity fractionation using Fuller’s earth allows maltene to separate into SARA components (saturates, aromatics, resins and asphaltenes). The SARA components are analyzed comprehensively using elemental analysis (EA), Fourier-transformed infrared (FTIR), ultraviolet-visible spectroscopy (UV-vis), high performance chromatography (HPLC) and thermogravimetric analysis (TGA). EA (C, H, N, S), heavy metals (Ni, V) concentrations, FT-IR and UV-vis tests provided the explanation of chemical composition. From IR spectra, maltene and saturates/aromatics (sat/aro) contained more aliphatic compounds than resin or asphaltene. Also, IR spectrum of sat/aro was similar to crude oil and VGO (vacuum gas oil). Different UV signal data clearly indicates the contribution of aromatic constituents in the fractions. Using optimized analysis conditions of HPLC, we successfully separated the peaks for bitumen and its fractions. The characteristic peak pattern of SARA (saturates, aromatics, resins, asphaltenes) fractions was observed, and also the peak pattern of sat/aro was similar to that of crude oil and VGO. However, TGA results revealed that thermal behavior for sat/aro was similar to that of crude oil but different from that of VGO. Also, from the comparison between decomposition temperature of TGA and boiling point, their correspondence was found.     

Pyrolysis kinetics of atmospheric residue and its SARA fractions

Thermal analysis of atmospheric residue from heavy crude oil and its SARA fractions was carried out and the tendency of each fraction toward coke formation was determined. The coke yield was 16.3 wt.% for atmospheric residue, 43.1 wt.% for asphaltenes, 4.6 wt.% for resins, 3.8 wt.% for aromatics, and 0.3 wt.% for saturates. Pyrolysis kinetics of residue and its fractions, i.e., asphaltenes, resins and aromatics was also investigated. The TG experiments were conducted at three different heating rates of 8, 12, and 16 °C/min from room temperature up to 800 °C under nitrogen atmosphere to verify the weight variation with reaction temperature. Isoconversional analysis to fit data assuming first order kinetics was employed. Asphaltenes was the fraction that produces coke in higher amount having a range of activation energy of 41.0–58.6 kcal mol⁻¹ whereas activation energy for atmospheric residue ranged from 11.5 to 30.0 kcal mol⁻¹.     

反应温度对催化裂化汽油芳构化的研究

以中国石油兰州炼油石化公司催化汽油为原料,采用小型固定流化床为芳构化反应装置,考察了反应温度对芳构化产物收率、转化率、马达法和研究法辛烷值、气体产品组成和液体产品组成的影响规律。实验结果表明,随着反应温度的升高,干气、液化气和焦炭收率呈上升趋势,而汽油和柴油收率呈下降趋势,FCC汽油的转化率都在94%左右,且随反应温度的升高先增大后减小;乙烯、丙烯、丁烯、乙烯和总低碳烯烃收率单调增加,而乙烯、丙烯、丁烯、乙烯和丙烯和总低碳烯烃收率的增加幅度各不相同;异构烷烃和烯烃收率随着反应温度的升高逐渐减少,而芳烃的收率和选择性随着反应温度的升高逐渐增加,正构烷烃和环烷烃的收率随着温度的增加先增加后减少。     

流化催化裂化汽油改质和增产低碳烯烃的研究

采用GL型催化剂,在小型固定流化床实验装置上考察了反应温度、剂油比、空速和水油比等操作条件对流化催化裂化(FCC)汽油催化改质汽油的产品分布、低碳烯烃(丁烯、丙烯和乙烯)产率和族组成的影响。实验结果表明,在一定反应条件下,FCC汽油通过催化改质可以降低烯烃含量,提高芳烃含量和辛烷值,在满足新汽油标准的同时提高了低碳烯烃的产率。此外,较高的反应温度、剂油比和水油比以及较低的空速有利于FCC汽油催化改质和增产低碳烯烃。     

油浆抽余油FCC反应

油浆经萃取分离得到以饱和烃为主的理想组分——抽余油。利用该油作为原料进行FCC反应,并与石蜡基重油从原料性质、反应工艺条件、产品分布及性质、再生剂性能等方面进行对比研究。结果表明：抽余油具有良好的FCC性能,其合适的反应条件为剂油比6.0、反应温度520 ℃、重时空速12.0 h?1;在各自最优工艺条件下,抽余油比重油液体收率增加1.69%,生焦率上升0.02%;在相同工艺条件即剂油比5.0、反应温度500 ℃、空速14.4 h?1,抽余油比重油液体收率增加0.19%,生焦率上升2.55%;与重油相比,抽余油FCC汽油辛烷值相当,FCC柴油十六烷值降低3.7,其再生剂失活程度较小。因此,抽余油完全可以替代重油作为FCC的原料,具有很好的工业应用前景。     

Study on reformulation of fluid catalytic cracking gasoline and increasing production of light olefins

The effects of reaction temperature, mass ratio of catalyst to oil, space velocity, and mass ratio of water to oil on the product distribution, the yields of light olefins (light olefins including ethylene, propylene and butylene) and the composition of the fluid catalytic cracking (FCC) gasoline upgraded over the self-made catalyst GL in a confined fluidized bed reactor were investigated. The experimental results showed that FCC gasoline was obviously reformulated under appropriate reaction conditions. The olefins (olefins with C atom number above 4) content of FCC gasoline was markedly reduced, and the aromatics content and octane number were increased. The upgraded gasoline met the new standard of gasoline, and meanwhile, higher yields of light olefins were obtained. Furthermore, higher reaction temperature, higher mass ratio of catalyst to oil, higher mass ratio of water to oil, and lower space velocity were found to be beneficial to FCC gasoline reformulation and light olefins production.     

委内瑞拉常压渣油萃取窄馏分催化裂化反应性能及产物中硫氮组成

以正戊烷为溶剂,采用超临界溶剂萃取分馏装置将委内瑞拉常压渣油分离为15个窄馏分和一个脱油残渣。采用LHO-1催化剂,在温度500 ℃、剂油质量比4和空速30 h^-1条件下,在小型固定流化床上对不同窄馏分进行催化裂化反应。结果表明,随着窄馏分的变重,干气产率从1.84%升至4.98%,液化气产率从12.18%升至14.47%,汽油产率则从37.49%降至16.73%,柴油产率由23.12%降至17.33%,焦炭产率由9.34%升至20.08%。窄馏分1^＃~4^＃具有良好的裂化性能,窄馏分5^＃~9^＃裂化性能中等,窄馏分10^＃~15^＃裂化性能较差。催化裂化汽油中硫化物主要以噻吩硫为主,尤其是短侧链烷基噻吩,约占90%。催化裂化柴油中硫化物主要为苯并噻吩,约为70%,其次是二苯并噻吩。催化裂化柴油中的含氮化合物主要为苯胺类、 喹啉类、吲哚类和咔唑类,其中,吲哚及其衍生物约占总氮含量的50%,而一甲基、二甲基和三甲基的氮化物含量占氮化物总量的70%以上。     

沸石孔结构对植物油催化裂化性能的影响

制备出硅铝比相近但介孔体积逐渐增加的超稳Y（USY）沸石，进而制备成微球状催化剂。本文在固定流化床装置上，考察了两种植物油的催化裂化性能。小桐子油的评价结果表明，催化剂中USY沸石的介孔体积越大，汽柴油收率越高；汽油族组成中烯烃收率越高，芳烃收率越低，汽油辛烷值和抗爆指数也越低；采用铵交换和水热改性制备介孔体积为0.142cm³/g的USY沸石催化剂的裂化产物中，汽柴油总收率为62.21%（质量分数），焦炭收率最低，汽油研究法辛烷值达到90.5；大豆油的催化裂化反应规律与小桐子油的一致，中等介孔催化剂裂化得到的汽油研究法辛烷值达到92.2。研究结果表明，采用催化裂化工艺，利用适当介孔的USY沸石催化剂，可以将植物油高效转化为车用轻质燃料，并且得到高辛烷值的汽油。     

空速对焦化汽油产物分布的影响

以抚顺焦化汽油为原料,采用小型固定流化床为反应装置,考察了空速对产物分布、轻油产品族组成、干气组成和液化气组成影响规律,同时通过实验数据建立了空速与干气收率、液化气收率、焦炭收率、轻油收率和总收率的关系式。实验结果表明,随着空速的增加,焦炭、干气和液化气收率逐渐下降,轻油收率逐渐增加,芳烃含量缓慢下降,而饱和烃含量基本没有变化。     

Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

DCR评价装置对重油催化裂化催化剂LDC-200的性能评价

采用DCR催化裂化评价装置,通过不同原料油及剂油比对重油催化裂化催化剂LDC-200的反应性能进行评价。结果表明,以中国石油天然气股份有限公司兰州石化公司3 Mt·a-1催化装置所用渣油为原料油,在剂油质量比大于8.4时,催化剂LDC-200裂化能力强,拥有良好的焦炭选择性,且异构化功能显著,明显提高汽油辛烷值。采用3 Mt·a-1催化装置所用渣油与蜡油质量分数各50%配成的原料油,在剂油质量比小于8.4时,能够在确保汽油收率的同时控制焦炭产率。     

Pilot synthesis and commercial application in FCC catalyst of MCM-41 zeolite

MCM-41 zeolite in the grade of 600 kg was successfully synthesized and the MCM-41 added FCC catalyst was firstly prepared. The results indicate that the pilot samples of mesoporous Al-MCM-41 bear the typically uniform mesopore structure and considerable acidity and hydrothermal stability. The MCM-41 added FCC catalyst is positively capable to crack heavy oil feedstock, in which the yields of the diesel and lighter oil increased 1.85 and 3.47%, respectively and coke yield decreased 0.29%. Commercial application in FCCU indicate that optimization of nanopores of MCM-41 added faujasite zeolite might result in an industrial process to design novel FCC catalysts.     

LOSA-1增产轻烯烃FCC助催化剂的开发及工业应用

在中国石化济南分公司800 kt·a^－1催化裂化装置上试应用了岳阳三生化工有限公司生产的LOSA-1增产轻烯烃FCC助催化剂，考察了该助催化剂催化裂化性能及其对汽油和柴油质量的影响。工业应用表明，增产轻烯烃助剂占系统催化剂总藏量4.0％时，丙烯（对催化进料）增加了1.19％，系统总液收及焦炭产率基本保持不变。     

降低油浆和焦炭的裂化催化剂RSC-2006的工业应用

催化裂化催化剂RSC-2006采用焦炭选择性较好的大孔富硅基质以降低焦炭收率;添加活性基质组分以增强催化剂的重油裂化能力,同时调节基质的表面酸性,在保证重油预裂化能力的同时改善焦炭选择性;对分子筛进行物化处理,清理和疏通分子筛的孔道,改善分子筛对劣质重油催化裂化的可接近性;引入抗金属污染组分,提高催化剂的抗金属污染能力。工业应用结果表明,催化剂具有优异的重油转化能力和优良的焦炭选择性。与对比催化剂相比,油浆和焦炭收率降低,大幅增加高价值产品收率,液化气+汽油+柴油收率提高。     

催化裂化汽油临氢异构化/芳构化改质过程的反应特性

采用工业Ni-Mo/Al₂O₃-HZSM-5催化剂在小型固定床加氢微反装置上对催化裂化（FCC）汽油临氢改质过程的反应特性进行了研究,通过考察反应温度、压力、空速和氢油体积比对改质后的FCC汽油烃类组成的影响,分析了汽油中不同烃类的转化性能。结果表明,氢油比对产物组成影响不大,高温、低压、低空速有利于增加芳烃的选择性,低温、高压、高空速则有利于增加异构烷烃的选择性;临氢改质后,FCC汽油的烯烃含量明显降低,芳烃和异构烷烃含量增加,因而产品汽油的辛烷值基本保持不变;全馏分、轻馏分和重馏分FCC汽油临氢改质实验结果表明,烯烃含量较高的轻馏分具有更高的转化活性;在FCC汽油临氢改质过程中,同碳数的端烯烃反应活性高于内烯烃,直链烯烃的反应活性高于支链烯烃。     

An experimental and modeling study of vacuum residue upgrading in supercritical water

Arabian Heavy crude oil was fractionated into distillate and vacuum residue fractions. The vacuum residue fraction was treated with supercritical water (SCW) at 450°C in a batch reactor for 15–90 min. The main products were gas, coke, and upgraded vacuum residue; the upgraded residue consisted of gasoline, diesel, and vacuum gas oil range components. The molecular composition of gas and upgraded vacuum residue was analyzed using gas chromatography (GC, GC × GC). SCW treatment converted higher carbon number aliphatics (≥C₂₁) and long‐chain (≥C₅) alkyl aromatic compounds into C₁?C₂₀ aliphatics, C₁?C₁₀ alkylaromatics, and multiringed species. The concentrations of gasoline and diesel range compounds were greater in the upgraded product, compared to the feed. A first‐order, five lump reaction network was developed to fit the yields of gas, coke, diesel, and gasoline range components obtained from SCW upgrading of vacuum residue. Distillation of crude oil followed by SCW treatment of the heavy fraction approximately doubled the yield of chemicals, gasoline, and diesel, while forming significantly less coke than conventional upgrading methods. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1732–1743, 2018