活性氧化铝及其在FCC催化剂中的应用

综述了活性氧化铝的性能及其在FCC催化剂中的应用,尤其是改性活性氧化铝对FCC催化剂酸性、抗磨性能、活性、焦炭选择性和基质的抗重金属能力等的影响.     

劣质重油裂化催化剂研发通过鉴定

由中国石化石油化工科学研究院、中国石化荆门分公司和中国石化催化剂齐鲁分公司共同承担的中国石化股份公司开发项目“高轻质油收率的劣质重油裂化催化剂研究开发和试生产”通过了股份公司科技开发部组织的技术鉴定。在硅溶胶中添加酸化铝石制备富硅基质FCC催化剂,改善了FCC催化剂基质的焦炭选择性和重油裂化能力。对超稳分子筛进行化学处理,并引入改性组分,     

具有抗镍性能的FCC催化剂基质

用两种不同比表面积和孔径分布的氧化铝作为基质添加组分制备催化剂，考察不同基质对FCC催化剂性能的影响。结果表明，添加大孔径、低比表面的氧化铝可改善FCC催化剂的重油转化能力、焦炭选择性以及抗镍性能。     

FCC工艺中提升增产丙烯助剂性能研究进展

流化催化裂化（FCC）是炼厂最重要的二次加工工艺,也是石油化工应用中丙烯的第二大来源。随着丙烯需求消费的不断增长,在FCC催化剂中添加增产丙烯助剂是一种灵活、高效提高丙烯收率的途径,其助剂主要由活性组分ZSM-5分子筛和基质组成。本文主要从活性组分ZSM-5分子筛和基质两方面分别介绍目前阶段增产丙烯助剂的研究现状,通过对ZSM-5分子筛的改性来提升活性组分的性能,重点综述了调变分子筛的酸度、改善孔结构及粒度和提高水热稳定性;分析了基质孔结构和酸性的梯度分布对助剂在FCC工艺中提高原料的转化、减少生焦和增产丙烯的重要作用。最后指出在合成分子筛过程中引入改性元素,减少元素流失,提高改性元素的利用率,同时在助剂基质方面的研究仍有不足,开发低成本、大孔径和适宜酸度的高性能基质也是增产丙烯助剂未来的研究方向。     

ZSM-5分子筛的复合改性及催化裂化性能

针对催化裂化反应中提高汽油辛烷值和增加丙烯收率，对择形分子筛ZSM-5的改性方法进行研究。通过磷、钴和稀土的复合改性，不仅提高改性元素磷的利用率，而且加强分子筛裂化汽油中C₅、C₆烯烃以及异构化和芳构化能力，达到增产丙烯同时生产清洁汽油的目的。小型固定流化床评价结果表明，常规FCC催化剂中添加复合共沉淀法改性分子筛制备的催化剂助剂后，液化气产率提高3.22个百分点，丙烯收率提高1.52个百分点以上，汽油研究法辛烷值提高2个单位以上。     

FCC回炼油加氢催化剂制备及其反应性能研究

研究复配催化剂对FCC回炼油催化加氢性能的影响。以NaY分子筛、拟薄水铝石分别作为原料制备HY分子筛、γ-Al₂O₃,并采用浸渍法制备P@γ-Al₂O₃改性载体。利用XRD、BET、Py-IR和SEM等对催化剂进行表征。采用高压反应釜进行FCC回炼油加氢催化实验,考察载体种类、活性组分Ni-Mo配比对催化反应性能的影响。结果表明,磷改性有利于提高γ-Al₂O₃的织构特性和B酸量。另外,将HY分子筛与P@γ-Al₂O₃复配后,其载体酸性及孔道分布得到进一步优化,在复配比为m(P@γ-Al₂O₃)∶m(HY)=8∶2、活性组分配比n(Ni)∶n(Mo)=1∶2时,催化加氢性能最好,所得产物中饱和分最多、氢碳比最高。     

碱改性ZSM-5分子筛制备与催化加氢脱硫芳构化性能

采用0.2 mol/L的NaOH溶液以及浓度均为0.2 mol/L的NaOH和TPAOH的混合溶液,分别对ZSM-5分子筛进行脱硅处理。利用XRD、N_2吸附-脱附、SEM及NH_3-TPD等方法对处理前后样品进行表征。以脱硅处理后的ZSM-5分子筛为载体,采用等体积浸渍法制备了Co-Mo-P/ZSM-5催化剂,以全馏分FCC汽油为原料,考察了该催化剂的加氢脱硫及芳构化性能。结果表明,单纯强碱NaOH溶液处理对ZSM-5分子筛的晶体结构影响较大,造成分子筛骨架结构坍塌,酸性降低;TPAOH的存在保护ZSM-5分子筛骨架结构,提高ZSM-5分子筛的结晶度,并且在生成介孔的同时,最大限度地保留了原微孔结构,并调变了酸性。碱处理后制得的Co-Mo-P/HZSM-5(C-T)催化剂表现出良好的加氢脱硫与芳构化性能。     

碱改性ZSM-5分子筛制备与催化加氢脱硫芳构化性能

采用0.2 mol/L的NaOH溶液以及浓度均为0.2 mol/L的NaOH和TPAOH的混合溶液,分别对ZSM-5分子筛进行脱硅处理。利用XRD、N_2吸附-脱附、SEM及NH_3-TPD等方法对处理前后样品进行表征。以脱硅处理后的ZSM-5分子筛为载体,采用等体积浸渍法制备了Co-Mo-P/ZSM-5催化剂,以全馏分FCC汽油为原料,考察了该催化剂的加氢脱硫及芳构化性能。结果表明,单纯强碱NaOH溶液处理对ZSM-5分子筛的晶体结构影响较大,造成分子筛骨架结构坍塌,酸性降低;TPAOH的存在保护ZSM-5分子筛骨架结构,提高ZSM-5分子筛的结晶度,并且在生成介孔的同时,最大限度地保留了原微孔结构,并调变了酸性。碱处理后制得的Co-Mo-P/HZSM-5(C-T)催化剂表现出良好的加氢脱硫与芳构化性能。     

P-HZSM-5和SAPO-34复合分子筛在甲醇制丙烯反应中的应用

采用等体积浸渍的方法对HZSM-5分子筛进行磷改性。通过将磷改性前后的HZSM-5分别与SAPO-34分子筛通过机械混合法和水热晶化法制备成复合分子筛,分别用XRD、SEM、FTIR、NH₃-TPD、BET等手段对分子筛样品的物化性质、酸性和孔结构进行表征分析。对比分析了磷改性和复合分子筛的两种制备方法对甲醇制丙烯(MTP)反应催化性能的影响。结果表明,磷改性HZSM-5分子筛的强酸强度和数量明显下降,丙烯选择性也得到了提升。而分子筛的机械混合改变了催化剂的酸性和孔结构,使得其在MTP反应中有较高的丙烯选择性和较长的催化寿命。在磷改性后的HZSM-5与SAPO-34分子筛机械混合得到的S/PZ-M分子筛上,MTP反应结果表明,反应进行30 h时,丙烯的选择性高达51.34%,丙烯/乙烯比为3.93。     

镧铈比对FCC催化剂性能的影响

用不同镧铈比改性由原位晶化合成的Y型分子筛,探索了其在离子交换和焙烧过程中的影响.利用XRD、微反活性评价、固定流化床反应性能评价等测试手段对催化剂样品进行了表征,研究了其对FCC催化剂反应活性、产品分布、选择性和抗镍钒污染性能的影响.结果表明:镧铈改性有利于提高Y型分子筛结构的稳定性,其中低稀土时,镧铈比为0∶1的作用更明显;而高温或水蒸气氛围焙烧时,镧铈比为1∶1和1∶0的作用更明显;经镧铈比为1∶1和1∶0改性的FCC催化剂转化率和液体产品收率较高,而经镧铈比为0∶1改性的FCC催化剂汽油和重油收率较高.不同镧铈比改性的FCC催化剂在抗镍钒重金属污染实验中都能保留较高的微反活性,其中镧铈比为1∶0的FCC催化剂抗镍钒重金属污染性能最好.     

Application of Novel Zeolite Y Nanoparticles in Catalytic Cracking Reactions

The cracking activity of a fluid catalytic cracking (FCC) catalyst containing novel zeolite Y nanoparticles fabricated using mesoporous silica (average particle size of 150 nm) was examined and compared with the performance of other catalysts. The activity experiments were carried out in a fluidized bench-scale batch riser simulator reactor. The bulky probing compound of 1,3,5-triisopropylbenzene (TIPB) was cracked to lighter compounds over a catalyst containing 25% of the developed zeolite. The synthesized sodium-type zeolite nanoparticles were subjected to two cycles of ion-exchange treatment using ammonium sulfate and lanthanum chloride and then to calcination. To investigate the effects of particle size on the activity, three additional catalysts were prepared with the mean particle size of the supported zeolites ranging from 450 to 1800 nm. The preparation of the FCC catalysts was conducted by mixing the highly aqueous dispersed zeolite Y nanoparticles with colloidal silica–alumina as a matrix and silica sol as a binder. The results of the catalytic cracking of TIPB demonstrated the significant effect of the size reduction of the synthesized zeolite Y nanoparticles on the catalytic performance of the catalyst. The FCC catalyst that contained zeolite Y nanoparticles (150 nm) showed superior conversion and selectivity percentages for the main products. The results of this study have a direct implication on the preparation of colloidal catalysts containing zeolite Y nanoparticles, which form stable emulsion with petroleum products. These emulsions can be utilized for slurry and ebullated bed reactors in heavy oil upgrading applications.     

不同高岭土系黏土性质及在催化裂化催化剂中的应用

随着原料油重质化、劣质化程度逐渐增高,催化裂化催化剂基质不仅需要保证催化剂有良好的磨损性能和流化性能,还需要具有适当的孔和一定的酸性对原料油中的大分子进行预裂化。半合成催化裂化催化剂中的高岭土系黏土对催化剂性能有重要影响。高岭土可直接或经酸、碱改性作为催化剂基质,也可通过原位晶化技术合成分子筛或含有Y型分子筛的催化剂。累托石通过交联反应可以合成层柱分子筛用于催化裂化催化剂制备。埃洛石因其管状结构,作为基质时催化剂具有孔体积和比表面积大及活性高的特点。对催化裂化催化剂中高岭土系黏土结构、改性方法及在催化裂化催化剂中应用进行综述,并对今后高岭土在催化裂化催化剂中的研究方向进行展望。     

Preparation and Properties of Fluid Cracking Catalysts for Residual Oil Conversion

Catalytic cracking of petroleum to produce gasoline began in about 1912. The early pioneering work was carried out by Eugene Houdry [1]. Modern fluid catalytic cracking (FCC) was conceived at Exxon and commercially developed in about 1940 [2] using amorphous catalysts. Fluid catalysts are small spherical particles ranging from 40 to 150 um in diameter with acid sites capable of cracking large petroleum molecules to products boiling in the gasoline range. One advantage of the FCC process is the absence of the diffusion limitations present in conventional gas oil cracking due to the small size of the catalyst particle. Since 1964 virtually all catalysts contain faujasite, a stable, large pore, Y-type zeolite dispersed in a silica/alumina matrix [3]. The catalytic aspects of contemporary FCC processes have been reviewed by Venuto and Habib [4], Gates, Katzer, and Schuit [5], Magee and Blazek [6], and Magee [7]. A more recent update of refinery trends has been made available by Blazek [8].     

Preparation and Properties of Fluid Cracking Catalysts for Residual Oil Conversion

Catalytic cracking of petroleum to produce gasoline began in about 1912. The early pioneering work was carried out by Eugene Houdry [1]. Modern fluid catalytic cracking (FCC) was conceived at Exxon and commercially developed in about 1940 [2] using amorphous catalysts. Fluid catalysts are small spherical particles ranging from 40 to 150 um in diameter with acid sites capable of cracking large petroleum molecules to products boiling in the gasoline range. One advantage of the FCC process is the absence of the diffusion limitations present in conventional gas oil cracking due to the small size of the catalyst particle. Since 1964 virtually all catalysts contain faujasite, a stable, large pore, Y-type zeolite dispersed in a silica/alumina matrix [3]. The catalytic aspects of contemporary FCC processes have been reviewed by Venuto and Habib [4], Gates, Katzer, and Schuit [5], Magee and Blazek [6], and Magee [7]. A more recent update of refinery trends has been made available by Blazek [8].     

Realumination of dealuminated HZSM-5 zeolite by citric acid treatment and its application in preparing FCC gasoline hydro-upgrading catalyst

This article describes a novel citric acid treatment method for realuminating dealuminated HZSM-5 zeolite and its application in enhancing the performance of the zeolite derived FCC gasoline hydro-upgrading catalysts. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and the influences of the different modification methods on the acidity, pore structure and catalytic performance of the modified HZSM-5 zeolite supported catalysts were compared in the present investigation. The results showed that compared with the single HCl or citric acid treatment, the steaming treatment, and the steaming/HCl treatments, the citric acid treatment after steaming exclusively increased the amount of framework Al species due to its realumination effect on the steamed HZSM-5 zeolite. This realumination effect of the citric acid treatment could optimize the ratio of framework Al to extra-framework Al in the steamed HZSM-5 zeolite and thus greatly improve the acidity distribution and pore structure of the corresponding catalyst. The catalytic performance assessments of the different zeolite supported catalysts for FCC gasoline hydro-upgrading revealed that the catalyst supported on the steaming/citric acid treated HZSM-5 zeolite had balanced initial and long-term activities in hydrodesulfurization, hydroisomerization and aromatization, high liquid yield and improved gasoline road octane number. The superior catalytic performance of the catalyst could be closely related to its suitable ratio of framework Al to extra-framework Al achieved by the combinational use of the steaming dealumination and the citric acid realumination, fully demonstrating the effectiveness of the steaming and citric acid treatments in optimizing the physicochemical properties and catalytic performance of HZSM-5 zeolite supported catalysts.     

磷改性对氯化Ni-W/SiO2/γ-Al2O3降烯烃催化剂性能的影响

采用氯化处理后的硅铝载体，通过等体积浸渍法分别制备了磷改性前后的两种Ni-W/硅铝催化剂。利用FR/IR-560和Digisorb-2400物理吸附仪对两种催化剂的酸度、比表面积、孔径和孔容等进行了表征，同时利用荧光指示剂吸附法对磷改性前后催化剂降烯烃的性能进行了考察。结果表明，磷改性使催化剂的B酸中心数量增加了0.02 mmol·g^－1，而B酸中心的增加有利于双分子的氢转移反应,避免反应过程中催化剂表面的积炭。在催化剂活性方面，磷改性使催化裂化汽油中的烯烃含量降低了3.06个百分点，同时提高了产品油的液体收率；从产品分布看，含磷催化剂的液体产品中异构烷烃和芳烃比例均有所提高，说明磷的加入增加了异构化和芳构化的反应活性。     

Synergisms between matrices and ZSM-5 in FCC gasoline non-hydrogenating upgrading catalysts

This article describes a novel non-hydrogenating FCC gasoline upgrading catalyst system consisting of a kaolin/γ-Al₂O₃ binary-matrix and an active component zeolite HZSM-5. Different catalysts made from the different combinations of HZSM-5 with the three matrices (two kaolins and γ-Al₂O₃) or their binary mixtures were prepared and their catalytic performances were assessed in a continuously flowing fixed-bed reactor using FCC gasoline as feedstock. The results showed that compared with the single-matrix based HZSM-5 catalysts, the binary-matrix based HZSM-5 catalysts had much better catalytic performance. The characterization results of the acidity, specific area and pore structure properties of the catalysts revealed that the synergisms between the matrices and HZSM-5 in the acidity and pore distribution of the binary-matrix based catalysts accounted for their improved catalytic performance. Our results demonstrated that the non-hydrogenating catalyst system developed in the present investigation can convert olefins in FCC gasoline into aromatics that have higher research octane number (RON) and thus has potential application for FCC gasoline upgrading because of its excellent olefin reduction ability and RON preservability.     

不同类型氧化铝对FCC轻汽油芳构化性能影响

针对第六阶段汽油国家（国Ⅵ）标准大幅度降烯烃同时保辛烷值的生产需要，本文通过改变氧化铝基质类型，制备了系列催化裂化（FCC）轻汽油芳构化催化剂，并对催化剂酸性质和织构性质进行调变。采用X射线衍射（XRD）、N₂吸附脱附、扫描电子显微镜（SEM）、红外光谱（IR）和吡啶红外光谱（Py-IR）等手段对催化剂的物理性质进行表征，并以工业FCC轻汽油为原料对催化剂芳构化性能进行评价。实验结果表明，不同类型氧化铝的引入未对ZSM-5分子筛晶型产生影响，但可以显著调变ZSM-5分子筛的表面酸性，增加L酸中心数量。具有均一和相对较小比表面积和孔容的氧化铝材料更有利于轻汽油芳构化性能，轻汽油产品中，烯烃大幅下降（体积分数减少18.18%），异构烷烃（体积分数提高10.51%）和芳烃（体积分数提高2.75%）增幅较为明显，辛烷值损失（-5.1）较小并且可控。     

中大孔催化裂化催化剂研究进展

发展中大孔型催化剂是催化裂化催化剂的主要发展方向之一,催化裂化催化剂中引入中大孔的主要方法有高岭土酸碱改性法、引入大孔硅铝基材料法、引入介孔分子筛法、原位晶化法和模板法。酸碱改性高岭土的孔结构受原料影响较大,孔径一般小于10 nm;制备大孔硅铝基材料替代拟薄水铝石可有效改善催化剂的孔结构,但应关注对催化剂强度的影响;分子筛中引入介孔又包括水热处理法,酸、碱处理法和引入不稳定位点法,工业应用范围广,但处理过程中易造成Y型分子筛结晶度下降,并缺乏连续、贯通型孔道;原位晶化法是工业上较成功的中大孔催化剂制备方法,但能耗相对高,流程长;模板法可通过改变模板类型、含量对催化剂孔结构调变,但应关注环保及催化剂强度问题。