抗铁污染催化裂化催化剂的制备及性能评价

采用原位构筑的方式,合成了拟薄水铝石改性高岭土复合材料,将其作为基质材料用于抗铁污染催化裂化（FCC）催化剂的制备,考察了所制备FCC催化剂的抗铁污染性能。表征结果表明,与常规高岭土相比,拟薄水铝石改性高岭土复合材料具有更高的比表面积、孔体积以及表面酸密度,分别可达112 m2/g、0.39 cm3/g和78.3 μmol/g。催化裂化性能评价结果表明,相同铁污染条件下,与常规FCC催化剂相比,使用以拟薄水铝石改性高岭土复合材料为基质的FCC催化剂时转化率提高了1.96百分点,油浆产率降低了1.22百分点,汽油收率和总液体收率分别提高了2.08百分点和2.23百分点,具有较好的抗铁污染性能。     

拟薄水铝石@高岭土复合材料的合成及其在FCC催化剂中的应用

以酸抽提高岭土生成的铝物种为酸性铝源、偏铝酸钠为外加碱性铝源,采用双铝中和法在高岭土结构中原位构筑了拟薄水铝石结构单元,合成了拟薄水铝石@高岭土复合材料,将所合成复合材料用于催化裂化催化剂的制备,考察了所制备催化剂的重油催化裂化反应性能,采用XRD、N_2吸附-脱附、氨气程序升温脱附、Py-FTIR等方法表征了所制备材料的物理化学性质。表征结果显示,拟薄水铝石结构单元被成功地引入到高岭土结构中,与常规高岭土相比,所制备的拟薄水铝石@高岭土复合材料具有更高的比表面积、孔体积和表面酸密度。实验结果表明,与使用常规高岭土制备的催化剂相比,使用拟薄水铝石@高岭土复合材料制备的催化剂的重油收率降低了1.50百分点,转化率提高2.85百分点,同时汽油收率和总液收率分别提高1.54和1.02百分点。     

抗铁污染催化裂化催化剂

采用碱抽提方法对传统高岭土进行改性并将其作为基质材料制备了催化裂化催化剂。利用N2吸附-脱附、FTIR、元素分析等方法分析了高岭土改性前后的结构和性能;通过重油催化裂化反应考察了催化剂的抗铁污染性能。表征结果显示,相对传统高岭土,改性高岭土具有更大的比表面积和孔体积,分别可达158 m~2/g和0.40 cm~3/g,同时Al_2O_3含量增至65.23%(w),提高了催化剂表面酸性中心可接近性,进而显著改善了催化剂的抗铁污染性能。在相同铁污染条件下,与传统高岭土制备的催化剂相比,使用改性高岭土制备的催化剂的重油转化率、汽油收率、总液体收率和轻质油收率分别提高了1.94,2.01,2.09,1.24百分点,而干气、焦炭和重油产率则分别降低了0.17,0.73,1.17百分点。     

研磨-焙烧-碱处理偏高岭土制备大孔催化剂基质

采用研磨-焙烧-碱处理的方法,以偏高岭土为原料,制备了流化催化裂化(FCC)催化剂大孔基质。采用自动压汞仪和扫描电子显微镜对制备的大孔基质的孔结构和表面形貌进行了表征;考察了研磨时间和碱量对偏高岭土孔结构的影响。实验结果表明,经研磨-焙烧-碱处理后,偏高岭土中形成了100～2000nm的大孔,所形成的大孔与偏高岭土中原有的介孔构成了介孔-大孔双峰分布;研磨时间和碱量对偏高岭土的孔道结构有较大影响,在研磨时间为3h、加入NaOH的质量分数为20%时,偏高岭土的孔结构最好,以此条件下得到的偏高岭土为FCC催化剂基质与以高岭土为FCC催化剂基质相比,重油裂化的汽油收率从28.82%提高到36.14%。     

利用废催化裂化催化剂合成含有沸石分子筛的复合材料及其应用

以催化裂化废催化剂为原料,在水热条件下晶化合成含有NaY分子筛的多级孔结构复合材料,材料中NaY分子筛的结晶度为56.7%,具有较大比表面、孔体积以及较强的水热稳定性;利用复合材料制备出的FCC催化剂具有独特的孔径分布有利于扩散能力的提高,产品分布得到优化和改善;催化剂表现出抗磨损能力强、活性高、抗重金属能力和重油转化能力强的特点,与对比剂相比,汽油产率和轻质油产率分别增加了1.61%和1.31%,焦炭降低了0.22%,汽油烯烃含量降低2.51%,汽油RON辛烷值提高0.7个单位。     

富B酸复合材料的制备及其在重油FCC催化剂中的应用

以偏铝酸钠抽提高岭土产生的硅为硅源、偏铝酸钠为铝源、十六烷基三甲基溴化铵为模板剂,利用模板组装原理在高岭土结构中原位构筑了有序介孔硅铝结构单元,制备了富B酸有序介孔硅铝/高岭土复合材料;采用XRD、N_2吸附-脱附和吡啶吸附红外光谱对所制备复合材料进行表征。结果表明,制备复合材料比表面积可达253m~2/g,孔体积可达0.43cm~3/g,具有丰富的表面B酸中心;作为基质材料,所制备复合材料不但显著提高了催化裂化催化剂的重油转化能力,并显著改善了裂化产品的选择性,可使转化率提高3.19百分点,同时使汽油和总液体收率分别提高2.95和2.47百分点,重油和焦炭收率分别下降2.12和0.41百分点。     

韩城高岭土的性质及其原位晶化所制FCC催化剂的研究

在实验室进行了韩城高岭土的性质及其原位晶化所制FCC催化剂的研究。结果表明韩城高岭土的基本性质符合全白土型原位晶化催化剂的要求;该高岭土在原位晶化体系中具有适度活性硅和较快活性铝的碱溶速度,以及良好的晶化性能和裂化性能。与现用的苏州高岭土相同工艺制备的对比剂相比,前者较后者的比表面积、孔体积和微反活性高,但磨损指数略大;以新疆减压宽馏分和减压渣油的混合油为原料,进行裂化性能考察的结果表明,汽油和轻质油收率较高,干气和焦炭收率略高,汽油中的烯烃含量较低,芳烃含量较高,辛烷值(MON)较高。     

硅藻土在催化裂化催化剂重油转化中的应用

对高岭土、埃洛石和硅藻土的物理化学性质和形貌进行了表征,并以此为载体,采用常规方法制备了催化裂化（FCC）催化剂。以减压蜡油与减压渣油（二者质量比为6∶4）混合物为原料,在催化剂/原料油（质量比）为5,反应温度为530 ℃,催化剂用量为9 g的条件下,对所制备催化剂的反应性能进行了评价。结果表明:以质量分数为7%的埃洛石等比例替换高岭土所制备的催化剂,其反应性能与100%高岭土者（催化剂1）相当;采用7%硅藻土等比例替换高岭土所制备的催化剂,产物汽油、轻质油和总液体收率较催化剂1依次提高了0.44,0.27,0.23个百分点,转化率提高了0.51个百分点,重油收率降低了0.35个百分点,表明硅藻土对改善产品性能有促进作用;但是,当硅藻土质量分数提高到15%时,重油转化能力降低。     

高岭土微球内置固体晶种原位合成Y型沸石

采用常规法和高岭土微球内置晶种法制备了NaY/高岭土复合微球，利用XRD、低温N2吸附-脱附、SEM等方法对制备的复合微球进行表征，并对NaY/高岭土复合微球进一步改性制得的原位晶化催化剂进行评价。实验结果表明，内置晶种法所制备的NaY/高岭土复合微球的结晶度从18%增加到28%，介孔孔体积从0.14 cm3/g增加到0.31 cm3/g，常规法所制备NaY/高岭土复合微球Y型分子筛主要分布在微球外表面，而采用内置晶种法后，微球内部可观察到更多的Y型分子筛。与常规方法相比，内置晶种法所制备催化剂的重油产率从8.16%下降到4.79%，汽油产率和总液收率分别从51.31%,83.40%增加到54.92%和86.41%，生焦因子从1.62下降到1.21。     

不同产地高岭土所制催化裂化催化剂的性能差异

对5种不同产地高岭土（美国高岭土、衡阳高岭土、漳州高岭土、贵州埃洛石以及合浦高岭土）进行理化性质分析,并考察以这5种高岭土为基质制备催化裂化（FCC）催化剂的性能差异。结果表明：5种高岭土的主要成分均是SiO₂和Al₂O₃;贵州埃洛石中Fe₂O₃和CaO的含量较高、比表面积最大、颗粒直径最大、所制备的FCC催化剂的磨损指数最高、催化裂化性能最差,提高铝溶胶加入量后可以降低所制备FCC催化剂的磨损指数;由漳州高岭土制备的催化剂上重油产率最低,为6.81%,液体收率最高,达到88.43%;由美国高岭土、衡阳高岭土和合浦高岭土制备的催化剂上液化气、汽油收率以及干气、焦炭产率基本相当。     

A FCC Catalyst Prepared by in situ Technique Based on Application of Filter Residue and Kaolin

This paper has provided an effective method to utilize the filter residue. A Y zeolite-containing composite and a fluid catalytic cracking(FCC) catalyst had been successfully prepared by an in-situ crystallization technology using filter residue and kaolin as raw materials. The samples were characterized by XRD, FT-IR, SEM, and N_2 adsorption-desorption techniques and evaluated in a bench FCC unit. In comparison to the reference samples synthesized from single kaolin,the silica/alumina molar ratio, the external surface area, and the total pore volume of the composite increased by 16.2%,14.5%, and 16.2%, respectively. The catalyst possessed more meso-and macro-pores and more acid sites than the reference catalyst, and exhibited better coke selectivity. The prepared catalyst had the optimum isomerization and aromatization performance. The olefin content in the cracked gasoline obtained over this catalyst was reduced by 5.05 percentage points with the research octane number of gasoline increased by 0.5 units.     

Synthesis and Application of a Zeolite-containing Composite Material Made from Spent FCC Catalyst

Novel composite material with a wide pore distribution was synthesized by an in situ technique using spent FCC catalyst as raw material. The characterization results indicated that the composite material contained 56.7% of zeolite Y and exhibited a much larger specific surface area and pore volume as well as strong hydrothermal stability. Fluid catalytic cracking(FCC) catalyst was prepared based on the composite material. The results indicated that the as-prepared catalyst possessed a unique pore structure that was advantageous to the diffusion-controlled reactions. In addition, the attrition resistance, activity and hydrothermal stability of the studied catalyst were superior to those of the reference catalyst. The catalyst also exhibited excellent nickel and vanadium passivation performance, strong bottoms upgrading selectivity, and better gasoline and coke selectivity. In comparison to the reference catalyst, the yields of the gasoline and light oil increased by 1.61 and 1.31 percentage points, respectively, and the coke yield decreased by 0.22 percentage points, and the olefin content in the produced gasoline reduced by 2.51 percentage points, with the research octane number increased by 0.7 unit.     

裂化催化剂的设计对清洁汽油生产的影响

根据FCC过程生产清洁汽油对催化剂的要求,从催化剂基质、分子筛平衡晶胞、沸石与基质的表面积之比（Z/M）、新功能组元的引入及其作用等方面提出了裂化催化剂的设计思路,并通过重油小型固定流化床反应进行验证.小试结果表明,有一定酸性的大孔基质材料起到很好的传质、传热作用,有助于提高催化剂活性中心的利用率;较大的平衡晶胞有利于双分子反应,改进汽油质量;较高的Z/M可以明显改善汽油的族组成;新功能组元增强了催化剂催化选择性氢转移反应和芳构化反应的能力.与常规裂化催化剂相比,设计的催化剂在焦炭选择性、重油裂化能力、汽油质量方面都有明显改善.     

利用废渣制备催化裂化催化剂及其催化性能研究

采用X射线荧光光谱、N₂吸附-脱附、吡啶吸附红外光谱等分析手段对催化裂化催化剂生产过程所产生的废渣进行分析,并研究了废渣脱除杂质的处理工艺;利用优化处理的废渣或/和高岭土为载体、分子筛为活性组分经喷雾干燥制备催化裂化催化剂,分析催化剂的物化性质,并利用固定流化床装置评价催化剂性能。结果表明：pH为3.0、搅拌时间为20 min、NH₄Cl投料比为20%、温度为60℃、洗涤介质为NH₄Cl、先洗涤后焙烧再洗涤是处理催化剂废渣的最佳工艺条件;在反应温度为480℃、剂油质量比为7.5、质量空速为4 h^-1、原料油为大庆减压蜡油的条件下,与以高岭土为载体的催化剂相比,综合考虑优选载体中废渣质量分数在10%～20%的催化剂具有更强的重油转化能力,产物液体收率和汽油选择性更高,汽油组成中异构烷烃含量高、烯烃含量低。     

LDR-100重油催化裂化催化剂的性能评价及工业应用

从中型试验和工业应用两个方面对兰州化工研究中心开发的LDR-100重油催化裂化催化剂的应用性能进行考察。中型试验表明,重油产率降低1.45百分点,丙烯收率提高0.74百分点,汽油辛烷值（RON）提高0.70个单位,汽油烯烃含量降低6.13百分点。工业应用表明,总液体收率提高0.42百分点,汽油辛烷值（RON）增加3个单位,催化剂单耗由2.24 kg/t降低到1.76 kg/t。经济效益可增加2 638.77万元/a。     

助剂LBO-A加入量对大庆常压渣油催化裂化反应的影响

在小型固定流化床实验装置上,以大庆常压渣油为原料,采用华北石化公司第Ⅱ套催化裂化装置的平衡剂为催化剂,在反应温度480～490 ℃、剂油质量比为6、空速为20 h-1的条件下,考察加入助剂LBO-A对催化裂化反应的影响。结果表明,随助剂LBO-A加入量的增加,重油裂化能力降低,汽油收率和液体收率减少,但汽油中芳烃含量增加;当助剂LBO-A加入量为10％时,催化裂化产品分布较合理,汽油中烯烃质量分数降低到20%以下,汽油中芳烃含量增加4.2个百分点。     

New resid FCC catalyst for maximizing gasoline yield

After surface acidity and pore modifications, the acid strength and pore distribution of composite were improved effectively. FTIR analysis showed that the acid distribution of the modified composite was more concentrated on the range of intermediate and strong acidity. This kind of modification can direct more hydrocarbons to enter into the pores to be converted and remarkably increases the possibility of gasoline forming through a cracking reaction. N₂ adsorption–desorption analysis showed that the composite had more meso- and macro-pores with a trimodal distribution. This kind of modification can effectively reduce the mass-transfer resistance in the reaction process and accelerate the diffusion of the product molecules. A FCC catalyst for maximizing gasoline yield was prepared based on the composite. The evaluated results indicated the catalyst can decrease the excessive cracking of mediate distillate and improved the gasoline yield effectively. The gasoline yield had been increased by 2.89%, while the coke yield has been decreased by 0.71%.     

Study on Reduction of Sulfur Content in FCC Gasoline

Reduction of sulfur content in FCC gasoline was studied in a fixed fluid bed (FFB) unit by using metal-modified LV-23 FCC catalyst. The results showed that the sulfur content in FCC gasoline could be reduced with LV-23 catalyst modified with zinc, palladium, zinc-palladium, zinc-cobalt, and zinc-nickel. Among these metals or metal combinations, palladium-containing catalyst was the most effective. Desulfufization of the heavy fraction of FCC gasoline was more effective than full-range gasoline under the same conditions with palladium-containing catalysts. A high reaction temperature was favorable to desulfurization, but it would reduce the yield of liquid product. After desulfurization reaction, the olefm content of product gasoline decreased while the aromatic and iso-alkane contents increased. Removal of thiophene and benzothiophene is higher.     

催化裂化增产汽油SGC-1催化剂的工业应用

介绍了增产汽油SGC-1重油裂化催化剂在中国石化北京燕山分公司第二套重油催化裂化装置上的工业应用情况。结果表明,与空白标定时使用VRCC催化剂相比,在最大汽油产率方案、最大装置加工量方案和最大掺渣率方案下,汽油产率分别达到47.57%,47.05%,47.10%,分别增加了4.56,4.04,4.09百分点,干气、汽油和焦炭的选择性有所改善,尤其是汽油的选择性明显提高,总液体收率变化不大。SGC-1催化剂对增产汽油产率效果明显、对原料适应性好、干气选择性好,满足催化裂化装置改善产品分布的要求。