A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching

This article describes a novel modification method consisting of steaming and subsequent citric acid leaching to finely tune acidity and pore structure of HZSM-5 zeolite and thereby to enhance the on-stream stability of the zeolite derived fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst. A series of dealuminated HZSM-5 zeolites and their derived catalysts were prepared and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), ²⁷Al MAS NMR, nitrogen adsorption, temperature programmed desorption of ammonium (NH₃-TPD) and infrared (IR) spectroscopy of chemisorbed pyridine. The results showed that the citric acid leaching could preferentially remove the extra-framework Al (EFAl) species formed by steaming treatment and thus reopen the EFAl-blocked pore channels of the steamed zeolite. The steaming treatment at a suitable temperature and subsequent citric acid leaching not only decreased the strength of acid sites to a desirable degree but also increased the ratio of medium and strong Lewis acidity to medium and strong Brönsted acidity, both of which conferred the resulting catalyst with superior selectivity to aromatics, good hydroisomerization activity and gasoline research octane number (RON) preservability, as well as enhanced on-stream stability. The results fully demonstrated that the treatments by steaming and followed citric acid leaching can serve as an important method for adjusting the physicochemical properties of HZSM-5 zeolite.     

A novel catalyst system based on quadruple silicoaluminophosphate and aluminosilicate zeolites for FCC gasoline upgrading

To develop a novel catalyst system that has excellent olefin reduction capability for FCC gasoline without loss in octane number, different catalysts supported on multiple composite carriers consisting of SAPO-11, Hβ, HMOR and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. The pore structure and acidity of the catalysts were characterized by N₂ adsorption and pyridine adsorption FTIR, respectively. Based on the results obtained over the catalysts supported on binary-zeolite carriers (Hβ/HZSM-5, HMOR/HZSM-5 and SAPO-11/HZSM-5) using FCC gasoline as the feedstock, various multiple-zeolite supported catalysts were developed from different combinations of the binary-zeolite systems. It was found that the SAPO-11/HMOR/β/ZSM-5 quadruple composite zeolite supported catalyst gave higher liquid yield, improved gasoline RON, and lower coke deposit amount for the hydro-upgrading of FCC gasoline and thus can be considered as a potential catalyst system. A comprehensive analysis based on the catalytic activities and acidity measurements revealed that acid strength and acid type were two very important factors influencing hydroisomerization and aromatization activities, and the difference in catalyst acid strength determined which factor predominates.     

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.     

Hβ/HZSM-5 Composite Carrier Supported Catalysts for Olefins Reduction of FCC Gasoline Via Hydroisomerization and Aromatization

In order to develop a novel catalyst system that has excellent olefin reduction ability for FCC gasoline without loss in research octane number (RON), different catalysts supported on single- and binary-zeolite carriers consisting of Hβ or/and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. Acidity measurements by pyridine-adsorbed Fourier transformed infrared spectroscopy (FTIR) showed that hydroisomerization and aromatization activities were closely related to the density of acid sites and the ratios of medium Lewis acidity and strong Br?nsted acidity to total acidity. Compared with the single HZSM-5 supported catalyst, the single Hβ supported catalyst was found to have much better olefin reduction performance, but the product RON still suffered from a loss of 1.6. Compared to the single-zeolite supported catalysts, the binary-zeolite Hβ/HZSM-5 supported catalysts with the mass ratio of Hβ to HZSM-5 at 6.6 offered much more stable activity and selectivity to arene, which played an important role in preserving gasoline RON.     

红外光谱法研究水汽处理纳米HZSM-5催化剂表面羟基及其酸性质

采用红外光谱法对系列不同温度水汽处理改性纳米HZSM-5催化剂表面羟基及其酸性质进行了研究,结果表明纳米HZSM-5催化剂经温和水汽处理后,其酸性的变化既体现出与常规尺寸分子筛相同的趋势,又体现出纳米粒子自身的特性,即其内外表面的强酸对水汽处理的敏感程度不同.水汽处理较易脱除的是催化剂外表面的铝羟基,从而导致催化剂外表面酸量的骤减,而内表面酸量变化不大.当水汽处理温度升高后,开始发生骨架铝的脱除,因而内表面酸量开始减少,而外表面酸量与低温水汽处理比较变化不明显.     

改性HZSM-5对甲醇制汽油反应性能的影响

对HZSM-5分子筛改性是提高甲醇制汽油反应催化性能的有效方式,分别用非金属、稀土金属及水热处理对HZSM-5分子筛催化剂进行改性,考察改性方法对HZSM-5分子筛酸性、孔径和比表面积等性质的影响,同时对改性HZSM-5分子筛催化剂催化甲醇制汽油的汽油收率和芳烃含量等指标进行比较。结果表明,经La改性的催化剂可明显提高汽油收率,水热处理的催化剂反应产物汽油中的均四甲苯含量大幅增加。改性催化剂对反应的影响可一定程度验证相关理论。     

水热处理磷改性HZSM-5催化剂的研究

以催化裂化轻汽油馏分为原料,以水热处理磷改性HZSM-5为催化剂,在小型固定床反应装置上考察了水热处理改性方法制备催化剂的催化裂解性能。通过对HZSM-5分子筛催化剂水热处理,调变其酸性,达到多产丙烯的目的。确定催化剂改性最佳条件为：水热处理温度650 ℃,处理时间2 h,处理空速2 h^-1。HZSM-5水热处理后,明显改善催化剂的水热稳定性和活性,提高丙烯选择性。     

高温水蒸汽处理对HZSM-5分子筛催化甲醇制丙烯的影响

考察不同硅铝比的HZSM-5分子筛催化剂和经过高温水蒸汽处理后的HZSM-5分子筛催化剂在甲醇制丙烯反应中的催化性能,考察温度和空速对催化反应的影响。结果表明,随着HZSM-5分子筛硅铝比的增加,产物中丙烯选择性增大,可能是分子筛的酸性降低所致;经过高温水蒸汽处理后的HZSM-5分子筛表面酸性降低,提高了催化剂的催化性能。在反应温度450 ℃和空速1.0 h^-1条件下,600 ℃高温水蒸汽处理后的催化剂HT-600的丙烯选择性从改性前的26.8%提高到33.5%。     

On-stream stability enhancement of HZSM-5 based fluid catalytic cracking naphtha hydro-upgrading catalyst via magnesium modification

On-stream stability of fluid catalytic cracking (FCC) naphtha hydro-upgrading catalysts that convert olefins into high-octane isoparaffins and aromatics is crucial for guaranteeing the long-term operation of industrial units, and therefore suppressing catalyst deactivation due to coking becomes the focus of FCC naphtha hydro-upgrading process and catalyst development. Here we report a simple and novel strategy to enhance the on-stream stability of a HZSM-5 based FCC naphtha hydro-upgrading catalyst by magnesium modification. The characterization and catalytic test results showed that the incorporation of a suitable amount of MgO can adjust the ratio of Lewis acid sites to Brönsted ones and thereby significantly improve stability of the resulting catalyst.     

Effect of hydrothermal treatment temperature on FCC gasoline upgrading properties of the modified nanoscale ZSM-5 catalyst

Nanoscale HZSM-5 zeolite was hydrothermally treated with ammonia water at different temperatures and then loaded with La₂O₃ and ZnO. The parent and the modified nanoscale HZSM-5 catalysts were characterized by SEM, NH₃-TPD, IR and XRF. The performance of the modified HZSM-5 catalysts for FCC gasoline upgrading was evaluated in a fixed bed reactor in the presence of hydrogen. The results indicated that the modified catalyst which was hydrothermally treated at 400 °C exhibited excellent aromatization activity, isomerization activity and higher ability of reducing olefin content in FCC gasoline. Under the given reaction conditions, the olefin content in FCC gasoline could be decreased from 49.6 to 8.1 vol.%. The catalytic performance of the modified nanoscale ZSM-5 catalyst hardly changed within 300 h time on stream, and the research octane number (RON) of gasoline was preserved.     

USY分子筛表面酸性的调变及其在催化脱除芳烃中烯烃的应用

详细论述了柠檬酸对USY分子筛的改性作用,以脱除高溴指数芳烃中烯烃的反应为例对其催化活性进行了评价。实验结果表明:0.2mol/L柠檬酸溶液酸性适宜,对分子筛的骨架铝以及非骨架铝进行了有效的脱除,脱除的铝在分子筛中以无定形的非骨架铝形式存在。柠檬酸改性过程可使分子筛的介孔面积以及介孔孔容增大,这十分有利于减缓分子筛的失活速率。柠檬酸改性过程使分子筛表面的强B酸减少,强L酸增多,这有助于减缓分子筛上积炭的生成速率。经过柠檬酸改性的USY分子筛对脱除芳烃中微量烯烃的催化效果明显高于目前工业中在用的普通白土和改性白土。再生实验说明,经3次焙烧再生后,改性分子筛的活性依然在90%以上,具有很好的可再生性。     

以Beta分子筛为酸性组分的柴油加氢改质催化剂

以Beta分子筛为酸性组分,共浸渍法制备Ni-Mo-P/Beta-Al₂O₃系列催化柴油加氢改质催化剂。采用BET、Py-IR和XRD等对催化剂进行分析,并在100 mL固定床加氢反应器上进行催化剂的加氢改质活性评价,考察Beta分子筛的加入对催化剂物化性质和加氢改质反应活性的影响。结果表明,添加Beta分子筛后,催化剂的比表面积显著增大,酸性增强,多钼酸盐的分布更加均匀;Ni-Mo-P/Beta-Al₂O₃系列催化剂表现出较好的加氢改质反应活性,可以在大幅度降低油品密度和硫氮杂质含量的同时,大幅度提高油品的十六烷值,并维持较高的柴油收率。     

Gasoline selective ZSM-5 FCC additives: effects of crystal size, SiO2/Al2O3, steaming, and other treatments on ZSM-5 diffusivity and selectivity in cracking of hexene/octene feed

ZSM-5 catalysts with silica/alumina ratios of 55/1 and 450/1, and with varying crystal size, were studied to better understand the operation of “gasoline selective” FCC additives. Most materials were steamed for 5 h at 1400°F, and some were subjected to other treatments such as mechanical milling, P addition, and HCl reflux. These materials were characterized for total Al content, tetrahedral Al, and sorption capacity and rate. The ratios of octene isomerization to octene cracking, and of octene cracking to hexene cracking, for a mixed hexene/octene feed at 538°C were used to assess the potential FCC gasoline selectivity of these catalysts.

Steaming generally led to a decrease in effective diffusivity, as calculated from uptake rates. HCl reflux of two steamed samples removed substantial quantities of non-framework alumina, resulting in increased diffusivities and higher selectivities. Density of acid sites did not appear to be important in determining the gasoline selectivity of the catalysts examined here. The effects of most catalyst treatments on reaction selectivities could be related to diffusional blockage, especially by non-framework alumina. However, not all results could be explained by a simple reaction/diffusion model. Factors other than diffusion, such as narrowing of available reaction space in the ZSM-5 channels, may also play a role in determining selectivities.     

碱改性介-微孔HZSM-5分子筛催化乙醇脱水制乙烯性能

对两种不同硅铝比的HZSM-5分子筛进行碱处理,制备介-微孔复合HZSM-5分子筛,研究乙醇脱水制乙烯的催化性能,并考察碱溶液浓度和处理温度对HZSM-5分子筛孔结构和表面酸性的影响。结果表明,适宜的碱处理条件有利于分子筛发生骨架脱硅和脱铝,从而形成介孔。碱处理对硅铝比低的HZSM-5分子筛酸性质影响明显,而硅铝比高的HZSM-5分子筛在碱处理过程中酸性质变化不明显,更易发生脱硅和脱铝而形成更多介孔。碱改性介-微孔HZSM-5分子筛催化剂使乙醇脱水制乙烯催化性能得到改善,尤其低温催化活性提高,这主要归功于碱处理中介孔的形成和表面酸性的调变。     

Characterization of Modified Nanoscale ZSM-5 Zeolite and Its Application in the Olefins Reduction in FCC Gasoline

Nanoscale HZSM-5 zeolite was hydrothermally treated with steam containing 0.8 wt% NH₃ at 773 K and then loaded with La₂O₃ and NiO. Both the parent nanoscale HZSM-5 and the modified nanoscale HZSM-5 zeolites catalysts were characterized by TEM, XRD, IR, NH₃-TPD and XRF, and then the performance of olefins reduction in fluidized catalytic cracking (FCC) gasoline over the modified nanoscale HZSM-5 zeolite catalyst was investigated. The IR and NH₃-TPD results showed that the amount of acids of the parent nanoscale HZSM-5 zeolite decreased after the combined modification, so did the strong acid sites deactivating catalysts. The stability of the catalyst was still satisfactory, though the initial activity decreased a little after the combined modification. The modification reduced the ability of aromatization of nanoscale HZSM-5 zeolite catalyst and increased its isomerization ability. After 300 h onstream, the average olefins content in the gasoline was reduced from 56.3 vol% to about 20 vol%, the aromatics (C₇–C₉ aromatics mainly) and paraffins contents in the product were increased from 11.6 vol% and 32.1 vol% to about 20 vol% and 60 vol% respectively. The ratio of i-paraffins/n-paraffins also increased from 3.2 to 6.6. The yield of gasoline was obtained at 97 wt%, while the Research Octane Number (RON) remained about 90.     

Synthesis of ZSM-5/SAPO-11 composite and its application in FCC gasoline hydro-upgrading catalyst

This article describes the synthesis, characterization and application of a novel aluminosilicate/silicoaluminophosphate composite zeolite ZSM-5/SAPO-11. The composite was synthesized by the in situ overgrowth of SAPO-11 on ZSM-5 and was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transformed infrared (FT-IR) spectrometry, N₂ adsorption and infrared spectroscopy of adsorbed pyridine. The results were compared with those of the mechanical mixture composed of individual ZSM-5 and SAPO-11. In the mechanical mixture, the ZSM-5 phase was morphologically separate from the SAPO-11 phase, while the ZSM-5/SAPO-11 composite existed in a form of a core-shell structure, with the ZSM-5 phase as the core and the SAPO-11 phase as the shell. Compared with the mechanical mixture, the composite had more mesopores and moderate acidity distribution, which could accelerate the diffusion of substances and enhance the synergetic effect between Brönsted and Lewis acids. The comparison of the catalytic performances of the mechanical mixture and the composite-based Ni–Mo catalysts for FCC gasoline hydro-upgrading showed that, due to the above advantages of the composite, the corresponding catalyst yielded improved gasoline research octane number, high liquid yield, good desulfurization activity and lower coke amount and thus could be considered as a potential catalyst system for hydro-upgrading FCC gasoline.     

焙烧温度对HZSM-5分子筛催化1-丁烯齐聚性能的影响

考察焙烧温度对HZSM-5分子筛催化剂结构及1-丁烯齐聚性能的影响,采用XRD、SEM和NH3-TPD对催化剂进行表征。结果表明,升高焙烧温度,对HZSM-5分子筛催化剂的晶相和晶粒尺寸没有影响,催化剂中弱酸与强酸的酸强度和酸量均随焙烧温度的升高逐渐减弱。在催化剂晶粒尺寸一定条件下,催化剂酸性对催化剂的齐聚性能有较大影响,焙烧温度500℃时,C5+收率和C10+选择性最佳。     

酸性组分对LCO改质催化剂反应性能的影响

借助XRD,IR,NH3-TPD、N2 物理吸附等分析手段对4种改性Y沸石进行了表征.考察了不同酸性组分对LCO加氢改质催化剂反应性能的影响,结果表明分子筛硅铝比高,晶形完整,水热稳定性好以及较高的酸强度和较高的B酸浓度有利于催化剂维持较高的催化性能.最终确定了一种晶形完整、耐氮能力强及酸性高的改性Y分子筛为LCO改质催化剂的主要酸性组分.     

Catalytic degradation of polypropylene I. Screening of catalysts

The catalytic degradation of polypropylene has been investigated in this study. Solid acid catalysts, such as silica-alumina and zeolites (HZSM-5, natural zeolite, Mordenite etc.), were screened for polypropylene degradation in the range of 350-450‡C. The degradation products of polypropylene, especially a liquid fraction, formed over solid acid catalysts, were analyzed by GC/MS. The degradation products are distributed in a narrow range of carbon number compared with those obtained by thermal degradation. The liquid fraction contained large amounts of iso-paraffins and aromatics as are present in the gasoline traction of petroleum. The natural zeolite catalyst (clinoptilolite structure, occurring in Youngil area of Korea) was an efficient catalyst for the polypropylene degradation. The acidity and characteristic pore structure of this zeolite appear to be responsible for the good performance. The effects of temperature and reaction tune on the product distribution have also been studied in this work.     

Enhanced Stability of HZSM-5 Supported Ga2O3 Catalyst in Propane Dehydrogenation by Dealumination

Gallium oxide catalysts supported on HZSM-5 with different Si/Al ratios were characterized by pyridine adsorption FT-IR, model reactions and XPS studies. As the Si/Al ratio of the support HZSM-5 zeolite rises, the acidity of the supported catalysts decreases accordingly, which comes from two aspects: the loss of acid sites present on HZSM-5 support and the loss of the acid sites present on gallium oxides. The latter was caused by the change in the interaction between Ga₂O₃ and support. The initial activity in the propane dehydrogenation decreases with increasing Si/Al ratio while the stability increases. The enhanced stability is thought to be caused by the decrease of the acidity of the catalysts, resulting in the suppression of the side reactions, such as cracking and oligomerization.