Catalytic cracking of VGO by hierarchical ZSM-5 zeolite containing mesoporous silica–aluminas using a Curie point pyrolyzer

Ishihara, Atsushi; Kimura, Kentarou; Owaki, Atsushi; Inui, Kentarou; Hashimoto, Tadanori; Nasu, Hiroyuki

doi:10.1016/j.catcom.2012.08.023

Cited by 42 publications

(51 citation statements)

References 28 publications

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“…In this study, the preparation and the characterization of novel hierarchical Y zeolite-containing mesoporous silica _ aluminas are reported, and a novel method to determine the catalytic cracking of VGO using a Curie point pyrolyzer (CPP) is introduced as a simple method for a catalyst evaluation. Our preliminary findings using ZSM-5 have already been reported 19) .…”

Section: Introductionsupporting

confidence: 61%

“…Y zeolite-containing silica _ alumina was synthesized by one step of the acid catalyzed sol-gel process using malic acid (MA) as a catalyst, a template and a reagent for Al dispersion as described in detail previously 19) . A typical method was as follows: Tetraethyl orthosilicate (TEOS) was added to a suspension of Y zeolite in ethanol and the mixture was stirred for 1 h at 25 .…”

Section: P R E P a R A T I O N A N D C H A R A C T E R I Z A T I Omentioning

confidence: 99%

“…Furthermore, hierarchical Y zeolite-containing mesopo-rous silica _ aluminas could be prepared using malic acid (MA) 18), 19) . In these studies, a model compound, ndodecane, was used as a feed material.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Cracking of VGO by Hierarchical Y Zeolite-containing Mesoporous Silica–Alumina Catalysts Using Curie Point Pyrolyzer

Ishihara

Kimura

Hashimoto

et al. 2014

J. Jpn. Petrol. Inst.

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Hierarchical Y zeolite-containing mesoporous silica _ aluminas were prepared by the one pot sol-gel method using malic acid. Properties for the catalytic cracking of vacuum gas oil (VGO) were estimated using a Curie point pyrolyzer, to establish a novel and very simple estimation method for the catalytic cracking of VGO. Prepared catalysts showed higher conversions and selectivities for gasoline than zeolite single, indicating that yields of gasoline for zeolite-containing catalysts increased compared with that of zeolite single. Higher content of aluminum species in the catalysts resulted in decreased olefin/paraffin ratios and increased iso-/n-ratios (ratio of branched products to straight-chained ones), indicating that hydrogen transfer and isomerization were promoted by the addition of acid sites into the matrix. Catalysts with mesopores tended to form larger amounts of multibranched products, which are very important in modern petroleum refining. When the yields of gasoline, singlebranched products and multi-branched products were plotted against the conversion of VGO, the linear relationships were observed and the effect of kinds of zeolite was rather small, indicating that the activity and the selectivity were largely affected by the presence of matrices. Comparison of the yields of gasoline, single-branched products and multi-branched products at the same conversions showed that Y zeolite-containing catalysts always showed the highest yields and ZSM-5-containing catalysts showed the lowest yields although the differences were small. Pore size of the zeolite probably also affected the yields in the treatment of large molecules such as VGO. The present findings suggest that the appropriate combination of zeolite and matrix is the most important factor to obtain high catalytic activity and high yields of gasoline and branched products.

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Section: Introductionsupporting

confidence: 61%

Section: P R E P a R A T I O N A N D C H A R A C T E R I Z A T I Omentioning

confidence: 99%

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Catalytic Cracking of VGO by Hierarchical Y Zeolite-containing Mesoporous Silica–Alumina Catalysts Using Curie Point Pyrolyzer

Ishihara

Kimura

Hashimoto

et al. 2014

J. Jpn. Petrol. Inst.

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“…This means that branched products are lost with increasing cracking rate. However, it has generally been accepted that hydrocarbons with higher molecular weight are cracked faster and produce larger amounts of branched products [3,25,26]. In the mechanism with the formation of the primary carbenium ion in catalytic cracking (Figure 14a route I and III), branched products do not decrease with cracking.…”

Section: Concerning Reaction Mechanismsmentioning

confidence: 98%

Large Mesopore Generation in an Amorphous Silica-Alumina by Controlling the Pore Size with the Gel Skeletal Reinforcement and Its Application to Catalytic Cracking

Ishihara¹,

Hashimoto²,

Nasu³

2012

Catalysts

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Tetraethoxy orthosilicate (TEOS) was used not only as a precursor of silica, but also as an agent which reinforces the skeleton of silica-gel to prepare an aerogel and resultant silica and silica-alumina with large pore size and pore volume. In this gel skeletal reinforcement, the strength of silica aerogel skeleton was enhanced by aging with TEOS/2-propanol mixed solution to prevent the shrink of the pores. When silica aerogel was reinforced by TEOS solution, the pore diameter and pore volume of calcined silica could be controlled by the amount of TEOS solution and reached 30 nm and 3.1 cm 3 /g. The results from N 2 adsorption measurement indicated that most of pores for this silica consisted of mesopores. Silica-alumina was prepared by the impregnation of an aluminum tri-sec-butoxide/2-butanol solution with obtained silica. Mixed catalysts were prepared by the combination of β-zeolite (26 wt%) and prepared silica-aluminas with large mesopore (58 wt%) and subsequently the effects of their pore sizes on the catalytic activity and the product selectivity were investigated in catalytic cracking of n-dodecane at 500 °C. The mixed catalysts exhibited not only comparable activity to that for single zeolite, but also unique selectivity where larger amounts of branched products were formed.

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“…The formation of novel hierarchical composite catalysts with both microporous zeolite and mesoporous matrices increased the selectivity for branched products with higher octane number because the large volumes within the mesoporous matrices around the active acid sites of the zeolite promoted the generation of more bulky branched hydrocarbons 14) 22) . Furthermore, the catalytic cracking of VGO using a Curie point pyrolyzer (CPP) was shown to be a very simple and convenient method to determine the catalytic activity and selectivity for products 19) . On the other hand, the detailed catalytic reactivity and structural properties of industrial catalysts consisting of zeolite and matrices still remain unknown.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Cracking of VGO by Zeolite–kaolin Mixed Catalysts Using Curie Point Pyrolyzer

篤

健太郎

忠範

et al. 2015

J. Jpn. Petrol. Inst.

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Mixed composite catalysts including three types of zeolite (Y, β and ZSM-5), kaolin and binder (Al2O3) were prepared as a model of an industrial catalyst for catalytic cracking and were tested in the catalytic cracking of VGO using a Curie point pyrolyzer (CPP) as a simple estimation method of catalysts for catalytic cracking. The mixed catalysts consisted of 26 wt% of zeolite, 58 wt% of kaolin and 16 wt% of a binder (Al2O3). The three mixed catalysts using Y (Si/Al2 5.5), β (37), ZSM-5 (90) zeolites were named MAT(kaolin)-Y, MAT(kaolin)-β and MAT(kaolin)-Z, respectively. MAT(kaolin)-Y and MAT(kaolin)-β showed higher selectivity for gasoline and higher RON value, and produced larger amounts of olefin and multi-branched products compared with single zeolite. These results indicated that both inhibition of over-cracking and dispersion of acid sites of zeolite were important to increase RON value. The SiO2/Al2O3 ratio of ZSM-5 used in this study was 90, and thus the density of acid sites of the mixed catalyst was much smaller than those for other zeolites used. Therefore, addition of kaolin to ZSM-5 significantly reduced the activity and the product selectivity. In this paper, the CPP method was found to be a simple and convenient tool to investigate the characteristics of catalysts for catalytic cracking of heavy feedstock such as VGO.

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Catalytic cracking of VGO by hierarchical ZSM-5 zeolite containing mesoporous silica–aluminas using a Curie point pyrolyzer

Cited by 42 publications

References 28 publications

Catalytic Cracking of VGO by Hierarchical Y Zeolite-containing Mesoporous Silica–Alumina Catalysts Using Curie Point Pyrolyzer

Catalytic Cracking of VGO by Hierarchical Y Zeolite-containing Mesoporous Silica–Alumina Catalysts Using Curie Point Pyrolyzer

Large Mesopore Generation in an Amorphous Silica-Alumina by Controlling the Pore Size with the Gel Skeletal Reinforcement and Its Application to Catalytic Cracking

Catalytic Cracking of VGO by Zeolite–kaolin Mixed Catalysts Using Curie Point Pyrolyzer

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