Davison zeolite catalysts

Products Company and Davison (W.R. Grace) Catalysts) and Hydrocarbon Technologies, Inc. ART provides non-zeolitic catalysts for ebullating residue hydrocracking and fixed bed pretreating HDT [140], A nanoscale iron based, slurry catalyst is recommended for coal liquefaction, while a molecule-sized and chemically in situ generated catalyst is employed for the high conversion of asphaltenic fractions or heavy oils [141],... 

Catalytic testing. The samples were exchanged by Ce ions, then calcined at 680°C in dry air. In two types of catalytic tests, a commercial zeolitic catalyst (super D from Grace Davison) was taken as reference. 

The FCC process is the most common conversion unit in use today. As such, it is important to determine the performance of an FCC when feeding hydrotreated shale oil. The two 650° F+ feeds shown in Table VI were evaluated in an FCC pilot plant operating in a fixed fluidized-bed mode. The catalyst was withdrawn from an operating commercial FCC unit. It is a zeolite catalyst, CBZ-1, produced by Davison Chemical Division of W. R. Grace and Company and is moderately active as well as contaminated with metals. 

The binder containing zeolite catalysts were prepared by physically mixing powdered silica gel (Fuji Davison) binder and the zeolite in its NH4 form [binder / zeolite (wt/wt) ratio = 0.1 and 1.0], pressing and crushing to 0.2-0.3 mm size particles and finally calcining at 600°C under N2 flow for 1 h. 

In quick succession, fluid catalyst products were announced and introduced to the petroleum industry in the Spring of 1964 by Davison and Esso (which eventually became ExxonMobil), and also by Filtrol, and the world witnessed a small revolution. In two years, 60% of the fluid bed units were using zeolitic catalysts, and in two more years about 85 % of those units were using them. Nalco and finally Cyanamid were forced to offer zeolite catalysts to stay in the business (67). In about 10 years, over 90% of a very cautious industry had embraced zeolites. 

In less than two years, 60% of the fluid units were using zeolitic catalysts, with Davison and Filtrol sharing the business. In four years, that number was up... 

When the advantages of the zeolite catalyst were recognized, Mobil came to Nalco and wanted enough royalty to make the catalyst cost 800/ton (75). At that time Nalco only got 300/ton for their catalyst that was based on synthetic silica-alumina and clay, and they told Mobil that nobody would think of paying 800/ton. However, by 1965, Nalco, Filtrol and Davison were into the business with zeolite containing catalysts, and the competition among them went on for years. 

Silica sol binders used in high-zeolite catalysts by Davison. 

USHY zeolite was kindly provided by GRACE DAVISON (Germany) in a calcinated powder size of 1pm. The catalyst was pressed into a large pellet using an infrared tableting press, crushed, and then sieved to 1.0-1.7 mm. Before the experiment, 0.5gr of the resulting catalyst were placed in an oven and heated to 200 "C for 2 hr, to remove humidity and ensure the desirable performance. 

Operationally, the basic difference between the Type X and Type Y structures was largely a matter of thermal stability, although acid strength-related differences in selectivity were also found. While the Type Y zeolite was much more stable, it was also much more expensive. Davison initially marketed their XZ-15 catalyst, containing steam-stabilized Y zeolite admixed with low-alumina silica-alumina, at a price of 800 per ton. This was quite a high price at the time, but despite that, about 15 refiners tried it. At the same time, Filtrol introduced their Grade 800 catalyst, and although they didn t officially claim that it contained molecular sieves, the product distributions clearly pointed to their presence (67). 

In response to this competitive pressure, Davison introduced a new molecular sieve catalyst in June of 1965. It was called XZ-25 and it was priced at 450 per ton. This was based on rare earth-exchanged Type X zeolite in a high-alumina semi-synthetic matrix, and had a lower zeolite content and a little less hydrothermal stability than the XZ-15. Acceptance was very rapid, and within half a year it was being used in 36 units, in eight of which it displaced the Filtrol Grade 800, reputedly on the basis of advantages in activity, selectivity and stability. Ultimately, XZ-25 was used in more than 116 units (67). 

Davison introduced its XP line of catalysts in 1986 to combine low coke and gas makes with bottoms cracking and attrition resistance, and in 1991 they built a new plant and came out with a rare earth-free product based on an improved ultrastable Zeolite Y. 

Spray dried zeolite bearing catalyst (Mobil). USY REY catalysts (Davison Division of W.R. Grace). 

A major milestone in the history of FCC was initiated in 1962 when two innovators (Plank and Rosinski, Mobil Oil) began to experiment with the incorporation of zeolites in FCC catalysts. The substantial improvement in both activity and yield selectivities led to a quantum improvement in the FCC process. Zeolite containing FCC catalysts began appearing in FCC units in 1964. The first manufacturers of these catalysts were Filtrol and Grace Davison. 

The first commercial application of truly fluidized catal)4ic cracking was in 1942 at the Standard Oil Co. of New Jersey s Baton Rouge, LA. refinery. The vaporized oil was cracked in a dense, fluidized bed of catalyst ( bed cracking ). Details of that Model I FCC are given by Avidan et al. (1989). Various hardware improvements were made to bed crackers over the ensuing 30 years, but the advent of Davison s synthetic Y zeolites signalled the demise of bed crackers as state-of-art. 

The attrition of the composite FCC particles was measured using the Davison Attrition Test. Higher values of the index indicate weaker particles that attrit easier. A series of catalysts were prepared by spray drying the USY zeolites with one of the two sols and the attrition of the composite was measured. The results are shown in Figure 4. 

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