Catalysts attrition resistance

Weeks, S. A., and Dumbill, P., Method Speeds FCC Catalyst Attrition Resistance Determinations, Oil GasJ., 88 38 (1990)... 

Work is now in progress to minimize the effects of decoking on catalyst attrition resistance. Significant results are discussed In the talk,... 

Previous work has indicated that attrition in iron FT catalysts is caused not just by a physical process, but that two chemical factors contribute to FT iron catalyst attrition. One is the catalyst transformation from magnetite to carbide which causes the crystals of magnetite to nucleate into ciystallites of the carbide phase [1,2]. The other cause of attrition is the deposition of carbon on the carbide surfaces which causes the carbide crystallites to further separate from one another [1,2]. Considering the discussion above, and the role carbide and the carbon covering the carbide surface plays in the activity of the catalyst, attrition resistance and activity may be at odds against one another. 

Weeks SA, Dumbill P. Method speeds FCC catalyst attrition resistance determinations. Oil Gas J 88 38-40, 1990. 

Fluidized-bed reactor systems put other unique stresses on the VPO catalyst system. The mixing action inside the reactor creates an environment that is too harsh for the mechanical strength of a vanadium phosphoms oxide catalyst, and thus requires that the catalyst be attrition resistant (121,140,141). To achieve this goal, vanadium phosphoms oxide is usually spray dried with coUoidal siUca [7631-86-9] or polysiUcic acid [1343-98-2]. Vanadium phosphoms oxide catalysts made with coUoidal sUica are reported to have a loss of selectivity, while no loss in selectivity is reported for catalysts spray dried with polysUicic acid (140). 

Much effort has been made by catalyst manufacturers to improve catalyst atttition resistance and thus reduce the formation of fines (see Catalysts, supported). In the 10-year petiod from 1980 to 1990, most catalyst manufacturers improved the atttition resistance of their catalyst by a factor of at least 3—4. This improvement was achieved even though the catalyst zeoHte content duting this petiod was continually increasing, a factor that makes achieving catalyst hardness more difficult. As an example of the type of atttition improvement that has been achieved, the catalyst atttition index, which is directiy related to catalyst loss rate in a laboratory attrition test, decreased from 1.0 to 0.35 for one constant catalyst grade during 1989—1990 (37). 

PSD is an important indicator of the fluidization characteristics of the catalyst, cyclone performance, and the attrition resistance of the catalyst. A drop in fines content indicates the loss of cyclone efficiency. This can be confirmed by the particle size of fines collected downstream of the cyclones. An increase in fines content of the E-cat indicates increased catalyst attrition. This can be due to changes in fresh catalyst binder quality, steam leaks, and/or internal mechanical problems, such as those involving the air distributor or slide vah es. 

The next level is that of shaped catalysts, in the form of extrudates, spheres, or monoliths on length scales varying from millimeters to centimeters, and occasionally even larger. Such matters are to a large extent the province of materials science. Typical issues of interest are porosity, strength, and attrition resistance such that catalysts are able to survive the conditions inside industrial reactors. This area of catalysis is mainly (though not exclusively) dealt with by industry, in particular by catalyst manufacturers. Consequently, much of the knowledge is covered by patents. 

Friability tests can be used for various purposes. They are widely used in quality control. Here, samples of produced material are subjected to a more or less arbitrary but well defined stress. The attrition extent is assessed by comparison with a standard value and a decision is reached whether the material meets the standard. Moreover, friability tests are often used for comparison of different materials to select the most attrition-resistant one. This is a usual procedure in the case of catalyst development. For example, Contractor et al. (1989) tested anew developed fluidized bed VPO-catalyst in a submerged-jet attrition test (described below). Furthermore, the specific attrition rate of a material in a certain process can be roughly estimated by friability tests. In this case the stress must be similar to that occurring in the process and the obtained degradation extent must be compared with those of other materials from which the process attrition rate is known. 

Both devices described above were developed in order to test the friability of fluid-cracking catalysts. Nowadays the application of these or similar tests is a common procedure in the development of fluidized bed catalysts. Contractor et al. (1989), for example, used a submerged-jet test to compare the attrition resistance of newly developed VPO catalysts. In fact, such tests can be applied to any type of fluidized bed processes. Sometimes they have to be slightly modified to adapt them to the process under consideration. The drilled plate may, for example, be substituted by... 

The choice of cyclone modification, from an operating point of view, becomes a balance of incremental profit from increased conversion, versus catalyst makeup charges, and from a capital cost point of view, the price of either of the cyclone modifications, which must be depreciated. In many instances, there is an additional background time element, involving ongoing development of more attrition resistant and/or active catalyst. 

Attrition resistant zeolite containing catalyst. US Patent 4,333,857. 

Of the various mechanical properties of a formed catalyst containing zeolite, attrition resistance is probably the most critical. This is particularly the case for FCC catalysts because of the impact on the addihon rate of fresh catalyst, particulate emissions of fines and overall catalyst flow in the reactor and regenerator. Most attrition methods are a relative determination by means of air jet attrition with samples in the 10 to 180 xm size range. For example the ASTM D5757 method attrites a humidified sample of powder with three high velocity jets of humidified air. The fines are continuously removed from the attrition zone by elucidation into a fines collection assembly. The relative attrition index is calculated from the elutriated fines removed at a specific time interval. 

We varied the gel-forming parameters, the content of Kaolin clay, the crystal size, and the thickness-to-diameter ratio in a series of experiments. A dual structure began to appear at about 35-40% Kaolin. If the clay content was increased to too high a level, the microspheres became too weak and began to have poor attrition resistance. The cost of the various grades also affected our choice. Figure 9 shows a comparison of pore volume distribution for a typical synthetic versus a clay modified catalyst. 

Attrition resistant catalysts are required, but preferably should possess a pore volume in the O.A to 0.5 cc/gm range. This increased pore volume apparently helps in facilitating accessibility to the catalyst interior by heavy viscous liquids, and dual pore structures containing pores over 100 Angstroms in diameter also appear to facilitate accessibility to the zeolite while keeping feeder pores open. A porous system, yet attrition resistant and inexpensive, was achieved by incorporation of platelet kaolin clay. 

The SCR catalysts are used in the form of honeycomb monoliths or plates to guarantee low pressure drops in view oflarge frontal area with parallel channels, high external surface area per unit volume of catalyst, high attrition resistance and low tendency for fly ash plugging. The SCR monoliths and plates are assembled into standard modules and inserted into the reactor to form catalyst layers. 

In China, most of the traditional RFCC catalysts (such as Orbit, DVR, and MFC mentioned above) are based on alnmina matrix, and the most widely used materials for alumina matrix preparation are alumina sol and modified active alumina [4]. Alumina matrix combines the virtnes of alumina-sol (better attrition resistance and coke selectivity) and active alnmina (higher cracking activity), thus improving the cracking activity and selectivity of the catalysts. However, the coke selectivity of the alumina matrix is nnsatisfactory when processing resid feed due to the insufficient amount of meso/macropores and higher concentration of acid sites. 

Optimizing the fresh catalyst physical properties including particle density, PSD, and attrition resistance is critical to maintaining acceptable fluidization and resulting circulation of the catalyst inventory. Excessive attrition of the catalyst will lead to nonuniform fluidization and disrupt circulation. Potential sources of attrition include ... 

Catalyst composition also depends on the type of reactor used. Fixed-bed iron catalysts are prepared by precipitation and have a high surface area. A silica support is commonly used with added alumina to prevent sintering. Catalysts for fluidized-bed application must be more attrition-resistant. Iron catalysts produced by fusion best satisfy this requirement. The resulting catalyst has a low specific surface area, requiring higher operating temperature. Copper, another additive used in the preparation of precipitated iron catalysts, does not affect product selectivity, but enhances the reducibility of iron. Lower reduction temperature is beneficial in that it causes less sintering. 

The phase transformations in the catalyst play an important role in determining the activity, attrition resistance, and deactivation of this catalyst. Activation of this precipitated catalyst transforms single crystals of hematite to smaller crystallites of carbide. While the transformation from hematite to magnetite is extremely rapid, the magnetite to carbide transition is much slower under the conditions of temperature and pressure employed in this study. As carbon deposits on the carbide particles, it serves to further prise the carbide particles apart. In a commercial slurry phase reactor the carbide particles break away leading to catalyst attrition. The implication of this work for the attrition resistance of iron FT catalysts is explored in detail elsewhere.18... 

In US Patent 5,569,785 an attrition-resistant zeolite catalyst is described that can be used for the production of methylamines in fluidized bed reactors. The technology claims to provide improved temperature control because of better heat transfer and more efficient solids handling in the fluidized bed. The process also offers more precise temperature control to maintain the activity of the catalyst and eliminate the formation of hot spots that lead to catalyst deactivation. 

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