Amorphous cracking

Even more efficient processes were introduced later in the war. Mobil developed a moving bed process called Thermofor Catalytic Cracking and a new synthetic amorphous cracking catalyst (Ref. 1), while Exxon led a group of companies in developing fluid cat cracking. These processes provided the Armed Forces with plentiful supplies of 100 octane aviation fuel in the latter stages of World War II and they were a decisive element in the final Allied victory in Europe. 

In some processes, 5 -10 % zeohte is added to amorphous cracking catalysts. This increases the activity by several orders of magnitude and drastically reduces coke formation. This is another example of shape-selective catalysis by zeolites, in which the coke-forming intermediates are restricted by the zeohte pores (see Section 7.3.1). 

Misawa et al. [10, 25] first investigated the mechanism of formation of constituents of atmospheric rust in aqueous solution and identified amorphous oxyhydroxide, FeOx(OH)3 2x, besides a FeOOH and y FeOOH in atmospheric rust. Again Misawa et al. [11] and Yamashita et al. [26] have reported that the y FeOOH forms at early stages of rusting and transforms into amorphous rust before converting to a FeOOH. Both Misawa [10] and Suzuki et al. [27] also concluded that the presence of Cu favours the formation of amorphous, crack-free uniform rust layer. 

Historically, the isomerization catalysts have included amorphous siUca-aluminas, zeoHtes, and metal-loaded oxides. AH of the catalysts contain acidity, which isomerizes the xylenes and if strong enough can also crack the EB and xylenes to benzene and toluene. Dual functional catalysts additionally contain a metal that is capable of converting EB to xylenes. 

In addition to the semicrystalline nylons, which comprise the vast majority of commercial resins, nylon is also available in an amorphous form that gives rise to transparency and improved toughness at the expense of high temperature properties and chemical stress crack resistance. Table 2 shows the properties of some different polyamide types. 

Resistance to Chemical Environments and Solubility. As a rule, amorphous plastics are susceptible, to various degrees, to cracking by certain chemical environments when the plastic material is placed under stress. The phenomenon is referred to as environmental stress cracking (ESC) and the resistance of the polymer to failure by this mode is known as environmental stress cracking resistance (ESCR). The tendency of a polymer to undergo ESC depends on several factors, the most important of which are appHed stress, temperature, and the concentration of the aggressive species. 

Zeolites and Catalytic Cracking. The best-understood metal oxide catalysts are zeoHtes, ie, crystalline aluminosihcates (77—79). The zeoHtes are well understood because they have much more nearly uniform compositions and stmctures than amorphous metal oxides such as siUca and alumina. Here the usage of amorphous refers to results of x-ray diffraction experiments the crystaUites of a metal oxide such as y-Al202 that constitute the microparticles are usually so small that sharp x-ray diffraction patterns are not measured consequendy the soHds are said to be x-ray amorphous or simply amorphous. 

Coke deposition is essentially independent of space velocity. These observations, which were developed from the study of amorphous catalysts during the early days of catalytic cracking (11), stiU characteri2e the coking of modem day 2eohte FCC catalysts over a wide range of hydrogen-transfer (H-transfer) capabihties. 

As may be expected of an amorphous polymer in the middle range of the solubility parameter table, poly(methyl methacrylate) is soluble in a number of solvents with similar solubility parameters. Some examples were given in the previous section. The polymer is attacked by mineral acids but is resistant to alkalis, water and most aqueous inorganic salt solutions. A number of organic materials although not solvents may cause crazing and cracking, e.g. aliphatic alcohols. 

Fig. 22. Nomialized pull-off energy measured for polyethylene-polyethylene contact measured using the SFA. (a) P versus rate of crack propagation for PE-PE contact. Change in the rate of separation does not seem to affect the measured pull-off force, (b) Normalized pull-off energy, Pn as a function of contact time for PE-PE contact. At shorter contact times, P does not significantly depend on contact time. However, as the surfaces remain in contact for long times, the pull-off energy increases with time. In seinicrystalline PE, the crystalline domains act as physical crosslinks for the relatively mobile amorphous domains. These amorphous domains can interdiffuse across the interface and thereby increase the adhesion of the interface. This time dependence of the adhesion strength is different from viscoelastic behavior in the sense that it is independent of rate of crack propagation.

Over the years, thousands of compounds have been tried as cracking catalysts. These compounds fall into two general categories natural and synthetic. Natural catalyst, as the name denotes, is a naturally occurring clay that is given relatively mild treating and screening before use. The synthetic catalysts are of more importance because of their widespread use. Of the synthetic catalysts, two main types are amorphous and zeolitic. 

In amorphous polymers it is possible that cracks may develop in the voids which are formed during viscous flow. 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable. Incorporating zeolites (crystalline alumina-silica) with the silica/alumina catalyst improves selectivity towards aromatics. These catalysts have both Fewis and Bronsted acid sites that promote carbonium ion formation. An important structural feature of zeolites is the presence of holes in the crystal lattice, which are formed by the silica-alumina tetrahedra. Each tetrahedron is made of four oxygen anions with either an aluminum or a silicon cation in the center. Each oxygen anion with a -2 oxidation state is shared between either two silicon, two aluminum, or an aluminum and a silicon cation. 

Zeolites as cracking catalysts are characterized hy higher activity and better selectivity toward middle distillates than amorphous silica-alumina catalysts. This is attrihuted to a greater acid sites density and a higher adsorption power for the reactants on the catalyst surface. 

Compared to amorphous silica-alumina catalysts, the zeolite catalysts are more active and more selective. The higher activity and selectivity translate to more profitable liquid product yields and additional cracking capacity. To take full advantage of the zeolite catalyst, refiners have revamped older units to crack more of the heavier, lower-value feedstocks. 

The CF and GF represent the coke- and gas-forming tendencies of an E-cat compared to a standard steam-aged catalyst sample at the same conversion. The CF and GF are influenced by the type of fresh catalyst and the level of metals deposited on the E-cat. Both the coke and gas factors can be indicative of the dehydrogenation activity of the metals on the catalyst. The addition of amorphous alumina to the catalyst will tend to increase the nonselective cracking, which forms coke and gas. 

Comparison of Yield Structure for Fluid Catalytic Cracking of Waxy Gas Oil over Commercial Equilibrium Zeolite and Amorphous Catalysts... 

Stress-corrosion cracking based on active-path corrosion of amorphous alloys has so far only been found when alloys of very low corrosion resistance are corroded under very high applied stresses . However, when the corrosion resistance is sufficiently high, plastic deformation does not affect the passive current density or the pitting potential , and hence amorphous alloys are immune from stress-corrosion cracking. 

Of the instances of so-called solvent cracking of amorphous polymers known to the author, the liquid involved is not usually a true solvent of the polymer but instead has a solubility parameter on the borderline of the solubility range. Examples are polystyrene and white spirit, polycarbonate and methanol and ethyl acetate with polysulphone. The propensity to solvent stress cracking is however far from predictable and intending users of a polymer would have to check on this before use. 

In the case of crystalline polymers it may be that solvents can cause cracking by activity in the amorphous zone. Examples of this are benzene and toluene with polyethylene. In polyethylene, however, the greater problem is that known as environmental stress cracking , which occurs with materials such as soap, alcohols, surfactants and silicone oils. Many of these are highly polar materials which cause no swelling but are simply absorbed either into or on to the polymer. This appears to weaken the surface and allows cracks to propagate from minute flaws. 

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