Cracking catalysts poisoning

These metals permanently poison the FCC catalyst by lowering the catalyst activity, thereby reducing its ability to produce the desiretl products. Virtually all the metals in the FCC feed are deposited on the cracking catalyst. Paraffinic feeds tend to contain more nickel than vanadium. Each metal has negative effects. 

The two limiting cases for the distribution of deactivated catalyst sites are representative of some of the situations that can be encountered in industrial practice. The formation of coke deposits on some relatively inactive cracking catalysts would be expected to occur uniformly throughout the catalyst pore structure. In other situations the coke may deposit as a peripheral shell that thickens with time on-stream. Poisoning by trace constituents of the feed stream often falls in the pore-mouth category. 

The reason for lack of microbial conversion of these molecules may be the difficulty in transporting them across the cell membrane. However, the possibility of an extracellular conversion exists. The enzymatic treatment of asphaltenes can be seen as an interesting alternative for the removal of heavy metals to reduce catalyst poisoning in hydrotreatment and cracking processes, for instance. 

Sulfur is a potential problem even at low levels for synthesis gas systems using certain types of catalysts. The production of methanol from synthesis gas, for example, uses catalysts that are poisoned by sulfur. Some tar cracking catalysts are also sulfur sensitive. In those systems, thorough removal of sulfur will be required. Fuel cell systems are also sulfur sensitive. 

The hydrogen sulfide and ammonia can be removed by amine extraction and acid washes respectively. Hydrotreating also removes metals from the feed that would otherwise poison the reforming and cracking catalysts. 

This paper identifies alumina, rare earths, platinum, and magnesia as important SOx capture materials. Alumina is either incorporated directly into the matrix of a cracking catalyst or added as a separate particle. Cerium is shown to promote the capture of SO2 on high alumina cracking catalyst, alumina, and magnesia. Other rare earths are ranked by their effectiveness. The promotional effect of platinum is shown between 1200 and 1400 F for SO2 capture on alumina. Silica, from free silica or silica-alumina in the matrix of cracking catalyst, acts as a poison by migrating to the additive. 

Steam Stability. Steam stability of SOx removal agents is strongly affected by temperature. We have seen previously that at 1350 F deactivation of cerium/alumina additive, caused by silica poisoning, was influenced by how long the additive was steamed and whether the additive was steamed in the presence or absence of cracking catalyst. These results were extended to other temperatures. 

In our test, steaming five commercial SOx additives in the presence of cracking catalyst, shown in Table VI, indicated that deactivation by silica poisoning is important. 

SOx emissions from FCCU s can be reduced by the use of SOx catalysts, especially SOx additives which can be added to the FCCU independently of the cracking catalyst. The effectiveness of these catalysts is favored by lower regenerator temperatures, the presence of combustion promoter, and higher oxygen concentrations. Deactivation of these catalysts occurs by loss of surface area and poisoning by silica. We believe that SOx additives will eventually be used by most refiners to control SOx emissions from FCCU s, either on a spot or continuous basis. 

Under FCCU operating conditions, almost 100% of the metal contaminants in the feed (such as nickel, vanadium, iron and copper porphyrins) are decomposed and deposited on the catalyst (2). The most harmful of these contaminants are vanadium and nickel. The deleterious effect of the deposited vanadium on catalyst performance and the manner in which vanadium is deposited on the cracking catalyst differ from those of nickel. The effect of vanadium on the catalyst performance is primarily a decrease in catalyst activity while the major effect of nickel is a selectivity change reflected in increased coke and gas yields (3). Recent laboratory studies (3-6) show that nickel distributes homogeneously over the catalyst surface while vanadium preferentially deposits on and reacts destructively with the zeolite. A mechanism for vanadium poisoning involving volatile vanadic acid as the... 

Faced with the need of obtaining more transportation fuels from a barrel of crude, Ashland developed the Reduced Crude Conversion Process (RCC ). To support this development, a residuum or reduced crude cracking catalyst was developed and over 1,000 tons were produced and employed in commercial operation. The catalyst possessed a large pore volume, dual pore structure, an Ultrastable Y zeolite with an acidic matrix equal in acidity to the acidity of the zeolite, and was partially treated with rare earth to enhance cracking activity and to resist vanadium poisoning. 

Catalytic cracking feedstocks Reduce catalyst poisoning... 

The characterization of petroleum cracking catalysts, with which a third of the world s crude oil is processed, presents a formidable analytical challenge. The catalyst particles are in the form of microspheres of 60-70 micron average diameter which are themselves composites of up to five different micron and submicron sized phases. In refinery operation the catalysts are poisoned by trace concentrations of nickel, vanadium and other contaminant metals. Due to the replacement of a small portion of equilibrium catalyst each day (generally around 1% of the total reactor inventory) the catalyst particles in a reactor exist as a mixture of differing particle ages, poisoning levels and activities. 

Crude oils contain a certain amount of combined nitrogen which sometimes breaks down in thermal crackers to form these harmful nitrogen compounds. California, West Texas, and Venezuelan crudes seem to break down this way much more readily than other crudes. Catalytic-cracking units convert the nitrogen compounds in their feed to these polymerization catalyst poisons almost without exception. Other basic materials which have poisoned polymerization catalyst at times are sodium hydroxide and diethanolamine. Both of these materials are used extensively for the removal of hydrogen sulfide from the feed to polymerization units. Catalyst poisons of a basic nature can be removed from the... 

Acid catalysts such as zeolites can be readily poisoned by basic organic compounds. One of the earlier studies of the deactivation of silica-alumina cracking catalysts by organic nitrogen compounds such as quinoline, quinaldine, pyrrole, piperidine, decylamine and aniline was done by Mills et al (6). The results of their partial poisoning studies showed an exponential dependence of the catalyst activity for cumene cracking reaction or... 

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