Carbonaceous deposits

This measurement characterizes the tendency of an oil to form carbonaceous deposits upon undergoing carbonization. 

Phosphates are the principal catalysts used in polymerization units the commercially used catalysts are Hquid phosphoric acid, phosphoric acid on kieselguhr, copper pyrophosphate pellets, and phosphoric acid film on quartz. The last is the least active and has the disadvantage that carbonaceous deposits must occasionally be burned off the support. Compared to other processes, the one using Hquid phosphoric acid catalyst is far more responsive to attempts to raise production by increasing temperature. 

Fires have often occurred when air is compressed. Above 140°C, lubricating oil oxidizes and forms a carbonaceous deposit on the walls of air compressor delivery lines. If the deposit is thin, it is kept cool by conduction through the pipework. But when deposits get too thick, they can catch fire. Sometimes the delivery pipe has gotten so hot that it has burst or the aftercooler has been damaged. In one case the fire vaporized some of the water in the aftercooler and set up a shock wave, which caused serious damage to the cooling-water lines. 

An interesting way to retard catalyst deactivation is to expose the reaction mixture to ultrasound. Ultrasound treatment of the mixture creates local hot spots, which lead to the formation of cavitation bubbles. These cavitation bubbles bombard the solid, dirty surface leading to the removal of carbonaceous deposits [38]. The ultrasound source can be inside the reactor vessel (ultrasound stick) or ultrasound generators can be placed in contact with the wall of the reactor. Both designs work in practice, and the catalyst lifetime can be essentially prolonged, leading to process intensification. The effects of ultrasound are discussed in detail in a review article [39]. 

The separation factors are relatively low and consequently the MR is not able to approach full conversion. With a molecular sieve silica (MSS) or a supported palladium film membrane, an (almost) absolute separation can be obtained (Table 10.1). The MSS membranes however, suffer from a flux/selectivity trade-off meaning that a high separation factor is combined with a relative low flux. Pd membranes do not suffer from this trade-off and can combine an absolute separation factor with very high fluxes. A favorable aspect for zeoHte membranes is their thermal and chemical stability. Pd membranes can become unstable due to impurities like CO, H2S, and carbonaceous deposits, and for the MSS membrane, hydrothermal stability is a major concern [62]. But the performance of the currently used zeolite membranes is insufficient to compete with other inorganic membranes, as was also concluded by Caro et al. [63] for the use of zeolite membranes for hydrogen purification. 

Figure 9.3. Coke is the name for the carbonaceous deposit that builds upon catalysts during the treatment of hydrocarbons. It consists of many aromatic structures and has a low H C ratio. Graphite,...

Figure 6 TPO of carbonaceous deposits left on the surface of INiSZ(s) after the adsorption/desorption of 1-butene. Evolution of CO2 and SO2 (curves A and B, respectively). Evolution of SO2 during the butene TPD (curve C, added for comparison).

Under the conditions used in this study, the catalytic activities were stable for NO reduction for all catalysts. However, in NOj reduction, deactivation was observed. For catalyst 1-7, there was a rapid, reversible deactivation that was more noticeable at lower temperatures. The activity could be restored by removing propene from the feed. Therefore, it was likely due to carbonaceous deposits on the catalyst. In addition, there was slow deactivation. For example, afto the experiment in Table 2 and cleaning in a flow ofN0/O2/H20 (0. l%/4.7%/1.5%, balance He) at SOOT, the catalyst showed an NO conversion of 33% and propene conversion of 42% at 450°C, versus 53 and 99%, respectively, before deactivation. For catalyst 1-5, only slow deactivation was observed. 

The selectivity in a system of parallel reactions does not depend much on the catalyst size if effective diffusivities of reactants, intermediates, and products are similar. The same applies to consecutive reactions with the product desired being the final product in the series. In contrast with this, for consecutive reactions in which the intermediate is the desired product, the selectivity much depends on the catalyst size. This was proven by Edvinsson and Cybulski (1994, 1995) for. selective hydrogenations and also by Colen et al. (1988) for the hydrogenation of unsaturated fats. Diffusion limitations can also affect catalyst deactivation. Poisoning by deposition of impurities in the feed is usually slower for larger particles. However, if carbonaceous depositions are formed on the catalyst internal surface, ageing might not depend very much on the catalyst size. 

Figure 2 illustrate the changes in propylene yield with time using pure N20 or N2O/O2 mixture. Use of the N20 alone (RS-1) induce a rapid decrease in the propylene yield, together with decrease of the propane and N20 conversions, probably due to formation of carbonaceous deposits. Experiment under mixed N20/02 stream (regime RS-3) shown that presence of a small amount of oxygen does not prevent deactivation of the catalyst but indicate some stabilization of the propylene yields after longer time periods. 

Recent work [4] showed that EU-1, an intermediate pore size (10MR) monodimensional zeolite, leads to very high isomerization selectivity during EB conversion. This results from the blockage by carbonaceous deposits of the access to the inner sites of micropores. 

H2/CO = 2 remove heavy products and carbonaceous deposits that diminish activity ... 

Figure 4.1 summarizes the different routes that can potentially lead to carbon deposition during FTS (a) CO dissociation occurs on cobalt to form an adsorbed atomic carbon, which is also referred to as surface carbide, which can further react to produce the FT intermediates and products. The adsorbed atomic carbon may also form bulk carbide or a polymeric type of carbon. Carbon deposition may also result (b) from the Boudouard reaction and (c) due to further reaction and dehydrogenation of the FTS product (what is commonly called coke), a reaction that should be limited at typical FT reaction conditions. Carbon formed on the surface of cobalt can also spill over or migrate to the support. This is reported to readily occur on Co/A1203 catalysts.43 The chemical nature of the carbonaceous deposits during FTS will depend on the conditions of temperature and pressure, the age of the catalyst, the chemical nature of the feed, and the products formed. 

Machocki, A. 1991. Formation of carbonaceous deposit and its effect on carbon monoxide hydrogenation on iron-based catalysts. Appl. Catal. 70 237-52. 

Figure 7.24 Photoelectron emission microscopy images of two Fe304 surfaces that were used as model catalyst in the dehydrogenation of ethylbenzene to styrene at 870 K, showing carbonaceous deposits (bright). These graphitic deposits grow in dots and streaks on a surface of low defect density, but form dendritic structures on surfaces rich in point and step detects (from Weiss et al. f731).

Weisz, P. B. (1966). Combustion of carbonaceous deposits within porous catalyst particles. III. The CO2/CO product ratio. J. Catal. 6, 425. 

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