Noble monoliths

Starting with a ceramic and depositing an aluminum oxide coating. The aluminum oxide makes the ceramic, which is fairly smooth, have a number of bumps. On those bumps a noble metal catalyst, such as platinum, palladium, or rubidium, is deposited. The active site, wherever the noble metal is deposited, is where the conversion will actually take place. An alternate to the ceramic substrate is a metallic substrate. In this process, the aluminum oxide is deposited on the metallic substrate to give the wavy contour. The precious metal is then deposited onto the aluminum oxide. Both forms of catalyst are called monoliths. 

An alternate form of catalyst is pellets. The pellets are available in various diameters or extruded forms. The pellets can have an aluminum oxide coating with a noble metal deposited as the catalyst. The beads are placed in a tray or bed and have a depth of anywhere from 6 to 10 inches. The larger the bead (1/4 inch versus 1/8 inch) the less the pressure drop through the catalyst bed. However, the larger the bead, the less surface area is present in the same volume which translates to less destruction efficiency. Higher pressure drop translates into higher horsepower required for the oxidation system. The noble metal monoliths have a relatively low pressure drop and are typically more expensive than the pellets for the same application. 

Base Metal Catalyst - An alternate to a noble metal catalyst is a base metal catalyst. A base metal catalyst can be deposited on a monolithic substrate or is available as a pellet. These pellets are normally extruded and hence are 100% catalyst rather than deposition on a substrate. A benefit of base metal extruded catalyst is that if any poisons are present in the process stream, a deposition of the poisons on the surface of the catalyst occurs. Depending on the type of contaminant, it can frequently be washed away with water. When it is washed, abraded, or atritted, the outer surface is removed and subsequently a new catalyst surface is exposed. Hence, the catalyst can be regenerated. Noble metal catalyst can also be regenerated but the process is more expensive. A noble metal catalyst, depending on the operation, will typically last 30,000 hours. As a rule of thumb, a single shift operation of 40 hours a week, 50 weeks a year results in a total of 2,000 hours per year. Hence, the catalyst might have a 15 year life expectancy. From a cost factor, a typical rule of thumb is that a catalyst might be 10%-15% of the overall capital cost of the equipment. 

The raw materials needed to supply about ten million new automobiles a year do not impose a difficult problem except in the case of the noble metals. Present technology indicates that each car may need up to ten pounds of pellets, two pounds of monoliths, or two pounds of metal alloys. The refractory oxide support materials are usually a mixture of silica, alumina, magnesia, lithium oxide, and zirconium oxide. Fifty thousand tons of such materials a year do not raise serious problems (47). The base metal oxides requirement per car may be 0.1 to 1 lb per car, or up to five thousand tons a year. The current U.S. annual consumption of copper, manganese, and chromium is above a million tons per year, and the consumption of nickel and tungsten above a hundred thousand tons per year. The only important metals used at the low rate of five thousand tons per year are cobalt, vanadium, and the rare earths. 

Diffusion effects can be expected in reactions that are very rapid. A great deal of effort has been made to shorten the diffusion path, which increases the efficiency of the catalysts. Pellets are made with all the active ingredients concentrated on a thin peripheral shell and monoliths are made with very thin washcoats containing the noble metals. In order to convert 90% of the CO from the inlet stream at a residence time of no more than 0.01 sec, one needs a first-order kinetic rate constant of about 230 sec-1. When the catalytic activity is distributed uniformly through a porous pellet of 0.15 cm radius with a diffusion coefficient of 0.01 cm2/sec, one obtains a Thiele modulus y> = 22.7. This would yield an effectiveness factor of 0.132 for a spherical geometry, and an apparent kinetic rate constant of 30.3 sec-1 (106). 

Figure 10.5. Monolith, washcoat and noble metal particles in an automotive exhaust catalyst.

The replacement of vanadia-based catalysts in the reduction of NOx with ammonia is of interest due to the toxicity of vanadium. Tentative investigations on the use of noble metals in the NO + NH3 reaction have been nicely reviewed by Bosch and Janssen [85], More recently, Seker et al. [86] did not completely succeed on Pt/Al203 with a significant formation of N20 according to the temperature and the water composition. Moreover, 25 ppm S02 has a detrimental effect on the selectivity with selectivity towards the oxidation of NH3 into NO enhanced above 300°C. Supported copper-based catalysts have shown to exhibit excellent activity for NOx abatement. Recently Suarez et al and Blanco et al. [87,88] reported high performances of Cu0/Ni0-Al203 monolithic catalysts with NO/NOz = 1 at low temperature. Different oxidic copper species have been previously identified in those catalytic systems with Cu2+, copper aluminate and CuO species [89], Subsequent additions of Ni2+ in octahedral sites of subsurface layers induce a redistribution of Cu2+ with a surface copper enrichment. Such redistribution... 

The conventional selective reduction of NOx for car passengers still competes but the efficient SCR with ammonia on V205/Ti02 for stationary sources is not available for mobile sources due to the toxicity of vanadium and its lower intrinsic activity than that of noble metals, which may imply higher amount of active phase for compensation. As illustrated in Figure 10.9, such a solution does not seem relevant because a subsequent increase in vanadium enhances the formation of undesirable nitrous oxide at low temperature. Presently, various attempts for the replacement of vanadium did not succeed regarding the complete conversion of NO into N2 at low temperature. Suarez et al. [87] who investigated the reduction of NO with NH3 on CuO-supported monolithic catalysts... 

An alternate to a noble metal catalyst is a base metal catalyst. A base metal catalyst can be deposited on a monolithic... 

Figure 9.12 Ni/Al203 (a) and noble metal-based monolith (b) catalysts.

O2/CH4 00, H2O/CH4 (yl, GHSV Figure 9.14 Results of CH4 ATR catalytic activity tests on noble metal-based monolith at lower temperature. 

The catalyst, used in the form of a ceramic honeycomb monolith, is constituted, as in mobile applications, by a noble metal and an absorber element, such as potassium, deposited on a Y-AI2O3 wash-coat layer. In the oxidation and absorption cycle, the SCON Ox catalyst works by simultaneously oxidizing CO and UHCs to CO2 and H2O, while NOj, are captured on the adsorber compound. Catalyst regeneration is accomplished by passing a controlled mixture of regeneration gases across the surface of the catalyst in the absence of oxygen. 

Figure 7-16 A highly simplified sketch of an automohile engine and catalytic converter with typical gas compositions indicated before and after the automotive catalytic converter. The catalytic converter is a tube wall reactor in which a noble-metal-impregnated wash coat on an extruded ceramic monolith creates surface on which reactions occur.

The gases move down the monolith ceramic cells of the ACC in plug flow with the noble metal catalyst deposited on the walls. This reactor is therefore a PFTR with catalyst... 

There are a number of examples of tube waU reactors, the most important being the automotive catalytic converter (ACC), which was described in the previous section. These reactors are made by coating an extruded ceramic monolith with noble metals supported on a thin wash coat of y-alumina. This reactor is used to oxidize hydrocarbons and CO to CO2 and H2O and also reduce NO to N2. The rates of these reactions are very fast after warmup, and the effectiveness factor within the porous wash coat is therefore very smaU. The reactions are also eternal mass transfer limited within the monohth after warmup. We wUl consider three limiting cases of this reactor, surface reaction limiting, external mass transfer limiting, and wash coat diffusion limiting. In each case we wiU assume a first-order irreversible reaction. 

Similarly, a Rh foam monolith with 0.56 wt.% Rh gave a lower optimal H2 selectivity than a Rh foam monolith with 9.83 wt.% Rh (75% vs. 87%). In both the Pt and the Rh experiments, the samples with the lower metal loa gs had significantly higher adiabatic reaction temperatures because of the heat generated by the formation of H2O. As demonstrated by these experiments, the formation of H2 occurs on the noble metal surface, not in the gas phase or on the catalyst support. 

We have shown that Cli can be oxidized directly to synthesis gas over a Pt or Rh monolith catalyst with surprisingly high selectivities for contact times of 10 to lO" s. Although these experiments do not give the equilibrium yields of H2 and CO reported in o Aer work at much longer residence times, they do show that both H2 and CO are primary products of the direct oxidation of CH4 over a noble metal catalyst. 

The differences in reactions at different reactor positions was studied by Springmann et al. who reported product compositions for ATR of model compounds as a function of reactor length in a metal monolith coated with a proprietary noble metal containing Rh. As expected, the oxidation reactions take place at the reactor inlet, followed by the SR, shift, and methanation reactions. Figure 32 shows the product concentration profiles for a 1-hexene feed, which are typical results for all the fuels tested. These results show that steam, formed from the oxidation reactions, reaches a maximum shortly after the reactor inlet, after which it is consumed in the shift and reforming reactions. H2, CO and CO2 concentrations increase with reactor length and temperature. In this reactor, shift equilibrium is not reached, and the increase in CO with distance from the inlet is the net result of the shift and SR reactions. Methane is... 

Several DOCs based on similar washcoat formulation but with varying noble-metal loading (90 150 g/ft3 monolith) and catalyst ageing status were... 

Shelef, M., Dalla Betta, R. A., Larson, J. A., Otto, K., and Yao, H. C., Poisoning of Monolithic Noble Metal Oxidation Catalysts in Automotive Exhaust Environment, Am. Inst. Chem. Eng., New Orleans Meet. (1973). 

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