Oxidation catalyst deactivation

All of the Au/metal oxide catalysts deactivate quickly, under the conditions shown in Figure 4. In addition, the deactivation of the Au/metal oxide catalysts appears to be enhanced in the presence of COj. In support of the theory that increased basicity of the metal oxides leads to lower stability, we carried out COj temperature programmed desorption experiments on the various catalysts. The COj TPD data also confirmed that an increase in the basicity of the metal oxides leads to an increase in the amount of COj adsorption on the catalysts. 

During hydrogenation of aldehydes, especially over platinum oxide, catalyst deactivation occurs. The reasons for this deactivation are not well understood and several theories exist.6... 

Hydrogenation of the oxides of carbon to methane according to the above reactions is sometimes referred to as the Sabatier reactions. Because of the high exothermicity of the methanization reactions, adequate and precise cooling is necessary in order to avoid catalyst deactivation, sintering, and carbon deposition by thermal cracking. 

In the mass-transfer limited region, conversion is most commonly increased by using more catalyst volume or by increasing cell density, which increases the catalytic wall area per volume of catalyst. When the temperature reaches a point where thermal oxidation begins to play a role, catalyst deactivation may become a concern. 

Catalyst contamination from sources such as turbine lubricant and boiler feed water additives is usuaUy much more severe than deactivation by sulfur compounds in the turbine exhaust. Catalyst formulation can be adjusted to improve poison tolerance, but no catalyst is immune to a contaminant that coats its surface and prevents access of CO to the active sites. Between 1986 and 1990 over 25 commercial CO oxidation catalyst systems operated on gas turbine cogeneration systems, meeting both CO conversion (40 to 90%) and pressure drop requirements. 

Similar approaches are applicable in the chemical industry. For example, maleic anhydride is manufactured by partial oxidation of benzene in a fixed catalyst bed tubular reactor. There is a potential for extremely high temperatures due to thermal runaway if feed ratios are not maintained within safe limits. Catalyst geometry, heat capacity, and partial catalyst deactivation have been used to create a self-regulatory mechanism to prevent excessive temperature (Raghaven, 1992). 

The space velocity was varied from 2539 to 9130 scf/hr ft3 catalyst. Carbon monoxide and ethane were at equilibrium conversion at all space velocities however, some carbon dioxide breakthrough was noticed at the higher space velocities. A bed of activated carbon and zinc oxide at 149 °C reduced the sulfur content of the feed gas from about 2 ppm to less than 0.1 ppm in order to avoid catalyst deactivation by sulfur poisoning. Subsequent tests have indicated that the catalyst is equally effective for feed gases containing up to 1 mole % benzene and 0.5 ppm sulfur (5). These are the maximum concentrations of impurities that can be present in methanation section feed gases. 

It has been pointed out (S2) that this type of operation might be widely applicable for organic oxidation processes, provided suitable inert carrier liquids can be found. It may be noted in this connection that the liquid must be reasonably resistant against oxidation and that it must not cause catalyst deactivation—for example, by chemisorption. 

Cyclodiphosphazanes(III) 27 shown in Scheme 16 undergo oxidation reactions to give the cyclodiphosphazanes(V) of type 28. These are prospective ligands in catalysis since these ligands due to lack of phosphorus lone-pairs are less susceptible to the destructive cycloreversion of the ligands. Hence they could prevent catalyst deactivation in the process. When treated with trimethyl aluminum the cyclodiphosphazanes form symmetrically substituted bimetallic species of type 29 [90]. Characterization by single-crystal X-ray studies show... 

Recycle of HBr to bromine is highly desirable both from an economic and an environmental standpoint. Catalytic oxidation offers the potential to recycle HBr from contaminated waste streams to bromine. We have demonstrated that the oxidation catalyst is stable against deactivation by a wide range of contaminants found in waste HBr streams. Strategies to deal with the contaminants will depend on the recycle applications in which the catalytic oxidation unit serves. 

Example 11.15 Coke formation is a major cause of catalyst deactivation. Decoking is accomplished by periodic oxidations in air. Consider a micro-porous catalyst that has its internal surface covered with a uniform layer of coke. Suppose that the decoking reaction is stopped short of completion. What is the distribution of residual coke under the following circumstances ... 

The plasma-catalyst system utilizes plasma to oxidize NO to NO2 which then reacts with a suitable reductant over a catalyst however, this plasma-assisted catalytic technology still comprises challenging tasks to resolve the formation of toxic by-products and the catalyst deactivation due to the deposition of organic products during the course of the reaction as well as to prepare cost effective and durable on-board plasma devices [47]. 

However, the pattern is complicated by several factors. The sugar molecules to be hydrogenated mutarotate in aqueous solutions thus coexisting as acyclic aldehydes and ketoses and as cyclic pyranoses and furanoses and reaction kinetics are complicated and involve side reactions, such as isomerization, hydrolysis, and oxidative dehydrogenation reactions. Moreover, catalysts deactivate and external and internal mass transfer limitations interfere with the kinetics, particularly under industrial circumstances. 

Proceedings of the Third World Congress on Oxidation Catalysis, San Diego, CA, U.S.A., 21-26 September 1997 edited by R.K. Grasselli,S.T.Oyama, A.M. Gaffney and J.E. Lyons Volume 111 Catalyst Deactivation 1997. 

The reduced catalyst deactivation compared to the analogous oxidations of glycerol and tartronic acid was attributed to the use of the calcium salt rather than the free acid. A recent publication describes a similar observation for the oxidation of sodium gluconate [15]. Sodium ions were assumed to counter catalyst deactivation by neutralizing the acid species responsible. 

Room temperature CO oxidation has been investigated on a series of Au/metal oxide catalysts at conditions typical of spacecraft atmospheres CO = 50 ppm, COj = 7,000 ppm, H2O = 40% (RH) at 25 C, balance = air, and gas hourly space velocities of 7,000- 60,000 hr . The addition of Au increases the room temperature CO oxidation activity of the metal oxides dramatically. All the Au/metal oxides deactivate during the CO oxidation reaction, especially in the presence of CO in the feed. The stability of the Au/metal oxide catalysts decreases in the following order TiOj > FejO, > NiO > CO3O4. The stability appears to decrease with an increase in the basicity of the metal oxides. In situ FTIR of CO adsorption on Au/Ti02 at 25 C indicates the formation of adsorbed CO, carboxylate, and carbonate species on the catalyst surface. 

The activity and stability of catalysts for methane-carbon dioxide reforming depend subtly upon the support and the active metal. Methane decomposes to carbon and hydrogen, forming carbon on the oxide support and the metal. Carbon on the metal is reactive and can be oxidized to CO by oxygen from dissociatively adsorbed COj. For noble metals this reaction is fast, leading to low coke accumulation on the metal particles The rate of carbon formation on the support is proportional to the concentration of Lewis acid sites. This carbon is non reactive and may cover the Pt particles causing catalyst deactivation. Hence, the combination of Pt with a support low in acid sites, such as ZrO, is well suited for long term stable operation. For non-noble metals such as Ni, the rate of CH4 dissociation exceeds the rate of oxidation drastically and carbon forms rapidly on the metal in the form of filaments. The rate of carbon filament formation is proportional to the particle size of Ni Below a critical Ni particle size (d<2 nm), formation of carbon slowed down dramatically Well dispersed Ni supported on ZrO is thus a viable alternative to the noble metal based materials. 

GP 3] ]R 3h] [R 4a] Safe operation in the explosive regime was demonstrated [103]. Catalytic runs with 1-butene concentrations up to 10 times higher than the explosion limit were performed (5-15% 1-butene in air 0.1 MPa 400 °C). A slight catalyst deactivation, possibly due to catalyst active center blockage by adsorption, was observed under these conditions and not found for lower 1-butene concentrations. Regeneration of the catalyst is possible by oxidation. 

Recent studies [193] of the CO oxidation activity exhibited by highly dispersed nano-gold (Au) catalysts have reached the following conclusions (a) bilayer structures of Au are critical (b) a strong interaction between Au and the support leads to wetting and electron rich Au (c) oxidative environments deactivate Au catalyst by re-ox-idizing the support, which causes the Au to de-wet and sinter. Recent results have shown that the direct intervention of the support is not necessary to facilitate the CO oxidation reaction therefore, an Au-only mechanism is sufficient to explain the reaction kinetics. 

The identification of surface adsorbed species has been carried out with FT-IR [69] and Raman spectroscopy [70] during reaction and with GC-MS after epoxidation reaction [72]. The aggregation of gold NPs is not appreciable during reaction at temperatures below 473 K [69,72]. Catalyst deactivation, which happens within a few hours causing a decrease in C3FI6 conversion by about 50%, can be accounted for by the accumulation of successively oxidized compounds after isomerization and cracking of... 

The heterogeneous catalytic system iron phthalocyanine (7) immobilized on silica and tert-butyl hydroperoxide, TBHP, has been proposed for allylic oxidation reactions (10). This catalytic system has shown good activity in the oxidation of 2,3,6-trimethylphenol for the production of 1,4-trimethylbenzoquinone (yield > 80%), a vitamin E precursor (11), and in the oxidation of alkynes and propargylic alcohols to a,p-acetylenic ketones (yields > 60%) (12). A 43% yield of 2-cyclohexen-l-one was obtained (10) over the p-oxo dimeric form of iron tetrasulfophthalocyanine (7a) immobilized on silica using TBHP as oxidant and CH3CN as solvent however, the catalyst deactivated under reaction conditions. 

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