Metallic catalyst poisoning

One of the most severe causes of metallic catalyst poisoning is the adsorption of species containing sulfur sulfur-containing compounds are present in natural sources of hydrocarbons and therefore will necessarily be found in industrial feedstocks. 

A catalyst can lose its activity or selectivity in many ways poisoning, fouling, loss of some active area or species [Satterfield, 1980]. For metal catalysts, poisoning and reduction of the active area are predominant Most of poisoning takes place when some impurity in the process stream adsorbs on the active sites of the catalyst and causes the catalyst activity to be lowered. Different compounds, sometimes even in trace quantity, can become poisons to different catalysts. 

The high theoretical efficiency of a fuel cell is substantially reduced by the finite rate of dynamic processes at various locations in the cell. Substantial efficiency losses at typical operating temperatures occur already in the anodic and cathodic catalyst layers due to the low intrinsic reaction rates of the oxygen reduction and, in the case of the DMFC, of the methanol oxidation reaction. (The catalytic oxidation of hydrogen with platinum catalysts is very fast and thus does not limit PEFC performance.) In addition, at low temperatures, turnover may be limited by noble metal catalyst poisoning due to sulfur... 

Hydrogenolysis of triphenylarsine (AsPh ) on alumina supported nickel (Ni/Al Oj) has been studied as model reaction for metallic catalyst poisoning. The hydrogenolysis of AsPh on Ni/Al Oj occurs at temperature ranging from 303 to 443 K under 12 bars of hydrogen and in n-heptane solution. It has been followed by kinetics analysis of the AsPh consumption and Benzene and cylohexane evolution as well as XRD measurements of the metallic and intermetallic phase(s). 

Other contaminants of concern include ammonia (membrane deterioration), alkali metals (catalyst poisoning, membrane degradation), particles, and heavy hydrocarbons (catalyst poisoning and plugging). Both the anode and cathode flows must be carefully filtered for these contaminants, as even ppb-level concentration can lead to premature cell and stack failure. 

The refining industry generally seeks either to eliminate asphaltenes or to convert them to lighter materials because the presence of heteroelements cause pollution problems, e.g., sulfur and nitrogen, catalyst poisoning, and corrosion (formation of metal vanadates during combustion). 

Upstream of the refornjiing unit, the feedstock undergoes hydrotreatment so as to eliminate impliritles such as S, N, olefins, and metals which are all catalyst poisons. 

Processing heavy oils and bitumens represents a challenge for the current refinery processes, because heavy oils and bitumens poison the metal catalysts used m the refineries. In our research at the Loker Institute, we found the use of superacid catalysts, which are less sensitive to heavy oils, an attractive solution to their processing, particularly hydrocracking. 

Rhodium was about three times the price of gold through 1988—1989 until skyrocketing to 74/g ( 2300/troy oz) in early 1990. Thus precious metal catalyst costs requite an absolute minimum level of use and maximum number of catalyst recycle uses when batch processing is employed. Starting material contaminants may effect catalyst poisoning, though process routes to overcome this by feed stream pretreatment may be devised (37,60). 

Some natural gases have also been found to contain mercury, which is a reformer catalyst poison when present in sufftciendy large amounts. Activated carbon beds impregnated with sulfur have been found to be effective in removing this metal. 

The typical industrial catalyst has both microscopic and macroscopic regions with different compositions and stmctures the surfaces of industrial catalysts are much more complex than those of the single crystals of metal investigated in ultrahigh vacuum experiments. Because surfaces of industrial catalysts are very difficult to characterize precisely and catalytic properties are sensitive to small stmctural details, it is usually not possible to identify the specific combinations of atoms on a surface, called catalytic sites or active sites, that are responsible for catalysis. Experiments with catalyst poisons, substances that bond strongly with catalyst surfaces and deactivate them, have shown that the catalytic sites are usually a small fraction of the catalyst surface. Most models of catalytic sites rest on rather shaky foundations. 

Catalysts commonly lose activity in operation as a result of accumulation of materials from the reactant stream. Catalyst poisoning is a chemical phenomenon, A catalyst poison is a component such as a feed impurity that as a result of chemisorption, even in smaH amounts, causes the catalyst to lose a substantial fraction of its activity. For example, sulfur compounds in trace amounts poison metal catalysts. Arsenic and phosphoms compounds are also poisons for a number of catalysts. Sometimes the catalyst surface has such a strong affinity for a poison that it scavenges it with a high efficiency. The... 

Reclamation, Disposal, and Toxicity. Removal of poisons and inorganic deposits from used catalysts is typically difficult and usually uneconomical. Thus some catalysts are used without regeneration, although they may be processed to reclaim expensive metal components. Used precious metal catalysts, including automobile exhaust conversion catalysts, are treated (often by the suppHers) to extract the metals, and recovery efficiencies are high. Some spent hydroprocessing catalysts may be used as sources of molybdenum and other valuable metals. 

In many of the other processes that use base metal catalysts, irreversible poisoning of the catalyst occurs as a result of deposition of metal contaminants from the process feedstock onto the catalyst surface. These catalysts are not considered to be regenerable by ordinary techniques. 

The mechanism of poisoning automobile exhaust catalysts has been identified (71). Upon combustion in the cylinder tetraethyllead (TEL) produces lead oxide which would accumulate in the combustion chamber except that ethylene dibromide [106-93-4] or other similar haUde compounds were added to the gasoline along with TEL to form volatile lead haUde compounds. Thus lead deposits in the cylinder and on the spark plugs are minimized. Volatile lead hahdes (bromides or chlorides) would then exit the combustion chamber, and such volatile compounds would diffuse to catalyst surfaces by the same mechanisms as do carbon monoxide compounds. When adsorbed on the precious metal catalyst site, lead haUde renders the catalytic site inactive. 

Lead compounds were not found on the surrounding activated coating layer, rather only associated with the precious metal. The Pt sites are less poisoned by lead than are Pd or Rh sites because the Pt sites are protected by the sulfur in the fuel. Fuel sulfur is converted to SO2 in the combustion process, and Pt easily oxidizes SO2 to SO on the catalyst site. The SO reacts with the lead compounds to form PbSO, which then moves off the catalyst site so that lead sulfate is not a severe catalyst poison. Neither Pd nor Rh is as active for the SO2 to SO reaction, and therefore do not enjoy the same protection as Pt. 

Each precious metal or base metal oxide has unique characteristics, and the correct metal or combination of metals must be selected for each exhaust control appHcation. The metal loading of the supported metal oxide catalysts is typically much greater than for nobel metals, because of the lower inherent activity pet exposed atom of catalyst. This higher overall metal loading, however, can make the system more tolerant of catalyst poisons. Some compounds can quickly poison the limited sites available on the noble metal catalysts (19). 

Toxic heavy metals and ions, eg, Pb, Hg, Bi, Sn, Zn, Cd, Cu, and Fe, may form alloys with catalytic metals (24). Materials such as metallic lead, ziac, and arsenic react irreversibly with precious metals and make the surface unavailable for catalytic reactions. Poisoning by heavy metals ordinarily destroys the activity of a precious-metal catalyst (8). 

Except for No. 2, fuel oil should not be considered as auxiliary fuel when usiag a catalytic system because of the sulfur and vanadium the fuel oil may contain (7). In some cases even the sulfur ia No. 2 fuel oil can present a problem. Galvanized metal should not be used ia process ovens or ductwork because ziac is a catalyst poison. 

Using 2eohte catalysts, the NO reduction takes place inside a molecular sieve ceramic body rather than on the surface of a metallic catalyst (see Molecularsieves). This difference is reported to reduce the effect of particulates, soot, SO2/SO2 conversions, heavy metals, etc, which poison, plug, and mask metal catalysts. ZeoHtes have been in use in Europe since the mid-1980s and there are approximately 100 installations on stream. Process applications range from use of natural gas to coal as fuel. Typically, nitrogen oxide levels are reduced 80 to 90% (37). 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

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. 

In contrast to heterogeneous metal catalysts, the chlororhodium complex is not sensitive to sulfur poisoning,thus allowing the saturation of double bonds in the presence of mercapto functions. 

The operation of a large synthetic ammonia plant based on natural gas involves a delicately balanced sequence of reactions. The gas is first desulfurized to remove compounds which will poison the metal catalysts, then compressed to 30 atm and reacted with steam over a nickel catalyst at 750°C in the primary steam reformer to produce H2 and oxides of carbon ... 

Apart from the activation of a biphasic reaction by extraction of catalyst poisons as described above, an ionic liquid solvent can activate homogeneously dissolved transition metal complexes by chemical interaction. 

As well as viscosity, other factors to be aware of include the purity of the ionic liquids. The presence of residual halide ions in neutral ionic liquids can poison transition metal catalysts, while different levels of proton impurities in chloroalumi-... 

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. 

Experimental evidence illustrating the effect that hydrides of nickel or its alloys with copper have on the catalytic activity of the respective metals is to be found in papers which discuss catalytic consequences of the special pretreatment of these metal catalysts with hydrogen during their preparation. One must also look very carefully into cases where self-poisoning has been reported as appearing in reactions of hydrogen with other reactants. 

Catalytic Oxidation of Acetylene in Air for Oxygen Manufacture J. Henry Rushton and K. A. Krieger The Poisoning of Metallic Catalysts E. B. Maxted... 

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