Halogen compounds, poisoning

Promoters may influence selectivity by poisoning undesired reactions or by increasing the rates of desired intermediate reactions so as to increase the yield of the desired product. If they act in the first sense, they are sometimes referred to as inhibitors. An example of this type of action involves the addition of halogen compounds to the catalyst used for oxidizing ethylene to ethylene oxide (silver supported on alumina). The halogens prevent complete oxidation of the ethylene to carbon dioxide and water, thus permitting the use of this catalyst for industrial purposes. 

Bismuth is flammable as a powder. The halogen compounds of bismuth are toxic when inhaled or ingested. Some of the salts of bismuth can cause metallic poisoning in a manner similar to mercury and lead. 

The only useful commercial catalyst now used is nickel, available at a 17-25% level on a support and suspended in hardened edible oil or tallow. This preserves the activity of the nickel in a form in which it can be safely and easily handled. Catalyst can be recovered and reused but will be less active. Reaction is usually effected at temperatures between 180°C and 200°C and at a pressure of about 0.3 MPa (3 bar). The catalyst is quickly poisoned by fatty acids, soaps, phospholipids, oxidized acids, sulfur compounds, halogen compounds, carbon monoxide, oxygen, and water. As a consequence, both the oil and the hydrogen should be as pure as possible. 

Higher starting material purities are being achieved by the use of guard catalysts that remove catalyst poisons such as sulfur and halogen compounds, metals, and organic impurities. Here the zeolites have advantages over conventional adsorbents such as activated carbons [8]. 

HMDS), phosphorous-compounds and halogen-compounds which are all catalyst poisons. The pretreated gas is fed to the zeolite honeycomb rotor for concentration. (Figure 22.2.4)... 

Gases are evolved from within the carbon-carbon composite during the oxidation process, mainly arising from active sites on the edges of layer planes and vacant sites formed by dislocations in the basal planes [104,105]. These sites can be blocked or poisoned and the composite porosity reduced by using inhibitors based on B, P and halogen compounds which lower the reactivity of C with O2 [106]. The choice of inhibitor is limited by the temperature of application. 

The presence of halogen compounds, alkaline compounds, arsenic, and ammonium bisulfate, which can poison the catalyst. Chen et al. (1991) and Balling et al. (1991) discuss several aspects of catalyst poisoning. 

Feed Ga.s Purifica.tion. Because nickel-based reforming catalysts are quite sensitive to sulfur, halogen, and heavy metal poisons which may be found ia natural gas, a feedstock purification system is normally required. Sulfur compounds, ia both organic and inorganic forms, are the most common... 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

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