Oxidant-lean processes

The shift from air-based, once-through processes to oxygen-based recycle processes, and the corresponding change from reactant-lean to oxidant-lean processes. This not only considerably reduces the emissions and makes purge streams more concentrated and hence more easily combusted but also may lead to improved selectivity and productivity. Examples are the oxychlorination of ethylene to 1,2-dichloroethane and the epoxidation of ethylene. 

Most of the world s commercial formaldehyde is manufactured from methanol and air either by a process using a silver catalyst or one using a metal oxide catalyst. Reactor feed to the former is on the methanol-rich side of a flammable mixture and virtually complete reaction of oxygen is obtained conversely, feed to the metal oxide catalyst is lean in methanol and almost complete conversion of methanol is achieved. 

Copper. Copper is economically extracted by smelting of a chalcopyrite concentrate. A copper electrowinning process was developed commercially in 1912 for the treatment of lean ores. It is also suitable for treatment of copper oxide or sulfate obtained by roasting of the concentrate. 

A derivative of the Claus process is the Recycle Selectox process, developed by Parsons and Unocal and Hcensed through UOP. Once-Thm Selectox is suitable for very lean acid gas streams (1—5 mol % hydrogen sulfide), which cannot be effectively processed in a Claus unit. As shown in Figure 9, the process is similar to a standard Claus plant, except that the thermal combustor and waste heat boiler have been replaced with a catalytic reactor. The Selectox catalyst promotes the selective oxidation of hydrogen sulfide to sulfur dioxide, ie, hydrocarbons in the feed are not oxidized. These plants typically employ two Claus catalytic stages downstream of the Selectox reactor, to achieve an overall sulfur recovery of 90—95%. 

The radicals and other reaction components are related by various equiUbria, and hence their decay by recombination reactions occurs in essence as one process on which the complete conversion of CO to CO2 depends. Therefore, the hot products of combustion of any lean hydrocarbon flame typically have a higher CO content than the equiUbrium value, slowly decreasing toward the equiUbrium concentration (CO afterburning) along with the radicals, so that the oxidation of CO is actually a radical recombination process. 

The third key section of the process deals with ethylene oxide purification. In this section of the process, a variety of column sequences have been practiced. The scheme shown in Figure 2 is typical. The ethylene oxide-rich water streams from both the main and purge absorbers are combined, and after heat exchange are fed to the top section of a desorber where the absorbate is steam stripped. The lean water from the lower section of the desorber is virtually free of oxide, and is recirculated to the main and purge absorbers. The concentrated ethylene oxide vapor overhead is fed to the ensuing stripper for further purification. If the desorber is operated under vacuum, a compressor is required. 

Currently, sulfur is mainly produced by the partial oxidation of hydrogen sulfide through the Claus process. The major sources of hydrogen sulfide are natural gas and petroleum refinery streams treatment operations. It has been estimated that 90-95% of the world s recovered sulfur is produced through the Claus process. Typical sulfur recovery ranges from 90% for a lean acid gas feed to 97% for a rich acid gas feed. ... 

The fact that Fischer-Tropsch fuels contain neither sulfur nor aromatics may become a strong selling point for the process. Less sulfur in the fuel has, of course, a direct effect on the sulfur oxides in the emissions, and the newly developed exhaust purification systems for lean burning engines that can be introduced means that all emissions, including GO2 and NOx, will diminish. Aromatics promote particulate formation in the combustion of diesel fuels and are therefore undesirable. We discuss this further in Ghapter 10. 

The NOx storage-reduction (NSR) catalyst, developed by Toyota and other companies, offers a solution based on a two step process, in which the engine switches periodically between a long lean-burn stage and a very short fuel-rich stage. The NSR catalyst combines the oxidation activity of platinum with a NOx storage compound based on barium oxide. Figure 10.10 illustrates the principle of operation. 

Examples of multi-disciplinary innovation can also be found in the field of environmental catalysis such as a newly developed catalyst system for exhaust emission control in lean burn automobiles. Japanese workers [17] have successfully merged the disciplines of catalysis, adsorption and process control to develop a so-called NOx-Storage-Reduction (NSR) lean burn emission control system. This NSR catalyst employs barium oxide as an adsorbent which stores NOx as a nitrate under lean burn conditions. The adsorbent is regenerated in a very short fuel rich cycle during which the released NOx is reduced to nitrogen over a conventional three-way catalyst. A process control system ensures for the correct cycle times and minimizes the effect on motor performance. 

As can be seen, the catalytic process over a zeolite-supported cation, or an oxide-supported cation, can be considered as a supported homogeneous catalysis, as far as adsorbed reactants and products behave like reactive ligands. The model developed for lean DcNO. catalysts over supported cations (function 3), as well as this supported homogeneous catalysis approach, is also suitable for stoichiometric mixture (TWC) comprising CO and H2 as reductants over supported transition metal cations [20-22],... 

One of the most promising processes is the active DeNO based on NO -trap materials. It has been developed for lean-burn gasoline engines. Cerium compounds are thought to intervene in different steps of the whole process (1) NO oxidation, (2) NO storage, (3) Nitrate desorption and NO reduction. Most probably, the main role of OSC materials is to accelerate HC partial oxidation during rich-spikes (giving CO and H2 as NO reducers). However, this beneficial effect of OSC compounds competes with a detrimental reaction,... 

---