Molecular regeneration

Rearrangement to an open chain imine (165) provides an intermediate whose acidity toward lithiomethylthiazole (162) is rather pronounced. Proton abstraction by 162 gives the dilithio intermediate (166) and regenerates 2-methylthiazole for further reaction. During the final hydrolysis, 166 affords the dimer (167) that could be isolated by molecular distillation (433). A proof in favor of this mechanism is that when a large excess of butyllithium is added to (161) at -78°C and the solution is allowed to warm to room temperature, the deuterolysis affords only dideuterated thiazole (170), with no evidence of any dimeric product. Under these conditions almost complete dianion formation results (169), and the concentration of nonmetalated thiazole is nil. (Scheme 79). This dimerization bears some similitude with the formation of 2-methylthia-zolium anhydrobase dealt with in Chapter DC. Meyers could confirm the independence of the formation of the benzyl-type (172) and the aryl-type... 

New Adsorbent Materials. SihcaUte and other hydrophobic molecular sieves, the new family of AlPO molecular sieves, and steadily increasing families of other new molecular sieves (including stmctures with much larger pores than those now commercially available), as well as new carbon molecular sieves and pillared interlayer clays (PILCS), will become more available for commercial appHcations, including adsorption. Adsorbents with enhanced performance, both highly selective physical adsorbents and easily regenerated, weak chemisorbents will be developed, as will new rate-selective adsorbents. 

Sohd sorbent materials have the abiUty to adsorb water vapor until an equiUbrium condition is attained. The total weight of water that can be adsorbed in a particular material is a function of the temperature of the material and of the relative humidity of the air (see Adsorption). To regenerate the sorbent, its temperature must be raised or the relative humidity lowered. The sohd sorbents most commonly used are siUca (qv), alumina (see Aluminum compounds), and molecular sieves (qv). 

Solid-Bed Dehydration. Sihca gel, bauxite, activated alurnina, or molecular sieves can be used for removing dissolved water to meet propane specifications. The soHd-bed dehydrators are used in a cycHc adsorption process. After an adsorption cycle has completed, the bed is heated with a purge gas or a vaporized Hquid-product stream for regeneration. If the latter is used, the Hquid product is condensed, separated from the free water, and returned to the process. After the beds are regenerated, they are cooled and returned to the adsorption cycle. 

Molecular Sieve Treatment. Molecular sieve treaters can be designed to remove H2S, organic sulfur compounds (including carbonyl sulfide), and water in one step. SoHd-bed units are utilized and regeneration occurs in the same manner as simple, soHd-bed dehydrators. 

A large use of molecular sieves ia the natural gas industry is LPG sweetening, in which H2S and other sulfur compounds are removed. Sweetening and dehydration are combined in one unit and the problem associated with the disposal of caustic wastes from Hquid treating systems is eliminated. The regeneration medium is typically natural gas. Commercial plants are processing from as Htde as ca 30 m /d (200 bbl/d) to over 8000 m /d (50,000 bbl/d). 

Ammonium Ion Removal. A fixed-bed molecular-sieve ion-exchange process has been commercialized for the removal of ammonium ions from secondary wastewater treatment effluents. This application takes advantage of the superior selectivity of molecular-sieve ion exchangers for ammonium ions. The first plants employed clinoptilolite as a potentially low cost material because of its availability in natural deposits. The bed is regenerated with a lime-salt solution that can be reused after the ammonia is removed by pH adjustment and air stripping. The ammonia is subsequentiy removed from the air stream by acid scmbbing. 

Do not regenerate molecular sieves by steaming water typically is strongly adsorbed and may not be easily displaced by adsorbent in next adsorption cycle. 

Molecular sieves are typically regenerated using a sHp stream of the treated gas at elevated temperature and reduced pressure. This regeneration step creates an enriched hydrogen sulfide stream which must then be further treated if the sulfur is to be recovered. A typical molecular sieve adsorption unit is shown schematically in Figure 2. 

Fig. 2. Molecular sieve process where Kl is a molecular sieve sorbent bed ( ), the adsorption system and (-), the regeneration system.

PAG sludge can be regenerated by wet air oxidation (WAO) or by a multiple-hearth furnace. Capacity losses might be high in WAO, particulady with low molecular weight organics. Weight loss in a furnace may exceed 20%. 

Complete removal of water from the pyrolysis gas is achieved with molecular sieve dryers. Typically, there are two dryers one is in normal operation while the other is being regenerated. The dryers are designed for 24 to 48 hours between successive regenerations and high pressure methane heated with steam at 225°C is the preferred regeneration medium. Activated alumina was used in older plants, but it is less selective than molecular sieves (qv). 

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