Hydrogen molecular sieve

The carbonylation of some alkyl halides such as iodocyclohexane (911) can be carried out under neutral conditions in the presence of N,N,N.N-tetre,-methylurea (TMU), which is a neutral compound, but catches generated hydrogen halide. Molecular sieves (MS-4A) are used for the same pur-pose[768]. Very reactive ethyl 3-iodobutyrate (912) is carbonylated to give ethyl methylsuccinate (913) in the presence of TMU. The expected elimination of HI to form crotonate, followed by carbonylation, does not occur. 

Adsorption systems employing molecular sieves are available for feed gases having low acid gas concentrations. Another option is based on the use of polymeric, semipermeable membranes which rely on the higher solubiHties and diffusion rates of carbon dioxide and hydrogen sulfide in the polymeric material relative to methane for membrane selectivity and separation of the various constituents. Membrane units have been designed that are effective at small and medium flow rates for the bulk removal of carbon dioxide. 

Highly pure / -hexane can be produced by adsorption on molecular sieves (qv) (see Adsorption, liquid separation) (43). The pores admit normal paraffins but exclude isoparaffins, cycloparaffins, and aromatics. The normal paraffins are recovered by changing the temperature and/or pressure of the system or by elution with a Hquid that can be easily separated from / -hexane by distillation. Other than ben2ene, commercial hexanes also may contain small concentrations of olefins (qv) and compounds of sulfur, oxygen, and chlorine. These compounds caimot be tolerated in some chemical and solvent appHcations. In such cases, the commercial hexanes must be purified by hydrogenation. 

A wide range and a number of purification steps are required to make available hydrogen/synthesis gas having the desired purity that depends on use. Technology is available in many forms and combinations for specific hydrogen purification requirements. Methods include physical and chemical treatments (solvent scmbbing) low temperature (cryogenic) systems adsorption on soHds, such as active carbon, metal oxides, and molecular sieves, and various membrane systems. Composition of the raw gas and the amount of impurities that can be tolerated in the product determine the selection of the most suitable process. 

ZeoHte-based materials are extremely versatile uses include detergent manufacture, ion-exchange resins (ie, water softeners), catalytic appHcations in the petroleum industry, separation processes (ie, molecular sieves), and as an adsorbent for water, carbon dioxide, mercaptans, and hydrogen sulfide. 

Synthetic Fuels. Hydrocarbon Hquids made from nonpetroleum sources can be used in steam crackers to produce olefins. Fischer-Tropsch Hquids, oil-shale Hquids, and coal-Hquefaction products are examples (61) (see Fuels, synthetic). Work using Fischer-Tropsch catalysts indicates that olefins can be made directly from synthesis gas—carbon monoxide and hydrogen (62,63). Shape-selective molecular sieves (qv) also are being evaluated (64). 

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. 

An extremely wide variety of catalysts, Lewis acids, Brmnsted acids, metal oxides, molecular sieves, dispersed sodium and potassium, and light, are effective (Table 5). Generally, acidic catalysts are required for skeletal isomerization and reaction is accompanied by polymerization, cracking, and hydrogen transfer, typical of carbenium ion iatermediates. Double-bond shift is accompHshed with high selectivity by the basic and metallic catalysts. 

Experience in air separation plant operations and other ciyogenic processing plants has shown that local freeze-out of impurities such as carbon dioxide can occur at concentrations well below the solubihty limit. For this reason, the carbon dioxide content of the feed gas sub-jec t to the minimum operating temperature is usually kept below 50 ppm. The amine process and the molecular sieve adsorption process are the most widely used methods for carbon dioxide removal. The amine process involves adsorption of the impurity by a lean aqueous organic amine solution. With sufficient amine recirculation rate, the carbon dioxide in the treated gas can be reduced to less than 25 ppm. Oxygen is removed by a catalytic reaction with hydrogen to form water. 

HYDROGEN SULFIDE CAPACfTY AT 25 Molecular Sieve Type A... 

Isobutyronitrile (2-methylpropionitrile, isopropyl cyanide) [78-82-0] M 69.1, b 103.6 , d 0.7650, n 1.378. Shaken with cone HCl (to remove isonitriles), then with water and aq NaHC03. After a preliminary drying with silica gel or Linde type 4A molecular sieves, it is shaken or stirred with CaH2 until hydrogen evolution ceases, then decanted and distd from P2O5 (not more than 5g/L, to minimize gel formation). Finally it is refluxed with, and slowly distd from CaH2 (5g/L), taking precautions to exclude moisture. 

Sulfolane (tetramethylenesulfone) [126-33-0] M 120.2, m 28.5 , b 153-154 /18mm, 285 /760mm, d 1.263, n 1.4820. Prepared commercially by Diels-Alder reaction of 1,3-butadiene and sulfur dioxide, followed by Raney nickel hydrogenation. The principle impurities are water, 3-sulfolene, 2-sulfolene and 2-isopropyl sulfolanyl ether. It is dried by passage through a column of molecular sieves. Distd... 

Helium [7440-59-7] M 4.0. Dried by passage through a column of Linde 5A molecular sieves and CaS04, then passed through an activated-charcoal trap cooled in liquid N2, to adsorb N2, argon, xenon and krypton. Passed over CuO pellets at 300° to remove hydrogen and hydrocarbons, over Ca chips at 600° to remove oxygen, and then over titanium chips at 700° to remove N2 [Arnold and Smith 7 Chem Soc, Faraday Trans 2 77 861 1981]. 

Molecular sieves (dehydrated zeolite) purify petroleum products with their strong affinity for polar compounds such as water, carbon dioxide, hydrogen sulfide, and mercaptans. The petroleum product is passed through the sieve until the impurity is sufficiently removed after which the sieve may be regenerated by heating to 400 - bOO F. 

Tlie cooled gaseous products are dried using an adsorbent such as molecular sieves and compressed to about 500 psig by a multistage compressor. The compressed gas is dien sent to an acetylene converter where acetylene is selectively hydrogenated to ediane. The gaseous mixture dien flows to die purification section of the plant where each component of die gas is recovered by means of cryogenic disdlladon. 

A five-column configuration of Such an analyser system is depicted in Figure 14.6. The first event in the process is the analysis of Hj by injection of the contents of sample loop 2 (SL2) onto column 5 (a packed molecular sieve column). Hydrogen is separated from the other compounds and detected by TCD 2, where nitrogen is used as a carrier gas. The next event is the injection of the contents of sample loop 1 (SLl), which is in series with SL2, onto column 1. After the separation of compounds up to and including C5, and backflushing the contents of column 1, all compounds above C5 (Q+) are detected by TCDl. The fraction up to and including C5 is directed to column 2, where air, CO, COj, Cj, and 2= (ethene) are separated from... 

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