Cryogenic purification

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. 

Final Purification. Oxygen containing compounds (CO, CO2, H2O) poison the ammonia synthesis catalyst and must be effectively removed or converted to inert species before entering the synthesis loop. Additionally, the presence of carbon dioxide in the synthesis gas can lead to the formation of ammonium carbamate, which can cause fouHng and stress-corrosion cracking in the compressor. Most plants use methanation to convert carbon oxides to methane. Cryogenic processes that are suitable for purification of synthesis gas have also been developed. 

Compact brazed aluminum plate-fin heat exchangers can be used in most cryogenic hydrogen purification apphcations. The use of these relatively low cost heat exchangers, combined with low separation energy requirements, results in a highly economical process for hydrogen purification. 

Fig. 3. A model integrated adsorption/electrothermal regeneration/cryogenic vapor recovery system for volatile organic compounds [91]. Reprinted from Gas Sep. Purif, Volume 10, Lordgooei, M., Carmichael, K. R., Kelly, T. W., Rood, M. J. and Larson, S. M., Activated carbon cloth adsorption cryogenic system to recover toxic volatile organic compounds, pp. 123-130, Copyright 1996, with permission from Elsevier Science.

Etliylene production involves liigh temperatures (1500°F) in tlie pyrolysis section and cryogenic temperatures in tlie purification section. The feedstocks, products, and by-products of pyrolysis are flaimnable and pose severe fire liazards. Benzene, wliich is produced in small amounts as a byproduct, is a known carcinogen. Table 21.7.1 summarizes some of the properties of etliane (feedstock) and tlie product gases. Figure 21.7.1 shows a simplified schematic diagram of the pyrolysis and waste heat recovery section on an etliylene plant. 

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. 

The analyte must be converted into a volatile compound suitable for mass-spectrometric analysis. Procedures for C, N, and O follow those developed for conventional organic microanalysis— oxidation of organic C to COj, reduction of organic N to N2, and conversion of O2 into CO or COj. In most procedures, cryogenic purification of the products is carried out before mass spectrometry, and both off-line and on-line procedures have been developed. 

HARP [Hybrid argon recovery process] A process for extracting argon from the hydrogen recycle stream in ammonia synthesis. Both PSA and a cryogenic process are used. Krishnamurthy, R., Lemer, S. L., and MacLean, D. M., Gas Sep. Purif, 1987,1, 16. 

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