Patent GB-977728-A (GB)
Title: Purification of gases
IPC: C01B3/56
Filed: 1961-03-07
Abstract: A process for removing concentrations of less than 50% of zeolite absorbable impurities from a gas stream wherein at least two beds of zeolite are provided together with an arrangement to permit the following operations to take place; passing the impurities containing gas stream through a first bed and removing from it essentially pure feed gas; simultaneously the second selective absorbent bed is depressurized thereby removing the entrapped product gas together with the deposited impurities as a desorbate gas stream; part of this desorbate gas stream is recycled with incoming fresh gas containing low concentrations of the impurities thereby forming fresh feed stream to the first selective absorbent bed; the flows between the absorbent beds are switched periodically so that the second selective bed which had been used on regeneration cycle duty now becomes the adsorption bed and vice-versa. The zeolite beds may have incorporated in them heat-exchangers through which a hot fluid may be passed during the regeneration cycle.  The external equipment may further incorporate a heat-exchanger system whereby the cold exit gas is used to cool the incoming gas carrying the impurities to a suitable temperature. The process is capable of removing from helium and hydrogen traces of oxygen, nitrogen, argon, krypton, ammonia, water, carbon dioxide, carbon monoxide and hydrogen sulphide.  It can also be employed for the removal of both saturated and unsaturated hydrocarbons from hydrogen and can affectively be used for purifying hydrogen, helium, nitrogen, argon, neon, krypton and oxygen from traces of carbon dioxide hydrogen sulphide, ammonia, water and sulphurdioxide.  The important feature of the process is recycling of at least a portion of the desorbate gas stream to the incoming fresh gas stream containing low, i.e. less than 50% concentrations of impurities which results in increased recoveries of the <PICT:0977728/C1/1> desired feed stream, zeolites capable of being used for the purposes of the invention include zeolite A both in the sodium form and forms in which part of the sodium is replaced by di- and trivalent ions by ion-exchange, chabzazite, erionite, zeolites R, D, L, Y, T and X, which are referred to in Specifications 777,232, 777,233, 841,812, 868,846, 909,264, 909,266, 912,936 and 972,831. Sodium zeolite A is the preferred absorbent for separating methane from hydrogen and has pore size of 4<\>rA units.  Separating air from helium is achieved preferably by means of zeolite A in which at least 40% of the sodium has been exchanged for calcium ions. calcium ions. The attached drawing shows a flow diagram of the apparatus.  Feed gas consisting of impurities containing feed together with some of the desorbate is compressed in compressor 50, cooled in heat exchanger 51 by means of product gas and is further cooled in heat exchanger 52. It is then directed through adsorption bed 53 and emerges as pure gas via line 24, through heat exchanger 51 and to storage via line 25. When the capacity of the exchange bed 53 has been exhausted the feed stream is then directed to absorption bed 54 while bed 54 is on the absorption cycle. The pressure in bed 53 is reduced by vacuum pump 55 the effluent of which may either be vented via valve 89 and line 30 or a portion of this exhaust is returned via control valve 90 and line 29 back to compressor 50 to the inlet side of the apparatus. The valve system 89 and 90 may either be operated in such a way that a continuous bleed of desorbate is added to the incoming gas stream or to add one particular portion of the desorbate back into the feed stream.  It is found that since the initial part of the desorbate contains more of the product gas than the remainder there is considerable advantage in adding all of this initial portion to the feed stream and then venting the remainder.  An alternative method of desorption is to apply heat to the bed of zeolite by means of heat exchangers located within the zeolite beds.  Another method of effecting the desorption cycle is to withdraw hot product gas from line 25 via valve 91 and pass it through the respective absorbent bed.  Any combination of the above procedures can be employed.  For obtaining best results, isothermal conditions of ad- and desorption should be employed and the temperature of operation should be at least as high as the critical temperature of the impurity being absorbed. The purity of the gaseous product depends upon the selection of the desorption cycle pressure which must be such that the partial pressure of the impurities left on the absorbent bed is such that upon switching back to the absorption cycle the partial pressure of the impurity divided by the total pressure of absorption is equal to the mol. fraction of impurities permissible in the product.  Thus in example 1,100 vols. of helium containing 1 vol. per cent of air per hour is combined with recycle desorbate gas containing 3.93 mols. per hour of helium and 4.42 mols. per hour of air forming a feed gas stream 5% by vol. of air or 102.93 mols. per hour of helium and 5.42 mols. per hour of air. This was compressed to 20.4 atmospheres and cooled to - 40 DEG  C. and was passed through an absorber packed with zeolite A pellets of pore size 5<\>rA units. The emergent gas stream was 98.11 mols. per hour or pure helium. During the desorption stroke the entrapped 4.82 mols. per hour of helium and the absorbed 5.42 mols. per hour of air were recovered by depressurizing to 15 mm. The gas flow during the desorption stroke was in a direction opposite to the absorption stroke in order to take advantage of the chromatographic effect.  As an alternative regeneration procedure the bed was evacuated to 200 mm. pressure of mercury and a small amount of hot purified product gas was used to sweep the air remaining in the bed. This was done until the air load on the zeolite had a partial pressure of 15 mm. of mercury at the absorption temperature operation in this manner resulted in a helium recovery of 99% with a purity of 100%, whereas operation of a single cycle of purification system with the same feed under identical conditions of temperature and pressure gave only a 90% recovery of helium.  A second example refers to the removal of methane from hydrogen.  Further, it is shown that as the absorption pressure is increased the efficiency of recovery decreases. However, the increased efficiency at lower pressures is counterbalanced by an increase in the amount of zeolite absorbent required for the separation and which further necessitates the use of a larger quantity of desorbate recycle.  A balance between these factors dictates the selection of correct absorbtion and desorption pressures to achieve greatest economy of operation.