GAS RECOVERY

Abstract: CO₂ is separated from a gas mixture containing medium boiling point gases, such as nitrogen, carbon monoxide, methane, and/or argon, and optionally also hydrogen by a pressure swing adsorption (PSA) process operated at above 50°C. The PSA cycle preferably employs two or more depressurisation stages: the final stage, which is preferably counter-current, gives higher purity CO₂ than the previous depressurisation stage or stages which are preferably co-­ current.

Description: Gas recovery This invention relates to gas and in particular to a process for recovery of carbon dioxide from a mixture thereof with one or more other gases of lower boiling point. It is often desired to recover carbon dioxide, (C02) from gas mixtures including hydrogen, (H2), and one or more gases of medium boiling point such as nitrogen, (N2), methane, (CH4), carbon monoxide, (CO), and argon, (Ar). Beretofore such C02 recovery has extensively been carried out by absorption in a liquid such as aqueous potash or an ethanolamine or a physical solvent and then expelling the C02 therefrom. Recently proposals have been made to recover the C02 by a pressure swing adsorption process using a solid adsorbent, but so far the C02 so recovered has been at such a low partial pressure that further processing is not economic. We have now devised a pressure swing adsorption (PSA) process for recovering C02 at substantially higher efficiency, comparable with that at which low boiling gases are purified in known adsorptive processes. According to the invention, a process for recovering carbon dioxide from a mixture thereof with at least one medium boiling gas having a boiling point, at atmospheric pressure, of between -1000C and -2300C and optionally also at least one low boiling point gas having a boiling point at atmospheric pressure below -23O0C, comprises (i) contacting the mixture at elevated pressure with a first charge of a solid adsorbent effective to adsorb carbon dioxide preferentially; (ii) when the first charge of adsorbent is sufficiently loaded with carbon dioxide, switching the mixture flow to a further charge of adsorbent which is fresh or regenerated; and (iii) obtaining a gas stream enriched in carbon dioxide as compared with the starting mixture by depressurising the first charge: and is characterised by carrying out such adsorption and depressurisation steps at a temperature of at least 500C. The second gas will hereinafter referred to as an anabbreviation for medium boiling gas". Typical medium boiling point gases often present in admixture with C02 are as follows: Gas Atmospheric pressure boiling point (OC) CO -190 N2 -195 CE -164 02 -183 Ar* -186 Kr* -151 Xe* -109 Typical low boiling point gases that may be present in admixture with C02 and MB are as follows: Gas Atmospheric pressure boiling point (OC) 2 -252 He -269 Ne* -246 Gases marked * will generally be present only in small amounts, if at all, in gas mixtures wherein at least one of the MB is N2 which has been derived from air. Helium, (He), will generally be present only in gas mixtures derived from natural gas. The problem of producing high purity C02 is particularly encountered when the MB/C02 volume ratio in the starting gas is above 0.1 and the invention is particularly applicable when this ratio is in the range 0.2 to 5. C02/MB gas mixtures often contain H2, usually in an amount of at least 10, and typically at least 20,Z V/v on a dry basis. One important application of the invention is in recovering C02 from raw ammonia synthesis gas made by catalytic steam reforming or air/steam reforming of a volatile hydrocarbon feedstock followed by the shift reaction. Such a synthesis gas will normally have a MB/C02 ratio in the range 1 to 5, for example, 1.3 to 2.5, as in the process described in our European Application 85301022 which will be published as EP-A-157480 and which corresponds to USSN 703531. The H2 content of the starting gas is then usually at least 40, for example in the range 50 to 70, Z V/v on a dry basis. As disclosed in that application, the H2/MB ratio is for example in the range 1.25 to 2.5, especially 1.5 to 2.1, by moles and, preferably, at least 90% V/v of the MB is N2. Another potentially important application of the invention is in recovering a C02 stream of low CO and H2 content from a crude gas made by non-catalytic partial oxidation of a carbonaceous feedstock, especially heavy oil or coal. Such a gas is subjected to the shift reaction to an extent depending on the H2/CO ratio required after C02 removal. If the crude gas has been made by a low temperature partial oxidation process using substantially pure oxygen, it will normally contain CE4: the invention is effective in limiting the CH4 content of the CO stream. If the crude gas has been made by partial oxidation using air, or air moderately enriched with oxygen, it will contain N2: in this case the invention is effective in limiting the N2 content of the C02 stream. Yet another potentially important application is in recovering C02 from mixtures with CH4, for example in natural gas. If the starting gas has been made by way of a reaction involving steam, it should be freed of unreacted steam before the adsorption step, eg by cooling to below 500C and separation of liquid water so as to obtain a gas stream preferably containing less than about 1Z V/v of vapour. The gas stream may be further dried before the adsorption step, but since water is readily desorbed at the temperature of operation and can easily be removed from the C02-rich stream, such further drying is generally not necessary. The adsorption/depressurisation temperature is preferably in the range 80 to 2500C. Conveniently it is about the same at adsorption and depressurisation, apart from changes due to isotherms of adsorption and endotherms of desorption. If it is desired to produce a C02 stream of high purity and/or pressure and the thoroughness of C02 removal from the starting gas is less important, the inlet temperature is preferably towards the upper end of this range and is particularly in the range 120 to 2000C and the absorbant should be selected such that, at the temperature of operation, the quantity of C02 adsorbed varies substantially with pressure. On the other hand, if very high purity of the C02 stream is not required but it is important that the unadsorbed gas is of low C02 content, the inlet temperature is preferably towards the lower end of the range, and is particularly in the range 80 to 1200C. The PSA treatment can be broadly of the type wherein there is a plurality of adsorbent charges, hereinafter termed beds, and each bed takes part, successively, in steps including adsorption, pressure equalisation, depressurisation to exterior, and repressurisation. In the ensuing description of the preferred PSA processes, the terms inlet" and "outlet refer to the direction of flow of gas during the adsorption step, and the terms "co-current" and "counter-current mean towards such outlet or inlet respectively. The pressure of the raw, or starting, gas mixture entering the bed is preferably in the range 25 to 50, especially 30 to 40, bar abs. In the adsorption step, switching of the supply of the raw gas to a second bed is effected when the tail of the C02 front is at, or almost at, the bed outlet. The nearer the tail of the C02 front to the bed outlet when switching occurs the greater will be the purity of the recovered C02 but the less the extent of C02 removal will be. The C02 content of the unadsorbed gas will vary as the adsorption proceeds but it is preferred that the switching takes place at such time that the unadsorbed gas contains 0.1 to 2Z V/v of C02 integrated over each adsorption step. After switching the raw gas supply to another bed, the pressure in the first bed is reduced by an equalisation step wherein gas from the outlet of the first bed is fed to a recipient bed which has been depressurised to the exterior and may have been partly repressurised. Preferably the equalisation is effected by feeding the gas from the outlet of the first bed to the outlet of the recipient bed: this moves the adsorption front backwards and, depending on how much C02 was allowed to pass out at the end of the adsorption step, may introduce a small quantity of C02 into the outlet end of the recipient bed. There may be one or more pressure equalisation steps. Thus, as in the relevant part of the 4-bed system depicted in figure 2 of USP 3430418, on which the system described hereinafter is based, there may be a single equalisation step. Alternatively, as in the relevant parts of the modified 4-bed system depicted in figure 2 of USP 3564816 or of the 5-bed system depicted in figure 3 of USP 3430418, there may be two equalisation steps. Alternatively, as in the relevant parts of the systems using 6 or more beds, for example the 8-bed and 10-bed systems depicted in USP 3986849, there may be three equalisation steps. Although the pressure equalisations are illustrated by those references, as described below the PSA cycles that may by used in the process of the invention differ from the disclosed cycles in other respects. After the pressure equalisation step, the bed is subjected to de-pressurisation. Whereas, in cycles shown in the above references, the depressurisation is co-current and the released gas is used to purge counter-currently another bed that has previously been counter-currently depressurised to exterior (usually to waste), this procedure is preferably only used if it is desired to maximise C02 recovery and moderate C02 purity is acceptable. A preferred depressurisation process is carried out in two or more parts and effects C02 product release at relatively low pressure. The first part, or parts, hereinafter termed the "penultimate" depressurisation is stopped at a pressure such that the desorbed gas stream is relatively lean in C02 but rich in MB and H2 (if present). Where this desorbed gas contains H2, CR4 and/or CO it is conveniently usable as fuel, especially for a gas turbine. Alternatively in such a multiple depressurisation, the penultimate depressurisation gas can be used to purge, preferably counter-currently, another bed. Thereafter a final depressurisation is carried out, giving a stream of desorbed gas which is rich in C02. In such a two or more part depressurisation, the penultimate depressurisation can be co-current or countercurrent. Co-current penultimate depressurisation is usually preferable since it removes more MB and H2 (if present) and less C02 and thus gives a gas stream of higher C02 purity in the final depressurisation. The terminal pressure of such a co-current penultimate depressurisation with C02 product release is preferably at least 2 bar abs. and typically up to 10 bar abs. The gas released in this step is leaner in C02 the higher the terminal pressure. The final depressurisation is preferably countercurrent but is not necesarily so. The terminal pressure of the final depressurisation is conveniently in the range 1 to 2 bar abs. The C02-rich stream released in this step is richer in C02 the lower the terminal pressure of the penultimate depressurisation. However the lower the latter pressure, the less will be the proportion of the C02 in the raw gas that is recovered in the final depressurisation C02 product stream. It will be apparent that further elaborations are possible, for example in which a first penultimate depressurisation gas, lean in C02, is taken, a second penultimate depressurisation is used to supply gas to purge another bed, a counter-current final depressurisation is effected to give a C02-rich product gas stream, and then the bed is purged counter-currently. As mentioned above, after final depressurisation, the bed may be purged with penultimate depressurisation gas from another bed. This can give further release, and hence recovery, of C02. Generally however no purge step using gas from outside the PSA cycle is needed. As an alternative to a multi-part depressurisation there may be a single depressurisation giving a single C02- containing gas stream, without the need for a purge. After final depressurisation, (and purge, if used) the bed is repressurised. The first part of the repressurisation may be by feeding to the bed outlet the gas from another bed that has just ended its adsorption step and is undergoing the aforementioned pressure equalisation. During or following this first repressurisation, the bed is repressurised with the unadsorbed product gas, ie the gas mixture from which C02 has been recovered, by diverting this product gas from the outlet stream of a bed undergoing adsorption duty into the bed outlet. This feed of product gas preferably takes place throughout the equalisation as well as after it, so that the rate of flow of such gas does not vary much during the whole cycle. Alternatively or additionally, the product gas feed may be from a reservoir. In order to limit the magnitude of fluctuations in the composition and flow rate of the gas streams leaving the PSA system, the latter preferaably includes enough beds to permit at least two beds to be used simultaneously, but out of step with one another, on each of the adsorption, depressurisation with C02 product release, and purge with C02 release (if used). The adsorbent can be any of those considered suitable for PSA, including silica gels, active carbons and zeolites. It preferably includes a zeolite, since zeolites are capable of adsorbing C02 much more preferentially to the NB gases than the other adsorbents. Such specificity is less at the high temperatures used in the process of the invention than at conventional PSA temperatures, but is fully adequate. The effect of the high temperature is to produce a C02 adsorption isotherm with a zeolite that resembles the ambient temperature isotherms for active carbon and silica gel. A suitable zeolite is of the A type, for example calcium zeolite A which is defined in D W Breck's "Zeolite Molecular Sieves and is available from several manufacturers under different trade names. Table 1 sets out values of the adsorption constants K, where K = kg. mols of adsorbed gas per kg of adsorbent pressure in bar abs. for C02 and N2 and of the ratio KC02/KN2 for a zeolite and an active carbon. The values at 30, 70 and 1000C are quoted from page 565 of Gas Purification" by A L Kohl and S C Riesenfeld, 3rd ed. 1979 (Gulf Publications, Houston, Texas, USA) and those at 1500C are obtained by Clausius Clapeyrontype calculation. Table 1 EMI9.1 <tb> <SEP> K, <SEP> kg. <SEP> <SEP> mol <SEP> kg-1 <SEP> bar <SEP> 1 <SEP> <SEP> at <SEP> TOC <SEP> <tb> <SEP> T <SEP> P <SEP> <SEP> 30 <SEP> T <SEP> - <SEP> 70 <SEP> T <SEP> - <SEP> 100 <SEP> T <SEP> o <SEP> <SEP> 150 <tb> Zeolite <SEP> N2 <SEP> 26 <SEP> x <SEP> 10 <SEP> -5 <SEP> 11.9 <SEP> x <SEP> 10 <SEP> -5 <SEP> 7.4 <SEP> x <SEP> 10 <SEP> -5 <SEP> 3.9 <SEP> x <SEP> 10-5 <tb> <SEP> CO2 <SEP> <SEP> 0.161 <SEP> 0.041 <SEP> 0.0179 <SEP> 0.0058 <tb> <SEP> ratio <SEP> 619 <SEP> 344 <SEP> 241 <SEP> 148 <tb> Carbon <SEP> N2 <SEP> 41.5 <SEP> x <SEP> 10 <SEP> -5 <SEP> 23.8 <SEP> x <SEP> 10- <SEP> 5 <SEP> 16.9 <SEP> x <SEP> 10 <SEP> 5- <SEP> 10.7 <SEP> x <SEP> 10-5 <SEP> <tb> <SEP> Co; <SEP> <SEP> 4.46 <SEP> x <SEP> 10-3 <SEP> <SEP> 1.45 <SEP> x <SEP> 10-3 <SEP> 0.73 <SEP> x <SEP> 10-3 <SEP> <SEP> 0.29 <SEP> x <SEP> 10-3 <SEP> <tb> <SEP> ratio <SEP> 10.7 <SEP> 6.1 <SEP> 4.33 <SEP> 2.71 <tb> The present invention is of particular use in combinations wherein (a) the unadsorbed gas obtained by the process of the invention from a gas mixture containing H2 as well as MB and C02 is fed to a downstream PSA system operated at a lower temperature: in the downstream PSA system some or all of the MB in the unadsorbed gas from the process of the invention is removed. In this case, where the MB comprises CO, the unabsorbed gas from the process of the invention may be subjected to selective CO removal, such as by oxidation or methanation, before the second PSA stage; and/or (b) the product C02-containing gas, whether it is a complete single depressurisation gas or the C02-rich final stage depressurisation gas, is fed to a C02 concentration system, such as an adsorptive or liquid-absorption or distillation C02 recovery system; for this purpose the product C02containing gas can, if desired, be compressed; and/or (c) with or without the above-mentioned C02 concentration, the C02-containing product gas is fed to urea synthesis; and/or (d) unadsorbed gas from the downstream PSA system of the aforementioned two PSA arrangement is fed to a hydrogenation process or, where the MB comprises N2, to ammonia synthesis, the latter advantageously being the source of ammonia for the urea synthesis where, as mentioned above, the CO2-containing product is fed to urea synthesis; and/or (e) if the process as a whole is to produce a hydrogen-rich gas stream or ammonia synthesis gas, the chemical stage preceding the PSA of the invention is a catalytic shift stage preferably decreasing the CO content to at most 1, preferably under 0.55X V/v as a dry basis. Cooling and water removal and possibly drying are effected before the PSA. If the process as a whole is to produce hydrocarbons or oxygenated hydrocarbons, the shift stage may be an incomplete or partially by-passed shift stage; where the process as a whole is to produce ammonia synthesis gas, upstream of shift and water removal the preferred stage is hydrocarbon air-steam reforming in which catalytic primary steam reforming is effected in indirect heat exchange with catalytic air reforming and the product raw gas has an (H2 + CO)/(MB + CO) molar ratio in the range 1.25 to 2.5, especially 1.5 to 2.1, a C02 content in the range 10 to 25Z V/v, on a dry basis, and at least 90% V/v of the MB is N2. Preferred forms of the invention are shown in the accompanying drawings, in which Figure 1 is a block diagram representing the use of the invention in producing high strength C02 and ammonia synthesis gas; and Figure 2 is a diagram of the steps involved in one PSA system using the process of the invention. In the process according to figure 1, which is an example of combination process (a) above, a stream of raw ammonia synthesis gas is produced by the sequence of natural gas/steam catalytic primary reforming, air secondary reforming, heat exchange between secondary reforming outlet as the source of heat for primary reforming, catalytic shift, cooling and water separation (combination (e) above). The water-depleted gas is fed at 10 to "hot" PSA unit 12, which includes at least 4 beds of adsorbent and programmed valves providing an uninterrupted succession of steps of adsorption, pressure equalisation, depressurisation and repressurisation. The cycle in unit 12 is characterised by two separate steps of depressurisation, the first down to a moderate level producing a gas stream 14 relatively lean in C02, the second from that moderate level downwards producing a gas stream 16 rich in C02. The C02-lean gas 14 is fed out for use as fuel, for example (being at superatmospheric pressure) in a gas turbine (not shown). The C02-rich gas 16 is fed out to C02 users (not shown). The unadsorbed gas from unit 12 is depleted in C02 but requires further adjustment and purification to produce ammonia synthesis gas. The unadsorbed gas 18 from unit 12 is cooled in heat exchanger 20 to a temperature at which 112 and MB gases can be separated adsorptively. As a result of the conditions of primary and secondary reforming, the R2/N2 ratio of the gas entering unit 12 was less than is required in ammonia synthesis and this is not much changed by the whole PSA of the invention. Thus part of the N2, as well as C02 and CH4 have to be removed; to this end the cooled gas from heat exchanger 20 is fed to a PSA unit 22 of the special type described in our European application 85301022 in which, in each adsorption step, the H2/N2 ratio is initially low, intermediately high, and finally low but integrates over the whole step to the required ratio, usually in the range 2.5 to 3.0. The unadsorbed gas 24 from this second PSA unit 22 is fed out to a compressor and an ammonia synthesis plant, which are conventional and not shown. The steps in PSA unit 22 can include pressure equalisation, depressurisation and repressurisation but, unlike unit 12, the gas evolved in cocurrent depressurisation is not, or not all, fed out separately but is, at least partly, used to purge a bed that has undergone counter-current depressurisation to exterior. The resulting depressurisation and purge gas 26 has some fuel value. To avoid gross fluctuations in gas compositions, units 12 and 22 both contain enough beds, for example 10 or more, to permit 3 beds to be simultaneously on each duty but out of phase with one another. Figure 2 shows a 4-bed system providing a preferred PSA cycle for use in the process of the invention. In this figure, each laterally aligned "box" represents a particular time interval, while successive "boxes" downwards represent successive time intervals, in the PSA cycle. The gas flows are represented so that the inlet to each bed is on the left hand side and the outlet on the right hand side. Although, for clarity, two adsorption "boxes" have been shown for each bed, it will be appreciated that, in each bed, the adsorption stage is continuous. Likewise two repressurisation boxes are shown. As described above, in the first repressurisation the bed may be receiving both gas from a bed undergoing pressure equialisation and unadsorbed gas from a bed undergoing adsorption duty. It will further be appreciated that each box does not necessarily indicate the same time interval: thus considering bed A, while the pressure equalisation step has to take place during the repressurisation of bed B, the penultimate and final depressurisation steps can occur at any subsequent time prior to the pressure equalisation step of bed B. In Figure 2 the following abbreviations are employed AD - adsorption EQ - equalisation PD - penultimate depressurisation FD - final depressurisation FR - first repressurisation SR s second repressurisation RG - raw gas UG - unadsorbed gas FG - final depressurisation product gas PG - penultimate depressurisation product gas As explained above, the process of the invention is characterised by a high operating temperature and, in preferred forms by at least one penultimate depressurisation to give at least one C02-lean gas 14 and by final depressurisation to give C02-rich gas 16. If the nonpreferred cycle using a purge step is used, then the penultimate depressurisation (or the last of these if there are more than one) is carried out co-currently and the gas is fed countercurrently through the recipient beds as follows: depressurising bed recipient bed A C B D C B D A The gas leaving the recipient bed during purge is usually united with the gas that left that bed during final depressurisation. As an example of the process of the invention, typical temperatures, pressures, and gas flow rates are shown in Table 2 for the recovery of C02 from a raw ammonia synthesis gas to be used in producing 1000 t. d 1 of ammonia. In this mode of operation, termed mode A, which is the mode depicted in Figure 2, the penultimate depressurisation is cocurrent and is stopped at a pressure of 3 bar abs to release a desorbed gas that is relatively C02-lean and is of use as a fuel. The final depressurisation, which is counter-current is to a terminal pressure of 1 bar abs. and gives a CO2-rich product stream. Other useful nodes of operation with the sale raw gas, inlet pressure and teMperature, are as follows: Mode B ;as node A but the penultimate depressurisation is counter-current. Mode C : the penultimate depressurisation is counter current and is continued to a terminal pressure of 2 bar abs; the bed is then purged, counter-current by depressurisation gas released cosurrently fran another bed. The gas released as a result of the penultimate depressurisation is mixed with that purged frow the bed to give a single CO2-containing product gas stream. Mode D : as node B but the terminal pressure of the final depressurisation is 1.1 bar abs and the gas released frou the penultinate depressurisation is Mixed with that fran the final depressurisation to give a single CO2-containing product stream. The perfornance of these nodes of operation is susiarised in Table 3, in comparison with a scold PSA handling the sase raw gas at a PSA inlet texperature of 350C. Table 2 EMI15.1 <tb> <SEP> press. <SEP> <SEP> Gas <SEP> flow <SEP> rate <SEP> (kg. <SEP> mol. <SEP> h-1) <SEP> <tb> <SEP> Stream <SEP> Temp <SEP> (bar <tb> <SEP> ( C) <SEP> abs) <SEP> CO <SEP> <SEP> C021 <SEP> <SEP> H2 <SEP> CR4 <SEP> <SEP> N2 <SEP> AT <SEP> Total <tb> 10 <SEP> raw <SEP> gas <SEP> 180 <SEP> 35 <SEP> 29 <SEP> 1303 <SEP> 438 <SEP> <SEP> 39 <SEP> 2383 <SEP> 59 <SEP> 8198 <tb> 14 <SEP> penult. <tb> <SEP> depress. <SEP> 175 <SEP> 3 <SEP> 7 <SEP> 90 <SEP> 104 <SEP> 5 <SEP> 126 <SEP> 12 <SEP> 344 <tb> 16 <SEP> final <SEP> depress. <SEP> 175 <SEP> 1 <SEP> 5 <SEP> 1112 <SEP> 14 <SEP> 0 <SEP> 14 <SEP> 0 <SEP> 1145 <tb> 18 <SEP> unadsorbed <SEP> 185) <tb> 22 <SEP> inlet <SEP> 35) <SEP> 34 <SEP> 17 <SEP> 101 <SEP> 4267 <SEP> 34 <SEP> 2243 <SEP> 47 <SEP> 6709 <tb> 24 <SEP> syngas <SEP> <SEP> 40 <SEP> 34 <SEP> 9 <SEP> 0 <SEP> 4101 <SEP> 10 <SEP> 1433 <SEP> 31 <SEP> 5584 <tb> 26 <SEP> waste <SEP> 30 <SEP> 3 <SEP> 8 <SEP> 101 <SEP> 166 <SEP> 24 <SEP> 810 <SEP> 16 <SEP> 1125 <tb> Table 3 EMI15.2 <tb> <SEP> unadsorbed <SEP> <tb> <SEP> C 2 <SEP> <SEP> product <SEP> stream <SEP> H2-rich <SEP> gas <SEP> stream <tb> <SEP> Mode <SEP> C02 <SEP> <SEP> C02 <SEP> <RTI ID=15.10> H2 <SEP> <SEP> C02 <SEP> <tb> <SEP> content <SEP> recovery <SEP> pressure <SEP> recovery <SEP> content <tb> <SEP> (zV/v) <SEP> <SEP> (t) <SEP> <SEP> (bar <SEP> abs. <SEP> (S) <SEP> <SEP> (% <SEP> V/v) <tb> <SEP> A <SEP> 97.1 <SEP> <SEP> 85 <SEP> 1 <SEP> 97.3 <SEP> 1.5 <tb> <SEP> B <SEP> 76.0 <SEP> 50 <SEP> 1 <SEP> 94.4 <SEP> 0.2 <tb> <SEP> C <SEP> 78.0 <SEP> 98 <SEP> 2.0 <SEP> 97.0 <SEP> 0.4 <tb> <SEP> D <SEP> 62.0 <SEP> 99 <SEP> 1.1 <SEP> 94.4 <SEP> 0.2 <tb> "cold" <SEP> 51.3 <SEP> 100 <SEP> 1.5 <SEP> 96.3 <SEP> 0 <tb> It is evident that mode A produces a high purity CO2 product stream 16 that can be very economically processed to further products, as well as a readily combustible fuel stream 14. The percentage H2 recovery in unadsorbed gas is also very high, but the C02 content of such gas is also relatively high. If the unadsorbed gas were subjected to CO removal by selective oxidation or selective methanation it could be converted to synthesis-ready ammonia synthesis gas by a second PSA stage as described in European application 85301022 without methanation after the second PSA stage. Alternatively it could be subjected to such a second PSA stage without such CO removal and the unadsorbed gas could be methanated to give synthesis-ready ammonia synthesis gas. Modes B and D produce as the unadsorbed gas, a R2- rich gas of lower C02 content: this H2-rich gas can be obtained, for example, by shortening the adsorption step so that less C02 breakthrough occurs. The percentage H2 recovery is correspondingly lower than in mode A. To obtain a C02-rich stream of adequate purity the penultimate depressurisation in mode B is larger and thus only a 50Z recovery of C02 in the final depressurisation is possible. Alternatively, in mode D, a single C02 stream is taken, with the result that a 99% C02 recovery at 62% purity is obtained. Such a purity level is, however, greater than in the "cold" PSA process of European application 85301022.

Claims: 1. A process for the recovery of carbon dioxide from a mixture thereof with at least one medium boiling gas having a boiling point, at atmospheric pressure, of between -1000C and 2300C and optionally also at least one low boiling point gas having a boiling point at atmospheric pressure below -2300C comprising a pressure swing adsorption sequence wherein (i) the mixture at elevated pressure is contacted with a first charge of a solid adsorbent effective to adsorb carbon dioxide preferentially; (ii) when the first charge of adsorbent is sufficiently loaded with carbon dioxide, the mixture flow is switched to a further charge of adsorbent which is fresh or regenerated; and (iii) a gas stream enriched in carbon dioxide as compared with the starting mixture is recovered by depressurising the first charge: characterised in that the adsorption and depressurisation steps are each carried out at a temperature of at least 5O0C. 2. A process according to claim 1 wherein the adsorption and depressurisation steps are each carried out at a temperature in the range 80 to 2500C. 3. A process according to claim 1 or claim 2 wherein there are a plurality of adsorbent charges and each charge takes part, successively, in steps including adsorption, pressure equalisation, depressurisation to exterior, and repressurisation and said depressurisation to exterior is effected in at least two stages. 4. A process according to claim 3 wherein the penultimate depressurisation is co-current. 5. A process according to claim 3 or claim 4 wherein the final depressurisation is counter-current. 6. A process according to any one of claims 3 to 5 wherein the pressure of the mixture fed to the adsorbent charge is in the range 25 to 50 bar abs., the terminal pressure of the penultimate depressurisation is in the range 2 to 10 bar abs, and the terminal pressure of the final depressurisation is in the range 1 to 2 bar abs. 7. A process according to any one of claims 1 to 6 wherein the gas mixture comprises carbon dioxide, hydrogen, and nitrogen. 8. A process according to any one of claims 1 to 7 wherein the volume ratio of said at least one medium boiling gas to carbon dioxide is in the range 0.2 to 5. 9. A process according to claim 8 wherein the gas mixture contains at least 40Z by volume of hydrogen, has a hydrogen to medium boiling gas molar ratio in the range 1.5 to 2.5, and at least 90D by volume of said at least one medium boiling gas is nitrogen. 10. A process according to claim 7 or claim 9 wherein the unadsorbed gas, comprising medium boiling gas and hydrogen, from the pressure swing adsorption sequence is fed, at a lower temperature, to a second pressure swing adsorption sequence effective to separate some or all of the medium boiling gas from the hydrogen.

Inventors: HASLETT, ANDREW MICHAEL, JOHNSON, JOHN BRIAN HANSEN
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1985
Main classification: B01D53
IPC codes: B01D53, C10K1, C01B3, C07C1, C01B31