Scribd Logo
Upload

Welcome to Scribd!

  • Ast

    Uploaded by

    Jay Parekh
    9 views12 pages
    st

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document
    st

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    9 views12 pages

    Ast

    Uploaded by

    Jay Parekh
    st

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 12
    852 ADSORPTION, GAS SEPARATION Vol. 1 proc The air fed to an air separation plant must be H4O- and COgtfree to prevent fouling of heat exchangers at cryogenic temperatures; 13X is typically used here. Another application for 4A.type zeolite is for CO» removal from base- load and peak-shaving natural gas liquefaction facilities. The removal of volatile organic compounds (VOC) from air is most often accomplished by TSA. Air streams needing treatment can be found in most chemi- cal and manufacturing plants, especially those using solvents. At concentrations from 500 to 15,000 ppm, recovery of the VOC from steam used to regenerate activated carbon adsorbent thermally is economically justified. Concentrations above 18,000 ppm are typically in the explosive range and require the use of inert. fas rather than air for regeneration. Below about 500 ppm, recovery is not economically justifiable, but environmenta? concerns often dictate adsorptive recovery followed by destruction. Activated carbon is the traditional adsorbent for these applications, which represent the second largest use for gas-phase carbons. New forms of activated carbon, such as carbon fabrics (56) and adsorbent. wheels (57), have been introduced to reduce the airflow pressure drop, which can result in large utility consumptions (see CARBON, ACTIVATED CARBON). A number of inorganic pollutants are removable by TSA processes. One of the major pollutants requiring removal is SO, from flue gases and from sulfuric acid plant tail gases. The Sulfacid and Hitachi fixed-bed processes, the Sumitomo and BF moving-bed processes, and the Westvaco fluidized-bed process all use activated carbon adsorbents for proven SO, removal (68). Zeolites with high acid resistance, such as mordenite and clinoptilolite, have proven to be effective adsorbents for dry SO, removal from sulfuric acid tail gas (69), and special zeolite adsorbents have been incorporated into the UOP PURASIV S process for this application (54). Zeolites have also proven applicable for removal of nitrogen oxides (NO,) from wet nitric acid plant tail gas (69) by the UOP PURASIV'N process (64). The removal of NO, from flue gases can also be accomplished by adsorption. The Unitaka process utilizes activated carbon with a catalyst for reaction of NO, with ammonia, and activated carbon has been used to convert NO to NO», which is removed by scrubbing (58). Mercury is another pollutant that can be removed and recovered by TSA. Activated carbon impregnated with elemental sulfur is effec- tive for removing Hg vapor from air and other gas streams; the Hg can be recovered by ex situ thermal oxidation in a retort (60). The UOP PURASIV Hg. Process recovers Hg from chlor-alkali plant vent streams using more conven. tional TSA regeneration (54). Mordenite and clinoptilolite zeolites are used to remove HCI from Cl, chlorinated hydrocarbons, and reformer catalyst gas streams (61). Activated aluminas are also used for such applications, and for the adsorption of fluorine and boron-fluorine compounds from alkylation (qv) pro. cesses (50). PRESSURE SWING A pressure-swing adsorption (PSA) cycle is one in which desorption takes place at & pressure much lower than adsorption. Its principal application is for bulk Separations where contaminants are present at high concentration. The PSA cycles are characterized by high residual loadings and low operating loadings. Fir pre Th mu bed 801] ste} S01 an! pre th Vol. 1 ADSORPTION, GAS SEPARATION 553 Figure 14 shows the operating loading (X-X2) that derives from the partial pressure at feed conditions and the lower pressure P, at the end of desorption. These low adsorption capacities for high concentrations mean that cycle times must be short, seconds to minutes, for reasonably sized beds. Fortunately, packed beds of adsorbent respond rapidly to changes in pressure. A purge usually re- moves the desorbed components from the bed, and the bed is returned to ad- sorption condition by repressurization. Applications may require additional steps, Systems with weakly adsorbed species are especially suited to PSA ad- sorption. The applications of PSA include drying, upgrading of Hy and fuel gases, + and air separation. Several broad reviews of PSA have been written (62-64). 1s Sia edge i Pes partial pressure = bes inne Be nie Tees, een mon mode forse pressure Adsorbed prodet i ‘Adsorbote partial pressure Fig. 14, Pressure-swing cycle (1). Principles. Ina PSA cycle bvo processes occur during regeneration, de- pressurizing, and purging. Depressurization must provide adequate reduction in the partial pressure of the adsorbates to allow desorption. Enough purge gas must 554 ADSORPTION, GAS SEPARATION Vol. 1 flow through the adsorbent to transfer the desorbed material away. Equilibrium determines the maximum capacity of the gas to accomplish this. ‘These cycles operate at nearly constant temperature and require no heating or cooling steps. They utilize the exothermic heat of adsorption remaining in the adsorbent to supply the endothermic heat of desorption. Pressure-swing cycles are classified as PSA, VSA (vacuum-swing adsorption), PSPP (prossure-swing parametric pump- ing) or RPSA (rapid pressureswing adsorption). PSA swings between a high superatmospheric and a low superatmospheric pressure, and VSA swings from a superatmospheric pressure to a subatmospheric pressure. Otherwise, the princi- ples involved afe the same. ‘The other means of accomplishing pressure eycling of an adsorbent is para- metric pumping, in which a single adsorbent bed is alternately pressurized with forward flow and depressurized with backward flow through the column from Feservoirs at each end. Like TSA parametric pumping, one component concen: trates in one reservoir anc! one in the other. As the name implies, pressure-swing parametric pumping embodies pressure changes that are more than pressuring and depressurizing a bed of adsorbent. Significant pressure gradients occur in the bed, much as vemperature gradients are imposed in TSA parametric pumping. These gradients are especially critical to the way that RPSA cycles operate and result in much smaller adsorbent beds and simpler processes (57). In most applications of adsorption, the separation is carried out by ade sorbing the more strongly adsorbed species from the less strongly adsorbed, These separations are thus equilibrium-limited. However, an adsorptive separation can also be based on a rate- or kinetically-limited system (65). Slightly larger mole- cules diffuse more slowly through a microporous adsorbent with properly selected pore diameter. Therefore, in a rapidly cycling process such as PSA, smaller molecules can be preferentially adsorbed even in the absence of any equilibrium selectivity. Indeed rate-limited PSA has preferentially adsorbed oxygen from air on 4A zeolite when the equilibrium selectivity favors Nz adsorption (52). Steps. A pressure-swing cycle has at least three steps: adsorption, blowdown, and repressurization. Although not always necessary, a purge step ig normally used. In finely tuned processes, cocurrent depressurization and pres- sure-equalization steps are frequently added, At the completion of adsorption, the less selectively adsorbed components have been recovered as product. However, a significant quantity of the weakly adsorbed species are held up in the bed, especially in the void spaces. A cocurrent depressurization step reduces the bed pressure by allowing flow out of the bed cocurrently to feed flow and thus reduces the amount of product retained in the Voids (holdup), improving product recovery, and increases the concentration of the more strongly adsorbed components in the bed. The purity of the more selectively adsorbed species has been shown to depend strongly on the cocurrent depressurization step for some applications (68). A cocurrent depressurization step is optional because a countercurrent one always exists. Criteria have been developed to indicate when the use of both is justified (67). None of the selectively adsorbed components is removed from the adsorption vessel until the countercurrent depressurization (blowdown) step. During this step, the strongly adsorbed species are desorbed and recovered at the adsorption inlet of the bed. The reduction in pressure also reduces the amount of gas in the Vol be. eye then con is ac resic plew feet! pus they to eres pres bie det Th. stey par En. ll Si Hee Vol.1 ADSORPTION, GAS SEPARATION 555, bed. By extending the blowdown with a vacuum (ie, VSA), the productivity of the cycle can be greatly increased. Additional stripping of the adsorbates from the adsorbent and purging of them from the voids is accomplished by the purge step. This step can occur concurrently with the end of the blowdown or be carried out afterward. This stop is accomplished with a flow of product into the product end to provide a low residual of the selectively adsorbed components at the effluent end of the bed. The repressurization step returns the adsorber to feed pressure and com- pletes the steps of a PSA cycle. Pressurization is carried out with product and/or feed. Pressurizing with product is done countercurrent to adsorption so that purging of the product end continues; indeed it may be merely a continuation af the purge step but with the ed exit valve closed, Pressurizing with feed cocurrent to adsorption in effect begins adsorption without producing any product. Pressure equalization steps are used to conserve gas and compression en- ergy. They are applied to reduce the quantity of feed or product gas needed to pressurize the beds. Portions of the effluent gas during depressurization, blowdown, and purge can be used for repressurization. Flow Sheet. The most common processing scheme has two or three fixed- bed adsorbers alternating between the adsorption step and the desorption steps. The simplest two-bed configuration is illustrated in Figure 14. However, the variations possible to achieve special separations are endless. Single beds with external surge vessels provide continuous flow: multiple beds are used to accom: modate additional steps. An example of the bed sequencing needed for multiple steps in a four-bed PSA is shown in Figure 15. Beds can be configured in series or parallel to accomplish coproduction.. vessel somber ‘adsorption JEQI] co [e02]Co] Puree Jeqzjea] ® 2 ala jalv] wv [viv] ED] Poe [ecejeqi| ‘Adsorston [eg] CO [EQ2| ivi vy [viv v [as |e Eqi} co |rqrjco| Pie jea2lear] A ‘sorption fia he ae ebaalicws| Uwe [vil hw za] RF Adsorston J EQI| CO 2/0] Aime [E02 ibs ivf Be al « jalvl v lv Fig. 15. Four-bed PSA system eyele sequence chart (64). EQ, equalization; C Da, cocurrent depressurization: C DY, countercurrent depressurization; R, repressurization; A, cocurrent flow; V. countercurrent flow. Courtesy of American Institute of Chemical Engineers. ‘The flow directions in a PSA process are fixed by the composition of the stream. The most common configuration is for adsorption to take place up-flow. All gases with compositions rich in adsorbate are introduced into the adsorption inlet end, and so effluent streams fromethe inlet end are rich in adsorbate, Similarly, adsorbate-lean streams to be used for purging or repressurizing must flow into the product end. : 556 ADSORPTION, GAS SEPARATION Vol. 4 or Because RPSA is applied to gain maximum product rate from minimum adsorbent, single beds are the norm. In such cycles where the steps take only a few seconds, flows to and from the bed are discontinuous. Therefore, surge vessels are usually used on feed and product streams to provide uninterrupted flow. Some RPSA cycles incorporate delay steps unique to these processes. During these steps, the adsorbent bed is completely isolated; and any pressure gradient is allowed to dissipate (68). The UOP Polybed PSA system uses five to ten beds to maximize the recovery of the less selectively adsorbed component and to extend the process to larger capacities (69). Purifications. The major purification applications for PSA are for hydro- gen, methane, and drying. One of the first commercial uses was for gas drying in which the original two-bed Skarstrom cycle was used. This cycle uses adsorption, countercurrent blowdown, countercurrent purge, and cocurrent repressurization to produce a dry air stream with less than 1 ppm HO (70). About half of all dryers of instrument air use a PSA cycle similar to this one, most commonly using activated alumina or silica gel (71). Zeolites are used to obtain the lowest possible dewpoints. Some applications for drying air do not require a low level of HO, but ! only a significant lowering of the dew point. The pneumatic compressor systems i used in vehicle air-brakes are an example; when a 10-30-K dew point depression is needed for higher discharge air temperatures in the presence of compressor oil, f zeolites have been demonstrated to have an advantage over activated alumina and silica gel (72). High purity H, is needed for applications such as hydrogenation, hydro- cracking, and ammonia and methanol production. As a significant source of such gas, PSA is able to produce purities as high as 99.9999% using technologies such as the UOP Polybed approach (69). Most H purification by PSA is associated with steam reforming of natural gas and with ethylene-plant and refinery off-gas streams (62). Hydrogen is also available in coke-oven gas, cracked ammonia, and coal-gasification gas. The contaminants that have to be removed by PSA include carbon oxides, Nz, O,, Ar, NH, CH,, and heavier hydrocarbons. To remove these components, adsorbent beds are compounded of activated carbon, zeolites, and carbon molecular sieves. Bulk Separations. Air separation, methane enrichment, and iso-/normal separations are the principal bulk separations for PSA. Others are the recovery of : CO and CO». i The PSA process is used to separate air into Nz and Op. Many companies market systems for PSA Op; zeolites 5A, 13X, clinoptilolite and mordenite, and carbon molecular sieves are commonly used in PSA, VSA, and RPSA cycles. The product purity ranges from 85 to 95% (limited by the argon, which remains with the 0,). About two-thirds of the O, produced is employed for electric furnace steel, with lesser amounts for waste water treating and solid waste and kilns (62) Smaller production units are used for patients requiring respiratory inhalation therapy in the hospital and at home (64) and for pilots on board aircraft (73). F Enriched air, 25 to 55% Oz, used to enhance combustion, chemical reactions, and ozone production can be produced by tuning PSA processes (63). High purity, up | to 99.99%, N, is produced by PSA and VSA cycles with zeolites and carbon & molecular sieves (74). The major use for the Ny is inert blanketing, such as in m a Jar tt mt Tr 8 ev fir wy Vol. 4 ADSORPTION, GAS SEPARATION 557 metal heat-treating furnaces; small units are used to purge aircraft fuel tanks (52) and in the food and beverage industry. ‘The upgrading of methane to natural gas pipeline quality is another signifi- cant PSA separation area. Methane is recovered from fermentation gases of landfills and wastewater purification plants and from poor-quality natural gas wells and tertiary oil recovery when CO, is the major bulk contaminant. Fermen- tation gases are saturated with water and contain “garbage” components such as sulfur and halogen compounds, alkanes, and aromatics (75). These impurities must first be removed by TSA using activated carbon or carbon molecular sieves. ‘The COs is then selectively adsorbed in a PSA cycle using either zeolites or silicn gel in an equilibrium separation, or carbon molecular sieve in a kinetic-nssisted equilibrium separation (76,77). One version of the UOP IsoSiv process uses PSA to separate normal paraf- fins from branched and cyclic hydrocarbons in the Cs to Cy range. Zeolite 5A is used because its pores can size-selectively adsorb straight-chain molecules while excluding branched and cyclic species. The normal hydrocarbon fraction has better than 95% purity, and the higher octane isomer fraction contains less than 2% normal hydrocarbons (64). PURGE SWING. A purge-swing adsorption cycle is one in which desorption’takes place at the same temperature and total pressure as adsorption. Regeneration is accomplished ei- ther by partial-pressure reduction by an inert gas purge or by adsorbate displace- ment by an adsorbable gas. Its major application is for bulk separations when contaminants are at high concentration. Like PSA, purge cycles are character- ized by high residual loadings, low operating loadings, and short cycle times (minutes). Mixtures of weakly adsorbed components are especially suited to purge-swing adsorption. Applications include the separation of normal from branched and cyclic hydrocarbons, gasoline vapor recovery, and bulk drying of Principles. Purging must provide adequate reduction in the partial pres- sure of the adsorbates to allow desorption. With enough purge volume, loadings as high as the loading X, in equilibrium with the feed partial pressure P; can be achieved, as shown in Figure 16. Reduction in partial pressure operates analo- gously to the reduction in system pressure in PSA cycles. Equilibrium determines the maximum capacity of the gas to purge the adsorbate. These cycles operate adiabatically at nearly constant inlet temperature and require no heating or cooling steps. As with PSA, purge processes utilize the exothermic heat of ad- sorption remaining in the adsorbent to supply the endothermic heat of desorption. Purge cycles are divided into two categories, inert purge and displacement purge. In inert-purge stripping, inert refers to the fact that the purge gas is not appre- ciably adsorbable at the cycle conditions. Inert purging desorbs the adsorbate solely by partial pressure reduction. In displacement-purge stripping, displacement refers to the displacing ac- tion of the purge gas caused by its ability to adsorb at the cycle conditions. This competitive adsorption tends to desorb the adsorbate in addition to the partial 370 _ DISTILLATION, AZEOTROPIC AND EXTRACTIVE Vol. 8 hanced oil-field recovery (41); (5) the separation of the pyridine—water azeotrope using bisphenol (42); (6) the dehydration of tetrahydrofuran using monopropylene glycol (43); (7) the separation of the cumene-phenol azeotrope using trisubsti. tuted phosphates (44); (8) the separation of the azeotropes formed by alcohols and their esters using aromatic hydrocarbons (45); (9) the separation of the methanol— methylene bromide azeotrope using ethylene bromide (46); (10) the separation of the phenol—cyclohexanone azeotrope using adipic acid diester (47); (11) the re- moval of close-boiling heptane isomers from cyclohexane, an important raw material for the manufacture of nylon precursors, using a mixture of solvents (48); (22) the separation of the low relative volatility mixture of propylene and propane using acrylonitrile (49); and (13) separating toluene from nonaromaties with phenol (50), All extractive distillations correspond to one of three possible residue curve maps; one for mixtures containing minimum boiling azeotropes, one for mixtures containing maximum boiling azeotropes, and one for nonazeotropic mixtures. ‘Thus extractive distillations can be divided into these three categories, Minimum Boiling Azeotropes. All extractive distillations of binary mini- mum boiling azeotropic mixtures are represented by the residue curve map and column sequence shown in Figure 6b. Typical tray-by-tray composition profiles are shown in Figure 7. In the distillation of ideal mixtures, the component having the lowest boiling point is always the one recovered as the distillate. This is not true for extractive distillations. Neither ean the design engineer freely pick which azeotropic com- ponent to recover overhead despite the apparent symmetry of the residue curve map (Fig. 6b). For a given solvent, one and only one component can be recovered in the extractive column and it need not be the pure component having the lowest Methane! 18 00 02 04 06 oon Witer ‘cstone Try 4 @ © Eig. 7. Extractive distillation column profiles for the acetone-methanol-water separation (£2). G@i Liguid composition versus theoretical tray location where (—) represents acctone, Crap methanol, and (-----) water; and (b) liquid composition profiles in mole fraction feordinates where a represents the azeotrope; A, the distillate, x, feed; ©, bottonn and *, tray composition (51). Vol. 8 DISTILLATION, AZEOTROPIC AND EXTRACTIVE 371 boiling point. For example, the extractive distillation of ethanol and water using gasoline (38), some phenols (53), cyclic ketones, or cyclic alcohols (54) causes water to be removed as the overhead product of the extractive column and the lower boiling ethanol to leave in the bottom stream with the solvent. The higher ketones distill methanol overhead from methanol-acetone mixtures (55,56) and furfural reverses the natural volatility of butane—butadiene mixtures (36). This phenom- enon of having the intermediate boiling pure component distill overhead in the extractive column results entirely from the way in which the solvent modifies the volatilities of the other components in the mixture. Drawing pseudo-binary y—x phase diagrams for the mixture to be separated is the easiest way to identily the distillate product component. A pseude-binary phase diagram is one in which the VLE data for the azeotropic constituents (com- ponents 1 and 2) are plotted on a solvent-free basis. When no solvent is present, the pseudo-binary y-x diagram is the true binary yx diagram (Fig. 8a). At the azeotrope, where the VLE curve crosses the 45° line, a2 = 1.0. To determine which component is the distillate, a series of pseudo-binary y-x plots must be drawn at increasing solvent compositions until the pseudo-azeotrope, the point where the solvent-free VLE curve crosses the 45° line, ie, where ay — 1.0, dis- appears into one of the pure component corners. The resulting pseudo-binary phase diagram is either Figure &b where the solvent increases the volatility of ‘component I relative to component 2, making component 1 the distillate, or Figure 8c, where the solvent has the opposite effect, making component 2 the distillate. ‘The expressions to “break” or “negate” an azeotrope originated from the use of these psdudo-binary phase diagrams because that is what appears to happen as the solvent composition increases. For example, aniline increases the volatility of cyclohexane (bp = 80.8°C) relative to benzene (bp = 80.1°C) (Fig. 8d). Thus the higher boiling cyclohexane would be recovered as the distillate in an extractive distillation. Pseudo-binary y-x phase diagrams can also be used to determine the product component for an extractive distillation of a nonazeotropic mixture. For example, phenol enhances the volatility of the nonaromatics relative to toluene 0 the nonaromaties can be distilled overhead (50). Because binary homogencous azeotropic mixtures cannot be separated into pure component products by isobaric distillation without a solvent, but can be separated in the presence of a sufficient amount of solvent, there is clearly some minimum amount of solvent that just makes the separation possible. The mini- mum solvent flow depends on the solvent used and offers one method for discrim- inating between solvents. A solvent having a small minimum solvent flow is a better solvent and should result in a lower cost design than a solvent having a large minimum solvent flow. The solvent composition required to just make the pscudo-azeotrope disappear on a pseudo-binary yx phase diagram, ie, to “break” the azeatrope, can be taken as a qualitative measure of the minimum solvent flow necessary to make a separation feasible. A simple method for estimating mini- mum solvent flows has been published (67) as has an exact quantitative method (51,58). Optimization. Optimization of the design variables is an important yet often neglected step in the design of extractive distillation sequences. The cost of the solvent recovery (qv) step affects the optimization and thus must also be in- cluded. Optimization not only yields the most efficient extractive distillation de- Vol. 8 DISTILLATION, AZEOTROPIC AND EXTRACTIVE 377 acetone and methanol into different distillation regions, making the separation impossible. The most common method for screening potential extractive solvents is to use gas-liquid chromatography (qv) to determine the infinite-dilution selectivity of the components to be separated in the presence of the various solvent candi- dates (71,72). The selectivity or separation factor is the relative volatility of the components to be separated (see eq. 3) in the presence of a solvent divided by the relative volatility of the same components at the same composition without the solvent present. A potential solvent can be examined in as little as 1-2 hours using this method. The tested solvents are then ranked in order of infinite-dilution selectivities, the larger values signify the better solvents. Favorable solvents se- lected by this method may in fact form azeotropes that render the desired sepa- ration infeasible. In addition to its ability to make the separation feasible or easier, the ideal solvent is inexpensive, readily available, nontoxic, noncorrosive, thermally stable, and nonreactive with and easily separated from the other components in the mix- ture. In reality some compromise in solvent properties is almost always required. Distillation Using tonic Salts Distillation using ionic salts (salt-effect distillation) is analogous to extractive distillation, but, rather than using a high boiling liquid solvent to alter the rela- tive volatility of the mixture to be separated, a nonvolatile and soluble ionic salt is added to modify the volatility. Examples include adding calcium chloride to separate ethanol (qv) and water (73), using magnesium nitrate to dehydrate nitric acid (qv) (see NITRIC ACID), and using ferrous, lithium, or calcium chloride to separate acrylic acid and water (74) (see ACRYLIC ACID AND DERIVATIVzS). Note that like liquid solvents, salts which have a significant effect on the volatility are preferred and some salts reverse the natural volatility difference, causing the intermediate boiling pure component to be distilled overhead. See Reference 74 for an example. For a more complete discussion of saltffect distilllation see References 15-77. Pressure-Swing Distillation It is well known that changing the system pressure can affect the azeotropes in a mixture, This effect can be exploited to separate a binary mixture containing either a minimum or maximum boiling azeotrope which appreciably changes com- position over a moderate pressure range in a sequence of two columns operated at different pressures. This process, called pressure-swing distillation, is often used industrially to separate tetrahydrofuran (THF) and water (78-81) (see FURAN DERIVATIVES). Pressure-swing distillation has also been proposed for separating ethanol and water (38,82), a variety of alcohol-ketone azeotropes (83), and the maximum boiling hydrogen chloride—water azeotrope (84). For a binary mixture forming a pressure-sensitive minimum boiling azeotrope, the separation 378 DISTILLATION, AZEOTROPIC AND EXTRACTIVE Vol. 8 sequence works as shown in Figure 12. The fresh feed, F, is mixed with the re- cycled stream from the second column to form the feed stream, F,, to the first column, which operates at pressure P,. Because F; lies to the right of the azeotrope at pressure P, (Fig. 12a), pure A is removed as the bottom product, B,, and a mixture near the azeotropic composition at pressure P, is the distillate, D,. Stream D, is changed to pressure P, and fed to the next column as stream F>. Because F, now lies to the left of the azeotropic composition at pressure Py (Big. 12a), the other pure component, B, can be recovered in the bottom stream, B, and a near azeotropic mixture becomes the distillate, D,, for recycling to the first column. An analogous procedure is used for binary maximum boiling azeotropes (86). Pressure P, | Pressure Py a 7 % Puree FR, Pare A ‘compasiton @ ® Fig. 12. Prossure-swing distillation of a minimum boiling binary azeotrope. (a) Tempor- ‘ature-composition phase diagram showing the effect of pressure on the azeotropic com- position; (b) column sequence (85). Pures, Pure B Only a fraction of the known azeotropes are sufficiently pressure-sensitive for the conventional pressure-swing distillation process to work. However, the concept can be extended to pressure-insensitive azeotropes by adding a separating agent which forms a pressure-sensitive azeotrope and distillation boundary. Then the pressure is varied to shift the location of the distillation boundary (85). Heterogeneous Azeotropic Distillation Heterogeneous azeotropic distillation, or simply azeotropic distillation, is widely used for separating nonideal mixtures. The technique uses minimum boiling azeo- tropes and liquid-liquid immiscibilities in combination to dvercome the effect of other azeotropes or tangent pinches in the mixture that would otherwise prevent the desired separation. The azeotropes and liquid heterogeneities that are used to make the desired separation feasible may either be induced by the addition of a separating agent, usually called the entrainer, or they may be intrinsically present, in which case the mixture is sometimes called self-entrained. The most corimon case is the former; it. includes such classic separations as ethanol dehy- dration using either benzene, heptane, ethyl ether, ete, as the entrainer, and ac be br in pi 164 Hydrogen um along the isotherm is atained very slowly. ‘The desorption energy requirements caused by the daprssurization lead toa sttong cooling of the adsorbent, which i the presence cof water va por can ead to formation of a igud phase and ‘thus to an imeversible damage of the ssorbent. ‘Poe main desorption takes place after the pressure has been lowered (point ¢ in Fig. 70) ‘mainly by ineeasing the temperature, in this case 10 200°C (point b oy if no previous de- ‘pressurization took place, point d), The requied neat is provided ether indirectly by means of seried heat exchanger cols or by direct heating with « purge gus a higher temperature, After regeneration, the adsorber is cooled to norms ‘operating temperature and pressurized back to normal edsorpion pressure. Applications, Before low-temperature. pu rifcation and separation canbe carted out (see Section $.1), gas components, which would at Tow temperatures for sold deposits inthe heat ‘exchangers and kaek-out drums, must be 16 moved, In synthesis gases from partial oxida sion and steam reforming these are in pastieu- lar water and carbon dioxide, whereas in rfn ery gases these are usualy higher hydrocarbons. Tn dealkylation and coke oven gases benzene, toluene, and other aromatics must be removed ‘whereas in sulfur-containing caw gases hydro- gen sulfide and carbonyl slide are the distr ‘ng components If hese impurities are present in higher on centrations, the major portion may fist be re- moved by condensation (water and hydrocar bons) and/or scrubbing (CO, HS and COS). Final putfcation is then by TSA. A process description of the removal of water and eae- bon dioxide ftom s watersich synthesis gas bby TSA is given elsewhere (+ Gas Production, Chap. 5.52), Furher applications for TSA inbydrogen pu- sification processes ate: 1) Removal of water and ammonia from am- 'monia purge gases before low-temperatare separation. 2) Purification of hydrogen from electrolysis Plans. The main impurities are water and ‘oxygen, The later is converted by means of eatalytic oxidation (ee Section 5.3) 10 wae ter and then removed by condensation and Vol. 17 ‘TSA. Hycrogen fom the chlocaal le. trlysis contains also aces of mercury This canbe removed by TSA on aspcil moee- bla sieve (223) Removal of various impure from pure hy- ‘deogen before liquefaction. Here the alsorp- tion scared oat at igquid nitrogen tempera tue, The regeneration i done with pu by- ‘drogen from the reeyele gas at ambien tem perature sce Chap. 6 3 5.2.3, Pressure Swing Adsorption (PSA) Adsorption Mechanisms. Contrary to ad- sonption with thermal regeneration, pressnre- swing adsorption operates at almost constant tempocatore using partial-pressure differences, However, the small ermperature gradients o¢- curring with ad- and desompion contribute con siderably othe mechanism ofthe process. The ‘components to be removed are adsorbed at hgh system pressure andhigh partial pressure andre ‘desorbed at low syst pressure in accordance with the appropriate equilibrium isotherms of the vacious impurities (see Fig. 69). RG oe acta ' © a eo (0 paetiat proseute, WPx = gure. Aden ties for 0 onrlear soe 2) Asari 6) Desepon Ads epscty Figure 72 shows, for the example of a hy- {drogen ~carbon monoxide mixture, how carbon monoxide, whichis easily adsorbed, reaches the ‘quilibrium loading, a, on the molecular sieve, ‘while pure hyérogen exits the adsorber. When the adsorber capacity is exhausted, the aso ‘ent must be regenerated. The carbon monoxide Vol. 17 a etelar tiated aw 35 Wycdrt.Co, a2 Hydrogen & yorogen row al gas buter an Figure 7, Sibel PSA nt Maa Noy fr eortin repteration, oumeriow epson (any), countess, 15 Tr pro by asrber A. Aber testi of hr adeno step set cesta ads Bt a a a or . loading onthe absorbent is zeduced by depres- surization and hydrogen porging. The difference isthe aailable working capacity ofthe aso. bent, However, asin the case of TSA, the actual working capaciy of the total adsorbent is intu- enced by the presence of mass transfer zones (MTZ) (se Fig. 71), The length of a MTZ.is ba- Sically determined by (1) the concentration of the component tobe removed inthe ra” gs, (2) by the requied produc purity, and (3) by kinetic effec "The PSA Process, Like the TSA. process the PSA process is cyclic, however, contrary to temperature swings, pressure changes can be ctied out more rapidly and allow a shorter sorption time. Typical cycle times are in the range of 3 to 10 min, Thus, removal of impari- ties present in high concentrations canbe accom- plished using moderstely sized adsorber vessels, ‘The essential steps cari out ina PSA unit ae showa in Figure 73 (224), Bach adsorber is ps orming a different task, depending on which phase of the complete PSA cycle is regarded, ‘The chronological sequence ofall stops consti- ties the eyele of one adsorber Page xin Dapesizon o oe Ey 1) Adsorption atthe pressure of the raw gas (highes system pressure), hydrogen produc: {ion adsorber A) 2) Cocuirent depressurization, provision of gas for pressure equalization and purging (adsor- bers Fand B); 3) Countereurent depressurization, production cof pat of the tall gas (adsocber 4) Countereurent purging (lowest system pres- sure), production of other part ofthe tail as (adsorber D); '5) Countercurent repressurization (adsorber 3) Figur 74 (225) shows th diferent process stages wit erpest tote eqis oaing on the adsorbent Te possibiiy of conning the decompression stg ino vectra shown “This later mode of operations inetd forthe cnvichment end recovery of te advert com- Pent. However production of concentrated byproducts ding the production of pe hy drogenis silly cared out ow-tesperatre proceses and ot by the adsorption press a Pressre—> Tigre 7. Tes pues of he su of PSA te. ers repet oe darig one deri eee 25) ‘dsr b)Cacune depresses) Coane ‘ent depresaintn; Prec) Depress oar= ta Reps: Bion det oe Pa aden ese, po pure gm pes; = fa ‘eu one ‘The mode of operation ofa PSA can be sum marized as follows: 1) Pure bydrogen is produced continuously at adsorption pressure, 2) Tall gas is produced coatinuously, the pres: sure, composition, and amount ‘of which fuctuate periodically. These floctutions are smoothed out by buffer vessels. 3) The eflciency of a PSA is defined by the amount of pure hydrogen produced in rela- tion 10 the total hydrogen amount present in the crude gas. Depending an the crvde as composition and the degree of techni calsophistcatonutized, the PSA efficiency ranges herween #9 30%, Technical PSA Plans. The simplest PSA system equites thee adsorber to enable con Lingus operation. Hydrogen yields of > 80% «an oly be attained i systems with more han adsorber. Since the size ofthe adsorber is usually tim ited because of mannfacturing oF anspor con- siderations, lrger quantities of crude gas can only bo tented if several aduorbers ace used in te adsorption phase simultaneously (mul bed process) (226), (27). With soch schemes PSA plans using 310 12 edsorbers can process mounts of erude es ranging fom 100 to more than 100000 n° (STPyM, > Vel. 17 ‘The masimum attainable hydrogen yield is influenced by a numberof factors, the mast in portant are » Composition ofthe crude gas. For the eBoaomical operation ofa plant the hydrogen costent of the erade gas should bbe at least 50°. The maximum iydrogen ‘content is 95-99%. Depending an the to- tal amount of gas, TA plants may be more suitable for such high-purity raw gases. The coscentraton and nace of impurities with respect to their ad- and desorption be- havior determines basically the sizeof the adsorber which in tom restts in higher or Tower loss of hysiogen B) Pressure rato feed gas: purge gas-Tbi fuences the sizeof the adsorber athe ex- teat ofthe effot necessary for regeneration. ‘Achigh pressure ratios the yields can be creased by using several pressure equaliza- tion seps (plants with more dhan 4 adsoe- bers), » Parity requirements and nature of impuri- fies The hydrogen puvity in the PSA. plants fs uoully 399.9%. Higher purities with re- spect to those compounds which are poorly adsorbed, such asthe nest gases nitrogen, ar- ‘gon, ear atainable atthe expense ofthe Yield, In spite of this, purities of 99.9999 %, i. Bydrogen with <1 ppm impuries, can be realized on an industria sale. o) Temperature ofthe feed gas High tempera tures (40°C) result in & lower capecity of the plan, or in a poorer yield. Lower tem pera’ are therefore favored. Care must be {aken, oweves, avoid condensation of cet= ‘ain impurities in the regeneration step. For ‘oxampl, liquid or freezing water can dam- age theadsorbent, Important developmensin the design oflage PSA plants were fist possible after the inro- ‘duction of microprocessor contol systems. The ‘main protlems fecing the control system are ‘caused by the speed and the precision required by the short cycles, For this reason, mod cern plantsare controlled by microprocessors us- ing a Is sequence achieving “rel time" con- vo.17 teol. Beyond this, i is now possible, nat only to control the sequence and valves, but also to ‘havea real process control system. This allows ‘aigh degree of flexibility forthe changing of various process parameters and the indication of disturbances. In particular, the automatic ii tiation of disturbance strategies in the case of process, pressure and valve failures eg, shut- ‘down of en upset adsorber without interupting hydrogen production, is possible. Very high r= {qucements are placed on the vessels and valves with up 0 $0000 cycles (i. valve closures) per year. The operational practice hes shown, how ‘ver that Use plans are very rlible, So tat ‘hey have become standard TRIS euRIRA BURNER EE ante of plate 1566 Tt Tete ao as aa Yer gute Weide copay 2 gespuiceton as ‘ih psa vig aepion shy (a ope an om 966101988) Inthe past years purification of hydrogen by ‘means of PSA hasineveased more than any oer ‘2s prfcation process, Figure 75 gives an i- pressionof the breakthrough ofthisnew technol- ‘gy. A eat be sen from the numberof plants corresponding to the plant capacity not ony the ‘numberof plants per year put on steam has in- ‘creased, but asa the amount of hydrogen puri- Hydrogen fied per plant Plants > 100 000m (STP 8 ae not common nowadays. Applications (224) Gas Purification in Steam Reforming P (see Section 41.3), Other gas purfication cesses have been more or less complete placed in this area (228). For the produ of hydrogen and carbon monoxide by § reforming, PSA in combination with a temperature plant can so be economi used, The amount of gas handed by the built ranges from S00~87000m? (STP) product gas. These plants use the tale duced to fre the reformer. Specially des ‘enteol loops and buffer systems lead to Jomogeneous til-zas flow which is disc with only small fivctation in composi flow, so that a elcble operation of the b is posit Refinery Gases (see Section 4.1.4). B ofthe increasing demand for hydrogen f

    You might also like