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Ind. Eng. Chem. Res.

2002, 41, 1389-1392 1389

COMMENTARIES

Pressure Swing Adsorption


Introduction sorption, and a multitude of complementary steps which
Pressure swing adsorption (PSA) is a very versatile are designed to control the product gas purity and
technology for separation and purification of gas mix- recovery and to optimize the overall separation perfor-
tures. Some of the key industrial applications include mance.9 The research trends are to (a) produce purer
(a) gas drying, (b) solvent vapor recovery, (c) fraction- products at higher recovery, (b) lower adsorbent inven-
ation of air, (d) production of hydrogen from steam- tory and energy of separation, and (c) increase the scale
methane reformer (SMR) and petroleum refinery off- of application at a lower overall cost.
gases, (e) separation of carbon dioxide and methane Unique PSA cycles are also designed to simulta-
from landfill gas, (f) carbon monoxide-hydrogen sepa- neously produce two pure products from a multicompo-
ration, (g) normal isoparaffin separation, and (h) alcohol nent feed gas (e.g., O2 and N2 from air, CO2 and H2 from
dehydration. There are several hundred thousand PSA SMR off-gas, and CO2 and CH4 from landfill gas) as well
units operating around the world servicing these and as to produce a product gas containing a component
other applications. In fact, PSA has become the state- which is not initially present in the feed gas (ammonia
of-the-art separation technology for application areas synthesis gas from SMR off-gas). These examples dem-
a-d listed above, and the sizes of these units range from onstrate the wide flexibility of PSA process designs.10,16,17
very small (∼300 SCFD units for the production of 90% The key reasons for such growth in this technology
O2 from air for personal medical use) to very large (∼100 are as follows:18
MMSCFD units for the production of 99.999+% hydro- (a) An extra degree of thermodynamic freedom for
gen from an SMR). Many of these processes are de- describing the adsorption process introduces immense
scribed in the published books and review papers on the flexibility in PSA process design as compared with other
subject.1-13 conventional separation tools such as distillation, ex-
The growth in the research and development of PSA traction, or absorption.
technology has been phenomenal since the first U.S. (b) Numerous microporous-mesoporous families of
patent on the subject, authored by C. W. Skarstrom, was adsorbents (new or modified) like activated carbons,
granted in 1960.14 A recent survey showed that ∼600 zeolites, aluminas, silica gels, and polymeric sorbents
U.S. patents on PSA were issued in the application exhibiting different adsorptive properties for separation
areas a, c, and d alone during 1980-2000, while the of gas mixtures (equilibria, kinetics, and heats) are
number of published papers with PSA as the keyword available.
exceeded 800 during the period of 1970-2000.15 (c) The optimum marriage between a material and a
The concept of PSA for gas separation is relatively process in designing the PSA separation scheme pro-
simple. Certain components of a gas mixture are motes innovations.
selectively adsorbed on a microporous-mesoporous solid (d) Many PSA process paths can be designed for the
adsorbent at a relatively high pressure by contacting same separation objectives.
the gas with the solid in a packed column of the A good example of items a-d listed above can be
adsorbent in order to produce a gas stream enriched in found in the area of air fractionation by adsorption.
the less strongly adsorbed components of the feed gas. Approximately 390 U.S. patents were issued on the
The adsorbed components are then desorbed from the subject during the last 20 years.15 The processes are
solid by lowering their superincumbent gas-phase par- designed to (a) separately produce ∼23-95% O2 from
tial pressures inside the column so that the adsorbent air, (b) separately produce 98-99.99+% N2 from air, and
can be reused. The desorbed gases are enriched in the (c) simultaneously produce ∼90+% O2 and 99+% N2
more strongly adsorbed components of the feed gas. No from air. Many different zeolites having different ther-
external heat is generally used for desorption. Many modynamic selectivities and capacities for adsorption
different nomenclatures are used to describe these of N2 over O2 are employed, and the processes are tailor-
concepts. A PSA process carries out the adsorption step made to fit the zeolite properties in order to produce
at a superambient pressure, and the desorption is the specific product demands for cases a and c.11 Many
achieved at a near-ambient pressure level. A vacuum different carbon molecular sieves having different ki-
swing adsorption (VSA) process undergoes the adsorp- netic selectivities and capacities for adsorption of O2
tion step at a near-ambient pressure level, and the over N2 are employed for case b with appropriate process
desorption is achieved under vacuum. A pressure- designs for controlling the N2 product purity and
vacuum swing adsorption (PVSA) process utilizes the recovery.19,20 These processes use many different de-
benefits of both concepts. Although simple in concept, signs of PSA, VSA, or PVSA cycles and operating
a practical PSA/VSA process can be fairly complex conditions in order to achieve the final goals. A key
because it involves a multicolumn design where the success in this area has been the lowering of the specific
adsorbers operate under a cyclic steady state using a power (<10 KWD/ton) of O2 production (∼90+%) from
series of sequential nonisothermal, nonisobaric, and air below that of the conventional cryogenic distillation
non-steady-state steps. These include adsorption, de- route by the use of LiX zeolite as the N2 selective
10.1021/ie0109758 CCC: $22.00 © 2002 American Chemical Society
Published on Web 02/09/2002
1390 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002

adsorbent,21,22 while retaining the traditional advantage gas.31 This process also used a chemisorbent for CO2
of lower capital cost for a PSA/VSA process. This opens (∼10-20 mol % in feed), and it recovered ∼80% of feed
up the door for increasing the sizes of O2-PSA processes CO2 as an essentially pure CO2 product (dry basis). The
beyond today’s standards. Parallel developments can be concept may be very attractive for controlling green-
cited in the other application areas.9,10,12,13 It is expected house effects by removing CO2 from a hot and wet flue
that this trend will continue in the future. New PSA gas without cooling the gas and removing the water.
cycles using old or new adsorbents (preferably tailor-
made for each other) will continue to be developed in
PSA Process Design
the existing and new application areas. Good combina-
tions of PSA processes and adsorbents are needed for Despite such growth in the practical applications of
bulk separation of N2 and CH4 at high pressures, this technology, the design and optimization of a PSA
separation of dilute O2 from Ar, and bulk separation of system still largely remains an experimental effort. A
propane-propylene mixtures. priori design of a practical PSA system that can
guarantee the commercial specifications without the use
Emerging Concepts of supporting data from a bench- or pilot-scale process
rig may not yet be feasible for the following two reasons.
Several very interesting PSA process developments
are emerging. They include (a) rapid PSA cycles, (b) First, most of the practical PSA processes are fairly
novel PSA adsorber designs, (c) sorption-enhanced reac- complex, involving a number of sequential but interact-
tion processes (SERP), and (d) high-temperature PSA ing unsteady-state cycle steps. It may be possible to
(HTPSA) cycles. formulate a rigorous mathematical framework (model)
(a) The rapid PSA processes are designed to increase to describe such processes, but it is usually expensive
the productivity of the processes by an order of magni- and time-consuming to solve such models with the
tude by using total process cycle times of seconds accuracy and reliability needed for industrial design. It
instead of minutes as in the case of the conventional requires repeated numerical solutions of a set of coupled
PSA cycles. This is achieved by simply running a nonlinear partial differential equations in the time and
conventional cycle faster using novel hardware (e.g., space domain with different initial and boundary condi-
rotary valves)23 or by changing both the adsorber and tions defining the steps of the process for any given cycle
the process cycle designs.11 However, separation ef- until a cyclic steady-state solution is achieved. The
ficiency and performance may be compromised (lower computation time for such calculations is often prohibi-
product purity or recovery) because of time limitations tive, and model simplification becomes imperative.10
in incorporating the complementary cyclic steps and Second, fundamental understanding of the multicom-
limitations caused by adsorption kinetics.24 ponent gas-solid interactions (thermodynamic and
(b) Faster PSA cycles are often limited by the hydro- kinetic) that govern the performance of a PSA adsorber
dynamic constraints (gas maldistribution, adsorbent is very limited because of their complexity. An accurate
fluidization, column pressure drop, etc.), which limit gas description of these interactions must be available
flow rates through packed beds. Radial bed adsorbers before the mathematical process model can be solved.10
where the adsorbent is placed between two concentric It is essential that these interactions are known under
cylinders and gas flows radially through the packed all conditions of temperature, pressure, and composition
section may alleviate many of these problems. These prevailing in a PSA adsorber during all steps of the
adsorbers, however, are more expensive. Many such process. Because these conditions may vary widely in a
designs have been proposed and developed which allow practical PSA process, the measurement and correlation
faster cycles, higher gas throughputs at lower pressure of such a massive volume of data are often impractical.
drops, and complete absence of fluidization.25,26 One needs to predict these interactions from a minimum
An interesting possibility will be the development of source of experimental data for the system of interest.
a PSA cycle using a rotary bed adsorber which has been Although much progress has been made in this area,
successfully employed for practicing thermal swing the state of the art is often not adequate for satisfying
adsorption concepts.27 the general design needs.
(c) The SERP is a hybrid concept where an equilib- A common practice is to develop a simplified and
rium-controlled reaction is carried out in the presence specific model for the PSA process of interest and use
of an adsorbent which selectively removes one of the simplistic descriptions (models or empirical) of the gas-
undesired reaction products from the reaction zone, thus solid interactions for the relevant system, to evaluate
increasing the yield and the rate of formation of another approximately the effects of the design variables on the
desired product by Le Chatelier’s principle. The adsor- performance of the PSA process and finally obtain a
bent is then regenerated periodically using the prin- crude optimum design. The effort is always closely tied
ciples of PSA. The concept has also been called pressure to experimental verification and fine-tuning by measur-
swing reactor.28 Very recently, a novel process called ing actual process data from a pilot plant. Such models
SERP-H2 was demonstrated in a pilot-scale unit for have often proved to be very useful for process optimiza-
production of CO- and CO2-free (<40 ppm) H2 by SMR tion and screening new ideas.10
using a CO2 selective chemisorbent and a SMR catalyst The partial differential equations to be solved are the
inside the reactor.29,30 The primary impurity in the 90+ coupled mass, momentum, and heat (both gas and
mol % H2 product (dry basis) was unreacted CH4. A high adsorbed phases) conservation equations describing the
conversion of CH4 to H2 at a much lower reaction state of the adsorber for each step of the PSA process.
temperature than the conventional SMR process could The key input data for solving these equations are (i)
be achieved. The concept may be useful for direct the multicomponent adsorption equilibria, (ii) the
production of CO-free H2 in a fuel cell application. multicomponent adsorptive/desorptive mass-transfer
(d) A HTPSA (∼200 °C) process was developed for characteristics, and (iii) the multicomponent isosteric
sequestering and recovering CO2 from a hot, wet waste heats of adsorption for the system of interest.
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1391

There lies the crux of the problem. The design It is apparent that realistic and accurate estimation
engineer must be able to predict these input data from of single-component or multicomponent gas-solid or
a limited source of experimental data because the range gas-gas interactions within such distributed energy
of conditions (pressure, temperature, and gas composi- fields inside the adsorbent pores (which often remains
tion) encountered within the adsorber of a practical PSA unknown) will be difficult, if not impossible. Even the
process can be immense. current experimental methods to characterize the pore
Although numerous efforts have been made in the structures of real heterogeneous microporous solids are
past 30 years to develop techniques to predict multi- very crude and full of uncertainty.
component adsorption characteristics (thermodynamic The challenge, therefore, is to develop methods for
and kinetic) from pure gas adsorption characteristics quantitative characterization of adsorbent heterogeneity
of the components, these models have met with only and to accurately predict multicomponent gas adsorp-
limited success.10,32 The state of the art does not allow tion characteristics (equilibria, kinetics, and heats)
a priori selection of these methods for the system of using a limited data source. The models, however, must
interest without extensive experimental testing of the also take into account dissimilar adsorbate properties
method. This obviously defeats the purpose. Currently, and lateral interactions between the adsorbates at
an extensive experimental database is needed (equilib- higher coverages. The models must also be analytical
ria and kinetic) for the design of each separation system in order to be practically useful. This area should be a
of interest. subject of serious research by adsorption scientists for
The quality of simulation of a PSA process perfor- many years to come because the problem is complex and
mance using a process model largely depends on the success will not be easy. Unfortunately, the topic is
detailedness of the model and the accuracy of the input being ignored in the recent years.
data.33 The results can be extremely sensitive to small There is also a desperate need to generate and
errors (say (10-15%) in the input data for many compile a multicomponent gas adsorption database. A
process designs because these models often act as large volume of pure gas and some binary gas adsorp-
amplifiers of errors. On the other hand, many industrial tion equilibrium data are currently available in the
PSA processes require very stringent product specifica- literature,35 but multicomponent gas equilibrium data
tions. For example, a PSA process for production of H2 are rare. The situation is identical for gas adsorption
from SMR off-gas must have a product H2 purity of kinetics data.36 The data for heats of adsorption are only
99.999+ mol % containing less than 10 ppm of COx emerging.37-39 These data will be needed to test the
impurities. Furthermore, a difference of (2% in the reliability of the theoretical models.
estimation of the product H2 recovery from the feed gas In conclusion, it can be said that the development of
can make or break the economics of a process design practical PSA processes for gas separation has been
for a medium-sized unit (∼50 MMSCFD H2). These extremely successful despite the fact that an “in-depth”
critical industrial demands are not often appreciated, understanding of the complex physicochemical phenom-
and a large volume of published literature on PSA enon governing this technology may be lacking. Much
models fails to seriously evaluate the quality of the more basic research is needed before a priori design of
model and the input data by comparing the model PSA processes can be made with acceptable accuracy
calculations with actual experimental process data only and confidence. A judicious balance between experi-
qualitatively. mental process development and theoretical designs
using process models will continue to be the state of the
Nature of the Problem art in the near future.
The problem at hand is by no means simple. The
adsorbents of practical use, such as activated carbons, Literature Cited
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Shivaji Sircar

Air Products and Chemicals, Inc.,


Allentown, Pennsylvania 18195
IE0109758

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