Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
M. E. Rezac, Georgia Institute of Technology, Atlanta, are listed in Table 1. Details relating to the large
GA, USA volume of research reported are provided in the Fur-
Copyright ^ 2000 Academic Press
ther Reading section. None of these membrane reac-
tors are in commercial use. But some } the selective
oxidation of methane, for example } are the subject
Introduction of a very large industrial research effort. If suc-
The concept of completing both a reaction and separ- cessfully developed, this process would change the
ation in a single process unit has motivated research feedstock basis of a number of petrochemical
into the development of catalytic membrane reactors. processes.
For example, it has long been recognized that pallad- Most research on the development of membrane
ium metal has the capacity both to permeate hydro- reactors involves the use of these devices to shift
gen and to promote a variety of reactions. Thus, equilibrium-limited reactions (often dehydrogena-
harnessing both of these features in a single device tions). The thermodynamic equilibrium of the react-
seemed a logical combination. In the mid 1960s, ants and products at the temperature and pressure of
Wood and co-workers demonstrated that the dehyd- the reaction determine the conversion achievable in
rogenation of cyclohexane to cyclohexene could be any given reaction. For dehydrogenation reactions,
increased if the hydrogen produced was removed increasing temperature and decreasing pressure pro-
from the reaction vessel through semipermeable pal- mote an enhanced reaction. Unfortunately, each of
ladium walls. In this case, the palladium walls also these solutions has an associated cost. Increasing the
acted to catalyse the dehydrogenation reaction. reaction temperature typically results in a reduced
A membrane reactor of this type is illustrated in
Figure 1.
In Russia, Gryaznov conducted much of the re-
search that followed. Starting in the late 1970s, Gry-
aznov began publishing his results on the use of
palladium membrane reactors both to produce and to
recover hydrogen from a myriad of dehydrogenation
reactions. In the dehydrogenation reactions, hydro-
gen leaves the reactor by permeating through the
semipermeable membrane. However, reactors can
also be used in reactions where hydrogen or other
reaction products enter the reaction chamber by pen-
etration through the membrane. The commonest Figure 1 Schematic of a membrane reactor using hydrogen-
classes of reactions that have been successfully in- permeable palladium membranes to shift the equilibrium of the
Suenced by the use of membrane reactor technology dehydrogenation reaction cyclohexane to cyclohexene.
II / MEMBRANE SEPARATIONS / Catalytic Membrane Reactors 1677
Partial oxidation Butane#O2P maleic anhydride Recovery of intermediate product of control reactant at
addition rate to promote formation of intermediate
product
Esterifications R}OOH#CH3OHPR}O}O}CH3#H2O Selective water removal to shift equilibrium limit without
loss of reactant
Syn gas CH4#12 O2PCO#2H2 Selective oxidation of methane
Oxidative coupling 2CH4#O2PC2H4#2H2O Selective oxidation of methane
catalytic selectivity for the desired product. Reducing lytic selectivity) goes through a pronounced max-
pressure comes at the cost of adding a diluent to the imum. Incorporation of an appropriately designed
reactor, paying for the additional capital to handle membrane into the reactor system results in the re-
this component and paying the price of downstream moval of hydrogen from the system. The catalytic
separation. selectivity does not appear to be inSuenced by this
Figure 2 provides a schematic representation of the process, but the conversion of butane to butene is
behaviour of a conventional reactor and a theoretical enhanced by the reduction in the hydrogen partial
membrane reactor. The conventional data are for pressure. Thus, the yield of the membrane reactor
a highly active butane dehydrogenation catalyst oper- system is markedly improved.
ating at 1 atm total pressure (pure normal butane The ability to operate at acceptable conversions
feed). In the conventional system, the selectivity of the while maintaining very high catalytic selectivity is
catalyst degrades rapidly at temperatures that are just a strong driving force for the use of membrane reactor
beginning to promote reaction. Thus, the catalytic technology. By operating in a high selectivity region,
yield (deRned as the product of conversion and cata- the production of by-products that can act as catalyst
poisons is minimized. This results in a longer catalyst
life between regenerations and reduced waste produc-
tion.
Figure 3 Common membrane reactor configurations. (A) Catalytic membrane; (B) membrane tube packed with catalyst;
(C) membrane-assisted batch reactor.
completely excluding all other compounds. The per- cluding stabilized zirconia, have been used in mem-
meation of hydrogen through metals is a multistep brane reactors. These membranes can successfully
process involving: transfer oxygen while barring the transport of all
other compounds. Current limitations relating to the
E chemisorption of hydrogen on to the metal surface
temperatures required for operation are discussed in
E dissociation of the hydrogen
subsequent sections.
E dissolution of the atomic hydrogen from the sur-
face into the bulk of the metal
E diffusion across the metal layer Nonspeci\c Membranes
E the desorption from the bulk of the metal to the Commercial utilization of membranes has relied al-
surface most exclusively on the use of nonspeciRc membrane
E reassociation materials. These materials have the ability to trans-
E desorption of molecular hydrogen from the metal port one component of a gas mixture in preference to
surface a second. However, they are permeable to all compo-
The diffusion of atomic hydrogen across the nents to at least some degree. Therefore, unlike pal-
metal layer is typically the rate-limiting step. There- ladium, which can act as a perfect separator, these
fore, the transport of the hydrogen can be modelled membranes transport all stream components. The
using a Fickian diffusion equation. properties of both porous ceramics and polymeric
Alloys of palladium have proven effective for membranes will be considered here.
the transport of hydrogen. Pure palladium undergoes
a phase transformation in the presence of hydrogen Porous ceramics Porous ceramic membranes, with
at moderate temperatures, and a density change pore sizes ranging from a few nanometers to several
ensues. Even though these changes are small, they are microns, have been produced and are commercially
sufRcient to produce a brittle, cracked and non- available. These membranes separate by size exclu-
selective material after only a few cycles. Therefore, sion. For the separation of gases and low molecular
few of the membranes evaluated are pure palladium weight liquids, Knudsen diffusion is typically
and most commercial metallic hydrogen puriRers are employed. For gases, Knudsen diffusion occurs for
prepared from a palladium/silver alloy containing pore sizes of about 4}100 nm. For systems operating
23% silver. under the Knudsen diffusion regime, the separ-
A signiRcant limitation to the use of palladium ation of two molecules can be deRned as:
membranes is their strong susceptibility to poisoning
by sulfur compounds and CO compounds frequently A/B"(MWB/MWA)0.5 [3]
found in the hydrocarbon streams of interest. Re-
search into the development of more resistant mater- Thus, high degrees of separation selectivity are only
ials is underway. However, the improved resistance possible if the molecular weight difference be-
has so far been attained at the cost of permeability. tween the two components is large. These materials
This issue must be resolved before these membranes have been employed for the separation of hydrogen
can be used in the chemical process industry. from hydrocarbon streams. The ideal separation sel-
ectivity for hydrogen over butane, for example, is 5.8.
Nonporous ceramics (oxygen) Ceramic membranes Thus, a small but measurable separation can be
have been developed which will selectively transport achieved.
hydrogen or oxygen. Hydrogen has been shown to be The microporous nature of these membranes
transportable through nonporous silicon dioxide. allows them to have very high transport rates, as
While the transport rates are extremely slow, the compared to nonporous palladium or ceramic mater-
selectivity to hydrogen transport is inRnite, just as in ials. Yet, the separation achievable is limited.
defect-free palladium. Silicon dioxide has the advant-
age of being more resistant to the presence of sulfur Polymers The Rnal category of membrane materials
compounds that act as poisons for palladium. Never- to be considered is polymers. Polymeric membranes
theless, the challenge of forming this material into are employed for the separation of gas streams, the
extremely thin layers has limited its use. Perhaps as recovery of organic vapour from air, the separation of
preparation techniques continue to improve, the use mixtures of organic liquids and Rltration of particles
of this material for the highly selective transport of from aqueous streams. Nonporous polymeric mem-
hydrogen will be re-examined. branes have been considered for membrane reactor
Nonporous ceramics have also been used for the applications. Nonporous polymeric membranes sep-
transport of oxygen. Oxide-conducting materials, in- arate on the basis of sorption of the component into
II / MEMBRANE SEPARATIONS / Catalytic Membrane Reactors 1681
Vacuum permeate An alternative method to pro- ganic, or hybrids of the two) for the selective separ-
duce a pressure drop is the use of a vacuum on the ation of liquid organic mixtures. If this research is
membrane permeate. This has been shown to be successful, it will allow for incorporation into liquid-
highly effective in laboratory settings. However, phase membrane reactors.
the economics are not favourable for the large scale
production of inexpensive components. Nevertheless, Control of Reactant Addition for Intermediate
Product Recovery
vacuum permeate systems may prove viable for small,
high value-added systems. A second area of immense current research activity is
the development of oxygen-permeable membranes to
Batch versus continuous Continuous reactor sys- inSuence the conversion of methane to either meth-
tems are preferred; they require less down time and anol or syn gas. The goal in these processes is a
have higher production rates than batch systems of mechanism for the conversion of natural gas to
similar size. However, as previously detailed, if the role a transportable liquid that may be further converted
of the membrane is to remove a product component, to high valued products. Current research has
the available partial pressure difference is limited shown that membranes can be developed and that the
and the process will always be working with a very appropriate catalysts are available for these conver-
limited pressure drop that will require very large mem- sions. Many engineering challenges lie ahead. These
brane areas. Batch and semi-batch processes allow the membrane reactor processes operate in excess of
system to develop some limited partial pressure dif- 7003C (sometimes much higher). Sealing these ce-
ference before membrane separation is attempted. ramic membranes into a housing remains a limita-
tion. Further, the thermal stresses, which develop
Membrane Degradation
when cycling from 25 to '7003C, may result in
The stability of the membrane is another important membrane damage. While these are complex prob-
consideration. Ideally, for integrated systems, the lems, the incentive to succeed is large and numerous
membrane should be stable in all possible reaction research efforts continue in this area.
environments: catalyst activation, normal reaction,
catalyst regeneration and any thermal cycling experi- Further Reading
enced upon transitions. This presents speciRc chal-
lenges for each system and there are few materials Armour JN (1989) Catalysis with permselective inorganic
that can satisfy all of these requirements. Thus, membranes. Applied Catalysis 49: 1.
special engineering solutions are necessary. Even if Gokhale YV, Noble RD and Falconer JL (1995) Effects
of reactant loss and membrane selectivity on a dehyd-
the membrane material can fulRl these speciRcations,
rogenation reaction in a membrane-enclosed catalytic
the many components needed to produce a mem- reactor. Journal of Membrane Science 103: 235.
brane reactor module may not. Govind R and Itoh N (eds) (1989) Membrane reactor
technology. AIChE Symposium Series 85: 268.
Saracco G, Versteeg GF and van Swaaij WPM (1994) Cur-
Future Possibilities rent hurdles to the success of high-temperature mem-
Organic Separations brane reactors. Journal of Membrane Science 95: 105.
Shu J, Grandjean BPA, Van Neste A and Kaliaguine S (1991)
A great deal of research is currently focusing on the Catalytic palladium-based membrane reactors: a review.
development of membranes (either polymeric, inor- Canadian Journal of Chemical Engineering 69: 1036.
Concentration Polarization
H. Wijmans, Membrane Technology and Research, in which the composition at the feed}membrane in-
Inc., Menlo Park, CA, USA terface differs from the composition in the bulk
of the feed mixture. This gradient in composition is
Copyright ^ 2000 Academic Press
generated by the separation performed by the mem-
brane and, as such, cannot be avoided. However, it is
Introduction important to minimize the effects of concentra-
tion polarization because the gradient in composition
All membrane separation processes are accompanied reduces the separation performance of the membrane
by a phenomenon called ‘concentration polarization’ and increases the potential for membrane fouling.