CHAPTER 9

CONCLUDING REMARKS

The work contained in this book has, by introducing an innovative method,

contributed to analyzing, designing, and synthesizing general separation
processes, with emphasis on membrane separation. It is believed that an
extremely useful and versatile technique has been developed. The method is
not restricted to a single type of membrane but, with the appropriate flux
equations, can easily be adapted for any membrane. Furthermore, by use of
appropriate composition modeling, any separation process can be analyzed,
since the techniques were devised for a general separation process. In
particular, the methods developed enable one to plot column profiles for
systems in which flow rates are not constant. Thus, the methods developed
here offer a tool for the analysis of distillation processes for which constant
molar overflow is not a valid assumption.
A significant result of this work is that it has shown that high-purity
separations are achievable using nonselective, Knudsen-type membranes,
demonstrating that the development and manufacture of highly selective
membranes is often not necessary. By offering a design and synthesis
technique applicable to any particular membrane, this work opens the door
for the implementation of cost-effective and robust membrane operations
throughout the chemical industry.

Membrane Process Design Using Residue Curve Maps, First Edition.

Mark Peters, David Glasser, Diane Hildebrandt, and Shehzaad Kauchali.
2011 John Wiley & Sons, Inc. Published 2011 by John Wiley & Sons, Inc.
169

170

CONCLUDING REMARKS

9.1 CONCLUSIONS
Although the M-RCM was developed for a batch membrane process, it has
been revealed how it is directly applicable to a wide range of continuous
processes. A number of important results emerged from this, each contributing
to the separations field in its own right.
.

.
.

The M-RCM can be used to explain and understand and graphically

visualize the behavior of the conventional industrial membrane permeators (see Chapters 3 and 4).
The same applies for total and infinite reflux membrane columns. While
these are not practical applications, the theoretical results they yield are
useful when explaining finite reflux arrangements (see Section 5.5.2).
The profiles in the M-RCM allow one to graphically visualize the change
in the retentate in either a batch still or continuous unit (see Section 3.3).
Furthermore, the M-RCM also provides some necessary design parameters such as what membrane area is needed to achieve a desired
separation in a continuous process, or the time taken in a batch process
(see Sections 5.5.1 and 5.4).

Complex membrane columns and cascade arrangements have been researched (e.g., Hwang and Ghalchi, 1982; Kothe et al., 1989), but a shortcut
method for design and synthesis for these was lacking. In this book, it has been
shown how, with the identification of a membrane column section, a novel
design tool is developed. Any arrangement, no matter how complex, can be
broken down into column sections. These are the basic building blocks that
make up any arrangement. An understanding of the behavior of each column
section allows one to synthesize and concatenate sections into a configuration
that achieves the desired result. The compositional change of the retentate in
any column section has been modeled mathematically using the difference
point equation. All possible flow cases within a column section were identified, and their corresponding profiles investigated. Some of the important
results are listed:
.
.

The DPE for a column section operating at total reflux reduces to the
M-RCM equation, as expected (see Section 6.4).
The behavior of a column profile, operating at finite conditions, is
influenced by the movement of the stable node pinch point locus
(see Sections 6.5 and 6.6).
A profile will continue to exist until either the retentate or permeate runs
out of material. When this occurs, the profile pinches, and the column
section terminates, normally in a finite area (see Section 6.6).

RECOMMENDATIONS AND FUTURE WORK

171

Using these results, thermally linked membrane columns were examined. It

was found that such an arrangement is feasible, provided that the top
composition was within a region bounded by the MBT and the appropriate
pinch point curve. Furthermore, there exists a minimum reflux for each
composition in that region. Operation would have to occur at or above the
minimum reflux (see Sections 7.4 and 7.5).
One of the most important and exciting results of the work in this book was
the research displayed on hybrid processes. By analyzing membrane permeation from the same mathematical viewpoint as distillation, combinations of
the two processes can be performed with ease. Also, since graphical techniques were developed for membrane systems as individual processes, any
configuration and design of distillation and membrane units is possible.
Analyzing them simultaneously (such as was done by Huang et al. (2004))
has a shortcoming in that it limits one to a single design. However, decoupling
the two unit operations from each other allows all possible configurations to
emerge, thus carrying out synthesis rather than design. This was evident from
the results obtained for the methanol/butene/MTBE systeman attainable
region for the process was determined (Chapter 8).
The technique also took on a different approach by collectively treating a
hybrid arrangement as a thermally coupled arrangement between distillation
and membrane units. With the use of column sections, general rules for
classifying regions of feasible arrangements were developed, as was done in
Chapter 7, Section 7.7.

9.2 RECOMMENDATIONS AND FUTURE WORK

It should be appreciated that the work presented is not only applicable to
membrane permeation and distillation, but can easily be adapted for any
separation method. Both constant and nonconstant flow assumptions have
been tackled here, equipping one to use the methods displayed for the
separation procedure of their choice. Of course, details of equilibrium/flux
model, flow assumptions and directions, and so on need to be decided upon.
But the method and results arrived at here would still apply. This could be the
basis of further research in the separations field.
Experimental validation of the profiles in the M-RCM is another possibility
that could be explored. This could then be extended to formulating a batch- or
continuous-scale experiment to mimic the finite reflux membrane column
section.
Further theoretical and experimental work can be conducted with regard to
hybrid designs and the use of column profiles to design such processes.
Ongoing work of this nature is taking place at the Centre of Material and

172

CONCLUDING REMARKS

Process Synthesis (COMPS) at the University of the Witwatersrand, extending

the theoretical understanding of membrane and hybrid separation processes,
as well as developing practical applications for these technologies.

9.3 DESIGN CONSIDERATIONS

The techniques developed throughout this book equip the reader with tools for
the synthesis, analysis, and conceptual design of membrane and hybrid
separation processes, but by no means do they constitute a rigorous and
complete design process. This section serves to bring to the readers attention a
number of design considerations and challenges involved in membrane and
hybrid separation process design. The reader is advised to take note that this is
not a checklist of design considerations and is not intended to be used as a
design guide. Rather, it is intended to stimulate thought and discussion by
putting forward ideas and identifying issues that have been anticipated by the
authors. Furthermore, the book considers membrane processes as part of a
separation sequence, with specified inputs and required outputs. However, like
any other unit operation, membrane separators need to be considered as part of
an overall process flow sheet. In this section, the authors undertake to discuss
their views on how a membrane separation process can best be incorporated
into an overall flow sheet, and how an overall flow sheet may be modified to
accommodate a membrane operation.
9.3.1 Processes for Which Membrane Separations Are
Particularly Suitable
For cheap and robust nonselective membranes, the constant relative permeability
model (Knudsen membrane)has beenfound to be a good approximation of actual
behavior. The similarity of the constant permeability model for membrane
separation to the constantrelativity modelfor distillation means that, in principle,
any separation that is achievable through distillation should also be achievable
through a membrane separation using a suitable membrane. However, in most
cases where either process is applicable, some degree ofoptimization and costing
is required before one can definitively decide on a process. Nevertheless,
there exist certain circumstances in which a membrane process will clearly be
more suitable. Several such cases are discussed here, but numerous others
may present themselves as membrane separation technology matures.
Azeotropic Systems
The existence of azeotropes can make distillation highly problematic. Since
M-RCMs possess different topology than D-RCMs, they will not feature the

DESIGN CONSIDERATIONS

173

same separation boundaries. Thus, distillation boundaries can be bypassed

by the use of membrane separation processes. The example discussed
in Chapter 8 was one such case and can be considered a good illustration
of the effectiveness of the hybrid process design techniques developed in
this book.
Gaseous Systems Not at Saturation
Distillation must be carried out at a temperature and pressure such that the
mixture being separated is saturated. As a result, when dealing with gaseous
systems, it is often necessary to either pressurize the gas or cool it to saturation
before feeding it to the column. This can result in large energy losses from the
process, as well as increased equipment costs for compression or refrigeration
equipment. Furthermore, if a distillation column is required to operate
under high-pressure conditions, or cryogenic conditions, the material costs
of that column are increased. Finally, constraining streams to saturation
conditions limits the degree of freedom of a designer when setting up the
overall flow sheet.
Gas-diffusion membranes are not constrained to operation at saturation and
can be operated at any conditions such that the mixture is a gas. In many cases,
this will make it possible to operate a membrane separator at conditions
matching those of its feed stream, while use of a distillation column would
have required either compression or refrigeration.
Systems for Which a Suitable Selective Membrane Is Available
A selective membrane can easily extract a single component in high purity.
If the component that is selectively permeated is also the desired product, then
using a selective membrane enables one to achieve a pure product with a single
separation process. Use of a selective membrane can greatly simplify the
design of a separation sequence. However, it must be noted that selective
membranes are often expensive to develop and manufacture, and that it will
often be possible to synthesize a process using a nonselective membrane that is
able to reach product specifications.
9.3.2 Processes for Which Membrane Operations Are Unsuitable
It is conceivable for processes to exist for which membrane separation will be
unsuitable. Various reasons for unsuitability can be identified.
Low Driving Force for Separation
Membrane processes may be unable to perform an effective separation. In
particular, this will be the case if the relative permeabilities for the system are
very low. An initial idea of the comparative separabilities offered by

174

CONCLUDING REMARKS

distillation and membrane separation could be gained by comparing the

magnitude of the relative volatilities in the distillation process to the relative
permeabilities in the membrane separation process. Note that different
membranes will offer different relative permeabilities, so various membrane
specifications will have to be considered.
High-Maintenance Operating Conditions
If operating conditions are such that the membrane is likely to be damaged or
clogged, then the cost of maintaining the membrane would become excessive,
and alternative methods of separation should be considered.
9.3.3 Pressure Difference as a Design Consideration
The pressure difference between the retentate and permeate sides results in an
unbalanced force on the membrane surface. Therefore, the membranes
structure must be sufficiently strong to withstand this force, or membrane
rupture will occur. Pressure specifications will vary between individual
membranes and will be provided by the manufacturer. A designer must be
aware of the pressure constraints on their selected membrane and take them
into consideration throughout the design process.
Selective Membranes
As shown in Section 4.5, selective membrane systems display arheotropes,
points on the M-RCM where the rate of flux becomes zero. The locus of the
arheotrope curve is affected by pressure, and it can be seen in Figure 4.4 that it
is only possible to achieve complete permeation of the permeating component
if the permeate pressure is zero. Thus, effective separation in a selective
membrane requires very low permeate pressure.
Nonselective Membranes
Although nonselective membranes rarely exhibit arheotropes in the manner of
selective membranes, pressure remains a major consideration in achieving
effective separations. Section 3.1 examined how the ratio of pressures affects
the ease of separation in a binary system. It was shown that a high pressure
ratio is desirable for effective separation (refer to Figure 3.3). An additional
consideration is the rate of permeation. Since the driving force for permeation
of a particular component is the difference in partial pressures of that
component, it is an intuitive result that increased pressure differences will
result in more rapid permeation. So, larger pressure differences will result in
smaller membrane areas, while larger pressure ratios will result in more
effective separation. It is for these reasons that it is considered desirable to
operate a membrane with a permeate vacuum. However, if the permeate is a

DESIGN CONSIDERATIONS

175

vacuum, then the retentate pressure is restricted by the allowable pressure

difference. This means that, in high-pressure systems, it may be necessary to
reduce the pressure of the feed stream to the retentate. This would result in
energy losses if it is necessary to recompress the retentate for use downstream.
The alternativeoperating with a nonvacuum permeate pressureaffects the
ease of separation. Thus, a designer of a membrane process must take several
factors into consideration when deciding on the pressure at which to operate a
membrane process.
9.3.4 Effect of Reflux in Membrane Columns
Reflux in countercurrent membrane columns refers to the transfer of material
either from the retenate to the permeate stream, at the bottom of the CS, or
from the permeate to the retentate stream, at the top of the CS. Permeate reflux
requires compression to match the pressure of the retentate stream, whereas
retentate reflux must be passed through a valve or throttle before being
introduced to the permeate stream.
Permeate Reflux
The analytical techniques developed over the course of the book make use of
XD, D, and rDT as the design variables, and the resulting designs are given in
terms of these variables. For a particular feed and product rate, once values for
rDT and D have been chosen, the top flow rates, RT and PT, become fixed.
Therefore, the permeate reflux ratio must be such that these flow rates are
achieved. As a result, permeate reflux is fixed once D and rDT have been
chosen.
Retentate Reflux
For a particular feed flow rate and a required product flow rate, the retentate
product flow rate is equal to D for the bottom CS. Now, with a known RT for
that CS, mass balance dictates that all material present in RT that is not
discharged as product must be transferred to the permeate stream. Material
can be transferred from retentate to permeate either by permeation or by
way of the recycle. Since a particular quantity of material must be transferred
in order to reach the flow rates specified by the mass balance, the sum of the
reflux rate and the permeation rate is established. Increasing the reflux
therefore reduces the total rate of permeation, therefore reducing the
degree of separation and thus affecting product composition, but potentially
decreasing the membrane area that is required to meet flow rate requirements.
Retentate reflux rate therefore may offer benefits in terms of the capital
cost of the membrane, which must be balanced against the effects on
composition.

176

CONCLUDING REMARKS

Note: These conclusions regarding reflux are the result of the topdown
approach to design. If a bottomup approach is taken, it is the retentate
reflux that becomes fixed while the permeate reflux becomes a variable.
Furthermore, these conclusions result from a design approach in which the
feed and product flow rates are specified before the membrane itself is
designed. Also, as was mentioned earlier, the designs developed in this book
make use of the assumption of vacuum permeate, which means that the
composition of the permeate is neglected when determining the driving force
for permeation. If permeate vacuum is not assumed, then retentate reflux
may be beneficial in terms of these driving forces. The reader is referred to the
work of Tsuru and Hwang (1995), which examines the effects of retentate
reflux in detail.

9.4 CHALLENGES FOR MEMBRANE PROCESS ENGINEERING

It is hoped that this work, in addition to providing analysis tools for membrane
and hybrid processes, has made apparent the potential of these separation
processes to provide versatile and efficient solutions to meet separation
requirements. However, membrane technology has yet to achieve extensive
proliferation in the chemical industry, in spite of its benefits. It is therefore the
task of engineers in the field of membrane research to consider the challenges
that must be overcome in order for membrane processes to play a full role in
the chemical industry.
In chemical engineering at present, the modification of existing processes
is of tremendous interest, perhaps even of importance comparable to that of the
development of new processes. Therefore, a new technology is of greatest
use if it can readily be incorporated into an existing process. The example
displayed in Chapter 8 achieves this goal admirably, integrating a membrane
separation with an existing distillation process. Furthermore, the design
method developed here is able to produce a design of a membrane with
specified product and feed rates and compositions, making it suitable for
retrofitting existing processes in which these variables are fixed.