Chemical Engineering and Processing 47 (2008) 20512060

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensication
journal homepage: www.elsevier.com/locate/cep

Review

Towards a methodology for the systematic analysis and design of efcient

chemical processes
Part 1. From unit operations to elementary process functions
Hannsjrg Freund a, , Kai Sundmacher a,b
a
b

Max Planck Institute for Dynamics of Complex Technical Systems, Physical and Chemical Process Engineering, Sandtorstrae 1, 39106 Magdeburg, Germany
Chair for Process Systems Engineering, Otto-von-Guericke University Magdeburg, Universittsplatz 2, 39106 Magdeburg, Germany

a r t i c l e

i n f o

Article history:
Received 11 April 2008
Accepted 31 July 2008
Available online 22 August 2008
Keywords:
Process intensication
Process route
Process analysis
Process design
Process synthesis
Unit operation
History of chemical engineering
Optimization
Flux
Resistance
State space

a b s t r a c t
A successful intensication of a chemical process requires a holistic view of the process and a systematic
debottlenecking, which is obtained by identifying and eliminating the main transport resistances that limit
the overall process performance and thus can be considered as rate determining steps on the process level.
In this paper, we will suggest a new approach that is not based on the classical unit operation concept,
but on the analysis of the basic functional principles that are encountered in chemical processes.
A review on the history of chemical engineering in general and more specically on the development
of the unit operation concept underlines the outstanding signicance of this concept in chemical and
process engineering. The unit operation concept is strongly linked with the idea of thinking in terms of
apparatuses, using technology off the shelf. The use of such ready solutions is of course convenient in the
analysis and design of chemical processes; however, it can also be a problem since it inherently reduces
the possibilities of process intensication measures.
Therefore, we break with the tradition of thinking in terms of unit apparatuses and suggest a new,
more rigorous function-based approach that focuses on the underlying fundamental physical and chemical
processes and uxes.
For this purpose, we decompose the chemical process into so-called functional modules that fulll
specic tasks in the course of the process. The functional modules itself can be further decomposed
and represented by a linear combination of elementary process functions. These are basis vectors in
thermodynamic state space. Within this theoretical framework we can individually examine possible
process routes and identify resistances in individual process steps. This allows us to analyze and propose
possible options for the intensication of the considered chemical process.
2008 Elsevier B.V. All rights reserved.

Contents
1.

2.

Historical development of chemical engineering and the emergence of unit operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.1.
Industrial organic chemistrythe forerunner of chemical engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Chemical engineering as an independent disciplineinuenced by the concept of unit operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.
The inclusion of catalysis and reaction engineering in chemical engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4.
The growing importance of transport phenomena and mathematical modeling in chemical engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5.
The separate development of chemical engineering in Germany . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6.
Further developments and trends in chemical and process engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.7.
Conclusions from history and new perspectives: unit operationsboth a blessing and a curse? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
History and denitions of the term process intensication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
How to dene process intensication? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Emergence of process intensication in chemical engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +49 391 6110 275; fax: +49 391 6110 634.
E-mail address: freund@mpi-magdeburg.mpg.de (H. Freund).
0255-2701/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2008.07.011

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3.

4.

5.

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

Possibilities and classication of measures for process intensication: current status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.1.
Process intensication at the phase level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Process intensication at the process unit level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Process intensication at the plant level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Paradigm shift in chemical engineering: from unit operations to elementary process functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Process representation based on the unit operation concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Process decomposition into functional modules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Functional module decomposition into elementary process functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Historical development of chemical engineering and the

emergence of unit operations
If we want to understand Process Intensication we rst have to
understand the way a chemical process is looked at today. For this,
we have to go back to the very beginnings of chemical engineering. However, a complete and comprehensive disquisition on the
historical development of chemical engineering although very
interesting and exciting is far beyond the scope of this section.
It is not necessary either since there are several books (e.g. [1,2]),
papers (e.g. [37]) and even websites (e.g. [810]) available that
describe in detail the historical developments from different angles.
Moreover, several contributions dealing with current and future
trends of chemical engineering address historical aspects as well
(e.g. [1113]).
1.1. Industrial organic chemistrythe forerunner of chemical
engineering
Assuming that industrial (organic) chemistry can be regarded as
a forerunner of chemical engineering, the starting point of something of the kind of chemical engineering education can be traced
back to the rst half of the 19th century in Germany [10]. Justus von
Liebig, a professor at the University of Gieen, introduced systematic courses that included lab experiments for training graduate
students in practicing organic chemistry. As a result, the University of Gieen together with the University of Gttingen (with
Professor Friedrich Whler) became prestigious training centers for ambitious chemistry graduate students from all over the
world. Several of Liebigs students later became famous professors
in chemistry themselves, for instance August Kekul and August
Wilhelm von Hofmann.
The beginning of chemical industries in Germany was characterized by the formation of numerous dye-producing factories in
the time period between 1860 and 1880 [4]. For the next several decades the main focus of the very successful chemical
industries in Germany remained on dyes and ne chemicals. The
education of the chemists was supplemented by some aspects of
chemical technologyhowever at a purely descriptive level at that
time [4].
In contrast, the chemical industries in the United States were
dominated by the production of bulk chemicals such as sulfuric
acid and alkali. The necessary scale-up of laboratory experiments
to large scale continuous processes initiated the call for a chemist
with sound engineering knowledgethe clear need for a chemical
engineer became obvious [8].
1.2. Chemical engineering as an independent
disciplineinuenced by the concept of unit operations
The rst steps of setting up chemical engineering as an independent discipline were done in England in 1887, when George

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E. Davis presented his 12 lectures on chemical engineering at

the Manchester Technical School. Only a short time later in 1888,
the rst chemical engineering course termed Course X (ten)
was established in the United States at MIT. Professor Lewis
M. Norton (who received a PhD in chemistry at the University
of Gttingen) taught this course within the department of chemistry, combining mechanical engineering with industrial chemistry
[8].
In 1901 Davis launched his Handbook of Chemical Engineering
[14] which was organized according to common basic operations.
William H. Walker (who also received a PhD in organic chemistry
at the University of Gttingen) together with Arthur D. Little
further developed the concept of common basic operations and in
1915, the term unit operations was coined for the rst time in
a report by Arthur D. Little. The concept of unit operations marks
a turning point in the history of chemical engineeringnot only in
the education but also in the denition and justication of chemical
engineers.
Up to the present day the chemical engineering education is
based on this concept with the advantage of imparting a general
and conceptual knowledge about the typical physical and chemical
operations that occur in a process. In doing so, the substancespecic knowledge about reactions and substances was replaced
by a more abstract process knowledge that can be applied to different processes. Combining the knowledge of mechanical engineers
and industrial chemists as a unique selling point, the chemical
engineer was now most welcome in the chemical industries and
the right for this new discipline to exist was no longer seriously
questioned.
Associated with the unit operation concept, Walker and Little
proposed the establishment of a school of chemical engineering
practice at MIT, which was then launched in 1916. Additionally,
a separate Department of Chemical Engineering, headed by Warren K. Lewis, was established at MIT in 1920. Lewis, Walker and
McAdams compiled the rst textbook of chemical engineering entitled Principles of Chemical Engineering in 1923 [15]. It was a
standard textbook for teaching for decades since it quantied unit
operations and thus provided tools to analyze chemical processes
[3,9].
1.3. The inclusion of catalysis and reaction engineering in
chemical engineering
In the 1930s and 1940s the chemical engineering discipline
was enriched with the elds of catalysis and reaction engineering.
Olaf A. Hougen and Kenneth M. Watson, professors at the University of Wisconsin, stressed the relevance of thermodynamics and
physical chemistry in their textbook Industrial Chemical Calculations in 1931 [16]. Their work found further expression in the
three volume textbook Chemical Process Principles [17] about
Material and Energy Balances, Thermodynamics and Kinetics and Catalysis that was published between 1943 and 1947
[6,8].

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

Speaking about heterogeneous catalysis, the paper Relation

between catalytic activity and size of particle by Ernest W. Thiele
[18] published in 1939 is denitely worth mentioning since it
pointed out the effects of diffusion limitation, which are quantied by introducing an effectiveness factor (and the so-called Thiele
modulus) [6].
As far as reactor modeling is concerned, a remarkable paper by
Irving Langmuir (who received a PhD in physical chemistry with
Nernst at Gttingen) was published in 1908 [19]. The paper dealt
with the theoretical analysis of continuous ow reactors and it
provided the equations and solutions for the limiting cases of completely back-mixed reactors and reactors without any back-mixing
(later labeled as CSTR and PFTR) [6]. It took, however, more than
two decades until the reactor modeling came back into the focus
in the 1930s and 1940s when Damkhler, Danckwerts and others
performed detailed and systematic analyses of chemical reactors.
1.4. The growing importance of transport phenomena and
mathematical modeling in chemical engineering
In the 1950s and 1960s R. Byron Bird, Warren E. Stewart and
Edwin N. Lightfoot (Professors at the University of Wisconsin)
pointed out the importance of a more fundamental understanding of the transport of mass, momentum and heat. Their famous
textbook Transport Phenomena [20] inuenced the chemical
engineering education signicantly and allowed for the teaching of
consistent and generalized equations rather than describing these
processes at a qualitative level only for a narrow range of applications.
Another major trend in the 1950s and 1960s signicantly inuenced by Neal R. Amundson and Rutherford Aris (Professors at the
University of Minnesota) was the growing importance of mathematical modeling in chemical engineering.
Two important books appeared in 1956: Unit operations of
chemical engineering [21] by Warren L. McCabe, Julian Smith and
Peter Harriott and Chemical Engineering Kinetics [22] by Joseph
M. Smith (Professor at Purdue). The rst one is an extensive work
of reference about unit operations that is still in use for university
teaching today. The latter one is worth mentioning since it contains, despite the title, also chapters on reactor design and thus
can be considered as the rst step into the direction of a textbook
in the eld of chemical reaction engineering [6]. The rst comprehensive textbook of chemical reaction engineering was then
published in 1962 by Octave Levenspiel (Professor at Oregon State
University). His textbook Chemical Reaction Engineering [23] has
become a standard for decades and still enjoys great popularity to
this day.
1.5. The separate development of chemical engineering in
Germany
The development in Germany differs completely from that in the
United States. This fact may partially be explained with the abovementioned fact that in Germany, chemical industries were focused
more on ne chemicals (often produced in simple batch processes)
rather than on bulk chemicals (produced in continuous ow processes) as in the United States. Even the Haber-Bosch process for
the production of ammonia (patented in 1910) did not give sufcient reasons to establish a chemical engineering education, since
it was the result of the classical German way of a collaboration
of a chemist and a mechanical engineer. Fritz Haber, rst professor at Karlsruhe Technical University, then (as from 1911) Director
of the Institute for Physical Chemistry and Electrochemistry at the
KaiserWilhelmGesellschaft in Berlin, was an expert in the elds
of high pressure synthesis and catalysis. Carl Bosch, on the other

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hand, was working as an engineer at the company BASF. He carried

out the scale-up of the Haber (laboratory) process by developing a
large-scale high-pressure reactor that could withstand the extreme
process conditionsa thing that has technically not been realized
before [24].
Even though Gerhard Damkhler established chemical reaction
engineering as a professor at the University of Gttingen between
1936 and 1944, chemical engineering as a new discipline as established in the United States was still rejected in Germany even in
the years following 1945 [4]. The situation was concisely summarized by Scriven [6]: So it was that although chemical engineering
was practiced very well within segments of German industry, and
the discipline had been compiled in ne scientic form, it could
not propagate without an academic base, nor could a profession
emerge without an industry that wanted it. . ..
At German universities, a coexistence of process engineering on
the one hand and technical chemistry as a branch of chemistry studies on the other hand prevailed for a long time. Examples for this
dualism date back to the 1920s, when on the process engineering
side Professor Emil Kirschbaum founded the chair of Chemische
Apparatekunde (chemical apparatus design) at the Technical University of Karlsruhe in 1928 (the establishment of a separate faculty
of chemical engineering, however, took more than four decades and
was nally realized in 1969). For the technical chemistry side, on
the other hand, Ernst Berl, who was a professor at the Technical
University of Darmstadt from 1919 to 1933, extended the education of chemistry students in chemical technology by incorporating
aspects of chemical engineering technology. Berl was also editor of
the extensive reference book Chemische Ingenieur-Technik that
appeared in 1935 [25]. At the same time, the encyclopedia Der
Chemie-Ingenieur [26] was published with the professors Arnold
Eucken (Gttingen) and Max Jakob (Berlin) as editors. The focus of
8 of the 12 volumes that appeared between 1932 and 1940 was on
unit operations. From the additional chapters the one from Gerhard Damkhler (like Ewald Wicke one of several famous scholars
of Eucken) focusing on chemical reaction engineering aspects is
probably the most well known one [6].
After World War II (and after the leave of several outstanding
professors such as Berl) Karl Schoenemann, a professor in Darmstadt from 1948 on, started lectures that at least in parts followed
the American prototype of chemical engineering. He stressed a
more quantitative view of chemical technology and introduced
a course where students carry out the planning and design of a
chemical process plant in order to learn the engineering aspects
of chemical technology. His successor, Professor Fritz Fetting, continued from 1966 on the orientation towards chemical engineering
in research and teaching and implemented the chemical technology as a major ingredient of the chemistry studies in Darmstadt
[27].
All these examples clearly illustrate the German way since
they have in common that the process engineering is regarded
as a part of the mechanical engineering and the chemical technology (or technical chemistry) is (if at all) considered as a
component of chemistry studies. It was nally Hanns Hofmann,
a professor in Erlangen, who for the rst time in (Western)
Germany merged the two branches of chemical engineering, technical chemistry and process engineering to an independent and
coherent chemical engineering institute and developed a corresponding study program. The establishment of the program started
in 1965 and was completed with the foundation of the Technical Faculty of the University of Erlangen in 1966. The Erlangen
chemical engineering program then served as a prototype for
other chemical engineering programs that have been established
in the following years at several other universities in Germany
[4].

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H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

1.6. Further developments and trends in chemical and process

engineering
A lot of developments in the eld of chemical and process engineering took place in the following decades, and again we have to
restrict ourselves here and will only look at some major events. In
the 1960s and 1970s more detailed studies on the dynamic behavior of chemical reactors were performed. In this regard, the work of
Gilles [28] and Gilles et al. [29], who enriched the eld of chemical engineering by introducing new concepts of control theory
for the stability analysis of reactors, is especially worth mentioning. In general, the development and consequential availability of
computers during these times inuenced the chemical engineering
discipline to a great extent and founded the beginnings of computer
aided process modeling. This trend was further intensied by the
overwhelming success of PCs in the 1980s. Consequently sophisticated commercial process simulation software tools appeared on
the market. Owing to the steady growth of computing power, the
enormous capacities of memory and computing power available in
the 1990s allowed more sophisticated and detailed modeling problems to be carried out with regard to additional aspects such as,
e.g. CFD studies of complex ows and the analysis of very extensive
reaction networks.
1.7. Conclusions from history and new perspectives: unit
operationsboth a blessing and a curse?
All the above-mentioned events contributed to form and
helped to develop the discipline of chemical engineering. As a
result, today this discipline is very sophisticated and technically
mature. We have learned that the unit operation concept has been
a key paradigm in chemical engineering for nearly 100 years and is
still today of outstanding signicance.
However, we think it is worth reconsidering the way of treating
a chemical process, since this determines (and possibly limits) the
options for our primary objective we have here, namely process
intensication. For this it is helpful to recall the reasons for the
introduction of the unit operation concept.
At the very beginning, it helped to justify the necessity of chemical engineering as a separate and independent discipline. Since
these times it has been used as a common organizing plan in
the curriculum of chemical engineering study programs, since it
allows for the teaching of general and abstract process knowledge
rather than substance-related knowledge about specic classes of
chemical species and reactions. Finally, the unit operations concept is used as methodology for process design and optimization,
since it allows for the precise differentiation of a process into
the subsequent sequential process steps (possibly with external
recycles).
At this point we should be aware that the framework of unit
operations is not always benecial. The problem is that usually
when thinking in terms of unit operations we automatically connect them with the apparatuses which perform these operations
like, e.g. a mixer, a reactor, a distillation tower, and so on. Therefore, the unit operation concept restricts our solution space to the
limited number of well-known ready solutions that are available.
With regard to the reasons for the introduction of the unit operation concept, we can be certain that today, a justication of chemical
engineering is no longer necessary. Thanks to the steadily increasing elds of application of chemical engineering knowledge the
necessity of this discipline is no longer seriously questioned. At
the same time, the requirements for the education of chemical
engineers have changed signicantly. For example, modeling and
simulation and in particular the understanding of processes on the
molecular level have become increasingly important.

All these facts together are the motivation for a new approach
that we propose in the present contribution. Instead of studying
unit apparatuses within the framework of the unit operation concept, we analyze the functions itself, i.e. the underlying elementary
physical and chemical processes that are conducted within the unit
operations. For such a function-oriented approach, we decompose
a chemical process down to elementary process functions that will
help us in identifying resistances in individual process steps.
2. History and denitions of the term process
intensication
2.1. How to dene process intensication?
It is difcult to give an appropriate and exact denition of the
term Process Intensication. Over the years, the meaning of this
term has changed and today, there is still no precise and generally
accepted denition. At least there is a general consensus about the
fact that process intensication requires a holistic view on the process, considering the process as a whole system. But the term itself
is essentially used as a collective term for diverse measures that
aim at a signicant improvement of a process with regard to its
efciency. The problem with that denition is how one can distinguish process intensication from classical process optimization.
We have to agree on the question to what extent an improvement
qualies as signicant (or drastic). In addition, the measure for
the efciency of a process can still be quite diverse (e.g. energy
efciency vs. time efciency) which makes things even more
difcult.
Often, process intensication is associated with striking but
vague catch phrases like cheaper, smaller, cleaner or making
more with less. This may be appropriate regarding current discussions in the context of sustainable development. For example,
as pointed out in the review article of Tsouris and Porcelli [30],
the possibly enhanced corporate image might amongst several
other factors be one reason for companies to implement process
intensication solutions.
However, all these purely descriptive and qualitative
attributes do not contribute to specify the term process
intensication more precisely. In the academic community, the lack of an appropriate and exact denition
has led to controversial discussions about whether it is
necessary at all to propagate process intensication as a new
discipline. Hence, there is a clear need of a distinct denition.
With this present sequence of two papers, we will propose a
new denition (see part 2) of process intensication which we
think is useful for the differentiation between classical process
optimization and process intensication.
2.2. Emergence of process intensication in chemical engineering
As far as the historical development of process intensication
is concerned, we will briey highlight some of the most important
events. Stankiewicz [31] reports about the rst emergence of the
term process intensication in the east European chemical engineering community in the 1970s [32]. During that time, however,
the term process intensication was used in the sense of process
improvement. One of the pioneers of process intensication under
the subsequently prevailing drastic improvement-paradigm is
Colin Ramshaw. His work on application of centrifugal elds (HiGee) in distillation processes in the early 1980s [33] can be
regarded as one of the rst examples of process intensication in
this modern sense, aiming at a signicant reduction of the plant
size and the installation costs [31].

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

In the 1990s, the interest of academia and industry in process

intensication increased signicantly. This can also be tracked by
the number of publications on this topic. When using the search
term process intensication for literature research in the Web of
Science the number of papers per decade rst rose slowly from 4
between 1966 and 1975 to 15 between 1976 and 1985 and then to
25 between 1986 and 1995. The year 1995, with the 1st Conference
on Process Intensication taking place, marks a turning point in
which the development accelerated. This is illustrated by the sharp
increase in publication numbers up to 49 papers in the following 5
years between 1996 and 2000.
Since 2001, after a further signicant increase, the number of
publications in the last few years seems to stabilize at a high level
of about 3070 papers per year. In addition, the rst text books on
process intensication, edited by Stankiewicz and Moulijn [34] and
Keil [35], respectively, were recently published.
It is this increasing signicance of the topic that in our opinion
makes it worth reconsidering the denition and the fundamentals
of process intensication. In Section 3 we therefore present the
current status of possibilities of process intensication measures
and give examples for appropriate classication schemes. Starting
from this current status we go a step further and present the basic
idea of the new elementary process function concept in Section 4,
which will hopefully provide a basis for a systematic treatment of
this topic.
3. Possibilities and classication of measures for process
intensication: current status
In the following we will outline possibilities for process intensication measures for which improvements in productivity have
been reported in the literature. These improvements can concern,
e.g. a reduction of the plant size by reducing the size of single apparatuses or by reducing the number of the latter by integrating two
or more unit operations into a multifunctional unit. Other intensication potentials concern, e.g. the specic energy consumption,
the amount of reactants used and of waste products being produced
for a specied production height (i.e. the feedstock efciency). As
stated before, these achievements are today often lumped together
and labeled with the collective term process intensication. In
many cases, the measures to perform the process improvements
have been found incidentally or in better cases as an empirical
result of a series of experimental studies. To summarize, there is
currently neither a theoretical basis nor are there scientic guidelines for process intensication available that can be generalized
and thus help to identify process intensication options when analyzing a chemical process as to its efciency.
In order to go a step further in this direction, suitable systematic categories in order to classify the measures have to be
introduced. In this regard, Stankiewicz and Moulijn [36] propose
to divide the eld of process intensication into two areas, namely
process-intensifying equipment and process-intensifying methods. Although this scheme allows a rough classication of the
different measures, this is of course only one of several possible
classication schemes one could imagine.
From a mechanistic point of view, we think it is worth considering a differentiation between (drastic) quantitative improvements
on the one hand and improvements as a result of qualitative
changes on the other hand. Micro-reaction technology, monolithic
reactors and reactive separations are examples of the rst category, since they allow for a signicantly improved mass and heat
transfer, while in principle the same physico-chemical mechanisms
still apply as in conventional apparatuses. Of course, in the case of,
e.g. micro-reactors, the signicance of the individual mechanisms
(e.g. diffusion processes) that contribute to the overall performance

2055

can be completely different. The second category comprises, e.g.

alternative forms of energy supply for chemical reactions such as
microwaves and ultrasound, the use of new reaction media such as
ionic liquids, micro-emulsions and supercritical phases, or the use
of new auxiliary agents such as phase transfer catalysts. All these
measures involve substantial qualitative changes in the process
since here new (additional) mechanisms come into play.
Finally, another possibility for the classication of process intensication measures which we will use in the following subsections
is to divide them into three superordinate groups (levels). The
most detailed level is the phase level, at which we consider molecule
populations that build up a thermodynamical phase. In the process,
the thermodynamical phase(s) are embedded into apparatuses, or
more abstract into individual process spaces. This is the process unit level. Usually, the process consists of several such process
units. The interconnection between the individual apparatuses and
thus the overall process owsheet can nally be analyzed at the
superordinated plant level.
It is obvious that some of the measures for process intensication that are discussed at the individual levels seem to t to more
than just one level. This overlap is due to the fact that a certain process intensication measure has in general an inuence also on the
other levels. In particular, changes at a certain level have in most
cases a strong impact on the levels above (e.g. changes at the
phase level imply alterations at the process unit level and the plant
level, respectively). For the classication of the process intensication measures into the individual levels it is essential to identify
the level at which the main inuence on the process is caused.
For each of the three levels, a survey of intensication possibilities is presented. However, the list makes no claim to be complete.
In fact, it should be regarded as a compilation of interesting and
inspiring examples worth to be considered as possible process
intensication measures rather than an exhaustive disquisition on
the topic. The same is true for the references; only a very limited number of related papers can be given here for each example,
however, these articles might serve as a starting point for further
literature research.
3.1. Process intensication at the phase level
The rst level comprises possibilities we have at the phase level,
i.e. at the level of molecule populations that build up a thermodynamic phase. Here we consider processes that occur within the
volume of a single (individual) phase or processes between the
phases. The measures for process intensication at this level can
give rise to both, thermodynamic effects as well as kinetic effects.
An important possibility is, e.g. the use of new reaction media
such as ionic liquids (e.g. [37,38]), micro-emulsions (e.g. [39,40]),
supercritical uids (e.g. [41,42]) and phase transfer catalysts (e.g.
[43,44]). Another possibility for process intensication at the phase
level is the use of alternative methods for mass, momentum and
energy transfer [45] such as microwave (e.g. [46,47]), photochemical induction (e.g. [48,49]), ultrasound (e.g. [50,51]), hydrodynamic
cavitation (e.g. [52,53]) and articial gravitational elds such as
centrifugal elds (e.g. [33,54]), electric elds (e.g. [55,56]), and
magnetic elds (e.g. [57,58]).
3.2. Process intensication at the process unit level
When analyzing a typical chemical process, we can identify
the level of individual apparatuses (process units). Such a process
unit comprises one or more of the aforementioned thermodynamic
phases.
At the process unit level we can realize measures of process intensication by designing the individual process spaces and thus by

2056

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

Fig. 1. Classical owchart of a chemical process.

controlling the local processes inside the process units. From the
numerous process intensication measures that can be identied
at this level the most important ones are briey highlighted in the
following.
The miniaturization of equipment [5961] falls into this category, with various options such as micro-reactors (e.g. [6265]),
micro-heat exchangers (e.g. [66,67]), micro-mixers (e.g. [68,69]),
micro-separators (e.g. [70,71]) or the use of mini-emulsion droplets
as micro-reactors (e.g. [72,73]).
Besides the miniaturization, the choice of special geometrical
structures for the reactors [74] such as monolithic structures (e.g.
[7577]), structured arrangements of catalyst particles in a channel (e.g. [78,79]), structured packings (e.g. [80,81]), foam structures
as catalyst support (e.g. [8284]) and nanobers as catalyst support (e.g. [85,86]) is proposed and currently investigated. Of course,
some of the possibilities mentioned before are investigated in theoretical studies rather than in industrial practice. However, e.g. the
application of structured packings that are lled with catalyst particles is by now in industrial reactive distillation processes common
practice (e.g. [87,88] and references therein).
Another option at the process unit level is the selective adjustment of well-dened ow patterns such as segregated (segmented)
ow (e.g. [8991]), or, if enhanced mixing is desired, e.g. the ow
in helically coiled tube reactors (e.g. [9294]).
3.3. Process intensication at the plant level
Finally, we can examine the interconnection between individual apparatuses (process units) and thus analyze the overall
process owsheet at the superordinated plant level. A great deal
of process intensication possibilities at the plant level is linked
with the sequence of the process operations and the potential
integration of unit operations into multifunctional process units,
respectively.
In this regard, one option is to integrate reaction and separation
(see e.g. [9597] and references therein) into a single apparatus
(reactive separation processes) as in the case of reactive distillation (e.g. [98100]), reactive pervaporation (e.g. [101,102]), reactive
extraction (e.g. [103,104]), reactive chromatography (e.g. [105,106]),
reactive crystallization (e.g. [107,108]), adsorptive reactors (e.g.
[109111]), and membrane reactors (e.g. [112115]).

Another possibility is to couple mechanical unit operations with

chemical reactions in a single unit. As examples for such mechanical integrated processes we should consider reactive ltration (e.g.
[116,117]), reactive milling (e.g. [118,119]), and reactive extrusion
(e.g. [120,121]).
A practicable approach with regard to heat integration and
temperature management is to couple reactions, e.g. exothermic
and endothermic reactions (e.g. [122124]). Further heat integration concepts include counter-current heat exchange reactors (e.g.
[125]) and the use of inert adsorbents for the desorptive cooling of
reactors (e.g. [126]).
Of course, individual separation methods can also be coupled
among each other (e.g. [127,128]) as in the case of, e.g. extractive
distillation (e.g. [129,130]), membrane adsorption (e.g. [131,132]),
membrane distillation (e.g. [133,134]), crystallizationdistillation
(e.g. [135]), adsorptive distillation (e.g. [136,137]) and liquid emulsion membranes (e.g. [138,139]).
Concerning the operational mode, dynamic/transient process
operation (e.g. [140]) such as cyclic reactor operation applying
ow-reversal strategies (e.g. [141145]) and circulation loop reactors (e.g. [146,147]) can be considered as interesting and promising
approaches towards process intensication.
Regardless of which categorization we choose, a successful
intensication of a chemical process requires in any case a systematic debottlenecking by identifying and eliminating the main
transport resistances that limit the overall process performance and
thus can be considered as rate determining steps of the process (in
analogy to the rate determining step concept for complex reaction
mechanisms). This aspect is especially emphasized in Section 4,
where we introduce a new systematic concept of elementary process functions that will help us in the identication of the process
bottlenecks.
4. Paradigm shift in chemical engineering: from unit
operations to elementary process functions
In the following, we will rst analyze the classical owchart of a
chemical process based on the unit operation concept. Using this as
a starting point, we then present the basic idea of the new elementary process functions approach which in a certain sense can be
regarded as an extension of the unit operation concept. However,

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

2057

Fig. 2. Representation of a chemical process in terms of a potential sequence of functional modules.

as stated before, the apparatuses are replaced by the functions that

have to be carried out in a chemical process.

immediately associate the unit operations that have to be performed with appropriate, well-established apparatuses (Fig. 1,
lower part).

4.1. Process representation based on the unit operation concept

4.2. Process decomposition into functional modules
The classical owchart of a typical chemical process is given
in Fig. 1. The rectangular boxes illustrate the individual stages
of the process, with a reactor-separator sequence in the center
and appropriate preprocessing and postprocessing steps. As indicated in the upper part of Fig. 1, at each of the individual stages
of the process, one or more unit operations have to be carried
out. Owing to the long and successful tradition of the unit operation concept in chemical engineering (see Section 1) both in
education as well as in industrial practice we can (and will)

If we focus on the functions that have to be performed in a chemical process, we will nd that the core of each chemical process
can be broken down into ve different functions which we will call
here functional modules. In the center of the chemical process we
dene the functional module Chemical Reaction. This functional
module must be supplied with reactants. In addition, an adequate
contacting of the reactants has to be ensured (functional module
Contacting) and the reactants need to be activated (functional

Fig. 3. Process route inside a functional module, determined by the generalized ux vector j and the elementary process functions ek (basis vectors in thermodynamic
state space).

2058

H. Freund, K. Sundmacher / Chemical Engineering and Processing 47 (2008) 20512060

module Activating). As a result of the functional module Chemical Reaction we generally obtain a mixture of different products
(and the fraction of the reactants that have not been converted), so
that the introduction of a functional module Separating is necessary. Since an energy exchange with the environment takes place
during the reaction we additionally need a functional module Heat
supply/removal. In addition to these core functional modules, we
have to consider the important preprocessing and postprocessing
functional modules Preprocessing of raw material and Product
formulation, respectively.
Below the functional modules some selected examples for the
different possibilities are given (whereby this list does not claim to
be exhaustive).
So far, the new concept proposed here seems to be quite similar
to the traditional unit operations approach. When comparing Fig. 2
with Fig. 1, we will nd that the overall structure of the owchart
is still maintained. The main intention of Fig. 2 as a rst step
towards the explanation of our new concept is to break with the
apparatus-based approach and to focus on the individual functions
of the chemical process.
4.3. Functional module decomposition into elementary process
functions
After the introduction of the functional modules, we have to
think about a suitable denition for them. For a more rigorous
understanding, a further abstraction of the functional modules is
necessary. We will explain this procedure using the illustration
shown in Fig. 3.
Let us consider a volume element that is traveling on the
process route, i.e. it passes a characteristic sequence of functional
modules (which is not necessarily the sequence exemplarily shown
in Fig. 2). We will track the volume element between the time ti
and ti+1 . The corresponding state vectors of the volume element
are x(ti ) and x(ti+1 ), respectively. The time interval is chosen such
that the volume element passes the individual functional module
. During this time interval, the state of the volume element is
changed inside the functional module by different types of uxes
(e.g. diffusion uxes, heat uxes, . . .).
For the analysis of the uxes we dene a generalized ux vector j that comprises all possible uxes that can in principle occur
during the course of a chemical process. The functional modules in
our concept are chosen such that each functional module is characterized by a unique structure of the corresponding generalized ux
vector. The generalized ux vector j of the functional module
for example will have at least one (generally more than one) active
component while all other components are zero. This set of active
uxes causes the changes in the state of the volume element.
If we want to quantify the change of the state vector x, we have to
calculate the rst derivative in time. For this, we need in addition to
the components of the ux vector the basis vectors ek . Each of these
basis vectors stands for a certain direction in the thermodynamic
state space, and the region which is attainable for the traveling volume element in the state space is determined by the entirety of
all basis vectors ek . Due to the outstanding signicance of these
basis vectors, we call them elementary process functions in our
concept.
To sum up, the change of the state of the traveling volume
element inside a functional module is determined by the corresponding set of active uxes and the respective basis vectors in
thermodynamic state space (elementary process functions).
The concept of elementary process functions is to a certain
extent the counterpart to the concept of elementary reactions in
chemistry, where a complex chemical reaction can be broken down
into a set of elementary reactions. In the elementary process func-

tion approach, in a more generalized way, the whole chemical

process is broken down in a similar manner. This allows for the
analysis of process routes in thermodynamic state space for each
of the different functional modules individually.
5. Conclusion
The present contribution is part 1 of a sequence of two papers on
a new approach for the systematic analysis and design of efcient
chemical processes. Of course, before presenting a new approach,
it is rst necessary to evaluate the current status of concepts. Furthermore, we should understand the reasons for their development
and their dominance in chemical and process engineering.
The review on important aspects of the history of chemical engineering as given in Section 1 clearly illustrates that the concept of
unit operations can be regarded as a key paradigm in the development of chemical engineering as an independent discipline. Nearly
100 years after its introduction, the unit operation concept is still
the dominant approach in the chemical and process engineering
communityboth in industry as well as in academia.
Without debasing the unit operation concept (which denitely
still has an undeniable value), we encourage to consider a new, more
abstract and fundamental way of looking at a chemical process.
We feel that the problem with the unit operation concept is that
it is strongly linked with the idea of thinking in terms of apparatuses. It provides us with ready solutions (e.g. mixers, reactors,
distillation columns, etc.) using technology off the shelf. However,
this is often a severe constraint for breakthroughs in productivity
and/or selectivity since it inherently narrows the solution space for
process design and optimization.
The elementary process function concept proposed here, in contrast, allows for thinking in terms of functions that have to be
fullled in the course of a chemical process. The functions are represented by functional modules, which in turn are characterized by
specic generalized ux vectors and elementary process functions
(basis vectors in thermodynamic state space). When a volume element is passing such a functional module, its state is changed as a
result of the uxes that occur. For the analysis of the process, we
therefore have to consider elementary steps in the thermodynamic
state space: we can design the whole process route from the starting point to the nal point by selectively adjusting the respective
ideal values of the uxes at each point.
Furthermore, the exibility of the concept allows for the inclusion of the whole spectrum of physico-chemical phenomena.
Extensions with regard to the adaptation of new methods and tools,
e.g. from materials science and biology, can be implemented if
required.
The new approach presented allows for a detailed analysis and
design of chemical processes, which helps to systematically identify and investigate suitable measures for process intensication. In
part 2 of our contribution, a sound theoretical basis of the concept
and a mathematical description will be given.
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