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

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.

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

Contents 1. 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2052 2052 2052 2052 2053 2053 2054 2054 2054 2054 2054

2.

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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4.

5.

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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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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

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].

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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

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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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].

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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

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

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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,

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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. 4.1. Process representation based on the unit operation concept

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

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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. References
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