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Winter 2003 1
ChE department
ChE at...
Vanderbilt
University
M. DOUGLAS LEVAN
Vanderbilt University • Nashville, TN 37235
L
ike our discipline, the Department of Chemical
Engineering at Vanderbilt University is experi-
encing a significant expansion beyond its tradi-
tional roots toward advanced materials, bioengineering,
and other product and application areas. To respond to
changes in the field and to take a strong leadership role
in research developments in the future, the Department
has concentrated on building expertise through faculty
recruitment, revising both undergraduate and graduate
curricula, and cultivating ambitious interdisciplinary re-
search thrusts. The University’s established world-class
research prominence in medicine, biology, and environ-
mental studies augments its advantages in reaching its
future goals.
Winter 2003 3
Vanderbilt’s Chemical Engineering Class of 2003.
Professor Balcarcel with PhD candidate Yuansheng Yang.
THE DEPARTMENT
OF CHEMICAL ENGINEERING
A Chemical Engineering Program was first announced at including space for a high-bay undergraduate unit opera-
Vanderbilt in 1903 as a joint program between engineering tions laboratory.
and chemistry. A Department of Chemical Engineering was
established in 1938 with the first head appointed in 1939. The Department provides an intimate environment for un-
dergraduate and graduate students. Each faculty member cares
The Department has had seven Chairs. The early ones were a great deal about education and student welfare. Classes are
Roy S. Hanslick (1939-1941), E. E. Litkenhous (1941-1961), small and are all taught by faculty members. Advising is done
and W. Dennis Threadgill (1961-1972). E. E. Litkenhous had face-to-face with faculty members.
influence far outside the field of chemical engineering; in
1930, while still an undergraduate at the University of Louis- We have many distinguished alumni. Our graduates hold
ville, he developed a system for rating athletic teams and pre- positions of major responsibility in large corporations, in small
dicting the outcome of a sporting event based on a “points entrepreneurial and consulting firms, and in federal and state
spread”—this basic system is still in use today. government agencies. Some PhDs continue their research in
post-doctoral positions or enter the teaching profession.
The School was reorganized in 1972 into a grid system
with John A. Roth as Chairman of the Division of Chemical, CURRENT FACULTY
Fluid, and Thermal Sciences, which was comprised of chemi-
cal engineering and mechanical engineering; Thomas M. M. Douglas LeVan joined the Department as Chair in 1997.
Goldbold (1972-1975) was Director of the Chemical Engi- At mid-year, the tenured/tenure-track faculty was all tenured
neering Program. In 1975, the School returned to a normal and consisted of Professors Robert J. Bayuzick, Kenneth A.
departmental structure. Debelak, Tomlinson Fort, M. Douglas LeVan, John A. Roth,
Karl B. Schnelle, Jr., and Robert D. Tanner. Each had well
Recent Chairs have been W. Dennis Threadgill (1975-1980), over 15 years of university teaching experience. We also had
Karl B. Schnelle, Jr. (1980-1988), Thomas M. Godbold (Act- two experienced research faculty, Professors William H.
ing Chair, 1988-1989), Tomlinson Fort (1989-1996), and M. Hofmeister and Ales Prokop. A clear opportunity existed to
Douglas LeVan (1997-present). hire new faculty.
The current home of the Department is Olin Hall, a gift of Three research thrust areas were identified: materials,
the Olin Foundation, which opened in 1974. The building is bioengineering, and environmental engineering. All are in-
occupied by the Department of Chemical Engineering, most terdisciplinary and important at Vanderbilt. We sought (and
of the Department of Mechanical Engineering, and much continue to seek) candidates who can contribute fundamen-
of the Interdisciplinary Materials Science Program. The tally and broadly to one or more of these focus areas. We also
Department occupies approximately 20,000 square feet, sought faculty with indications of excellent teaching abili-
TABLE 1
Current Chemical Engineering Faculty at Vanderbilt University
Winter 2003 5
mention. A practice was The changes for the cur-
started by Professors rent academic year in-
Debelak and Roth of devel- volved improving the struc-
oping written communica- ture of our thermodynam-
tion skills in design and ics sequence, eliminating
laboratory courses through engineering courses (but
the team-teaching efforts of not physics courses) in stat-
an expert in technical ics-dynamics and electrical
communications. Their ef- circuits, and adding flex-
forts won an ASEE best pa- ibility. We are now teach-
per award in 1983. Dr. ing all of thermodynamics,
Sharp has been involved not relying on the Depart-
with the Department as the ment of Chemistry. We are
expert in technical commu- also increasing the expo-
nications since 1982. Each sure of our sophomores to
semester she co-teaches the Professor Rogers with BS/MS student Virginia Wahlig. simulation; instead of
undergraduate laboratory teaching just Aspen, we
courses, where she instructs now also apply additional
students in written and oral communications, and in addition programming and numerical problem-solving methods to
she teaches two sections of a technical communications course chemical engineering problems.
for the School, for which she serves as coordinator. She is The new open curriculum makes it easy for students to mi-
active within the ASEE and regularly publishes her research nor or pursue their own chosen direction. There are six hu-
on learning styles. She has been instrumental in the consider- manities-social science electives spread uniformly through-
ation of Kolb learning styles within the School of Engineer- out the curriculum. We have moved all technical and open
ing. Her efforts have won praise from alumni and ABET. electives into the junior and senior years, and as a result, stu-
In addition to those shown in Table 1, five faculty currently dents have a technical elective each semester of the junior
have secondary appointments in the Department. Professors and senior years plus two open electives in the senior year.
Todd D. Giorgio, Thomas R. Harris, K. Arthur Overholser, The Department encourages minors in environmental engi-
and Robert J. Roselli (all former faculty in the Department of neering, materials science and engineering, and management
Chemical Engineering) have their primary appointments in of technology; these require 15 hours. Students also minor in
the Department of Biomedical Engineering. Professor David chemistry, mathematics, economics, etc. The Department is
S. Kosson has his primary appointment in the Department of offering a new concentration in biotechnology that requires
Civil and Environmental Engineering. 13 hours. Additionally, a special, intensive program leads to
In addition, the Department is fortunate to have the ser- a dual degree in chemical and biomedical engineering.
vices of staff members Margarita Talavera, Mary M. Gilleran, For the last four years, the School of Engineering has of-
Anita K. Patterson, and Mark V. Holmes. fered elective seminar courses to entering freshmen. The
Department has participated heavily, offering several courses.
UNDERGRADUATE PROGRAM Our regular offering, however, has been the course “Fron-
The undergraduate program in chemical engineering was tiers in Chemical Engineering,” which has been team-taught
accredited by the Engineers’ Council for Professional Devel- every year by our assistant professors based on their research
opment (ECPD) in 1952. Accreditation by the Accreditation interests. (This course is the subject of an article published in
Board for Engineering and Technology (ABET) followed this issue of Chemical Engineering Education.)
beginning in the 1980s as ECPD was replaced. The most re- Our undergraduates have research opportunities also. Each
cent accreditation visit occurred in October 2001. year many of them work side-by-side with graduate students
The undergraduate curriculum was revised for the 1998- in our research laboratories. In the summers, external and
1999 academic year and again for the 2002-2003 academic School support has been available to provide research expe-
year. Both of these curricula are on our website. The changes riences for undergraduates.
for 1998-99 were made to present material in a more logical We have an active AIChE student chapter with a long his-
order, to change computer languages, and to increase effi- tory. A Chemical Engineering Club, formed in 1936, became
ciency. We retained a 3-hour engineering economy course, the Tau Alpha Tau Society in 1940 and then the Vanderbilt
but collapsed two 3-hour senior design courses into a single Chapter of the American Institute of Chemical Engineers in
4-hour capstone course. Graduation requirements were re- 1947. Students participate in a wide variety of activities, in-
duced to 128 hours. cluding Rube Goldberg competitions. Last year eight under-
6 Chemical Engineering Education
graduates attended the AIChE Student Conference in Puerto We currently have an annual Tis Lahiri Memorial Seminar,
Rico. For the 2002 Annual AIChE Meeting, the Department named after a former graduate student and supported by an
supported a trip for 12 undergraduates to attend. endowment. This seminar has an educational flavor. Recent
speakers include H. Scott Fogler, Richard M. Felder, Phillip
GRADUATE PROGRAM AND RESEARCH C. Wankat, Ronald W. Rousseau, John M. Prausnitz, Edward
L. Cussler, and Arthur W. Westerberg.
A majority of our graduate students are PhD students. Most
are supported in their first year as teaching assistants, although We also have an active Chemical Engineering Graduate
some support for new students as research assistants is usu- Student Association (ChEGSA) that represents graduate
ally available. After the first academic year, almost all stu- student interests and sponsors a variety of social events.
dents are supported as research assistants from research grants They have had great leadership and help the Department
for the duration of their studies. Some multi-year “topping” in many ways.
awards are also available.
OUR FUTURE
Graduate course requirements were changed for the 1999-
2000 academic year and again for the 2002-2003 academic The Chemical Engineering Department has changed con-
year. For 1999-2000, we revised our graduate core course siderably in the last six years. Nine of the fourteen full-time
requirements, moving to a more research-oriented chemical faculty members listed in Table 1 were not in the Department
engineering science core. For 2002-2003, we reduced in late 1996. We have been working toward improved under-
coursework requirements for PhD students and made some graduate and graduate curricula and expanding our research
modifications to our core course structure. We now offer six activities. The changes will continue.
core courses: applied mathematics for chemical engineers, Our curricula and research programs reflect the broaden-
thermodynamics, transport phenomena, chemical kinetics, ing of the chemical engineering profession from its chemical
simulation, and separation science and engineering. and petrochemical heritage toward advanced materials,
An MS student must take 24 hours of coursework, a gradu- bioengineering, environmental concerns, and other applica-
ate school requirement. This includes five core courses. A tion-based and product areas. Vanderbilt University as a whole
thesis is required. (The Master of Engineering, an ad- is strong in biological research, with a world-class research
vanced professional degree, is offered by the School of hospital; this creates broad opportunities for collaborative
Engineering.) research on biologically related topics.
We require a PhD student to take a minimum of 30 hours We seek advice on our programs in many ways. A princi-
of coursework beyond the bachelor’s degree. This includes pal avenue is through our Departmental External Advisory
the six core courses. Many students take more than 30 hours Committee. We also seek advice from alumni and corporate
of coursework, but this load is designed to allow students to friends through a newsletter, “The Catalyst,” edited by Pro-
spend the majority of their studies on original research for fessors Schnelle and Sharp. The Chair has formed an Under-
the dissertation. PhD students work with their research advi- graduate Student Council, which provides him with advice
sor under the guidance of a PhD committee towards fulfill- on the undergraduate program, and he serves as advisor to
ing all requirements for the degree. ChEGSA.
Research laboratories within the Department are equipped Essentially all Departments want to improve not only their
for experimental and computational investigations of mate- rankings but also their quality and visibility. We are certainly
rials, bioengineering, environmental engineering, adsorption no exception. We have been working on improvements from
and surface chemistry, chemical reaction engineering, and all angles. We recognize the many opportunities that we have
process modeling and control. Interdisciplinary research op- at Vanderbilt.
portunities exist with researchers in other departments in the Information: More information on the Department is avail-
School of Engineering, the natural sciences, and medicine. able at http://www/vuse.vanderbilt.edu/~cheinfo/che.htm.
Our faculty participate in the Interdisciplinary Program in Questions should be directed to cheinfo@vuse.vanderbilt.edu.
Materials Science and in an NSF-sponsored Engineering
Research Center for Bioengineering Educational Technolo- Acknowledgements: Photographs were taken by David
gies. We also participate in two new University-supported Crenshaw and Darryl Nelson. Kenneth A. Debelak, Vivian F.
interdisciplinary research initiatives—the Vanderbilt Institute Cooper-Capps, and Julie E. Sharp provided many helpful
for Nanoscale Science and Engineering (VINSE) and the comments.
Vanderbilt Institute for Integrative Bioengineering Research Reference: Jacobs, D., “102 Years: A Story of the First Cen-
and Education (VIIBRE). Activities are currently develop- tury of Vanderbilt University School of Engineering,”
ing within the Vanderbilt Institute for Environmental Risk Vanderbilt University Alumni Association, Nashville, 1975.
and Resources Management (VIERRM). ❐
Winter 2003 7
ChE educator
Robert Hesketh
of Rowan University
C. STEWART SLATER
Rowan University • Glassboro, NJ 08028
I
first met Robert Hesketh at the 1992 Chemical Engineering Sum-
mer School in Bozeman, Montana. Phil Wankat and I led a work-
shop that he attended, and I immediately noticed his enthusiasm
for engineering education. As a result of that meeting, he and I later co-
authored an article on separations for CEE.[1] Little did I know that I
would eventually have the opportunity to hire him as one of the found-
ing members of the Rowan Chemical Engineering Department!
During Robert’s faculty interview at Rowan we were impressed with
his enthusiasm and his ideas for the freshman engineering program.
We knew that his ideas on the use of a coffee machine would work as a
basis for our hands-on approach to engineering education at Rowan.
We felt he was a perfect fit for the new engineering education program
at Rowan, and his dedication to teaching has since been rewarded by
several educational awards from ASEE, including the 2002 Robert G.
Quinn Award, the 1999 Ray W. Fahien Award, the 1998 Dow Out-
standing New Faculty Award, the 2001, 1999, and 1998 Joseph J.
Martin Awards, and four other teaching awards. To date he has
obtained over $2 million in external funding from federal, state
and industrial sources.
As one of the founding faculty members of the College of Engineer-
ing and Chemical Engineering Department at Rowan University, Rob-
ert has spearheaded an effort to develop the industrial component of
the four-year sequence of the multidisciplinary engineering clinic. In
addition, he has created several courses that integrate experiments and
lectures in an inductive framework within chemical engineering. He
has made many major contributions in laboratory methods that dem-
onstrate chemical engineering practice and principles, the most notable
of which uses the coffee maker. He has helped advance the state-of-
the-art in laboratory-based education nationally through his many
publications, presentations, and seminars at ASEE and workshops
supported by NSF.
Winter 2003 9
Robert, far
right holding
the dog, at the
start of a 1974
backpacking
trip (brother
Ryan at
other
end).
Hands-on
Robert and Fiona Cutting their house
cello wedding cake, 1990. construction
of parent’s
house in
Carbondale, 1978.
Hiking
with
Alexander,
Natasha,
and Fiona
in Rocky
Mountain
National
Park.
Longs
Running in the Peak in
Philadelphia back-
Half-Marathon ground,
in 1983. 2002.
Robert continued his work on environmental engineering tion for a population balance model; he had found numerous
problems through two summers of employment in Orlando, complicated models and was trying to figure out which was
Florida, for an environmental engineering consulting firm, the best. Fraser, with the wisdom of experience, looked at
Cross-Tessitore and Associates. During this time Robert ex- him and asked, “Have you tried a first-order rate?” Fraser’s
perienced not only the rigors of environmental audits and ability to look for the simple solution to problems remains a
assessments, but also the Florida life style of Frank Cross. cornerstone in Robert’s teaching philosophy.
He felt fortunate to be able to live with the Cross family, who
introduced him to white-water kayaking! CAMBRIDGE UNIVERSITY
In 1982 Robert graduated with a BS with Distinction in After completing graduate school, Robert had both a job
Chemical Engineering from the University of Illinois and offer with a major pharmaceutical company and an offer of
started graduate school at the University of Delaware. At the postdoctoral work at Cambridge University in England. Rob-
University of Delaware, Robert had a special opportunity to ert was destined for academics, however, and chose to work
work with T. W. Fraser Russell[5] and Arthur W. Etchells, who with Professor and Department Head, John F. Davidson, at
is now a DuPont Fellow distinguished by his work in mix- Cambridge University. There, he added very fast chemical
ing. Working with both Fraser Russell and Art Etchells fur- kinetics to multiphase fluid flow by working on combustion
thered Robert’s appreciation for the practical side of engi- problems in fluidized beds. This work continued his envi-
neering. In this work, Robert developed a correlation for ronmental theme of working with coal combustion that results
bubble size in turbulent fluid flow that has been cited in over in lower emissions of pollutants than conventional burners.
25 journal articles and is currently being used in the chemi-
cal industry for the design of multiphase reactors and piping Robert enjoyed his stay in England from 1987 to 1990, and
networks. Both Fraser and Art have helped Robert immensely while there he also decided to improve his musical abilities
throughout his career, from shaping and guiding his research by taking cello lessons. Attending a concert in 1987, he com-
to giving him advice on career moves. He recalls one inci- pared a list of cello teachers with the concert program and
dence when he was struggling with a bubble breakage func- found a match; not only for cello lessons, but for the person
who later became the love of his life—Fiona L. Stafford! Rob-
10 Chemical Engineering Education
ert became one of Fiona’s biggest fans. Their wedding in where he worked with Martin Abraham, John Henshaw (ME),
1990 was notable in that the cello section of the Cam- and Keith Wisecarver. In these programs Robert expanded
bridge Philharmonic Society played before the wedding his coffee-machine experience into a series of young schol-
and their cake was in the shape of a cello! As a special ars experiments and as an outreach tool for student recruit-
treat for Robert’s relatives, he held the wedding rehearsal ment. At Tulsa Robert also was influenced by the work of
dinner at Trinity College, where they got a real taste of Ramon Cerro in both his hands-on laboratory experiments as
Cambridge University life. well as his love of theory.
Robert’s passion for engineering education
had its genesis at Cambridge. The English love A NEW STYLE OF
tea, which is served twice a day to all the fac- He is one of ENGINEERING EDUCATION:
ulty, staff and students, but Robert wanted real the founding ROWAN
coffee (not the jars of instant had by all other professors of Robert is a leader in teaching innovations at
postgrads) and formed a coffee club. It was the new and Rowan. He is one of the founding professors of
highly successful until the coffee machine innovative the new and innovative engineering clinic. His
plugged up. So, Robert and his future best man, forward-looking ideas on measurement, design,
engineering
A. B. Pandit, took the coffee machine apart and course content were incorporated into the
and cleaned out the tubular heat exchanger. clinic. His for-
engineering clinic starting from the time of his
He learned two things: that Cambridge has ward-looking
first interview at Rowan University. After ob-
very hard water and that coffee machines are ideas on mea- serving Robert’s excellent leadership skills,
fascinating. surement, de- Dean James Tracey chose him to be the Fresh-
sign, and course man Engineering Clinic Coordinator. The en-
TULSA UNIVERSITY content were gineering clinic at Rowan is unique to engineer-
Robert’s next decision was whether to accept incorporated into ing education in that engineers are actively
a job offer from a British university or one from the engineering engaged in hands-on engineering science and
Tulsa University in Oklahoma. He had intro- clinic starting practice through the interdisciplinary clinic
duced Fiona to San Francisco at the 1989 AIChE from the time of for eight semesters.
annual meeting and apparently convinced her his first inter-
that the rest of the United States was just like view at Rowan ENGINEERING CLINIC SEQUENCE
San Francisco, so Tulsa won out. University. As a founding faculty member of the Col-
At Tulsa Robert was profoundly influenced lege of Engineering, Robert has taken a lead-
in engineering education by his colleagues Ri- ing role in developing the engineering clinic
chard Thompson, Ramon Cerro, and Martin Abraham. As program—one of the most innovative vehicles for educating
Department Chair, Rich Thompson introduced Robert to the engineers. Starting from the novel hands-on freshman semes-
American Society of Engineering Education by sending him ters in measurement and reverse engineering, he has influ-
to his first Chemical Engineering Summer School in Mon- enced each subsequent engineering clinic. In the sophomore
tana. The friendships he formed at this first summer school clinic, he started the detailed planning of the original linkage
helped guide him as an engineering educator. Rich Felder between the writing faculty and the engineering projects. This
and Rebecca Brent are still major influences on his teaching planning was further developed by Drs. Anthony Marchese
style. He has attended at least four effective-teaching work- and Jim Newell. The junior and senior clinics have been de-
shops and has avidly tried new teaching strategies from each veloped into industrially related engineering projects. Rob-
workshop. Based on these workshops, he has employed co- ert brought the first industrially funded project and helped
operative learning and an inductive teaching style in his formulate the Clinic Affiliates program where industry is
classes. He has also gained important aspects of teaching from asked to sponsor engineering clinic projects for the junior
educational leaders such as Jim Stice (instructional objec- and senior years. The upper-level engineering clinic has been
tives) and Don Woods (problem-based learning). vertically integrated by having juniors, seniors, and graduate
Robert also developed a successful teaching and research students work on projects funded by industry and the gov-
program at Tulsa and ultimately received three teaching ernment. He has also worked on integrating the Rowan hall-
awards, including Professor of the Year in the College of En- marks into the syllabus of the clinic. None of these achieve-
gineering and Applied Sciences. By the end of his tenure in ments would have been possible without the energetic, inno-
Tulsa, he had obtained $670,000 in external funding, includ- vative, idea-generating faculty of the engineering college.
ing NSF Research Initiation and DuPont Young Professor Robert works with every member of the chemical engi-
awards. An outlet for Robert’s teaching enthusiasm was found neering faculty on industrial and classroom projects. He serves
in a series of three NSF Young Scholars Programs at Tulsa, as a mentor for faculty to bring in these projects and has
Winter 2003 11
worked with our chemical engineering faculty on almost ev- calculate material and energy balances on two heat exchang-
ery industrial project. As a result, his industrial involvement ers. First, the students used their readings as input for a chemi-
has included relationships with companies such as Johnson cal process simulation, using HYSYS, to determine the heat
Matthey, Sony Music, Givaudan-Roure, Campbell Soup Co., duty for each heat exchanger. Then for homework they manu-
Pepperidge Farm, Value Recovery, General Mills, and ally calculated the heat duty using all of the engineering equa-
DuPont. Because of this industrial involvement, Robert has tions used by the simulator. This experience was a simula-
had the opportunity to work in fields such as supercritical tion of the day in the life of a chemical process engineer–
fluid extraction, microfiltration, liquid-liquid extraction, elec- truly a unique experience for freshmen.
trochemical separations such as plating and electrodialysis, ad-
sorption, and ion exchange. He says that the clinic experience COOPERATIVE LEARNING
is one of the greatest joys of his work at Rowan University. Robert uses the technique of cooperative learning in his
courses. He creatively employs cooperative learning in lec-
FRESHMAN ENGINEERING CLINIC tures and in homework and semester design projects. In the
In the Freshman year of the clinic, Robert uses a common classroom, students form small groups and within a short
consumer product, the coffee period of time solve engineering
machine, as a vehicle for illus- problems. Robert creatively
trating engineering science and works with these groups to help
practice. It contains examples them focus on the problem dur-
of engineering principles from ing this session. Using coopera-
many disciplines. For example, tive learning in the classroom
chemical and mechanical engi- creates an active learning expe-
neers are required to design rience for students and improves
heaters, condensers, and sys- their retention of the material
tems for multiphase transport of over a pure lecture format. In
fluids, and to fabricate plastic group homework and design
and glass components. The pro- problems he has employed a va-
cess of leaching the organic riety of assessment tools to make
compounds from the coffee each person in the group account-
beans uses principles from mass Robert examining the internals of a able for achieving all the objec-
coffee machine.
transfer, which is unique to tives. This technique is at the
chemical engineering. Automa- forefront of engineering educa-
tion of processes requires concepts from electrical, mechani- tion methods and Robert’s use of it shows that he is at the
cal, and chemical engineering. Finally, engineering decisions leading edge of teaching pedagogy.
are required to select the components of a system and place
them within an affordable, compact unit that can be easily INDUCTIVE LEARNING
used by the consumer. This innovative example has been Robert has been transforming his courses so that both the
adopted for use at many other institutions. Robert has contin- content and the lecture format are in an inductive order. With
ued his development of the freshman clinic with Dr. Stephanie the inductive order of presentation the professor starts with
Farrell in grants from the National Science Foundation on an experiment, demonstration, or the results of an experiment
reaction engineering and drug delivery. and finishes the lecture with the derivation and solution of
The first year the coffee machine was used, the students equations describing these results. The second concept is plac-
not only reverse engineered the unit, but also designed a ing the course content in an inductive order. For example,
new system. This is the only project I am aware of where heat transfer could be taught starting with heat exchangers
the students actually used what they were making so that and overall heat transfer coefficients followed by sections on
they could do an “all-nighter” to ready their final presen- the factors that contribute to the overall heat transfer coeffi-
tations in freshman clinic! cient, such as conduction and convection. Finally this area
Another innovation Robert incorporated into the freshman of transport could end with coverage of unsteady-state
clinic is a module on process measurements using the heat transfer. Each of the lectures presented in this novel
university’s cogeneration facility. He worked with the plant’s topical order can be done in an inductive manner, starting
director to set up tours for each of the five sections (115 stu- from experimental observations and ending with a deri-
dents). On the tour, students took readings of pressure, tem- vation and solution of the governing equation. Robert has
perature, and flow from gauges, thermometers, and the plant’s been working with Stephanie Farrell on converting lec-
data-acquisition system. They used these measurements to tures, courses, and labs to an inductive order for fluid
Winter 2003 13
ChE classroom
INTRODUCING THE
STOCHASTIC SIMULATION OF
CHEMICAL REACTIONS
Using the Gillespie Algorithm and MATLAB
T
here are two main approaches to numerically model ganisms. McAdams and Arkin[4] have pointed out that
and simulate the time evolution of chemical reacting . . . Even in clonal cell populations and under the most uniform
systems. In the deterministic approach, the set of dif- experimental conditions, considerable variation is observed in the
ferential equations describing the time evolution of the con- rates of development, morphology, and the concentration of each
molecular species in each cell. These fluctuations . . . play a
centrations is solved using either analytical or numerical meth-
fundamental role in the evolution of the living systems. . . .
ods such as Euler or Runge-Kutta. It is assumed that the com-
plete time evolution of the reacting system is contained in These fluctuations may be predicted and explained by the
the solution of the set of equations, i.e., given a set of initial stochastic models but not by the deterministic ones.
conditions, only one trajectory is possible. In this paper, a Traditionally, the deterministic methods are by far the most
trajectory is a concentration-time curve. It corresponds to a commonly used in modeling the time evolution of chemical
reacting species in a given experiment and describes the time
evolution of the reacting system in such an experiment.
Joaquín Martinez Urreaga is Associate Pro-
In the stochastic approach, each individual reaction is con- fessor in the Department of Industrial Chemical
Engineering at the Universidad Politécnica de
sidered a random event that can take place with a certain prob- Madrid, Spain. He received his MSc (1982) and
ability. Thus the time evolution of the concentrations depends PhD (1988) from the Universidad de Zaragoza
(Spain). His current fields of interest include
on a series of consecutive probabilistic events. Given a set of teaching chemistry and research on interfaces
initial conditions, there are many possible trajectories, each and degradation in materials.
with its own probability and with the sum of probabilities
adding up to one. These trajectories may be drawn by using
the probabilistic rate law.
José Mira obtained a Masters Degree in En-
The increasing interest of stochastic methods has been gineering in 1986 and in 1995 a PhD in Ap-
pointed out by Schieber in this journal.[1] More recently, plied Statistics, both from the Universidad
Politécnica de Madrid. He is presently an As-
Scappin and Canu[2] have reviewed the use of stochastic mod- sociate Professor at that University.
els for simulating the dynamics of complex chemical sys-
tems and have shown that these models allow for easy iden-
tification of the main reaction paths in reacting systems in-
volving hundreds of elementary steps. Camino González-Fernández obtained her de-
gree in Nuclear Engineering in 1987 and her
[3,4]
In addition, several other authors have pointed out that PhD in 1993, both from the Universidad
Politécnica de Madrid. She is Associate Pro-
deterministic models cannot accurately simulate the dynam- fessor in the Department of Statistics at the
ics of systems in which the time evolution depends on the Universidad Politécnica de Madrid. Her current
fields of interest include teaching and research
behavior of a very small number of molecules. Interesting on applied statistics.
examples of such systems are individual cells in living or-
O
ne of the major objectives of a thermodynamics system, this paper demonstrates the construction of three-di-
course is to introduce the modeling of vapor-liquid mensional, P-xy-T, phase envelopes based on two indepen-
equilibrium (VLE). Over the past 25 years, Profes- dent procedures in Mathcad; both examples have served as
sor Kenneth Jolls has developed visual aides to graphically the templates in our pedagogical process. In the first approach,
demonstrate various thermodynamic functions and phase dia- the phase envelope is constructed based on Barker’s algo-
grams. According to Dr. Jolls, “One of the problems with rithm along with the Wilson equations and virial EOS for the
thermodynamics is that, to many students, it has no solid be- estimations of the activity coefficients and fugacity coeffi-
ginning. It doesn’t start with concrete notions.”[1] The devel- cients, respectively. In the second approach, the phase dia-
opment and implementation of three-dimensional graphics gram is constructed based on the Peng-Robinson equation of
facilitate the cognition of important building blocks of chemi- state along with the one- and two-parameter models of the
cal engineering thermodynamics. Its significance is also re- van der Waals mixing rule. Regression of three sets of P-xy
flected by the fact that P-xy-T phase diagrams are shown on data at three different temperatures yields the parameters
the covers of the newest editions of the two popular text- in these governing equations. Using these parameters, the
books on chemical engineering thermodynamics.[2,3] P-xy-T envelopes were generated and extended to the
There have been various engines used to generate three- mixture’s critical region.
dimensional graphs. In Dr. Jolls’s earliest attempts to display MODEL DEVELOPMENT AND DISCUSSION
the steam tables graphically, a simple, locally developed 3-D
graphing program was used to generate the plots.[1,4,5] Since The experimental data used for the VLE modeling was
that time, he has used more sophisticated software to pro- obtained from Hermsen and Prausnitz.[6] The data included
duce more complicated plots. For example, he used the graph- total pressures and liquid-phase compositions for the ben-
ing package MOVIE.BYU[1] to produce the three-dimensional zene/cyclopentane system at three temperatures: 25°C,
surfaces of the Peng-Robinson equation of state (PR EOS). 35°C, and 45°C. The component properties were obtained
Using these drawings, the unstable, metastable, and stable zones from Reid, et al.[7]
can easily be illustrated. He has also developed three-dimen-
Jasper L. Dickson received his MS and BS in Chemical Engineering from
sional graphs for the ideal and the van der Waals gases as well the University of Mississippi. He is currently pursuing a PhD in Chemical
as the Joule-Thomson expansion coefficient.[1] Engineering at the University of Texas at Austin. His research interests
have been in the area of colloid science.
Several commercial software packages have been devel- John A. Hart, IV is a graduate student at the Department of Chemical
oped over the years for various computational applications Engineering of the University of Mississippi. He has received his BS in
Forensic Chemistry and his BS in Chemical Engineering from the Univer-
in teaching, including the construction of three-dimensional sity of Mississippi also. His research interest is environmental remediation.
diagrams. At the University of Mississippi, Mathcad is intro- Wei-Yin Chen is Professor of Chemical Engineering at the University of
duced early in the chemical engineering curriculum and is Mississippi. His teaching and research interests have been in reaction
engineering, thermodynamics, and mathematical modeling. He received a
used as one of the computational tools for courses at differ- PhD in Chemical Engineering from the City University of New York, an MS
ent levels; it is also selected as the principal computational in Chemical Engineering from the Polytechnic Institute of New York, an
MS in Applied Mathematics and Statistics from the State University of New
workhorse for courses on thermodynamics. York at Stony Brook, and a BS in Chemical Engineering from Tunghai
University.
Using limited P-x and P-xy data of a benzene/cyclopentane
© Copyright ChE Division of ASEE 2003
b i PV P( V − b )
2
∑ y ja ji
( )
b i V + 1 + 2 b
a
ln φ i = − 1 − ln − j
− ln ( 4)
b RT RT 2 2 bRT
a (
b V + 1− 2 b
)
CONCLUSIONS
Vapor-liquid equilibrium data were modeled in Mathcad
using both Barker’s algorithm and the Peng-Robinson cubic
equation of state model. Using the experimental data at three
temperatures, Mathcad was capable of calculating the neces-
Figure 3. Extended phase envelope developed by Barker’s sary parameters for each of the two models. Once the param-
algorithm. eters were determined, Mathcad was used to predict the sys-
tem pressure and the vapor- and liquid-phase compositions.
Both models yielded reasonable fits with the experimental
data. The three-dimensional P-xy-T phase diagrams were then
extended to the mixture’s critical region. The data reduction
procedures described herein are representative for students
who are learning VLE for the first time; moreover, the three-
dimensional phase envelopes give students concrete notions
concerning the phase behaviors.
REFERENCES
Figure 4. Phase envelope developed by Peng-Robinson equa- 1. Jolls, K.R., “Visualization in Classical Thermodynamics,” Proc. ABET
tion of state and two-parameter van der Waals mixing rule. Ann. Meet., p. 28 (1996)
2. Sandler, S.I., Chemical and Engineering Thermodynamics, 3rd ed., Wiley,
New York (1999)
3. Smith, J.M., H.C. van Ness, and M.M. Abbott, Introduction to Chemical
Engineering Thermodynamics, 6th ed. McGraw-Hill, New York (2001)
4. Balbuena, P.B., “An Eye for the Abstract,” Science, 286, p. 430 (1999)
5. Jolls, K.R., and K.S. Tian, “Fluid-Phase Equilibria from a Chemical Pro-
cess Simulator,” Paper presented at the Annual Meeting of the ASEE,
Milwaukee, WI (1997)
6. Hermsen, R.W., and J.M. Prausnitz, “Thermodynamics Properties of the
Benzene and Cyclopentane System,” Chem. Eng. Science, 18, p. 485
(1963)
7. Reid, R.C., J.M. Prausnitz, and B.E. Poling, The Properties of Gases
and Liquids, 4th ed., McGraw-Hill, New York (1987)
8. Prausnitz, J.M., R.N. Lichtenthaler, and E.G. de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, 3rd ed., Prentice Hall, New
Jersey, p. 236 (1999)
Figure 5. Extended phase envelope developed by Peng- 9. Orbey, H., and S.I. Sandler, Modeling Vapor-Liquid Equilibria, Cubic
Robinson equation of state and two-parameter van der Waals Equations of State, and Their Mixing Rules, Cambridge University Press,
mixing rule. New York (1998) ❐
Winter 2003 23
ChE curriculum
FRONTIERS OF
CHEMICAL ENGINEERING
A Chemical Engineering Freshman Seminar
I
n this paper we will describe a new seminar elective for We feel that our chemical engineering profession has an
freshman engineering students titled “Frontiers of Chemi- obligation to educate prospective chemical engineering stu-
cal Engineering.” We have designed the seminar to in- dents regarding the broad applicability of chemical engineer-
troduce freshmen to the field and profession of chemical en- ing principles, the multitude of available career paths, and
gineering by using examples from cutting-edge research to the many other opportunities that our graduates normally re-
illustrate fundamental concepts. Exposing students to chemi- ceive. Such information should be made available to students
cal engineering in their first semester provides an earlier as early as possible—certainly to new students in the first
chance for them to catch the excitement of chemical engi- semester of their freshman year.
neering and should help them make better-informed decisions Many engineering programs across the country have modi-
regarding their educational plans. fied their freshman curricula to address these challenges. A
Chemical engineering students at many universities receive variety of approaches has been used, including general engi-
little, if any, exposure to chemical engineering as freshmen. neering courses, design-based courses, [1-4] orientation
For example, at Vanderbilt University freshman chemical courses,[5-8] and seminars.[9-11] General engineering courses
engineering majors primarily take large lecture courses in bring together students from all engineering majors to pro-
math, physics, chemistry, and general engineering. Their vide a consistent grounding in basic engineering principles
sophomore year consists of only a single chemical engineer- and skills, such as engineering problem solving, communi-
ing course each term, along with organic chemistry, math, cation tools and skills, basic computer literacy, mathematical
and physics. This traditional curriculum leaves students with
few opportunities to interact with professors in their major
Frank Bowman is Assistant Professor of Chemical Engineering at
until their junior and senior years. Additionally, the large in- Vanderbilt University. He received his BS from Brigham Young Univer-
troductory lecture courses of the freshman year, which of- sity in 1991 and his PhD from Caltech in 1997, both in chemical engi-
ten provide little opportunity for student involvement, set neering. His research interests include atmospheric aerosol modeling
and chemical mechanism analysis.
a pattern of expectation, hopefully incorrect, for the learn- Robert Balcarcel is Assistant Professor of Chemical Engineering at
ing and teaching methods to be used throughout the re- Vanderbilt University. He received his BS from the University of Califor-
nia, Berkeley, in 1993 and his PhD from MIT in 1999, both in chemical
mainder of their program. engineering. His research interests include improvement and metabolic
engineering of mammalian cell cultures for biopharmaceutical produc-
Compounding these problems, most freshmen have a poor tion and analysis of chemical and biological agents.
understanding of the engineering profession in general and Kane Jennings is Assistant Professor of Chemical Engineering at
chemical engineering in particular. Often, students do not Vanderbilt University. He received his BS in chemical engineering from
Auburn University in 1993, an MS in chemical engineering practice from
begin to see the big picture of the chemical engineering pro- MIT in 1996, and a PhD in chemical engineering from MIT in 1998. His
fession until the senior capstone design course. Consequently, research is focused on ultrathin organic films.
Bridget Rogers is Assistant Professor of Chemical Engineering at
they form impressions of chemical engineering, make deci- Vanderbilt University. She received her PhD and MS degrees from Ari-
sions on which major to pursue, and set expectations for zona State University and her BS degree from the University of Colo-
rado, Boulder, all in chemical engineering. Her research program fo-
the college learning environment early in the college ca- cuses on film formation, microstructure evolution, and material proper-
reer—all based almost entirely on non-engineering courses ties of UHV-CVD deposited high permittivity dielectric thin films.
and professors.
© Copyright ChE Division of ASEE 2003
Winter 2003 25
the need for teamwork as well as the need to be informed with discussions of student-selected current issues in at-
about how the unit processes of a production flow affect those mospheric pollution such as global warming, the ozone
preceeding and following it. hole, and urban smog.
The class meets for 75 minutes once a week for a total of To teach students about molecular self-assembly, the in-
15 weeks. An outline of course topics from the fall 2001 semi- structor uses a hands-on demonstration involving the forma-
nar is shown in Table 2. When the course was taught in fall tion of a self-assembled monolayer to convey introductory
2000, the semiconductor fabrication unit was not included, chemical engineering concepts in both thermodynamics and
and the other research units were each expanded to four weeks. kinetics. Since chemical engineers should ultimately develop
The design of the course is such that different research units a molecular perspective, this unit also emphasizes how mo-
can rotate or be replaced from year to year depending on fac- lecular-level effects can influence macroscopic surface prop-
ulty availability and interest. erties. For example, the students find it extremely interesting
Class sessions take a variety of forms. The “Chemical En- and intuitive that a hydroxyl-terminated self-assembled mono-
gineering” and “Tying it All Together” sessions at the begin- layer is wet by water while a methyl-terminated monolayer
ning and end of the semester are taught by all of the profes- repels water. The instructor also discusses the potential ap-
sors. As part of the first class, small groups of three to four plications of these monolayer films to introduce students to
students and a professor work to develop lists of chemical- fundamental concepts in separations and mass transfer.
engineering-related products and companies. For the last class, While studying semiconductor fabrication, students are
similar groups create lists of the research topics discussed introduced to the unit operations of a typical process flow for
and match them up with the underlying chemical engineer- a complementary metal-oxide-semiconductor (CMOS) tran-
ing principles (see Table 3). sistor. A video tape is used to help students visualize the clean-
Homework assignments are given out each week. They room environment and the process equipment used in micro-
contain a mixture of writing, data analysis and interpretation, electronics manufacturing. After viewing the video, the class
mathematical calculation, and experimental design. Students participates in a group exercise focused on one of the process
are encouraged to collaborate on the homework but are re- steps. In 2001 we focused on chemical vapor deposition
quired to submit individual assignments. The homework con- (CVD). This exercise started with a brief lecture of the mecha-
tributes 70% to the course grade, with a comprehensive final nisms involved in CVD—transport of reactants into the re-
exam worth 30%. actor, diffusion of reactants to the substrate’s surface, re-
action, surface diffusion of adatoms to form islands lead-
The seminar enrolled 9 students in 1999, 11 students in
2000, and 13 students in 2001. Each year, approximately TABLE 2
half the students intended to major in chemical engineer- Course Topics
ing, with the other half divided among the other engineer-
ing majors or undecided. Week Topic
Research Units 1 Chemical Engineering, Profession and Curriculum
The research units are taught by individual professors and Semiconductor Manufacturing
are structured to take advantage of their respective research 2 Microelectronic Device Processing
programs. Each of the units is described below. The semi- 3 Silicon Oxidation
4 Chemical Vapor Deposition
conductor manufacturing and biopharmaceutical production
units are discussed in greater detail to illustrate the level at Atmospheric Particles
which material is presented. While each research unit fo- 5 Particles in the Atmosphere
cuses on a specific research area, an important objective 6 Why do Particles Grow?
7 How Fast do Particles Grow?
is to illustrate the underlying chemical engineering prin-
ciples that are common to all areas. Table 3 summarizes Biopharmaceutical Production
four of the main principles that are highlighted through- 8 Biotechnology and Cell Culture
out the course and examples of how they are presented in 9 Producing a Therapeutic Protein: Part I
10 Producing a Therapeutic Protein: Part II
the different research units.
For the atmospheric particles unit, students spend most of Molecular Self-Assembly
the class period working in groups with a computer model 11 Chemistry of the Kitchen Sink: An Introduction to Self-Assembly
12 Self-Assembled Monolayer Films
that simulates gas-particle equilibrium and growth. They use 13 Use of Molecular Films in Corrosion Prevention
the model to run simulated experiments and try to discover
how variables such as particle size, number concentration, 14 Tying it All Together
vapor pressure, temperature, and diffusivity influence par-
15 Final Exam
ticle growth. These computer exercises are supplemented
Winter 2003 29
Random Thoughts . . .
HOW TO
SURVIVE ENGINEERING SCHOOL
RICHARD M. FELDER
North Carolina State University • Raleigh, NC 27695
TIP 2 TIP 5
Read Believe that you have what it takes
Some textbooks try to clarify difficult material by giving to be a good engineer.
practical illustrations and explanations. Check out those parts If this advice is hard for you to take now, you’re probably
of your text if you’re having trouble rather than just search- suffering from what psychologists refer to as the Impostor
ing for solved examples that look like the homework prob- Phenomenon, which is like a tape that plays inside people’s
lems. Another good strategy is to look at a second refer- heads. If you’re an engineering student looking around at your
ence on the same subject—a different text, a handbook, classmates, the tape goes something like this: “These people
or a Web site. Even if you can’t find the crystal-clear ex- are good—they understand all this stuff. They really belong
planations and examples you’d like, just reading about here…but I don’t. Over the years I’ve somehow managed to
the same topic in two different places can make a big dif- fool them all—my family, my friends, my teachers. They all
ference in understanding. think I’m smart enough to be here, but I know better…and
the very next hard test or hard question I get in class will
TIP 3 finally reveal me as the impostor I am.” And what would
Work with other students happen next is too horrible to contemplate, so at that point
When you work alone and get stuck on something, you you just rewind and replay the tape.
may be tempted to give up, where in a group someone can What you don’t know is that almost everyone else in the
usually find a way past the difficulty. Working with others class is playing the same tape, and the student in the front
may also show you better ways to solve problems than the row with the straight-A average is playing it louder than any-
way you have been using. Here are two ideas for making one else. Furthermore, the tape is usually wrong. If you sur-
groupwork effective. vived your first year of engineering school, you almost cer-
Outline problem solutions by yourself first and then work tainly have what it takes to be an engineer. Just remember all
out the details in your group. Someone in every group is gen- your predecessors who had the same self-doubts you have
erally fastest at figuring out how to start problem solutions now and did just fine. You do belong here, and you’ll get
and does it for every problem. If that student isn’t you, you through it just like they did. Try to relax and enjoy the trip.[1]
may have to figure it out for the first time on the test, which Sincerely,
is not a particularly good time to do it. Outlining the solu- Richard Felder
tions before meeting with the group is the way to avoid this
disaster.
1. For more about student survival skills and the Impostor Phenomenon,
Get group members—especially the weaker ones—to see <www.ncsu.edu/felder-public/Student_handouts.html>
All of the Random Thoughts columns are now available on the World Wide Web at
http://www.ncsu.edu/effective_teaching and at http://che.ufl.edu/~cee/
Winter 2003 31
INTRODUCTION
TO SPECIAL SECTION ON
MEMBRANES IN
CHEMICAL ENGINEERING EDUCATION
Andrew L. Zydney
The Pennsylvania State University • University Park, PA 16802
When I was an undergraduate studying chemical en- logically,” beginning with examples of how to introduce
gineering, there really was no significant membrane in- membrane technology in the Introduction to Chemical
dustry worth mentioning. That has certainly changed. Engineering course and then moving through examples
Today, the membrane industry has sales of several bil- in mass transfer, separations, the undergraduate labora-
lion dollars a year. This includes major applications in tory, and senior design. The specific problems/examples
the treatment of kidney disease by hemodialysis, the cover the full range of membrane applications, includ-
separation of commodity gases such as oxygen and ni- ing problems in
trogen, the purification of therapeutic proteins and phar-
maceuticals, and the treatment and desalination of natu- 1) Design of appropriate hemodialysis therapy for the
ral and industrial waters. treatment of kidney disease
2) Optimization of gas separations using hollow fiber
About two years ago, the North American Membrane modules
Society conducted a survey to determine the extent to 3) Removal of impurities from therapeutic proteins using
which membrane science and technology was covered membrane diafiltration
in the undergraduate chemical engineering curriculum. 4) Desalination of salt water by reverse osmosis or
This survey revealed a number of programs with sig- electrodialysis
nificant membrane-related material, including specific 5) Recovery of precious metals from spent catalysts
laboratory experiments, open-ended design problems, 6) Concentration of apple juice using ultrafiltration
and significant sections in both core and elective ChE 7) Production of ethylene in a ceramic membrane reactor
courses. In most cases, however, the teaching was done Our hope is that these papers will provide faculty with
by only one or two “experts,” typically faculty who had examples that they can use in their classes so that all
significant personal experience in the membrane field. chemical engineering undergraduates can be exposed to
Departments that had no faculty working on membranes some of the important principles and applications of
tended to have little if any coverage of membrane prob- membrane technology. The authors have tried, wherever
lems within their undergradute programs. possible, to provide sufficient details and references so
Motivated in large part by the results of this survey, that faculty can use these examples in their teaching. In
the Membrane-Based Separations Area and the Educa- addition, all of the authors have indicated they would be
tion Division of the AIChE decided to co-sponsor a ses- happy to answer questions about the problems, and sev-
sion on Membranes in the Chemical Engineering Cur- eral of the papers contain URLs that provide links to
riculum at the 2001 Annual Meeting. The session was more detailed descriptions of the process simulators or
an enormous success, with a series of fascinating pre- lab experiments.
sentations covering a wide range of membrane problems The North American Membrane Society (NAMS) will
within the undergraduate curriculum. The papers pre- also be hosting an education section on its website
sented in this issue of Chemical Engineering Education (www.membranes.org), and anyone who is using these
are a direct result of this session, and I would like to (or other) membrane problems within their courses is
personally thank Tim Anderson for his encouragement strongly encouraged to contact NAMS so that this infor-
and support in putting this special issue together. mation can be disseminated as effectively as possible
The papers that follow have been organized “chrono- throughout the chemical engineering community.
ANALYSIS OF
MEMBRANE PROCESSES
In the Introduction-to-ChE Course
ANDREW L. ZYDNEY
University of Delaware • Newark, DE 19716
T
he introductory course in most chemical engineering for the rate of inflow and outflow, and they provide little
departments is designed to meet a broad range of edu- opportunity for the students to think about process design
cational goals. They typically include: 1) providing considerations.
information that will enable students to determine if chemi- The University of Delaware uses the text by Russell and
cal engineering is the “correct” major for them; 2) providing Denn[4] as the basis for its introductory chemical engineering
a foundation for subsequent courses in the curriculum; and course, which is taught in the spring semester of the fresh-
3) teaching significant chemical engineering principles, par- man year. The course is divided into three main sections:
ticularly in the area of mass balances.[1] Traditional introduc-
• Transient mass balances in nonreacting systems
tory courses, e.g., those based on the classical book by Felder
• Transient mass balances in reacting systems, including the
and Rousseau,[2] focus primarily on the use of steady-state
analysis of batch reactors and CSTRs
mass (and energy) balances to describe the behavior of a wide • Interfacial mass transfer
range of chemical processes. These courses often include a
small section on transient processes at the end of the semes- The traditional material in this course has been supplemented
ter, such as Chapter 11 in the Felder and Rousseau[2] text or with a series of membrane problems specifically designed to
Chapter 7 of Himmelblau.[3] Russell and Denn[4] take a very illustrate the key concepts involved in the analysis of tran-
different approach, emphasizing transient balance equations sient mass balances. These membrane problems are “real,”
right from the beginning. This approach has the advantage of they are easy for students to relate to, they tend to be much
allowing the instructor to focus on the key concepts of “rate” more interesting than the traditional tank draining and filling
and characteristic times, an aspect that is often lost in courses problem, they provide a much better introduction to the range
that emphasize steady-state processes. of problems and application areas of interest to chemical en-
gineers, and they give students an opportunity to think about
One of the challenges of introducing students to transient real design issues, even when they are freshmen.
mass balances is a lack of interesting and effective problems
that analyze the behavior of non-reacting systems (batch re- APPLE JUICE CONCENTRATION
actor problems provide a very effective introduction to time-
USING REVERSE OSMOSIS
dependent reacting systems). Russell and Denn[4] devote more
than an entire chapter to the analysis of draining and filling Apple juice can be concentrated by a reverse osmosis sytem
tanks—a problem that illustrates the important concepts but
one that generates very little excitement and enthusiasm Andrew Zydney is currently Professor and
Endowed Chair in the Department of Chemi-
among the students. Himmelblau[3] also uses the tank drain- cal Engineering at The Pennsylvania State Uni-
ing problem as a primary example, along with problems on versity. He received his PhD from MIT in 1985
diluting a salt solution with water. Felder and Rousseau[2] try and was a faculty member at the University of
Delaware from 1985 to 2001. He has been
to make the tank draining problem a little more interesting actively involved in membrane research for
by examining the water level in a reservoir during a period of more than twenty years, with emphasis on bio-
technological and biomedical applications.
drought and the water volume in a storage tank that has a
leak. But students often see these problems as artificial, in
part because of the seemingly arbitrary functions given
© Copyright ChE Division of ASEE 2003
Winter 2003 33
Membranes in ChE Education
using the fed-batch process shown in Figure 1. Fresh juice is where the concentration of flavor components in the recycle
fed to a recycle tank, with the juice from the recycle tank tank at the start of the process is equal to Cfeed. This equation
then passing through the reverse osmosis unit where water is can be easily solved for the final concentration of flavor com-
removed through the membrane. The concentrated juice is ponents, with t evaluated as the time required to process
returned to the recycle tank—the system is designed to oper- 10,000 L of juice (or in this case, to add 9,500 L of juice to
ate so that the volume in the recycle tank remains constant the 500 L initially present in the recycle tank). The overall
throughout the process. At the end of the process, a concen- flavor recovery is then evaluated as the ratio of the final mass
trated juice product is obtained in the recycle tank. It can be of flavor components in the juice (VCfinal) to the initial mass
frozen and sold as “apple juice concentrate” or the concen- of flavor components
trated juice can be shipped and then reconstituted at a remote
site by simply adding water. This latter process can lead to V − V
V − V(1 − S) exp −S total
significant cost-savings since a much smaller volume of juice VC final V
Recov ery = =
needs to be shipped across the country. One of the concerns Vtotal C feed SVtotal
with this process is that the membrane is never “perfect,”
meaning that there will be a small loss of flavor components
( 4)
through the membrane during the concentration process. This where Vtotal is the total amount of juice (in this case, 10,000
is why many juice companies will specifically advertise on L).
the label that their juice is “not from concentrate.” Cheryan
and Alvarez[5] provide a more detailed discussion of mem- In addition to solving the mass balance equations, there are
brane processes for juice concentration. a number of interesting design issues that the students can
begin to think about, such as what would happen to the final
The goal of the problem is to evaluate the fraction of flavor concentration of flavor components in the recycle tank if it
components that are lost during a process designed to take were poorly mixed. For example, if the recycle stream is re-
10,000 L of fresh juice and produce 500 L of apple juice con- turned to the top of the recycle tank, then the concentration
centrate. To simplify the analysis, we assume that the con- of flavor components will be lower in the bottom of the tank
centration of flavor components in the filtrate stream collected (near the tank exit), which will reduce the amount of flavor
through the membrane is equal to a certain fraction (S) of the that is lost through the membrane. Although this situation
flavor concentration in the stream that enters the membrane cannot be modeled quantitatively this early in the curricu-
unit. This latter assumption is simply the definition of the lum, the qualitative behavior of the system is quite easy to
membrane sieving coefficient. This type of constitutive rela- explain. The discussion of mixing provides a great opportu-
tion must be determined experimentally, playing a role analo- nity for the instructor to talk about the residence time in the
gous to the rate expression in batch reactor problems.[4] recycle tank and the different design approaches that can be
The problem is solved by writing both total and compo- used to achieve good mixing in a large tank.
nent mass balances around the recycle tank and the reverse The students can also be asked to consider what (if any)
osmosis unit (shown by the dashed line in Figure 1): difference would occur if the juice concentration were ac-
complished using a batch process instead of the fed-batch
d(ρV) system shown in Figure 1. In this case, all of the juice is
= ρ feed Q feed − ρ filtrate Q filtrate (1)
dt placed in a single large tank, the feed stream entering the
d(VC)
= Q feed C feed − SQ filtrate C (2 )
dt
C − SC SQ feed t
ln feed = − (3)
(1 − S)C feed V Figure 1. Fed-batch system for producing apple juice
concentrate.
Winter 2003 35
Membranes in ChE Education
including the need to achieve essentially complete virus re- readily developed by integration of Eq. (9) to give
moval/inactivation while at the same time avoiding denatur-
ation of the recombinant protein product and minimizing C Vblood Vblood
potential complications from the presence of trace amounts ln blood 1 + − =
C blood,0 Vdialysate Vdialysate
of any viral inactivation agents. It is important for students
to recognize that even though the membrane diafiltration 1 1
is very effective at removing residual solvents and deter- − k m At + (11)
gents, it is impossible to achieve 100% removal of these Vblood Vdialysate
components using a finite volume of diafiltration buffer—
where Cblood,0 is the urea concentration in the blood at the start
the exponential decay provides an asymptotic approach
of the dialysis. It is easy to show that Eq. (11) approaches the
to zero concentration.
steady-state solution in the limit of t → ∞ as required.
UREA REMOVAL DURING HEMODIALYSIS After analyzing the transient hemodialysis system, the stu-
dents can think about why this isn’t the way hemodialysis is
Another interesting membrane problem that is readily in-
actually performed clinically. Most students recognize the
corporated into the introductory mass balance course is analy-
problem of having a large portion of the patient’s blood out-
sis of urea removal during hemodialysis.[8] Hemodialysis is
side of the body, and some will even appreciate the logistical
currently used to treat chronic kidney failure in more than
challenge of insuring that the right blood is returned to the
500,000 patients around the world—patients who would die
right patient. It thus becomes relatively easy to motivate the
within about two weeks without the availability of this type
need for using a continuous-flow system for hemodialysis
of artificial kidney. Urea removal in hemodialysis can first
(bottom panel of Figure 2). A simple solution for this prob-
be examined by analyzing a transient batch process for re-
lem can be developed by assuming that the urea concentra-
moving urea from blood across a semi-permeable membrane
tions are at steady state and that the blood and dialysate solu-
(top panel in Figure 2). The dialysate contains all the key
tions are both well-mixed. The steady-state assumption can
salts and sugars normally found in plasma to insure that
often be confusing since the urea concentration in the
these components aren’t removed during the dialysis. The
patient’s blood clearly decreases with time during the
membrane is impermeable to all blood cells and proteins,
hemodialysis. But the time constant for concentration
but it allows urea to be removed at a rate that is propor-
changes in the dialyzer is so much shorter than the time
tional to the concentration difference between the blood
constant for the body due to the small extracorporeal vol-
and the dialysate solution
ume, that it is appropriate to use this type of pseudo-
[
ṁ transfer = k m A C blood − C dialysate ] (8)
where km is the membrane mass transfer coefficient (or per-
meability) and A is the membrane area. Component mass
balances are written for the urea concentration in the blood
and in the total system (blood plus dialysate)
Vblood
dC blood
dt
[
= − k m A C blood − C dialysate ] ( 9)
dC blood dC dialysate
Vblood + Vdialysate =0 (10)
dt dt
where CBout and CBin are the urea concentrations in the blood SUMMARY
leaving and entering the dialyzer, and QB and QD are the The membrane problems described in this paper provide
blood and dialysate flow rates. More sophisticated solu- an attractive set of examples for introducing students to key
tions can be developed for countercurrent flow if the stu- concepts in the analysis of transient material balances in non-
dents are able to handle the concepts and mathematics reacting systems. Related problems can also be developed
required for analysis of the position-dependent differen- for the analysis of gas separation membrane processes (e.g.,
tial mass balances in this system.[8] the production of oxygen from air) and on the behavior of
Although the well-mixed analysis provides a simple ana- membrane reactors (e.g., the use of palladium membranes to
lytical expression, most students don’t immediately appreci- remove hydrogen and thereby improve product yield in equi-
ate the implications of the final result. For example, the analy- librium-limited dehydrogenation reactions).
sis clearly shows that the outlet urea concentration in the blood All of these membrane problems are of real commercial
doesn’t go to zero as the membrane area becomes infinite. In interest, they provide students some exposure to new appli-
addition, this equation seems to imply that increasing the cation areas of chemical engineering, and they give the in-
blood flow rate is detrimental since it increases the urea con- structor an opportunity to introduce basic concepts of pro-
centration in the blood stream that is returned to the patient cess design at a very early stage in the curriculum.
(although it also increases the rate of urea removal from the Student response to these problems in the Introduction to
body). This leads nicely into a discussion of the key design Chemical Engineering course at the University of Delaware
criteria for the dialyzer. has been outstanding. They definitely appreciate being able
It is also relatively easy to couple analysis of the to analyze real-world problems even as freshmen, and they
hemodialyzer with the transient mass balances describing the clearly enjoy the opportunity to begin thinking about process
urea concentration within the body (treated as a well-mixed design issues. In addition, these membrane examples give
“tank”). The resulting equations can be used to examine the students a perspective into the kinds of problems and pro-
performance of a clinical dialysis session at reducing the urea cesses that they will encounter throughout their undergradu-
concentration to a safe level. Current clinical practice is for ate chemical engineering education.
patients with complete kidnez•¶ailure to undergo four-hour
dialysis sessions three times a week, 52 weeks a year. The REFERENCES
total cost of providing hemodialysis in the United States is 1. Solen, K.A., and J. Harb, “An Introductory ChE Course for First-Year
approximately $15 billion per year, essentially all of which Students,” Chem. Eng. Ed., 32(1), 52 (1998)
is paid by the Federal government. This is a great opportu- 2. Felder, R.M., and R.W. Rousseau, Elementary Principles of Chemical
Processes, 3rd ed., John Wiley & Sons, Inc., New York, NY (2000)
nity for a discussion about some of the ethical and economic
3. Himmelblau, D.M., Basic Principles and Calculations in Chemical
issues involved in the development and delivery of expen- Engineering, 6th ed., Prentice Hall, Upper Saddle River, NJ (1996)
sive new medical technologies, an issue that is likely to be- 4. Russell, T.W.F., and M.M. Denn, Introduction to Chemical Engineer-
come even more important in the coming years. ing Analysis, John Wiley & Sons, Inc., New York, NY (1972)
5. Cheryan, M., and J. Alvarez, “Food and Beverage Industry Applica-
Another hemodialysis design issue that can be worth dis- tions,” in Membrane Separations Technology: Principles and Appli-
cussing is the importance of minimizing the extracorporeal cations, R.D. Noble and S. A. Sterns, eds., Elsevier, Amsterdam (1995)
blood volume while maintaining a large surface area for mass 6. Glock, B.R., and J.J. Pasternak, Molecular Biotechnology: Principles
and Applications of Recombinant DNA, 2nd ed., American Society for
transfer. Current clinical dialyzers use a parallel array of more Microbiology Press, Washington, DC (1998)
than 10,000 narrow hollow fiber membranes (inner diameter 7. van Reis, R., and A.L. Zydney, “Protein Ultrafiltration,” in Encyclo-
of about 200 µm) to achieve a surface area of close to two pedia of Bioprocess Technology: Fermentation, Biocatalysis, and
square meters. Smaller diameter fibers, approaching the 6-8 Bioseparation, M.C. Flickinger and S.W. Drew, eds., pp 2197-2214,
John Wiley & Sons, Inc., New York, NY (1999)
µm diameter of the blood capillaries within the kidney, would 8. Galletti, P.M., C.K. Colton, and M.J. Lysaght, “Artificial Kidney,” in
further increase the ratio of surface area to blood volume. The Biomedical Engineering Handbook, Vol. II, 2nd ed., J.D. Bronzino,
Blood clotting becomes a major problem in these very nar- ed., CRC Press, Boca Raton, FL (2000) ❐
Winter 2003 37
Membranes in ChE Education
A PRESS RO SYSTEM
An Interdisciplinary Reverse Osmosis Project
for First-Year Engineering Students
A
ttempting to create a project that includes chemical, the support structure.[13] In very few cases does one project
civil, electrical, and mechanical engineering is a chal- include concepts from both chemical engineering and other
lenging task. At Lafayette College we try to include branches of engineering.
such a project in our Introduction to Engineering course. For many years, C.S. Slater (Rowan University) has devel-
While finding electro-mechanical projects is relatively easy, oped and advocated several reverse osmosis experiments
it is difficult to include the process nature of chemical engi- based on PUR brand portable RO systems.[5,14] Both the Uni-
neering in projects that are typically product oriented. versity of Minnesota at Duluth and Manhattan College have
Among engineering programs that use an introduction-to- also developed laboratories based on the PUR systems.[15,16]
engineering course, a wide range of projects and laboratories We have developed a project based on a simple dead-end
is used. At the 2002 ASEE annual meeting, several mechani- reverse osmosis (RO) test system at Lafayette College. The
cal or electro-mechanical projects were described, including equipment consists of a cylindrical vessel with a small pis-
a sundial, wind power for a ski resort public-transit system, ton-and-lever arm used to create the pressure. Each disci-
and an orbital sander.[1-3] At Rowan University, the Freshman pline examines different issues with the device: in the chemi-
Clinic provides a year-long lab experience with
multidisciplinary experiments that use measurement as the S. Scott Moor is Assistant Professor of Chemical Engineering at Lafayette
College. He received a BS and MS in Chemical Engineering from M.I.T.
theme.[4,5] They use a wide range of approaches and projects, in 1978. After a decade in industry he returned to academia at the Uni-
including reverse engineering, engineering analysis of the versity of California, Berkeley, where he received a PhD in Chemical En-
gineering and an MA in Statistics in 1995. His current research focuses
human body,[6] and the production of beer.[7] Recently, they on educational materials development and on the visualization of fluid
included a project that involves using a membrane fuel cell and transport dynamics in Wurster coating, in fluidized beds, and in spray
to charge batteries for a LEGO® Mindstorms robot.[8] drying.
Edmond Saliklis is Assistant Professor in the Department of Civil and
Many programs rotate through several different labs that Environmental Engineering at Lafayette College. He received his BS from
the University of Illinois-Chicago in 1984, his MS from Syracuse Univer-
illustrate different disciplines in order to include chemical sity in 1988, and his PhD from the University of Wisconsin-Madison in
engineering. At Notre Dame, a year-long introductory course 1992, all in Civil Engineering. His current research focuses on the me-
chanics of thin wood-based plates and thin concrete and masonry shells.
uses four projects with the LEGO Mindstorms brick—con-
Scott Hummel is Assistant Professor of Mechanical Engineering at
trol of pH is one of these four projects.[9] North Carolina State Lafayette College. He earned a BS at the University of Hartford in 1988,
uses a series of laboratories, one of which is a reverse osmo- an MS at Stevens Institute of Technology in 1996, and a PhD at Lehigh
University in 1998. His current research focuses on the wear properties
sis experiment.[10] At Virginia Tech several laboratories and of nonlubricated stainless steel components and on the LENS rapid
projects are used with one laboratory being focused on a prototyping process.
simple mass balance,[11] while Drexel University’s E4 program Yih-Choung Yu is Assistant Professor of Electrical and Computer Engi-
neering at Lafayette College. He received a BSEE degree from Chinese
uses a laboratory focused on measurements to introduce stu- Culture University in Taipei, Taiwan, in 1987, an MSEE degree from the
dents to engineering.[12] The environmental engineering pro- State University of New York at Binghamton in 1992, and a PhD degree
from the University of Pittsburgh. His research interests include control
gram at the University of Dayton uses a sand-and-charcoal applications for bioengineering and medical device development.
filter where students analyze both the filtration process and
© Copyright ChE Division of ASEE 2003
Winter 2003 39
Membranes in ChE Education
6). It also provides concrete examples of the application of complete version of the theory would include a second re-
each of the engineering disciplines (goal 7). It is hoped that flection coefficient.[19] Using the first two equations, students
the project will be interesting, enjoyable, and accessible to are able to complete a design problem determining a pres-
our first-year students. sure drop and membrane area that will meet a given purifica-
tion need. For these simple first-pass sizing problems, we
CHEMICAL ENGINEERING BLOCK assume that the solute flux will be negligible.
This project provides a wealth of chemical engineering top- The concepts behind these equations and their simplifica-
ics, including osmotic pressure, equilibrium, flux, rate based tions are explained to the students. We then ask them to evalu-
separation, and fluid processing. The general concepts of os- ate how well these concepts (particularly the simplifications)
motic pressure and solution equilibrium are discussed. The are playing out in our experimental system. A short section
van’t Hoff equation is used to estimate osmotic pressure in Perry’s on reverse osmosis and nanofiltration provides some
helpful conceptual background in a brief presentation.[20] The
∏ = CRT (1)
issues considered include the nature of membranes, recov-
where II is the osmotic pressure, C is the molar concentra- ery, concentration polarization, pretreatment, rate-based sepa-
tion of ions, R is the universal gas constant, and T is the ab- rations, and cartridge configurations.
solute temperature. This equation assumes a dilute ideal so- Concentration polarization is a particularly important is-
lution that follows Raoult’s law. For the solutions, we are sue. The salt concentration near the membrane is increased
using (0-14 g/l NaCl), the van’t Hoff equation predicts 3-5% because salt is being transported to the membrane by bulk
high and is adequate for our needs.[17] Wankat presents the flow, but then it is being retained by the membrane. This in-
theory for more accurate estimations of osmotic pressure for crease in concentration near the membrane affects the os-
other situations.[18] motic pressure and the potential flux of solute. A mass diffu-
There is some disagreement on the exact mechanism for sion model is required to estimate this effect.[18,21-23]
reverse osmosis, but the solution-diffusion theory is the most Students experiment on the press RO system, examining
widely accepted.[18,19] In this picture of membrane function, the impact of pressure and salt concentration on the purified
the membrane has no true pores. Rather, the membrane is water flow rate. They determine the water permeability con-
treated as a separate phase. The solvent and solute dissolve
in and diffuse through the membrane.
Students are then introduced to the concept of flux and its
proportionality to driving force. We present the simplified
case of the driving force as the pressure above osmotic. The
resulting equation for flux is
q
Jw = = A( ∆P − σ∆II ) (2 )
S
where Jw is the volumetric flux of water through the mem-
brane, q is the total flow through the membrane, A is the wa-
ter permeability constant, σ is the Staverman coefficient, S
is the membrane area, and ∆P is the applied pressure across
the membrane.[19] Assuming that the Staverman coefficient
equals one in Eq. (2) implies that the solute is perfectly ex-
cluded. This is a simplification of the real case, but it is fre-
quently used.[5,17,18,20]
Equation (3) shows a simple and common model for the
solute (salt) flux through the membrane under a concentra-
tion gradient:
(
J s = B C feed − C product ) (3)
where Js is the molar flux of solvent, B is the salt permeabil-
ity constant, and the driving force (Cfeed - Cproduct) is the salt
concentration difference across the membrane. Again, a more Figure 3. A press RO system ready to run.
p 2
router
σ thick = 2 1 + 2 ( 4)
k −1 r
The project was evaluated based on re-examining final This project was designed from the beginning to be
project reports from half of the student groups involved in multidisciplinary. Almost all student reports mention aspects
the class (16 out of 32 groups) and based on instructors’ ob- from all four BS engineering disciplines. The instructors found
servations. Reports were re-examined with a particular that they needed each other’s skills to design and understand
focus on the students’ demonstration of experimentation this project. We freely pointed this out to the students.
skills (goal 2) and design skills (goal 3). Throughout this
analysis it is difficult to separate the project impact from CONCLUSION
the course as a whole. A dead-end RO system provides the basis for a truly inter-
The chance for students to experiment with the system disciplinary project that provides a wealth of problems and
Winter 2003 43
examples for many different branches of engineering. In ad- 11. Connor, J.B., and J.C. Malzahn Kampe, “First-Year Engineering at
Virginia Polytechnic Institute and State University: A Changing Ap-
dition, it is used to connect a calculus course to the engineer-
proach,” Proc. Conf. Amer. Soc. Eng. Ed., Session 2553 (2002)
ing curriculum. The project provided a particularly good in- 12. Quinn, R.G., “E4 Introductory Engineering Test, Design, and Simula-
troduction to engineering experimentation. Student design tion Laboratory,” J. Eng. Ed., 82(4), 223 (1993)
work on the project was good, but could be strengthened— 13. Safferman, S.I., M. Zoghi, and D.H. Farhey, “First-Year Civil and
particularly in the details of full design calculations and eco- Environmental Engineering Design Experience,” J. Eng. Ed., 90(4),
nomic analysis. 645 (2001)
14. Slater, C.S., and J.D. Paccione, “A Reverse Osmosis System for an
Advanced Separation Process Laboratory,” Chem. Eng. Ed., 22, 138
REFERENCES (1987)
1. Johnson, R., and L. Anneberg, “Sundials Make Interesting Freshman 15. Lodge, K.B., R.A. Davis, D. Dorland, and D.N. Baria, “Experiments
Design Projects,” Proc. Conf. Amer. Soc. Eng. Ed., Session 2793 (2002) in Waste Processing for Undergraduates,” Proc. Conf. Amer. Soc. Eng.
2. Soysal, O.A., “Project Based Learning of Energy Conversion Prin- Ed., Session 2513 (1997)
ciples at Freshman Level,” Proc. Conf. Amer. Soc. Eng. Ed., Session 16. Assif-Anid, N.M., and H. C. Hollein, “Incorporating Biotechnology
2533 (2002) in the Chemical Engineering Curriculum,” Proc. Conf. Amer. Soc. Eng.
3. Ochs, J.B., T.A. Watkins, and B.W. Boothe, “Cultivating an Entrepre- Ed., Session 2276 (2002)
neurial Spirit through Cross-Disciplinary Student Teams in Freshman 17. Baker, R.W., E.L. Cussler, W. Eykamp. W.J. Koros, R.L. Riley, and H.
Projects Course,” Proc. Conf. Amer. Soc. Eng. Ed., Session 3454 (2002) Strathman, Membrane Separation Systems: Research and Develop-
4. Hesketh, R.P., K. Jahan, A.J. Marchese, T.R. Chandrupatla, R.A. ment Needs Assessment, Final Report, Contract Number DE-AC01-
Dusseau, C.S. Slater, and J.L. Schmalzel, “Multidisciplinary Experi- 88ER30133, U.S. Department of Energy (1990)
mental Experiences in the Freshman Clinic at Rowan University,” Proc. 18. Wankat, P.C., “Membranes,” Part III in Rate Controlled Separations,
Conf. Amer. Soc. Eng. Ed., Session 2326 (1997) Klawer, Amsterdam (1990)
5. Hesketh, R.P., and C.S. Slater, “Innovative and Economical Bench- 19. Cussler, E.L., “Membranes,” Chapter 17 in Diffusion: Mass Transfer
Scale Process Engineering Experiments,” Int. J. Eng. Ed., 16(4), 327 in Fluid Systems, 2nd ed., Cambridge University Press (1997)
(2000) 20. Eykamp, W., “Reverse Osmosis and Nanofiltration,” in Perry’s Chemi-
6. Farrell, S., R. Hesketh, K. Hollar, M. Savelski, C.S. Slater, R. Spect, cal Engineers’ Handbook, 7th ed., R.H. Perry, D.W. Green, and J.O.
“Don’t Waste Your Breath,” Proc. Conf. Amer. Soc. Eng. Ed., Session Maloney, eds., pp. 22-48 thru 22-52, McGraw-Hill (1997)
1613 (2002) 21. McCabe, W.L., J.C. Smith, and P. Harriott, “Membrane Separation
7. Farrell, S., R.P. Hesketh, J.A. Newell, and C.S. Slater, “Introducing Processes,” Chapter 26 in Unit Operations of Chemical Engineering,
Freshmen to Reverse Process Engineering and Design through Inves- 6th ed., McGraw-Hill, 857 (2001)
tigation of the Brewing Process,” Int. J. Eng. Ed., 17(6), 588 (2001) 22. Mahlab, D., N. Ben Joseph, and G. Belfort, “Interferometric Measure-
8. Hollar, K., F. Lau, L. Head, K. Jahan, E. Constans, P. von Lockette, ment of Concentration Polarization Profile for Dissolved Species in
and B. Pietrucha, “Bugbots! A Multidisciplinary Design Project for Unstirred Batch Hyperfiltration (Reverse Osmosis),” Chem. Eng.
Engineering Students,” Proc. Conf. Amer. Soc. Eng. Ed., Session 2426 Comm., 6, 225 (1980)
(2002) 23. Ho, W.S.W., and K.K. Sirkar, Membrane Handbook, Van Nostrand
9. Brockman, J.B., T.E. Fuja, and S.M. Batill, “A Multidisciplinary Course Reinhold (1992)
Sequence for First-Year Engineering Students,” Proc. Conf. Amer. Soc. 24. Proctor & Gamble, PUR Survivor 06, at http://www.purwater.com/
Eng. Ed., Session 2253 (2002) L3_mar_end_06.shtml, retrieved 7/2002
10. Beaudoin, D.L., and D.F. Ollis, “A Product and Process Engineering 25. Avedissian, E., Cape May’s Desalination Plant’s No Albatross!, at http:/
Laboratory for Freshmen,” J. Eng. Ed., 84(3), 279 (1995) /www.capemay.com/Desalination.html, retrieved 7/2002 ❐
This book is intended as a reference volume by the au- ing by static elements, and heat transfer in agitated tanks.
thor. Educators will find the book useful for several top- There is also a chapter (47 pages) that introduces the
ics that are not covered by textbooks or other reference use of computational fluid dynamic simulators for study-
volumes. ing mixing and flow in reactors. That chapter discusses
In addition to standard chapters on residence time dis- examples of mixing and reaction in a stirred tank and flow
tribution and reactor models for non-ideal flow, there is in a radial flow catalyst bed. On the CD, there are beauti-
an extensive chapter (91 pages) on mixing in tanks, mix- ful and informative color images of transient mixing and
44 Chemical Engineering Education
reaction of a competitive-consecutive reaction in a stirred Other programs are Windows double-clickable
tank. executables that display text output in the output window
Other chapters in the book, which aren’t covered or are and write output files to disk. A recommendation for fu-
covered only briefly by other books, include a chapter ture editions is to change the file extensions to “txt” from
(80 pages) on biochemical reactions and reactors. There those used for the input (“dat”) and output (“res”) so that
is an extensive chapter (134 pages) on safety, including they can be accessed easily by double-clicking.
descriptions of calorimeters used to characterize reactions, There are several topics that are not covered by the book.
calculations of vent sizes, and a brief discussion of Other than brief mention and sketches in a chapter men-
HAZOP analysis. Scale-up of reactors is considered in a tioning types of reactors, there is nothing on multiple-
chapter (47 pages) that discusses the use of dimensional phase reaction systems. There is nothing on reaction-dif-
similitude in combination with reactor models. fusion in porous catalysts or non-catalytic solids. There
Another strong point of the book is the numerous ex- is brief discussion on pressure drop but none on the effect
amples that are worked in detail. Many of these example of pressure drop of gases on reaction rate. There are a
problems are supplemented by Excel spreadsheets and couple brief discussions of selectivity and yield in two-
computer programs on the CD. reaction systems, but nothing on more complex multiple-
reaction systems. The thermodynamics section would ben-
The CD also has a unit conversion program and PDF efit from a worked example on reaction equilibrium com-
files with explanations of numerical methods and a cross- position. There are no end-of-chapter problems that can
reference between examples in the book and supporting be used for student assignments.
material on the CD. Source code (Fortran 77) for all of
the software programs on the CD is included along with Other chapters in the book cover standard material such
the executables. Unfortunately, temporary files produced as reaction mechanisms, analysis of kinetic data, design
during compilation (object, make, compiler interface) are and comparison of the “ideal” reactor types, thermal ef-
also included, which (in addition to the lack of sub-fold- fects, and residence time distribution.
ers in each chapter’s folder) makes finding the file needed
to run the program harder than necessary. A DOS pro- Richard K. Herz
gram is available for calculating heats of reaction at reac- Chemical Engineering Program and
tion temperature with input of stoichiometry, standard Mechanical & Aerospace Eng. Dept.
heats of formation, and heat capacity formula coefficients. University of California, San Diego
Winter 2003 45
Membranes in ChE Education
A COMPENDIUM OF
OPEN-ENDED MEMBRANE PROBLEMS
IN THE CURRICULUM
G. GLENN LIPSCOMB
University of Toledo • Toledo, OH 43606-3390
M
embrane separation processes have infiltrated both plant, but hemodialysis (or other replacement therapy such
the academic and industrial worlds. Commercial as peritoneal dialysis) is required when a donor is not avail-
successes have engendered a wealth of research able or the failure is expected to be temporary.
activity and collaboration on projects ranging from nitrogen Hemodialysis only partially replaces kidney function. The
production to hemodialysis. Coverage of membrane topics primary goals are removal of cell metabolism waste products
in the undergraduate curriculum has lagged, however, as and maintenance of the body’s water balance. Typically, three
authors and educators wait to see if membrane processes times per week a patient will spend three to four hours in a
are “for real.” clinic connected to a dialysis machine. Blood is taken from
In this paper we present three design projects that have been the patient and passed through an artificial kidney
used in chemical engineering classes to introduce membrane (hemodialyzer) where water and wastes are removed before
processes. The first project requires students to specify a treat- being returned to the patient.
ment plan for individuals undergoing hemodialysis. The sec- Within the hemodialyzer, the patient’s blood flows through
ond and third projects highlight the manufacturing process the lumen of 10,000 to 15,000 hollow fiber membranes while
used to produce hollow fiber membranes. One requires the simultaneously dialysate is pumped around the exterior of
design of a water distribution system for spinline quench the fibers. The dialysate serves as a reservoir for accumula-
baths, while the other seeks to recover solvent from the di- tion of metabolism wastes as they diffuse across the porous
lute, aqueous waste stream produced by the process. These fiber wall. The incoming dialysate stream possesses a com-
projects do not require extensive knowledge of membrane position similar to blood plasma, excluding the wastes, to
transport phenomena, modules, or processes, but they do re- minimize loss of electrolytes and other low molecular weight
quire application of fundamental chemical engineering prin- plasma components. Large components such as red blood cells
ciples for design purposes while simultaneously providing and albumin cannot diffuse or flow across the wall because
an introduction to the manufacture and use of membranes. the pores are too small.
For the design problem, students are asked to specify a treat-
Project 1 ment schedule (the time required for treatment, td, and the
Hemodialysis Treatment time interval between treatments, tb) for a patient weighing
(Mass and Energy Balances)
G. Glenn Lipscomb is Professor of Chemical
This design problem, given to freshmen and sophomores and Environmental Engineering at the Univer-
sity of Toledo. After graduating from the Uni-
in mass and energy balances classes, builds upon the hemo- versity of California at Berkeley, he worked for
dialysis problem in Felder and Rousseau.[1] Instructors might three years in Dow Chemical’s Western Divi-
sion Applied Science and Technology Labora-
encourage students to look up the dialysis process on the tory in Walnut Creek, CA. He was part of the
equipment CD that accompanies Felder and Rousseau or in team that developed Dow’s second-generation
the Membrane Handbook.[2] Hemodialysis replaces kidney oxygen/nitrogen membrane separation system.
His research interests lie primarily in module
function for individuals who have experienced total or par- design and membrane formation.
tial kidney failure. The preferred treatment is a kidney trans-
© Copyright ChE Division of ASEE 2003
1 − exp[ − N(1 − Z )]
where cb,d is the blood concentration at the beginning of treat-
( )
Q b c b − c b, o = Q b c b (1) ment and τ is given by
1 − Z exp[ − N(1 − Z )]
V 1 − Z exp[ − N(1 − Z )]
where Qb is the blood flow rate, cb is the inlet blood urea τ= ( 4)
concentration, cb,o is the outlet concentration, N = (kA)/Qb, Q b 1 − exp[ − N(1 − Z )]
Given values for M, kA, Qb, and Qd, these two equations in-
volve four unknowns: cb,b, cb,d, td. and tb. Therefore, one must Project 2
specify two more variables before the problem is fully speci- Hollow Fiber Spinning Plant
fied and the remaining dependent variables can be calculated. Water Distribution System Design
A spreadsheet can be used to rapidly solve the equations for (Fluid Mechanics)
a range of values for each variable. A typical solution is illus-
trated in Figure 2. Polymeric membranes in the form of fine hollow fibers are
used almost exclusively to form modules for gas separations
With this analysis, students are asked to answer the fol- and hemodialysis. The fibers are produced in a spinning pro-
lowing questions: cess similar to that used to produce textile and structural fibers.
• How long should each dialysis treatment last? In this process, the polymer is mixed with one or more
• What are the desired flow rates of blood and dialysate? solvents to form a “spin dope.” The spin dope is pumped
• What is the body fluid urea concentration at the beginning through a spinneret to form a hollow liquid cylinder; a single
of treatment? At the end of treatment? extruder may feed multiple spinnerets while a single spin-
• How much dialysate is used during each treatment? neret may produce from 10 to over 100 filaments. A second
liquid or gas stream is fed to the spinneret to fill the cylinders
• How long can a person wait between treatments? Specify a
practical treatment schedule; for example, it is not and keep them from collapsing. The filaments pass through
practical for a patient to visit the clinic every 2.3 days, so an air gap (“draw zone”) and then one or more liquid baths
patients typically are scheduled at the same time on (“quench baths”) to induce a desired wall structure and ex-
specific days during the week. tract solvent. The most commonly used liquid is water. The
• Is the assumption of no urea generation during dialysis a filaments produced by a single spinneret travel through
good one? the process in a group referred to as a “tow.” Figure 3
illustrates the process.
Students are encouraged to minimize the time required for The membranes produced by this process commonly pos-
each treatment (to reduce treatment costs and improve pa- sess a porous wall in which pore size depends on position in
tient well being), maximize the time between treatments (also the wall. Typically, the smallest pores are adjacent to one wall
to reduce treatment costs and improve patient well being),
and minimize the amount of dialysate used (to reduce di-
alysate costs). One cannot achieve all of these goals si-
multaneously!
Past experiences with this problem have been positive. The
subject intrigues students—the problem also challenges them.
The challenge comes not from the mathematics involved but
from setting up the equations from the problem statement
and identifying the constants, independent variables, and de-
pendent variables in each. This is often their first experience
with an unstructured, open-ended design problem—one that
requires arbitrarily specifying some variables to calculate
others and to synthesize a solution from information presented
not in order of use and in a variety of unit systems.
Additionally, the problem involves processes and concepts Figure 2. Urea concentration changes during treatment and
that may not be familiar to them. With a little guidance and between treatments for Qb = 400 ml/min, Qd = 800 ml/min,
encouragement, though, they can obtain a solution. The pri- cb,d = 1.5 g/L, and td = 240 min. For these conditions, cb,b =
mary negative feedback is that the students didn’t want to 0.85 g/L and tb = 4900 min (3.4 days).
TABLE 1
Design Constraints for Water Distribution System
Winter 2003 49
Membranes in ChE Education
comments on course evaluation forms included “I liked the
group project” and “The design project was a good idea ex- TABLE 2
Typical Equipment Inventory for
cept for the whole group work thing.” As with the previous
Water Distribution System
problem, students were not comfortable working in groups
despite attempts to address their concerns. 5-hp centrifugal pump (160 psig discharge) for water supply to
baths from storage tank
6-hp centrifugal pump (210 psig discharge) for water return to
Project 3 storage tank from baths
230 ft 7/8 in OD 12-gauge stainless steel tubing
Hollow Fiber Spinning Plant Solvent Recovery Four stainless steel 7/8-in tees
(Senior Design) Ten globe valves
Two vessels (1m x 3m) for packed beds
In the senior design class, students were asked to design a
2 m3 packing for packed beds
separation system to recover solvent from the water leaving One vessel (2m x 2m) for the storage tank (illustrated in Figure 4)
the quench baths for recycle within the process. The econom- Four water baths (illustrated in Figure 5)
ics of membrane manufacture can be very sensitive to sol-
vent losses and environmental costs associated with waste
TABLE 3
disposal. Consequently, this problem might be used as a pol-
Fiber Spinning Process Specifications
lution prevention example in the design course.
The spin dope consists of 32.5 weight percent N-methyl
The spinning process for this problem is illustrated in Fig- pyrrolidone (C5H9NO), 15.5 weight percent ethylene glycol, and
ure 6. The primary difference between this process and the the balance polycarbonate.
process illustrated in Figure 3 is that two quench baths in The spin dope is extruded at a rate of 5 lbm/min. This is fed to three
series are used to remove the solvent. Students were given spinnerets that each produce 60 fibers.
The 180 liquid filaments enter into a water bath maintained at 5°C
essential process specifications (see Table 3) and asked to and spend approximately 5 seconds in the bath.
design the recovery process. A fiber spinning process with Upon exiting from the first bath, approximately 65% of the
similar characteristics is described in the patent literature.[5] ethylene glycol is removed and 45% of the N-methyl pyrrolidone.
An equal volume of water replaces the organic solvents.
Each student group had to provide the following design
The total solvent composition of the first bath must be kept below
information: one weight percent.
• What is the required makeup water flow rate for each The fiber enters a second bath maintained at a temperature of 85°C
bath? At what rate is water removed from each bath and spends approximately 10 minutes in the bath.
Upon exiting from the second bath, virtually all of the organic
for treatment? solvents have been removed and replaced by an equal volume of
• What are the design specifications for each unit water.
operation in the solvent recovery process? The total solvent composition of the second bath must be kept
• Provide a complete PFD for the process, including a below 10 weight percent.
Makeup water for the baths comes from city water lines but must
table of stream and unit operation properties. be distilled to purify it.
• Estimate process costs and compare to the cost of Makeup water should be returned at the temperature of the bath.
simply returning the wastewater to the city sewer However, you do not have to provide temperature control for either
system at a concentration of less than 0.1 weight bath.
percent organics. To reuse the solvents, the water content must be less than one
weight percent.
As one might expect, most groups considered dis-
tillation processes. Common process simulators
(e.g., ChemCAD) can be used for the design of in-
dividual columns and column trains. Consideration
of other unit operations such as reverse osmosis,
pervaporation, or adsorption requires hand calcula-
tions and contact with potential vendors.
The separation process design is complicated by
the tight requirements on the water effluent from
the first bath —total solvent concentration less than
1% by weight. For the given process specifications, Figure 6. Schematic of a typical fiber spinning plant with
a minimum of approximately 120 lbm/min of water two quench baths.
Winter 2003 51
Membranes in ChE Education
EXPLORING THE
POTENTIAL
OF ELECTRODIALYSIS
STEPHANIE FARRELL, ROBERT P. HESKETH, C. STEWART SLATER
Rowan University • Glassboro, NJ 08028
E
lectrodialysis is an electrochemical membrane sepa- pressure gradients, in contrast to electrodialysis, which uses
ration technique for ionic solutions that has been used electrical potential to drive the separation. The first treatment
in industry for several decades.[1] It can be used in of electrodialysis in the educational literature appeared in
the separation and concentration of salts, acids, and bases 1931.[10] In this work, Kendall and Gebauer-Fuelnegg present
from aqueous solutions, the separation of monovalent ions three reasons why electrodialysis remains among the “ne-
from multivalent ions, and the separation of ionic compounds glected methods” of organic chemistry: 1) its treatment in
from uncharged molecules. It can be used for either electro- textbooks is inadequate, 2) its advantages and applicability
lyte reduction in feed streams or recovery of ions from dilute are not generally recognized, and 3) simple and efficient types
streams.[2-4] Industrial applications encompass several indus- of electrodialyzers are not generally available. While bench-
tries and include the production of potable water from scale electrodialysis equipment is now readily available from
brackish water, removal of metals from wastewater, dem- various manufacturers, electrodialysis is not commonly ad-
ineralization of whey, deacidification of fruit juices, and dressed in chemical engineering curricula, due primarily to
the removal of organic acids from fermentation broth.[1,2- the first two reasons presented above. Several reference books
5]
Additional examples of the applications of electrodi- include excellent treatment of electrodialysis theory and ap-
alysis are given in Table 1. plications,[1,3-5,11] but this material is not easily “distilled” into
As a selective transport technique, electrodialysis uses an material that can be introduced in the undergraduate class-
ion-selective membrane as a physical barrier through which room or laboratory, particularly if the professor has limited
ions are transported away from a feed solution. An energy- experience with membrane separations.
intensive phase change is unnecessary, in contrast to the com- Increasing interest in electrochemical education is reflected
mon separation techniques of distillation and freezing.[6] The by recent publications that address electrochemical reactors
use of an organic solvent, as is often required with other se- for synthesis and pollution control.[12-17] Kendall and Gebauer-
lective transport techniques such as liquid extraction, is
avoided with electrodialysis. In addition, electrodialysis is Stephanie Farrell is Associate Professor of Chemical Engineering at
typically performed under mild temperature conditions, mak- Rowan University. She received her BS in 1986 from the University of
Pennsylvania, her MS in 1992 from Stevens Institute of Technology, and
ing it particularly attractive for food, beverage, and pharma- her PhD in 1996 from New Jersey Institute of Technology. Her teaching
ceutical applications that deal with heat liable substances. and research interests are in controlled drug delivery and biomedical en-
gineering.
In typical chemical engineering undergraduate curricula, Robert Hesketh is Professor of Chemical Engineering at Rowan Univer-
sity. He received his BS in 1982 from the University of Illinois and his PhD
students are exposed to traditional separations methods with from the University of Delaware in 1987. His research is in the areas of
a heavy emphasis on operations such as distillation, extrac- reaction engineering, novel separations, and green engineering.
tion, and absorption. The need for incorporation of membrane C. Stewart Slater is Chair of the Chemical Engineering Department at
Rowan University. He is a two-time recipient of the Martin Award, and
technology into the chemical engineering curriculum has at- other awards include the Westinghouse, Carlson, and Dow. He is the found-
tracted recent attention.[7-9] ing chair of the innovative, hands-on undergraduate-focused chemical
engineering program at Rowan. He is on the editorial board of Chemical
The membrane separation processes mentioned above em- Engineering Education and The International Journal of Engineering Edu-
cation.
ploy “traditional” driving forces such as concentration and
© Copyright ChE Division of ASEE 2003
Winter 2003 55
Membranes in ChE Education
temperature probes (K-1, AMEL, Milan, Italy), programmable are often cross-linked to ensure stability. Fixed ionic moi-
microprocessor conductivity/resistivity indicator (model eties such as SO3-, COO-, PO32-, HPO2-, AsO32-, and SeO3- are
SIRIO, AMEL s.r.l., Milan, Italy), Teflon impeller flow sen- commonly used for cation exchange membranes, and NH3+,
sor (model U-33110-05, Cole Parmer, Vernon Hills, IL) with RNH2+, R3N+, R2N+, R3P+, R2S+, are common choices for an-
ratemeter/totalizer (model DP78A, Omega Engineering, Inc., ion-exchange membranes.[5]
Stamford, CT). Determination of cation concentrations for There are several manufacturers of ion-selective membranes
mixed monovalent-divalent cation solutions was made using for a variety of electrochemical process applications. Table 3
ion selective electrodes (divalent cation electrode Model 93- provides information on the materials and features of several
32 and ammonium electrode model 93-18 with sensing mod- ion exchange membranes used in electrodialysis applications.
ule, Thermo Orion, Beverly, MA). Detailed information on membrane manufacturers and mem-
The electrodialysis process is shown schematically in Fig- brane characteristics is provided in reference books[3,21] and
ure 2, and a photograph of the system is shown in the com- directly from the manufacturers. Membrane replacement costs
panion paper by Farrell, et al., (Figure 2a).[20] The system is are on the order of $100/m2.
operated in batch recirculation mode. Continuous and batch Tokuyama Soda Neosepta® ion-exchange membranes are
modes of operation, along with their relative advantages and used in our experiments. Two Neosepta cation exchange
disadvantages, are described by Shaffer and Mintz.[6] membanes, CMX and CMS, were investigated, while the same
anion exchange membranes, Neosepta AMX, were used in
ION EXCHANGE MEMBRANES all experiments. Neosepta AMX and CMX membranes are
The performance of ion-permeable membranes used in elec- standard grade, general-purpose polystyrene-based ion ex-
trochemical processes depends on several properties. The change membranes. Neosepta CMS membranes have a thin
desirable characteristics of membranes used in electrodialy- cationic charged layer on the membrane surface that increases
sis applications include[5,21] selectivity between ions of oppo- the selectivity between monovalent cations (i.e., NH4+) and
site charge, high ionic conductivity, low electrical conduc- multivalent cations (i.e., Mg2+). Neosepta membranes have
tion, long-term chemical stability, mechanical strength, and high ionic selectivity, low electric resistance, and a low dif-
resistance to fouling. These characteristics are determined by fusion coefficient for solute or solvent. They exhibit high me-
the membrj„ı matrix polymer and the fixed ionic moiety that chanical strength and high dimensional stability, and are
effects the ion selectivity of the membrane. Strathmann[5] highly resistant to chemical attack.
describes the challenges of optimization of these properties.
Polymer materials such as polystyrene, polyethylene, and EXPERIMENTAL
polysulfone are often chosen for the membrane matrix and Ammonium cations and chloride anions are contaminating
TABLE 3
Ion Exchange Membranes Used in Electrodialysis Applications
(Information from References 3, 21, and Membrane Manufacturers)
Manufacturer Tradename Material Special Features Location
Solvay Perfluorinated film with fixed pyridine (anion-permeable) or France
sulfonic acid (cation-permeable)
FuMA-Tech Polyetherketones, polysulfone, polyphenylene oxide Germany
®
Tokuyama Soda Neosepta Styrene-divinyl benzene Robust high mechanical strength; Japan
Moderate electrical resistance
Asahi Glass Selemiom® Polystyrene-based Very low electrical resistance Japan
®
Asahi Chemical Aciplex Styrene-divinyl benzene/PVC backing Japan
Ionics, Inc. Heterogeneous polystyrene-based/acrylic fabric, with fixed Rugged, low resistance, high select- MA, USA
sulfonate (cation-permeable) and quarternary ammonium cations ivity, chemically stable, low fouling
(anion-permeable)
Dupont Co. Nafion® Perflourinated sulfuric acid polymer Cation permeable NC, USA
®
Sybron Ionac Heterogeneous resin-PVDF/fabric High mechanical strength NJ, USA
Winter 2003 59
Membranes in ChE Education
G
as separation with polymer membranes is rapidly be- are typical. The air gases permeate through the wall of the
coming a mainstream separation technology. The fibers into the shell of the hollow-fiber module, which is
most widely practiced separations are enriched ni- maintained at essentially atmospheric pressure. The gas per-
trogen production from air, hydrogen separation in ammonia meating through the fibers and into the shell is collected and
plants and refineries, removal of carbon dioxide from natural leaves the module as the permeate stream.
gas, removal of volatile organic compounds (e.g., ethylene Because oxygen, water, and carbon dioxide are more per-
or propylene) from mixures with light gases (e.g., nitrogen) meable than nitrogen and argon, the gas in the fiber bore is
in polyolefin purge gas purification, and water vapor removal enriched in N2 and Ar as it moves through the fiber lumens
from air.[1-3] Relative to conventional separation technologies, from the feed to the residue end of the module. This process
membranes are low-energy unit operations, since no phase can produce 99+% N2 in the residue stream.
change is required for separation. Additionally, membranes
have a small footprint, making them ideal for use in applica- Such purified nitrogen is widely used for blanketing or
tions on offshore platforms, aboard aircraft, and on refriger- inerting applications in, for example, the aviation (fuel tank
ated shipping containers, where space is at a premium or blanketing), shipping (food container/packaging blanketing),
where portability is important. They have no moving parts, and chemical industries (storage tank and line blanketing or
making them mechanically robust and increasing their suitabil-
ity for use in remote locations where reliability is critical.[3]
Gas separation membranes are often packaged in hollow-
fiber modules—a cartoon of such a module is presented in
Figure 1. A full-scale industrial module for air separation may
contain from 300,000 to 500,000 individual fibers in a tubu-
lar housing that is 6 to 12 inches in diameter and approxi-
mately 40 inches long. Each fiber will have inside and out-
side diameters on the order of 150 and 300 micrometers, re-
spectively. For a typical case, the fiber wall, approximately
75 micrometers thick, consists of a very thin, dense separa-
tion membrane layer on the order of 500 to 1000 Å (0.05 to Figure 1. Cartoon of hollow-fiber module used for air
0.1 micrometers) thick, on the outside of the fiber. This thin separation. From <www.medal.com> and Ref. 4.
layer provides, ideally, all of the mass transfer resistance and
separation ability of the hollow fiber. The remaining 74.9 to David T. Coker provides engineering software services for Research Tri-
74.95 micrometers of the fiber wall comprise a porous poly- angle Institute. He holds a BS in Chemical Engineering (1997) from North
Carolina State University.
mer layer that provides mechanical support for the thin mem- Rajeev Prabhakar is currently working toward his PhD in chemical engi-
brane, but offers little or no mass transfer resistance. (To put neering at the University of Texas at Austin. His research relates to the
development of membrane-based systems for removal of carbon dioxide
fiber dimensions in perspective, the diameter of a typical from natural gas streams. He received his BTech in chemical engineering
human hair is about 100 micrometers.) from the Indian Institute of Technology (Kharagpur) and his MS from North
Carolina State University.
Gas (air in this example) flows under pressure into the Benny D. Freeman is the Matthew van Winkle Professor of Chemical En-
module, where it is distributed to the bores of the fibers. In gineering at the University of Texas at Austin. His research is in polymers,
particularly the sorption, diffusion, and permeation of small molecules
air separation, feed pressures of approximately 10 to 15 bar through polymers and polymer-based composites.
* University of Texas at Austin, Austin, TX 78758 © Copyright ChE Division of ASEE 2003
Winter 2003 61
Membranes in ChE Education
one gas to the next, and it is this property that allows the polymer to be discussed is the pressure ratio limit. As membrane
to separate gas mixtures. The data in Table 1 indicate that oxygen selectivity increases, the permeate mole fraction, yA, will
is always more permeable than nitrogen in all polymers, and the increase, but yA can only increase up to the point that the
ratio of O2 to N2 permeability, the selectivity, varies from 1.6 to partial pressure of component A on the upstream side (xAPL)
7.8 in the materials shown. Typically, as the permeability of a of the membrane equals that on the downstream side (yAPV).
polymer to oxygen increases, its selectivity decreases, and vice At this point, the driving force for transport of A across the
versa.[8.9] In the most widely used gas separation membranes, per- membrane is zero, the flux of component A goes to zero,
meability coefficients often decrease with increasing gas mol- and there can be no further increase in the mole fraction of
ecule size, so most gas separation membranes are more perme- component A in the permeate. Therefore, in the limit of very
able to small molecules (e.g., H2) than to larger molecules (e.g., high selectivity (i.e., as α → ∞ in Eq. 5 and, therefore, Eq
CH4). There are interesting exceptions to this general rule, and 4), Eq. (5) reduces to
membranes based on such materials may become more common-
y A = Rx A (6 )
place in the near future.[10-12]
That is, at high selectivity, the purity of gas produced is
limited by the pressure ratio. Of course, the value of yA can
ANALYTICAL CROSSFLOW MODEL
never be greater than unity.
The mole fraction of gas A on the permeate or downstream side This limit has industrial significance in situations were
of the membrane is given by the flux of component A through the selectivity is very high and process conditions dictate a small
membrane divided by the total gas flux through the membrane pressure ratio between permeate and feed streams. An ex-
ample is the removal of hydrogen from mixtures with hy-
NA
PA
t
(
xAPL − yAPV ) drocarbons in hydrotreaters in refineries.[3] The hydrocar-
yA = = bons in such a mixture would be methane and higher hy-
t
A ( A
t
)
( A) ( A) [
N A + N B PA x P L − y P V + PB 1 − x P L − 1 − y P V
] drocarbons, all of which are less permeable than methane
in the membranes used for such separations. Typically, H2
(3) is hundreds of times more permeable than CH4 and other
This expression can be reorganized as follows to permit a direct components in such a mixture.[2] But typical upstream and
calculation of permeate purity: downstream pressures would be 120 and 30 bar, respec-
tively,[3] so the pressure ratio would only be 4. In such a
1/ 2 case, having very high selectivity does not result in much
1 + x
1 + ( α − 1)R A
4
(1 − α )αx A
1 + − 1
yA =
R ( 4)
2 2
(1 − α ) 1
R 1 + (α − 1) R + x A
Figure 5. Schematic of hollow-fiber module divided into N stages. In analogy with labeling conventions used in distillation,
the flow rate of gas leaving the upstream (i.e., residue) side of stage k is labeled Lk, and the flow rate of gas leaving the
downstream (i.e., permeate) side of stage k is labeled Vk. The flow rate of gas of component j that permeates from the
upstream to the downstream side of stage k is ṁ j,k . The mole fractions of component j leaving stage k on the upstream and
downstream sides of the membrane are xj,k and yj,k, respectively. Adapted from the literature.[4]
Winter 2003 65
Membranes in ChE Education
ever, and it is of interest to allow students to figure out Other interesting problems include calculating purity/re-
what other factors (i.e., driving force for other compo- covery curves for other polymers to understand how the choice
nents in the feed gas, etc.) might also influence the resi- of polymer material influences the separation. In this regard,
due-gas flow rate for such problems. there is a large database of permeability values in the Poly-
The second example is hydrogen recovery from a mer Handbook.[19] Also, the hydrotreater example as well as
hydrotreatment unit in a refinery. In hydrotreatment, petro- the air separation example involve multicomponent mixtures,
leum intermediates are contacted with hydrogen to reduce and one could track the distribution of each of the other com-
sulfur, nitrogen, metals, asphaltene, and carbon residue con- ponents as polymer selectivity, flowrate, feed, or permeate
tent. This process requires substantial amounts of hydrogen pressure changes. We have used the analytical simulator as
gas, and much of the excess hydrogen can be recycled. Mem- well as the Internet version of the simulator in the senior-
branes are often used to purify the recycled hydrogen. The level design course, and it should be suitable for an under-
major impurities are light hydrocarbons. A typical stream graduate unit operations course as well.
might contain 65 mol % H2, 21 mol % CH4, and the balance The Internet simulator allows exploration of the effects of
will be other hydrocarbons, such as C2 and C3.[4] operating the module with bore-side feed or shell-side feed.
It is of interest to compare the same separation (e.g., air sepa-
In the conventional membranes used in this process, hy-
ration) using bore- and shell-side feed and to explain differ-
drogen is by far the most permeable component in the mix-
ences in the separation results. Basically, when the membrane
ture, followed by methane and then by the other hydrocar-
module is fed on the bore side, the permeate gas is collected
bons. H2/CH4 selectivity values can be of the order of several
on the shell side of the module and experiences essentially no
hundred in commercially used membrane materials.
pressure drop traveling from one end of the module to the other.
The objective of this separation is to generate highly puri- There is a slight decrease in pressure along the bore of the fi-
fied hydrogen for recycle to the process. Because this is a bers, but this decrease is typically small relative to the feed
high-pressure process and because the H2 product appears in pressure and has a small impact on separation performance.
the permeate stream, permeate pressure must be kept as close With shell-side feed, however, the permeate gas flows in
to the feed pressure as possible to minimize recompression the bore of the fibers, and pressures are much lower in the
costs. So the pressure ratio is typically not very high. At fixed permeate stream than in the residue stream. Small pressure
feed and permeate pressure, the more feed gas that is allowed changes along the bore of the fibers, estimated according to
to permeate through the membrane (by having lower flow the Hagen-Poisseulle relation, can lead to decreases in sepa-
rates or larger membrane area, or both), the higher is the re-
covery of hydrogen in the permeate, but the purity of the per-
meate stream is lower. So it is instructive to construct so-
called purity/recovery curves for this separation.
One example is shown in Figure 9. The curves in this fig-
ure were generated by varying the feed flow rate to a module
and noting the permeate H2 purity and flowrate. That is, at
very high flow rates, one can produce relatively pure H2,
but the amount of H2 recovered in the permeate stream is very
low. At the opposite extreme, at very low flow rates, most of
the H2 and CH2 gas permeates through the membrane, so H2
recovery is very high, but the purity is quite low. The ideal situ-
ation would be to have both high recovery and high purity, but
these factors typically work against one another.
Figure 9 also illustrates the impact of pressure ratio on the
results. Two pressure scenarios are presented. In both cases,
the difference between feed and permeate pressure is identi-
Figure 9. Effect of pressure ratio on H2 purity and recovery
cal. The case with lower feed pressure and higher pressure in a hydrotreater application. The membrane properties
ratio yields superior membrane separation performance, how- and module conditions as well as the feed composition are
ever. Such sensitivity of purity/recovery curves is an indica- given in Coker, et al.[4] H2 recovery in the permeate is the
tion that the separation is being performed in a pressure-ra- molar flowrate of hydrogen in the permeate divided by the
tio-limited regime. molar flowrate of hydrogen fed to the module.
Winter 2003 67
Membranes in ChE Education
MEMBRANE PROJECTS
WITH AN INDUSTRIAL FOCUS
In The Curriculum
STEPHANIE FARRELL, ROBERT P. HESKETH, MARIANO J. SAVELSKI,
KEVIN D. DAHM, C. STEWART SLATER
Rowan University • Glassboro, NJ 08028
E
ducational initiatives are crucial to the continued tech- in this curriculum development: an ability to function in multi-
nical growth and wide-scale commercialization of disciplinary teams, designing and conducting experiments,
membrane processes. This paper discusses innovative understanding safety and environmental issues, analyzing and
use of membrane technology in a project-oriented curricu- interpreting data, and using modern engineering tools.[15]
lum, building on the prior work of Slater, et al., who devel-
oped membrane experiments in a conventional chemical engi- ROWAN UNIVERSITY’S
neering laboratory setting.[1-7] At Rowan University, the authors ENGINEERING CLINIC
have integrated membrane technology throughout the engineer- Rowan University is a comprehensive regional state uni-
ing curriculum and involved student teams in a unique versity with six colleges: Business Administration, Commu-
multidisciplinary laboratory project experience—the clinics.[8] nications, Education, Engineering, Fine and Performing Arts,
Chemical engineering education is traditionally a process- and Liberal Arts and Sciences. The College of Engineering
or systems-oriented curriculum, producing graduates who can was initiated using a major gift in 1992 from the Rowan Foun-
apply their process expertise in many industries. Some ver- dation.[16] The engineering program is taking a leadership role
satility has been lost over the last several decades due to the by using innovative methods of teaching and learning, as rec-
overwhelming emphasis on unit operations and design prob- ommended by ASEE,[17] to prepare students for entry into a
lems pertaining to the petroleum industry. Separation-pro-
Stephanie Farrell is Associate Professor of Chemical Engineering at
cess needs exist both in the traditional process industries and Rowan University. She received her BS in 1986 from the University of
in emerging areas such as biochemical engineering, specialty Pennsylvania, her MS in 1992 from Stevens Institute of Technology, and
chemical manufacture, hazardous waste management, food her PhD in 1996 from New Jersey Institute of Technology. Her teaching
and research interests are in controlled drug delivery and biomedical en-
and beverage processing, microelectronics production, and gineering.
biomedical engineering.[9,10] Growth in these technologies will Robert Hesketh is Professor of Chemical Engineering at Rowan Univer-
sity. He received his BS in 1982 from the University of Illinois and his PhD
depend on engineers who are well-educated in the field and from the University of Delaware in 1987. His research is in the areas of
have a working knowledge of membrane applications in these reaction engineering, novel separations, and green engineering.
Mariano J. Savelski is Assistant Professor of Chemical Engineering at
areas. Education should have a multidisciplinary perspective Rowan University. He received his BS in 1991 from the University of Buenos
where students from other fields can apply their expertise to Aires, his ME in 1994 from the University of Tulsa, and his PhD in 1999
solving membrane-related process problems.[11] from the University of Oklahoma. His technical research is in the area of
process design and optimization with over seven years of industrial expe-
The need for more instruction in membrane technology and rience.
Kevin Dahm is Assistant Professor of Chemical Engineering at Rowan
in many other advanced separation processes has been previ- University. He received his PhD in 1998 from Massachusetts Institute of
ously addressed.[12,13] Many schools have graduate courses in Technology. His primary technical expertise is in chemical kinetics and
mechanisms, and his recent educational scholarship focuses on incorpo-
advanced mass transfer and some have courses in membrane rating computing and simulation into the curriculum.
technology, but introducing it to the undergraduate chemical C. Stewart Slater is Professor and Chair of the Department of Chemical
engineering curriculum is rare. A 1995 study[14] revealed that Engineering at Rowan University. He received his BS, MS, and PhD from
Rutgers University. His research and teaching interests are in separation
only 2.6% of lecture time in an undergraduate mass transfer and purification technology, laboratory development, and investigating
course is on the subject of membrane processes. ABET’s Cri- novel processes for fields such as bio/pharmaceutical/food engineering
and specialty chemical manufacture.
teria 2000 specifies many of the outcomes that are included
© Copyright ChE Division of ASEE 2003
Winter 2003 69
Membranes in ChE Education
familiarity with Food and Drug Administration regulations, was electrodialysis process development for separation of a
good manufacturing practices, and labeling requirements. precious metal chloride salt solution that was contaminated
Engineers from Campbell’s demonstrated a high level of with unwanted acids and salts. The traditional separation and
commitment to the project by attending monthly progress purification steps used in the production of these metal com-
meetings where the students gave oral presentations on their pound solutions include multiple precipitation and dilution steps
progress. This was followed by brainstorming and discus- that are time-consuming and labor intensive and result in a sig-
sion sessions where the industrial representatives and faculty nificant loss of product. Development of an alternative separa-
refocused and fine-tuned the project. This industrial interac- tion and purification technique was the aim of this project.
tion helped maintain a high level of motivation among the The specific objectives of the projects were
students and maintained the focus and a fast pace of produc- • To design and build an electrodialysis unit for the separa-
tivity. In addition to the progress meetings, the student team tion and purification of the desired process stream
also conducted a “lunch-and-learn” seminar at Campbell’s to • To investigate the performance of electrodialysis in the
share their research with engineers, scientists, and marketing removal of the salt contaminant from the product on a
representatives from the company. The ethusiastic response laboratory scale
of the audience at Campbell’s reaffirmed the industrial rel-
evance and impact of the team’s clinic research project. a
Campbell Soup Company is a strong supporter of our pro-
gram, not only by supporting the clinic project mentioned
above, but also by employing both full-time and internship
students from our program. In the summer following the veg-
etable processing project, two undergraduate students ac-
cepted summer internships at Campbell’s. The students had
the rewarding experience of successfully implementing two
of the technologies developed at Rowan into Campbell’s pro-
cessing facilities in California and New Jersey.
Metals Purification Processes
Various metals purification projects have been sponsored
by Johnson Matthey, Inc. A precious metals “refinery” is op-
erated at West Deptford, New Jersey, which is less than ten
b
minutes from our campus. This close proximity facilitates
numerous interactions and projects that we have with Johnson
Matthey. The company has sponsored three years of engi-
neering clinic projects with the objective of investigating
novel techniques that have the potential to replace current
“traditional” refinery process units.
At the refinery, precious metals such as Pt, Pd, and Rh are
purified from feed streams containing many unwanted metal
species and other impurities. The feed streams are made up
of spent catalysts from which precious metals are recovered
and recycled to feed stream from mines. In the refinery, there
are many dissolution, selective-precipitation, and filtration
steps. Using innovative membrane processes, the plant ca-
pacity, product purity, and processing costs have the poten-
tial to be improved. In essence, students have an opportunity
in the engineering clinic to conduct engineering projects that
are equivalent in scope to those done by engineers in the plant.
Our most successful project resulted in Johnson Matthey add-
ing several new processing units to their refinery. Figure 2. (a) Electrodialysis process system used in pre-
cious metals separation clinic project. (b) Electrodialysis
One of the Johnson Matthey projects involving membranes cell used in the process system.
TABLE 1
ABET Criterion 3 (a-k) in the Membrane Projects
Winter 2003 73
Membranes in ChE Education
M
embrane applications for gas separations have made rapid ad-
vances over the past decde.[1] In some cases, membrane tech-
nologies have been used to enhance or replace more traditional
methods of gas purification. The need for educating undergraduate chemi-
cal engineering students about membrane-based separations has not gone
unnoticed. Newer editions of popular separations textbooks have added
chapters on membranes with sections on gas permeation.[2-4]
Earlier, Davis and Sandall[5] described an undergraduate laboratory mem-
brane experiment and analysis for separating the components of air. It
remains relevant today as one approach to providing students with hands-
on experience with this important technology. The experimental objec-
tives included an inverse mass transfer analysis of experimental data for
key membrane transport parameters. The original analysis involved solv-
ing a set of differential species balances and fitting the results to experi-
mental data by iterative, trial-and-error techniques. They found that the
numerical methods required to implement their analysis were beyond the
scope of the undergraduate chemical engineering laboratory experience.
Consequently, they provided students with True BASIC programs that
were used to solve the model equations. Unfortunately, the programs were
limited to the specific membrane configuration in the laboratory. Stu-
dents were unable to explore alternative designs using the validated mod-
els without modifying the programs. In the meantime, several popular,
modern, computational software applications (such as Excel, Mathcad,
Matlab, or Polymath) have emerged that provide readily accessible tools Figure 1. Prism hollow-fiber membrane
for solving complex problems that involve nonlinear algebraic and dif- apparatus.
ferential equations. The drawbacks in the original analysis, along with
developments in computational tools, have led to a simpler alternative Richard A. Davis is Associate Professor in the Department of
Chemical Engineering at the University of Minnesota Duluth.
analysis described in this paper. He earned his BS in Chemical Engineering from Brigham Young
University and his PhD from the University of California, Santa
Barbara. He teaches a variety of courses in transport phenom-
EXPERIMENT ena and separations, and his current research interests include
process modeling and optimization.
Davis and Sandall[5] provided specific details of the experimental ob- Orville C. Sandall is Professor of Chemical Engineering at
jectives, apparatus, and procedure for a commercial hollow-fiber mem- the University of California, Santa Barbara. He is a graduate of
brane unit for air separation. The Prism separator developed by Permea the University of Alberta (BSc and MSc) and the University of
California, Berkeley (PhD). His teaching and research inter-
ests are in the areas of mass transfer and separation processes.
* University of California, Santa Barbara, CA 93106
© Copyright ChE Division of ASEE 2003
Differential Model
Walawender and Stern[6] derived the differential equations
for a binary gas system in countercurrent and cocurrent plug
flow patterns, shown ideally in Figures 3 and 4. Details of
the derivation are available in several references.[3,5,6] For a
binary gas system, the total mole and O2 species balances
Figure 4. Ideal countercurrent flow pattern. around the separator are
Winter 2003 75
Membranes in ChE Education
nF = nR + np (1) x = xR
xFnF = xRnR + ypnp (2 ) y = y i at A * = 0 (13)
n * = 1
where nF, nR, and np are the molar flow rates of the feed,
retentate, and permeate streams, respectively, and xF, xR, and Note the discontinuity in Eq. (6) at x = xR requires
xp are the feed, retentate, and permeate O2 mole fractions, application of l’Hôpital’s rule.[6]
respectively. The species balances around a differential vol- The dimensionless cocurrent flow model equations are
ume element in the membrane give
x−y *
d( xn ) = Q'O 2 ( xP − yp)dA (3) KF
dx
=
dA * y − x F
{ [
α (1 − x)( xr − y) − x (1 − x)r − (1 − y) ]}
[
d[(1 − x)n ] = Q'N 2 (1 − x)P − (1 − y)p dA ] ( 4) (14)
Q'j x−y *
where is the permeance of species j, A is the membrane
surface area, and P and p are the average retentate and per-
KF
dy
dA *
= { [
α (1 − y)( xr − y) − y (1 − x)r − (1 − y)
x − xF
]}
meate side pressures, respectively.
(15)
For convenience in the analysis, Eqs. (1) to (4) were com-
bined into the following dimensionless equations for coun- where
tercurrent flow: nF
KF = ' (16)
dx x − y *
{ ]}
QN2 AMp
KR =
dA * x R − y i
[
α (1 − x)( xr − y) − x (1 − x)r − (1 − y)
The cocurrent model equations are integrated from the feed
(5) end, subject to the initial conditions
x = xF
dy x − y *
*
at A = 0 (17)
KR =
dA * x R − x
{ [
α (1 − y)( xr − y) − y (1 − x)r − (1 − y) ]} y = yi
K R = n R / Q'N 2 A m p (10) yi =
2(α * − 1)
α * = Q'O 2 / Q'N 2 (11)
(19)
*
n = n / nR (12)
Davis and Sandall successfully used the differential model
where Am is the total membrane area. The ideal separa- in their analysis of O2/N2 separation in the membrane mod-
tion factor, α * , was assumed constant, but the dimensionless ule. At the time, they found that the background required to
transport parameter, KR, was defined as a function of the solve the model equations for α * and KR was beyond the
retentate molar flow rate. The solution to Eq. (7) was used to scope of an undergraduate student in their laboratory course.
check the assumptions leading to the algebraic model of Consequently, they developed True BASIC programs that
the next section. The countercurrent flow equations are were provided to the students to solve the model equations.
integrated from the retentate end of the membrane, sub- Since then, advances in computational software (such as
ject to the initial conditions Mathcad) have simplified the process of solving the model
d( xn ) ( xn ) R − ( xn ) F
= (22)
Figure 5. Example of Mathcad programming for inverse d∆ ∆R − ∆F
mass transfer analysis for α * and KR. Combine eqs. (2), (3), and (22), separate variables and inte-
Winter 2003 77
Membranes in ChE Education
grate 128 RTµLn p
∆R A pc = p2 + (35)
d∆ πd f4 N f
ypnp ∫ = Q'O 2 ( ∆ R − ∆ F ) dA ∫ (23)
∆ Solution Method
∆F 0
Figure 8.
Correlation of
KR
with nr
Figure 7. Example of Mathcad calculation for inverse for a
mass transfer analysis using the log-mean model. single
counter-
current
TABLE 1
flow
Calibration Data[5] and Results for Single Countercurrent Column
column
Experimental Data Differential Model Algebraic Model
nRx102
P(kPa) (gmol/s) xR yp α* KR α* KR
377 0.73 0.18 0.43 5.81 31.1 5.82 31.1 Figure 9.
377 0.74 0.18 0.43 5.81 31.1 5.82 31.1 Comparison
377 1.03 0.19 0.44 5.98 49.6 5.98 49.6
of
377 1.32 0.19 0.44 5.98 49.6 5.98 49.6
377 2.54 0.20 0.44 5.71 98.7 5.71 98.6 predictions
with
515 0.62 0.15 0.45 5.93 26.2 5.97 26.1
515 0.73 0.16 0.46 6.02 33.3 6.05 33.2 experimental
515 0.95 0.17 0.47 6.12 43.9 6.14 43.9 results for air
515 1.51 0.18 0.47 5.85 58.2 5.86 58.2 separation
515 2.25 0.19 0.48 5.96 92.1 5.96 92.1 in the four-
653 0.74 0.14 0.46 5.78 31.5 5.84 31.4 column
653 0.95 0.15 0.47 5.84 38.8 5.88 38.7 configura-
653 1.32 0.16 0.48 5.90 49.1 5.93 49.0 tion:
653 2.18 0.18 0.49 5.73 85.7 5.74 85.6 =377kPa,
653 3.44 0.19 0.5 5.81 135 5.81 135
Average 5.88 5.90 =515 kPa,
=653 kPa.
Winter 2003 79
Membranes in ChE Education
For example, students usually start by comparing the perfor- z variable fiber length, m
mance of cocurrent and countercurrent flow. This leads to a Greek Symbols
design for one column operating in countercurrent flow with α experimental separation factor
the same membrane surface area as the four columns. The ∆ transmembrane partial pressure, kPa
µ viscosity, N-m/s
single column design gives a predicted increase of 10% N2
θ cut of feed to permeate stream
recovery when compared to the modular design. Students may
Subscripts/Superscripts
use the models to predict a dimensionless membrane area, c closed end of fiber bore
1/K, to recover a desired fraction of oxygen fed to the e experimental
permeator. Other designs include four columns operating in f fiber
parallel with countercurrent flow or four columns with the F feed
feed side in series and the permeate side in parallel. i closed end of permeate stream
lm log-mean result
The Mathcad files used in the analysis are available at
m membrane
<www.d.umn.edu/~rdavis/cee> N2 nitrogen
O2 oxygen
CONCLUSIONS p predicted
A membrane experiment for investigating gas separation R retentate
has been in use for over ten years in the undergraduate labo- * dimensionless or ideal parameter
ratory at the University of California, Santa Barbara. A simple REFERENCES
analysis method was presented that requires only the solu-
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that introduce the high-pressure feed to the fiber bores in or- cal Engineering, 5th ed., McGraw-Hill, New York, NY (1993)
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(1991)
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