Академический Документы
Профессиональный Документы
Культура Документы
A Report on
by
Žarko Olujić
ZO Consulting
Associate Professor
BASF SE
z.olujic@tudelft.nl 1
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
CONTENTS
FOREWORD 5
1. INTRODUCTION 8
2.2 FRI 11
z.olujic@tudelft.nl 2
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
3.10 Reproducibility 22
NOMENCLATURE 36
REFERENCES 37
APPENDICES
A1 Orto- / Para-Xylene 42
Table A1 – FRI data
z.olujic@tudelft.nl 3
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
A2 Chlorobenzene/Ethylbenzene (CB/EB) 42
Table A2a – Bayer Technology Services data
Table A2b - Sulzer data
Table A2c – Billet’s data
A3 Cyclohexane/n-Heptane (CH/nH) 44
Table A3a – SRP data
Table A3b - FRI data
Table A3c - TU Delft data
A4 Methanol/Water (M/W) 45
Table A4 – TU Delft data
A5 Methanol/Ethanol (M/E) 46
Table A5 – TU Delft data
A6 Isobutane/n-Butane (IB/nB) 46
Table A6 – FRI data
NOTES: 48
z.olujic@tudelft.nl 4
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
FOREWORD
In what follows you will find a document that summarizes the results of a
literature study that was encouraged and supported by BASF SE. The objective was
to collect and evaluate relevant, publicly available information, and to come with a
proposal for standardization of structured packing efficiency measurements, which, in
turn, should lead toward obtaining more reliable basic performance data to be used
with more confidence in (re)design of industrial packed columns.
Upon critical evaluation of the present text, the potential contributors are
encouraged to come with comments, discussions, and suggestions for
improvements, which should enable us to arrive at best practices. However, only the
productive proposals will be implemented, and this will occur upon approval of
involved contributors. This will be posted as new version and exposed to critical
evaluations, in form of an open forum. However, coordinator will try to ensure
convergence within a few iterations, i.e. achieving the best solution, to be accepted
and considered to serve as a general standard in the near future.
This could then serve as basis for establishing basic standards for testing all
types of gas or vapour/liquid contacting devices used in separation processes.
z.olujic@tudelft.nl 5
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 6
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 7
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
1. INTRODUCTION
There is no doubt that distillation was and still is by far the most widely applied
separation technique in process industries. Regarding the ever growing needs for
bulk-chemicals and the extent of grow of process industries in Far East it seems that
its importance will even increase in the foreseeable future. A major consequence of
this strong grows is that larger and larger equipment is built to stay competitive,
which implies further challenges regarding the scale-up and design practices. The
amounts of capital and energy involved require as tight as possible column designs
and this posses challenges on scale-up know-how side, which, in turn relies mainly
on efficiency and hydraulics’ data obtained from total reflux experiments carried out
with much smaller equipment using one of standard test systems, often at conditions
different from that of intended application.
Although a lot of experimental work has been done in the past and well
established large companies have also collected addition practical knowledge from
operation of their plants, the design of new as well as redesign of existing columns
still encompasses a wide range of concerns. These are mainly related to
uncertainties with respect to expected hydraulic and mass transfer performance of
novel, performance improving gas/vapour-liquid contacting devices, developed and
brought to the market in the meantime by equipment manufacturers.
All three main families of vapour (gas)-liquid (G-L) contactors for distillation
and related separations, i.e. trays, random packing, and structured packings have
experienced significant improvements in this respect. The main stream of such
developments is concerned with capacity increase (revamps-retrofits) or size
reduction (new designs) of distillation columns, accompanied, if feasible, by energy
saving per unit of product (reduction of external reflux), but most of these
developments aim at reaching the capacity increase goal without affecting the
separation efficiency adversely. The certainty regarding the hydraulic and mass
transfer performance of the G-L contactor considered plays a crucial role for success
of such a total cost reduction effort. In order to get this certainty, i.e. to minimize risks
associated with building very expensive industrial plants, user companies tend to
have dedicated pilot plant scale tests performed, which may be used to
validate/verify the predictive models.
The emphasis of this study is on the performance characteristics of structured
packings, more precisely on clearing the issues associated with usability of total
reflux measurements, carried out with established test systems in pilot to semi-
industrial scale test installations, for (re)design purposes. In this respect the report
follows the line of a presentation given by T. Friese of BASF, at GVC-Fachausschuss
Fluidverfahrenstechniek meeting held in February 2005 in Luebeck, Germany [1].
This presentation moved a group of distillation user companies to consider
establishing standardized testing procedures as a measure to arrive at more
confidence in this respect, and this expectation has been considered and handled
accordingly in this report.
z.olujic@tudelft.nl 8
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
Packing hydraulics’ related experiments are usually carried out using air-water
system at ambient conditions, to observe the suitability of the packing with respect to
the liquid hold-up, pressure drop and capacity. Promising configurations are then
exposed to distillation experiments, most commonly under total reflux conditions, to
get impression on achievable efficiency. In general, the main objective of pilot testing
of a packing under total reflux conditions is to determine:
Usually the packing performance data are generated using large enough total
reflux distillation columns in conjunction with one of established test systems,
described in the booklet “Recommended Test Mixtures for Distillation Columns” [2,3].
Namely, long ago it has been realised that some standardisation is required
regarding the choice of the test system, and the EFCE Working Party on Distillation
came with a proposal in this respect and produced in 1960s under editorship of F.
Zuiderweg the first edition of this booklet [2]. The next, thoroughly revised and
updated edition, written by Onken und Arlt , was published in 1990 [3].
There are several more or less accessible sources of total reflux data. First we
should mention Billets books [4,5]. Until the retirement of Prof. R. Billet the University
of Bochum was the place where many conventional and novel random, and certainly
all first generation structured packings were tested. Unfortunately, the total reflux
column used for these purposes had an insufficient diameter (d = 0.22 m) to be
considered as source of data to be used directly for scale-up purposes. All the details
around this installation, test systems used and many of generated results produced
in cooperation with Dr. J. Mackowiak and later on Dr. M. Schultes are well
documented in Billet’s book Packed Towers [5]. Additional information on packings
tested in Bochum can be found in Mackowiak’s book “Fluiddynamik von Kolonnen mit
modernen Füllkörpern …” [6]. Billet’s book contains also some data on performance
of conventional random packings obtained in a column with an internal diameter of
0.5 m. This one as well as a column with an even larger internal diameter (0.8 m),
available in 1960s at BASF in Ludwigshafen, were extensively used to generate
scale-up know how, needed for design and/or operation of, at that time, extremely
large columns for separation of ethylbenzene/styrene mixture. It should be noted
that in these devoted experiments, the ethylbenzene/styrene system was used at
appropriate operating pressure. A detailed description of the test installations and
obtained results including Sulzer gauze packing BX performance evaluation can be
found in Billets book “Industrial Destillation” [4]. It should however be noted that 0.8
m diameter was chosen for the purposes of testing tray performances appropriately,
and that a 0.5 m diameter total reflux column was considered as large enough
regarding the scale-up needs for packed columns. A recent BASF based study [7],
discussing the needs for even larger, industrial scale testing facilities, suggests that
operating pressure should be considered when choosing the diameter of the test
z.olujic@tudelft.nl 9
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
column, indicating that for most common packed column applications (0.1 bar to
atmospheric pressure operations) the diameters above 0.3 m should be sufficient.
Large scale equipment manufacturers, like presently Koch-Glitsch and Sulzer
Chemtech prefer to relay on their own facilities, and their data are generally not
publicly available. Most prominent source of distillation equipment test data is
Fractionation Research Inc. (FRI), and their data are available to member companies
only. FRI as well as some other institutions (Bayer Technology Services, BTS, and
Separations Research Program, SRP) are willing to perform commercial tests for
customers, which implies that the customer decides whether and to whom to release
the data, and these remain mainly unavailable to public. The chance that some
performance data will be published is largest with data produced using adequate
facilities available at universities, however these are the least consistent regarding
the nature of experimentation and available equipment and technical support. Finally,
the user-companies have often adequate facilities to be used preferably for own
purposes only. However, it must be realized that during the last two decades of last
century due to increased costs and reduced technical support, most of the bulk
chemicals manufacturing companies abandoned this practice. In fact this occurred
everywhere and today there are few facilities left, which can satisfy the growing
needs in this respect. The exceptions in this respect are air distilling companies.
Distilling air at cryogenic conditions to produce high purity oxygen, nitrogen and
argon, respectively, is a very specific activity and a really large scale worldwide
business, and the competition of big players in this field is especially strong.
Therefore they all prefer to use own test facilities, which, due to the nature of the
system and cryogenic test conditions, have been held on smaller size. With the need
to design the columns with larger and larger diameters for very sharp separations
they also got confronted with the need to consider performing experiments at the
scale close to their industrial operations and conditions. From these reasons, few
years ago Air Products decided to design and build a large enough (industrial scale)
test column. On the other hand, Koch-Glitsch invested into transformation of suitable
former industrial column into a test unit. However, soon after performing first series of
dedicated tests, the related expenses appeared that high that this discouraged
offering these facilities for commercial purposes and even discouraged similar efforts
for own purposes. Therefore it looks to be that present day, state of the art facilities
have to be as small as bearable, i.e. technically responsible, to have a chance to be
used frequently.
Regarding this fact, it appears that the overall quality and usability of data
produced using adequate – as small as good enough - size facilities becomes a
concern. In what follows an overview is given of available total reflux test facilities.
z.olujic@tudelft.nl 10
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
laboratory in Winterthur there are also total reflux columns with smaller diameter
which can be operated at high pressures, as well as a number of hydraulic, air-water
installations which provide for collecting all range of data of interest for understanding
and properly correlating the performance of new packings. The collected data have
been correlated and can be found for all Sulzer packings in the software package
Sulpak, which is available on request from Sulzer Chemtech via their website. It
should be noted that Sulpak simulates the hydraulics of Sulzer structured packings
well, but there are no provisions made for estimation of the packing efficiency with
different systems. The only efficiency related information contained is that on
experimentally determined number of equilibrium stages (theoretical plates)
contained per unit bed height for main types and sizes of Sulzer packings as
determined with CB/EB system using Sulzer test facilities. Occasionally, some of
efficiency data are presented at conferences [8-11], and the results obtained over the
years with Mellapak 250.Y at FRI have been published [12].
2.2 FRI
This well known independent distillation equipment testing institution makes
dedicated performance tests in one of two 1.2 m internal diameter column, covering a
wide range of operating pressures, from high vacuum (down to 0.1 bar) to high
pressure (up to 27 bar) using appropriate test systems. FRI member companies are
well acquinted with all technical details related to FRI installations and test
procedures. Tables A1, A3b, and A6 in Appendix A summarise average properties of
tests systems used at FRI for performance evaluation and interpretation purposes. A
z.olujic@tudelft.nl 11
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
detailed description of the test facilities and procedures adopted can be found in
recent publications [12,17].
z.olujic@tudelft.nl 12
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
2.3.2 TU Delft
Thanks to an equipment donation from J. Montz GmbH, the Laboratory for
Process Equipment managed to assemble in the late 1990s a state of the art total
reflux distillation facility, which however appeared to be suitable for a smooth
operation at atmospheric pressure only. This unit was extensively used for screening
test during development of new generation of high capacity Montz packings.
Subsequently it was used for performance evaluation of new generation of Sulzer
catalytic packings from Katapak SP series [21]. A detailed description of this plant
with a column with an internal diameter of 0.45 m and packed heights up to 2.5 m
can be found in a most recent publication on performance evaluation of Sulzer high
performance structured packing MellapakPlus 752.Y [22]. Table A3c in Appendix A
contains the physical properties of the CH/nH system, corresponding to the middle of
the bed temperature.
The tests carried so far at TU Delft have been carried out under direct
supervision of the PhD student and carried out by a number of MSc students who did
their work as part of their graduation programme. These students stayed six to twelve
months with the group and proved to be highly responsible and skilled operators.
There have been some day and night operations carried out and after evaluation it
appeared that there is no visible difference in measurements when compared to
common daily operation practice, provided enough time has been allowed for
reaching the steady state after start-up and each change of conditions. The non-stop
operation enabled completing a test for a packing within one week, while the
discontinuous operation required two to three weeks to complete a test (8 to 10
points). Since the non-stop operation proved to be practically impossible, because a
PhD student or permanent staff member had to be part of the “dead-man shift” from
safety reasons and for students this also appeared to be unacceptable for a longer
period, the TU Delft adopted common daily operation which effectively means that at
least three weeks are needed for a full scale test. Bringing changes, like liquid
distribution quality manipulation, or other research motivated modifications of the
hardware requires additional time and cannot simply be expressed in money.
As reported in [22], the TU Delft column was also operated with non-ideal
Methanol/Water system (M/W), which also was employed in some studies carried out
at the University of Alberta in Edmonton [23]. Properties of M/W system can be found
in Table A4 in Appendix A. Table A5 contains properties of Methanol/Ethanol system
(M/E) which was used earlier at TU Delft [24,25], during imposed maldistribution
studies performed with some of first generation sheet metal, and Montz expanded
metal packings, respectively. Both M/W and M/E belong to recommended tests
systems [3].
z.olujic@tudelft.nl 13
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
2.4.4 Praxair
A column with 0.305 m internal diameter operated at total reflux with argon
and nitrogen under cryogenic conditions was used extensively for evaluation of basic
performance of commercially available structured packings suitable for application in
cryogenic distillations. The packed height was typically 2.4 m. This unit was also
used to evaluate performance of new generation of high capacity structured
packings, as introduced by researchers from this organisation [27].
It should be noted that newest generation of air distilling columns with feed
rates well above 100 t/h, require large diameters (large specific area packings are
preferred to reduce column height from energy conserving reasons) and this poses a
challenge regarding the uncertainties related to scale-up based on small column
diameter data. In answer to this Air Products decided to design and operate a small
industrial scale column, described in following section.
z.olujic@tudelft.nl 14
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
than that obtained with small column. Hydraulics was also affected but not so
pronouncedly as efficiency.
This section addresses factors of importance for test equipment design and
operation as well as operating procedures and measurements.
z.olujic@tudelft.nl 15
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
packing and, in same cases, F-factor. So if a packing with 250 m2/m3 is taken as
reference size and 15 theoretical stages as a basis than 6 m height reserved for
packing installation would be a good choice, in conjunction with a close boiling
system like chlorobenzene/ethylbenzene, which allows having such a high number of
theoretical stages without compromising the above mentioned overheads purity. If
single bed, packing performance comparison studies are main purpose, then a
packed height of 4 m will be sufficient.
Another consideration related to the height of a bed is the mechanical strength
of the packing and the support system. With present very low material thickness
(about 0.1 mm) the weight of packing elements fitting into a test column is that low
that this is not a concern. In any case, the packing should be supported by a highly
open flat grid and installed in layers with each element rotated 90 degrees to
previous one. This is a normal bed configuration, providing for maximum large scale
mixing of both phases. According to our knowledge only Norton deviated from this
practice by rotating the subsequent layers by 60 to 70 degrees, which was most
probably done to keep the pressure drop acceptable. Namely, the surface of Norton
Intalox Structured Packing was very rough, thus causing a pronounced pressure drop
due to skin friction, which had to be compensated somehow, and reducing the angle
of rotation of packing layers was a practical solution to this.
z.olujic@tudelft.nl 16
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 17
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 18
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
F-factors well above 3 Pa0.5. Operation with this system at higher pressure is avoided
because it imposes impractical (very high) operating temperature. CH/nH system is
better in this respect, and 4 bar operation, as adopted at SRP [18,19], allows
reaching specific liquid loads up to 50 m3/m2h at an operating temperature which is
50 degrees lower than that corresponding to the pressure required to reach the same
specific liquid load with CB/EB system (around 200 oC).
In general, 0.1 bar and 1 bar pressures as applied in conjunction with CB/EB
system are standard operating pressures adopted at BTS and Sulzer, which covers
most of industrial applications of structured packings. These two operating pressures
are well established reference values. Going deeper into vacuum, say to 0.05 bar, is
useful because it approaches closer conditions associated with distillation of fine
chemicals, which is usually carried out using high specific geometric area, wire gauze
packings like A3 series from Montz or BX series from Sulzer. An intermediate value,
say 0.3 (roughly factor 3 to both, 0.1 bar on lower and 1 bar on upper side) could be
attempted, but it may prove unnecessary. While going below 0.1 bar is rather easy to
accomplish, provided enough heat transfer area is installed, above-atmospheric
pressure operation with CB/EB system may prove demanding. Major concern is, as
mentioned above, the rather high operating temperature. In addition, relative volatility
is then expected to drop below 1.1, where sensitivity to measurement errors may
become substantial.
For data interpretation and performance modelling studies following properties will be
needed:
z.olujic@tudelft.nl 19
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
For instance, for an ideal tests system like CB/EB, the relative volatility is
equal to the ratio of vapour pressures of pure components, which can be determined
using Antoine equation with corresponding constants. Gas density can be estimated
with confidence using the ideal gas law based expression. However for liquid density
and for other properties it is best to use polynomials with experimentally determined
coefficients, covering the full range of operating conditions.
The related sensitivities and uncertainties in conjunction with possible sources
of errors will be discussed later on where appropriate.
z.olujic@tudelft.nl 20
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
matching the range of change produced during test. This should be done at frequent
basis and duplicate samples should be provided for sample and analysis verification.
z.olujic@tudelft.nl 21
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
3.10 Reproducibility
Two to three points at different F-factors should be repeated at the end of the
measurement series, and in some cases the same packing should be tested again,
z.olujic@tudelft.nl 22
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
after a while, to get experience and the confidence regarding the data reproducibility
and interpretation. This implies that the method of installing packing needs to be fixed
and repeated every time a column is (re)packed, as discussed under 3.3.
One of worrying problems associated with this is that running up and down
with respect to vapour load can lead to some hysteresis effect, which is a difficult
situation and needs to be handled with care, to avoid excessive discrepancies in the
same data points. The time required to establish a steady state when going from
higher to lower F-factors is longer than that associated with going up in F-factor.
Liquid hold-up is the most sensitive parameter in this respect, and higher than normal
vales of pressure drop could be expected when going down too fast. Dedicated
experiments should provide proper answer to this question, i.e. to establish the test
procedure and related time intervals.
z.olujic@tudelft.nl 23
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
option from the standpoint of operation and the quality of measurements, however,
such operation requires continuous availability of people (shift work) and compliance
with safety regulations, which may differ from company to company. In any case,
once established a test procedure must be adopted as a standard.
z.olujic@tudelft.nl 24
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
experiment without insulation. Also, the effect of sub-cooling, which is dealt with in
elaborated way later on, needs to be evaluated appropriately.
Anyhow running a distillation pilot plant will bring necessary amount of
headache to those involved, if striving for absolute accuracy/certainty, which is
difficult if not impossible to achieve in practice.
Usually, the HETP and pressure drop of the tested packing are presented in
performance plots as a function of the superficial (based on full cross section area of
z.olujic@tudelft.nl 25
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
the column) vapour load, i.e. F-factor, FG, or/and capacity factor, cG, which are
related through the square of the difference between liquid and vapour densities:
FG = uGs ρ G (1)
and
ρG FGs
cG = uGs = (2)
ρ L − ρG ρ L − ρG
where uGs (m/s) is the superficial vapour (gas) velocity, ρG (kg/m3) is the gas density
and ρL (kg/m3) is the liquid density.
The superficial gas velocity is obtained by dividing the volumetric flow rate, i.e.
the ratio of mass flow rate and the density of vapour, and the cross sectional area of
the column.
MG
uGs = (3)
⎛ π d c2 ⎞
ρ G ⎜⎜ ⎟⎟
⎝ 4 ⎠
where dc (m) is the internal column diameter and MG (kg/s) is mass flow rate of gas.
In case of the total reflux, mass flows of gas and liquid streams along the
column are equal, and the corresponding superficial liquid velocity is:
ρG ρG
u Ls = uGs = FG (4)
ρL ρL
z.olujic@tudelft.nl 26
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
0.4 16
B1-500MN, TUD, CH/nH, 1.013 bar , d = 0.45 m, h = 1.58 m
0.2 8
HETP - top
HETP - average
HETP - bottom
0.1 dp/dz - top 4
dp/dz - average
dp/dz - bottom
0.0 0
0 0.5 1 1.5 2 2.5
0.5
F-factor (Pa )
Figure 1 – Effect of operating conditions on packing efficiency and pressure drop for
CH/nH system at top pressure of 1.02 bar
0.5 15
B1-250MN, BTS, CB/EB, total reflux, 0.1 bar, dc = 0.6 m, hpb = 2 m
HETP, top
0.4 HETP, bottom 12
HETP, average
F-factor uLs
(Pa0.5) (m3/m2h)
0.54 1.29
0.2 1.04 2.50 6
1.55 3.74
1.92 4.66
2.27 5.54
2.59 6.35
2.94 7.27
0.1 3.22 7.98 3
3.54 8.85
3.67 9.23
3.78 9.56
4.16 10.67
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
0.5
F-factor [Pa ]
Figure 2 – Effect of operating conditions on packing efficiency and pressure drop for
CB/EB system at top pressure of 0.1 bar.
z.olujic@tudelft.nl 27
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
It should be noted that the F-factors shown in Fig. 1 and Fig. 2 were calculated
taking into account the effect of bed pressure drop.
The extent of temperature effect is elaborated in more detail for all important
design and operating parameters in what follows. Usually the average values based
on top and bottom of the bed conditions are taken as representative for test results
presentation.
MG
FG = (5)
⎛ π d c2 ⎞
ρ G ⎜⎜ ⎟⎟
⎝ 4 ⎠
indicating that for a given column internal diameter the F-factor is proportional to
internal mass flow rate of the vapour and to the inverse of the square root of vapour
(gas) density. Due to difference in top and bottom pressure and temperature as well
as vapour mixture composition, vapour density will be different at the top and the
bottom of a bed.
The density of the vapour at the top of the bed is defined by the top pressure
and temperature and can be determined for an ideal mixture from:
pT M w,G ,T
ρ G ,T = (6)
R TT
where pT (bar) is pressure of the top of the column, Mw,G,T (kg/kmol) is molecular
weight of the gas mixture, TT (K) is absolute top temperature, and R (kJ/kmol K) is
universal gas constant. In conjunction with pressure expressed in bar: R = 0.08314.
Similarly, for bottom conditions:
( pT + ∆p ) M w,G ,B
ρ G ,B = (7)
R TB
where ∆p (bar) is the measured pressure drop of the packed bed, Mw,G,B (kg/kmol) is
molecular weight of the vapour mixture, and TB (K) is absolute temperature at bottom
of the bed.
A simple arithmetic average of gas density can be taken as representative of
the middle of the bed conditions:
ρ G ,aver =
(ρ G ,T + ρ G ,B )
(8)
2
The situation with the representative internal mass flow rate of vapour
however is not so simple. Namely, as appeared in practice, it is always somewhat
larger than that based on measured reflux flow rate.
Per definition, under total reflux the molar flows of gas and liquid are equal and
constant along the column, however the reflux, obtained by total condensation of the
vapour leaving the top of the bed, returns into the column subcooled. According to
z.olujic@tudelft.nl 28
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
my knowledge, based on evaluation of BTS, FRI, SRP and TU Delft data, the reflux
returns to the top of the column as a liquid at a temperature 10 to 20 degrees K
below its boiling point. Upon entering the column this sub-cooled liquid is heated up
to reach its boiling temperature, and the heat for this is provided by condensation of a
part of the rising vapour. In other words latent heat or enthalpy of condensation of
vapour provides the sensible enthalpy to heat the subcooled liquid to its boiling point.
Fortunately a relatively small amount of total heat is required to get this done.
The liquid created by the condensation of vapour joins the reflux, i.e. liquid
introduced through the distributor, and, therefore, it is reasonable to expect that the
flow rate of this “internal reflux” is greater than the measured flow rate of “external
reflux”. In order to obtain a reasonable estimate of the internal reflux, Seader and
Henley [38] recommend an equation derived from an approximate energy balance
around the top of the bed, which is transformed here into mass units to express the
mass flow rate of the gas at bottom conditions, assuming that under total reflux the
molar/mass flow rates of gas and liquid streams are equal:
⎡ c p ,L ,T TT − c p , L , R TR ⎤
M G ,B = M G ,T ⎢1 + ⎥ (9)
⎢⎣ ∆hv , B ⎥⎦
where cp,L (kJ/kg K) is the specific heat of the liquid at corresponding temperature:
top, TT (K), or reflux, TR (K), and ∆hv,B (kJ/kg) is specific enthalpy of vaporisation or
condensation at bottom temperature.
Then, keeping in mind the fact that the gas flow rate at the top is equal to
(measured) reflux flow rate, a reasonable representative F-factor is that obtained as
an arithmetic average of top and bottom values:
⎡ ⎤
1⎢ M G ,T M G ,B ⎥
FG ,aver = ⎢ + ⎥
2⎢ ⎛ πd c ⎞ ⎛ π dc ⎞ ⎥ (10)
⎢ ρ G ,T ⎜⎝ 4 ⎟⎠ ρ G ,B ⎜ ⎟
⎝ 4 ⎠ ⎥⎦
⎣
Specific vaporisation enthalpies and specific heat capacities of top and bottom
binary mixtures can be determined from pure component properties on additive
basis, using experimentally determined mass fractions of more volatile component.
Suitable simple polynomial equations, with experimentally determined coefficients,
can be used to describe pure component properties.
In case of larger bed heights the pressure drop effect will be more pronounced
and may cause even larger difference between top and bottom related F-factors.
Nevertheless, an average representing the middle of the bed conditions can always
be used with confidence for the purposes of packing performance comparisons.
z.olujic@tudelft.nl 29
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
difference between relative volatilities of the top and bottom of the bed, resulting, as
demonstrated in Fig. 1, in a rather strong effect on efficiency.
In the case shown in Fig. 1, the bottom temperature was 10 0C higher than the
top temperature, and corresponding relative volatilities were 1.75 at the top and 1.6
at the bottom, respectively. This, nearly ten percent difference in relative volatilities,
results in a nearly twenty percent difference in corresponding HETP values. In other
words, for the same composition change, at bottom conditions more theoretical
plates are contained in given bed height, resulting in a lower HETP value, i.e. better
efficiency.
This is based on assumption of ideal behaviour of CH/nH mixture, which is
generally valid for CH/nH system. However, by considering a certain degree of non-
ideal behaviour in liquid phase, the situation can turn upside down, i.e. a larger
relative volatility obtained at the bottom than at the top conditions. The extent of this
will depend on the method used to estimate the characteristic activity coefficient.
However it should be noted that in this case the average value remained nearly the
same. These kind of thermodynamics related uncertainties is generally avoided if a
close boiling mixture like CB/EB system is used.
If an average is taken then the geometric average of top and bottom values is
preferred:
α = αT ⋅ α B [11]
For binary mixtures, the chosen relative volatility in conjunction with the
representative composition (mole fraction of more volatile component, x) determines
the slope of the equilibrium line, m, via:
dy α
m= =
dx [1 + x(α − 1)] 2
[12]
For total reflux case, (L/G) = 1, the stripping factor, λ = mG/L = m/(L/G), which
represents the ratio of slopes of equilibrium and operating lines, is equal to the slope
of the equilibrium line (λ = m). L and G represent molar flow rates of the liquid and
vapour (gas), respectively.
z.olujic@tudelft.nl 30
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
Another theoretically more appropriate measure is the HTUoG (or HoG), i.e the
height of an overall gas side transfer unit, which however requires the information on
the number of transfer units contained in a bed:
hbed
HTU oG = [14]
NTU oG
The number of transfer units is not readily available and the most common
practice is to use HETP, which is based on the number of theoretical plates, which in
turn can easily be determined using established graphical or analytical methods in
conjunction with accurate equilibrium data.
For ideal systems (CB/EB) and nearly ideal systems (CH/nH), the number of
theoretical plates or stages generated in the installed bed during a total reflux
experiment can be determined with confidence using well known Fenske equation:
⎡⎛ x ⎞ ⎛ 1 − x ⎞ ⎤
ln ⎢ ⎜ ⎟ ⎜ ⎟ ⎥
⎣ ⎝1 − x ⎠D ⎝ x ⎠B ⎦
N = [15]
ln α
where x (-) is the mole fraction of more volatile component in the binary mixture and
α (-) is the relative volatility, i.e. its representative value, most frequently the
geometric mean of top and bottom values (Eq. 11).
The sensitivity of this equation to measurement errors in relative volatility and
compositions on both ends has been thoroughly elaborated in a paper by Deibele
and Brandt [39], indicating that the effect of deviation in relative volatility is stronger
and tends to increase with decreasing relative volatility, and that keeping the mole
fraction of more volatile component in the bottoms in the range between 10 and 40
mole % and in the top between 60 and 90 mole % ensures that relative error will be
kept below 2 %. This exercise clearly indicates that significant errors can be
expected if dealing with relative volatility below 1.1, which is a value the CB/EB
system could assume if operated at pressures above 2 bar. Certainly, it is essential
to use accurate equilibrium data for the test system in question.
From time to time doubts arise about the reliability of Fenske equation. A
recent study of B. Kaibel [40] introduced an alternative, in a way mathematically more
rigorous, integral solution based analytical form of McCabe-Thiele plot, which
indicated that Fenske equation may be wrong to some extent, depending on
difference in top and bottom compositions, which however becomes pronounced at
relative volatilities above 1.5, and should definitely be considered if dealing with non-
sharp separations. From the evaluation of SRP data on Montz structured packings
[17] it appeared that CH/nH system is practically insensitive in this respect and in
case of CB/EB system with relative volatilities in the range 1.1 to 1.2 there is no
effect at all. This means, that Fenske equation in conjunction with proper
thermodynamic model and measured top and bottom compositions can be
considered to be a reliable tool for determination of mass transfer efficiency of
packings tested under total reflux conditions.
z.olujic@tudelft.nl 31
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
Applying the Eq. [15] to Eq. [13] yields the working expression used widely to
determine the efficiency of a packing from measured top and bottom compositions:
h pb ln α
HETP = [16]
⎡⎛ x ⎞ ⎛ 1 − x ⎞ ⎤
ln ⎢⎜ ⎟ ⎜ ⎟ ⎥
⎣⎝ 1 − x ⎠ D ⎝ x ⎠ B ⎦
There are also stage by stage methods available, used in conjunction with
commercial software, but these are useful mainly if it is dealt with multicomponent
mixtures. A common practice for wide boiling binary mixtures is to use McCabe-
Thiele plot cut into concentration regions where the equilibrium line can be
approximated as a straight line and the representative average HETP obtained in
additive way.
HETP and HTUoG are related to each other through stripping factor, λ, i.e. the
ratio of slopes of equilibrium and operating lines in the McCabe-Thiele plot of the
given case. If the equilibrium and operating lines are straight and in parallel: HETP =
HTUoG, and this is the case with CB/EB system. If the lines are straight but not
parallel then following expression holds:
ln λ
HETP = HTU oG [17]
λ −1
A practical demonstration of this equation can be found in a most recent
reference discussing the effect of the test system as experienced during a total reflux
distillation study carried out with a high performance, high specific surface area
packing (Mellapak 752.Y) [21].
Also, it should be noted that the additional internal reflux generated by
condensing the vapour along the column wall is not so pronounced in the columns
with diameters as considered here, to have a substantial influence on efficiency.
Practically, the same is with sub-cooling effect that effectively creates additional
internal reflux, which, however, in total reflux situation appeared to be much less
influential than generally anticipated. However, one should not forget that a
pronounced difference in enthalpies of vaporisation of two components forming the
test mixture could do some harm to efficiency and should be recognised and
accounted for appropriately. This is not a concern with CH/nH and CB/EB systems,
but it is recommended to perform the necessary calculation exercise to determine the
extent of the effect and make appropriate decisions toward standardisation of
calculation methods. The same is recommended for subcooling and heat loss related
effects.
z.olujic@tudelft.nl 32
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
there is a certain length of empty column included. For such a rather short tube the
friction with the column walls may be considered negligible, however, if the operating
pressure is high, i.e. well above atmospheric, the static pressure of the empty column
could play a significant role. In such a case, the packing pressure is that obtained by
detracting the static pressure of the empty part of the column from the measured
pressure drop. If, in conjunction with a short bed, the liquid distributor is placed below
the upper pressure tap, then this needs to be considered, particularly if the free area
of used liquid distributor is on lower side, i.e. well below 50%, and high gas velocities
are involved. As suggested elsewhere [35], for a test column operating at 100 mbar
at a F-factor of 3 Pa0.5, a narrow trough distributor with 40 % free area would cause a
pressure drop of about 0.2 mbar, which is not significant if the measured pressure
drop is above 10 mbar. Also, if a chimney-tray or chevron type liquid collector is used
to distribute gas, and placed above the bottom side pressure tap, then a significant
additional pressure drop can be expected. Reference [35] contains correlations which
enable estimation of related pressure drop of these frequently used devices.
In other words, the pressure drop per meter packed height is:
where subscript pb refers to packed bed, and subscripts st, ld, and lc denote
pressure drop associated with static pressure of empty column, liquid distributor and
liquid collector, respectively.
z.olujic@tudelft.nl 33
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
There is no doubt that for a company manufacturing fine and bulk chemicals
the best practice is to have at disposal a test unit of a size sufficient to ensure
obtaining representative packing performance data, to understand and to minimize
technical risk associated with (re)design and operation of an industrial scale
installation if equipped with a new type of packing.
For structured packings, a column diameter of 0.4 m or larger in conjunction
with a maximum bed height of 4 m, allowing 5 to 25 theoretical stages to be
developed, depending on packing size, looks to be a reasonable choice.
Total reflux operation is a natural choice and provisions can be easily made to
ensure performing some tests with a liquid to vapour flow rate ratio below or above
one.
Since structured packings are mainly considered for application under vacuum
(100 mbar is a representative value) and nearly atmospheric pressures, the
reasonable choice is to have an installation capable of covering this range of
operating pressures with one test system and using one, high turndown, high free
area narrow trough liquid distributor with drip tubes to ensure constancy in initial
liquid distribution pattern.
The ideal CB/EB mixture is a good test system, however, being a low
(constant) volatility system it provides higher efficiencies from those obtained with
common wide boiling hydrocarbon mixtures, with like CH/nH system. Also, because
of high operating temperature this system is not suitable for above atmospheric
operation. In other words, it cannot be used for the purposes of evaluating a packing
performance under relatively high liquid load, say above 20 m3/m2h. The exceptions
in this respect are tests carried at atmospheric pressure in conjunction with low
specific surface area, high capacity packings, which operate at F-factors well above 3
Pa0.5. In case of the CH/nH system, operated at SRP at 4.14 bar, at highest F-factor
liquid loads up to 50 m3/m2h are generated, without any temperature imposed
limitation.
Test procedure should be established based on own evaluations and accepted
as a standard to ensure consistence of test results. A continuous, i.e. non-stop
z.olujic@tudelft.nl 34
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
operation is preferred. If safety and/or personal reasons require daily operation then
the equipment size should be minimised, to reduce stabilisation times required to
arrive at steady state conditions after start-up and changes in column loads.
Evaluations of relevant factors, summarised in this report have provided a
good guidance regarding pilot-plant column design and operation, however further
experiences, based on pilot-plant building, start-up and dedicated operation are
needed to arrive at desired final goal, i.e. definition and adoption of a standard total
reflux distillation test, to be considered useful for scale-up purposes.
z.olujic@tudelft.nl 35
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
Nomenclature
Greek letters
α relative volatility, -
∆p pressure drop, bar or mbar
λ stripping factor, -
ρG vapour density, kg/m3
ρL liquid density, kg/m3
Subscripts
z.olujic@tudelft.nl 36
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
References
[4] Billet, R.
Industrielle Destillation
Verlag Chemie, Weinheim, 1973.
[5] Billet, R.
Packed Towers
VCH, Weinheim, 1995.
[6] Mackowiak, J.
Fluiddynamik von Kolonnen mit modernen Füelkörpern und Packungen für
Gas/Flüssigkeitssysteme
Salle+Saueerlander, Frankfurt aM, 1991.
[9] Spiegel, L.
Mellapak für die Hochdruckrektifikation und –absorption
Swiss Chem 8 (1986) No. 2a, 23-28.
z.olujic@tudelft.nl 37
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
[19] Olujic, Z., Seibert, A. F., Kaibel, B., Jansen, H., Rietfort, T., Zich, E.
Performance Characteristics of a New High Capacity Structured Packing
Chem. Eng. Processing 42 (2003) 55-60.
z.olujic@tudelft.nl 38
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
[31] Olujic, Z.
Effect of Column Diameter on Pressure Drop of Corrugated Sheet Structured
Packing
Trans. IChemE, Part A, Chem. Eng. Res. Des. 77 (1999) 505-510.
z.olujic@tudelft.nl 39
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
[34] Potthoff, R.
Maldistribution in Füllkorperkolonnen, Fortschritberichte VDI, Nr. 294, VDI-Verlag,
Düsseldorf, 1992.
[37] Mori, H., Ibuki, R., Taguchi, K., Futamara, K., Olujić, Ž.
Three-Component Distillation Using Structured Packings: Performance Evaluation
and Model Validation
Chem. Eng. Sci., 61 (2006) 1760-1766.
[40] Kaibel, B.
Untersuchung zur Verbesserung von Durchsatz und Trennleistung von
Destillationspackungen
Diplomaarbeit, Universitat Karlsruhe (TH), Institüt für Thermische Verfahrenstechnik,
1999, 86 pages.
z.olujic@tudelft.nl 40
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
[43] Olujic, Z., Jansen, H., Kaibel, B., Rietfort, T., Zich, E.
Stretching the Capacity of Structured Packings
Ind. Eng. Chem. Res. 40 (2001) 6172-6180.
z.olujic@tudelft.nl 41
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
APPENDICES
z.olujic@tudelft.nl 42
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 43
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 44
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 45
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 46
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
Operating conditions: Total reflux, CB/EB system, 0.1 bar, column diameter: 0.45 m, packed height: 2 m
Run number X-A1 X-A2 X-A3 X-B1 X-B2 X-B3 X-C1 X-C2 X-C3 X-D1 …
Packing tested (type) B1-250MN B1-250MN B1-250MN B1-250MN
z.olujic@tudelft.nl 47
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
NOTES:
z.olujic@tudelft.nl 48
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 49
VERSION 1 - Standardization of Structured Packing Efficiency Measurements 14 March 2008
z.olujic@tudelft.nl 50