Report Summary

The design of a continuous adsorber is a critical aspect of chemical engineering that involves the
removal of impurities or the separation of components from a fluid stream using adsorption
principles. The continuous adsorber is a dynamic system that operates in a steady-state mode,
allowing for a continuous and uninterrupted process. The key components of the design include
selecting appropriate adsorbents, determining optimal operating conditions, and establishing a
robust regeneration strategy. The choice of adsorbent material depends on the specific
characteristics of the target molecules and the nature of the fluid stream. Factors such as surface
area, pore size, and affinity for the adsorbate play a crucial role in the selection process.

The continuous adsorber design focuses on achieving high efficiency and productivity while
maintaining a stable and sustainable operation. This involves optimizing parameters such as bed
height, flow rate, and temperature to maximize adsorption capacity and minimize energy
consumption.

Moreover, safety considerations, environmental impact, and cost-effectiveness are integral

components of the overall design strategy. By incorporating these factors, the continuous adsorber
design aims to deliver a reliable and economically viable solution for industrial applications.

In this report, we will explore the design and functionality of a continuous adsorber, a crucial
component in various industrial processes. From its purpose to design considerations, operating
parameters, benefits, and limitations, we will delve into every aspect to provide a comprehensive
understanding of this innovative technology.
TABLE OF CONTENTS
01 INTRODUCTION

02 MATERIALS AND METHODS

03 EXPERIMENTAL DEVICES

04 BATCH AND CONTINUOUS MODEL DESIGNS

05 RESULTS AND DISCUSSION

06 CONCLUSION
1
 Introduction
Adsorption is a technique for separating substances from gas or liquid phase onto surface
of adsorbent. This is one of the methods for selective separation mechanisms in which it
adsorbs one or more components from the mixture on a surface. Materials used to adsorb
components are called as adsorbent while adsorbate is the component that being adsorbed.
Adsorbent can be classified as synthetic adsorbent, natural adsorbent and semi-synthetic
adsorbent. Synthetic adsorbent is most popular adsorbent used for researcher because of
high adsorption capacities but, highly in cost production. Natural adsorbent such as plant,
flower and leaf give very low-cost production but also give low adsorption capacity. While
the semi-synthetic adsorbent that can be define as natural material combining with
chemical that possess high adsorption capacity and low cost compared to synthetic

adsorbent. In adsorption, it can be categorizing as physical adsorption and chemical

adsorption, where it is classified according to the bonding forces between the adsorbent
and adsorbate. Physical adsorption is happening due to the attraction force of weak Van der
Waal while chemical sorption happens due to the chemical bonding between adsorbate and
adsorbent. When there is concentration difference between adsorbate and adsorbent, the
adsorbate molecules in solution move and bind onto surface of adsorbate. To simplify,
adsorption involves bonding of molecules between adsorbent and adsorbate. Generally,
most solid have adsorbent characteristics but the performance of adsorption differs
according to their functional groups. Currently, adsorption technology is adopted in treating
textile effluents which contains several mixtures of dyes and heavy metals. There is
common adsorbent have been extensively studied and commercialized such as silica gel,
activated alumina and activated carbon. Activated carbon is the main adsorbent that are
used for the water treatment. Researchers came out with idea of using activated carbon due
to its simplicity and ability to remove broad ranges of pollutants with lower cost. Not
limited to small scale focus, researchers also conducted study on activated carbon usage
for waste streams purification. Materials for activated carbon usually have a high
percentage of carbon and the adsorption capacity varies depending on their porous
structure. In addition, it should be noted that characteristics of carbon precursor and

2
 techniques during synthesis including the experimental condition have significant effect to
the final pore size distribution for activated carbon. This also led to varying adsorption
performance. Besides activated carbon, widely increasing studies on adsorbent has
produced many types of adsorbents, developed to eliminate heavy metals from effluents.
The various adsorbent study is sawdust, carbon aero gel, herbaceous peat, fly ash , modified
clay, activated carbon-zeolite composite and many more. Modifications to the surface of
adsorbent was done depending on particle that is going to pass through. These
modifications such as graft copolymerization helps to enhance properties of adsorbent by
modifying the physical structure and addition of new functional groups to the adsorbent
molecules. This helps to increase the ability of the adsorbent to attract dye having anionic
properties. The use of zeolite as an adsorbent also increasingly widespread equivalent to
another adsorbent. Zeolite is known as crystalline compound consist of alumino-silicates.
It has uniform cavities and excellent ion exchange capacity. Zeolites remove heavy metals
through two mechanisms; adsorption and ion exchange. Substitution of alumina molecules
for silicon produce negative charge density, which is good to attract cations heavy metal.
The presence of metal ions in zeolite framework helps to balance the charges. Due to their
superior features, zeolite is studied for utilization in several applications. Some uses
clinoptilolite in their studies to eliminate metals such as aluminium, copper and zinc from
copper mine effluents. Ion exchange method is different from adsorption. For ion exchange
mechanism in removal of heavy metals, exchange process between sodium ions and zeolite
(Zeolite NaX) with different types of metal ions are widely investigated. The process
performance of is affected by Zeolites’ pore opening and equilibrium exchange between
the solution and Zeolite NaX. Heavy metals are classified as non-biodegradable component
. Presence of heavy metals in water threaten the living organisms as it can cause health
issues to not only plants but also humans and animals. Most common heavy metal found
in drinking water and waste water is Lead (Pb). Some health hazards possessed by Pb if
consumed unnecessarily are mental retardation, decrease in amount of blood hemoglobin
and causing damage to nervous system. Industrial waste water contains numerous mixtures
of both inorganic and organic chemicals which complicates the treatment procedure. Batch
adsorption studies give an important data and parameter on the removal of adsorbate, while
column adsorption provide information on adsorption study with different of adsorbent
used. The small-scale experiment from the batch study can give the important information
on the parameter used for adapted in industry scale by fixed bed column. In comparison to
batch adsorption, continuous column is more advantageous as it is easy to operate, faster
adsorption process and simplicity of scale up process. However, batch adsorption is favored
by researchers at laboratory scale investigation as only small amount of material is used
and it is less time consuming. Nevertheless, batch adsorption is convenient for small scale
study but not suitable for real scale application. Study of adsorption by equilibrium in batch
mode enable the prediction performance of adsorbent before application in larger scale. To
add, the equilibrium study also provides critical information about the efficacy of particular
adsorbate-adsorbent system. In column adsorption, the contact time is not long as in batch
adsorption and thus, equilibrium is not reach for certain adsorption. It can be said that
results from batch studies might not accurate for scale up column adsorption due to less

3
 contact time but still applicable for predicting the performance. Therefore, it is crucial to
check the practicality of adsorbent in continuous mode. Fixed bed adsorption is widely
utilized to purify liquid mixture including mixture from industrial waste water. Recently,
this method is studied for a large-scale removal of heavy metal effluent. To calculate and
predict the performance of adsorption, mathematical model has been developed and used
to estimate the breakthrough curves. Also, the mathematical equation is employed in
current removal of organic pollutant from waste water. Two information that are required
in order to design an adsorption fixed bed is its dynamics and rate data. Consideration that
needs to be taken is the influence of operating parameters on the adsorption by fixed bed.
Researchers studied the process kinetics by using mathematical equation that inclusive of
resistance by external and internal mass transfer, fluid velocity along the column and type
of flow along the column. Large scale effluents need continuous flow as the volume is high
and continuous flow provide advantage for cyclic adsorption/desorption. The breakthrough
curves obtained from mathematical calculation determined the life span of a column bed
and its regeneration time. Only few literatures reported on metal removal via continuous
mode. Based on kinetic models established by previous researcher, kinetic of fixed-bed (or
packed bed) model can be determined through the breakthrough curve. As presence of
heavy metals from industrial effluent possesses high environmental risk, industries
employed fixed-bed column for their adsorption process. The industry scale adsorption
runs in the continuous mode due to high volume of wastewater. Industry looking for the
column adsorption method by knowing the advantages of the model are simple and reliable.
Few dynamic bioadsorption studies have been reported since past decade. Also, some
adsorbents studied for copper ions removal via fixed-bed adsorbent such as coconut-shell,
chitosan immobilized bentonite, zeolite/cellulose acetate blend fiber and rice husk-based
activated carbon were published. Another researcher attempted to eliminate Nickel ions
using activated carbon extracted from sugarcane bagasse and tea factory waste. In
summary, adsorption is more beneficial compared to other water treatment techniques
available as it is easy to operate, lower cost of operation and simplicity of design.

Fluid–solid adsorption is a common industrial technique that is normally used for both
product separation and wastewater treatment. In the field of water purification, the removal
of dyes from wastewaters is an argument of great interest in chemical engineering science.
Over 100,000 kinds of dyes are produced every year with a production of more than 7 -
105 tons y1 ; they are widely used in a variety of industries like textile, leather, paper and
others. By considering such employment, the dye removal is a key factor both for
environmental and quality aspects. In fact, even concentrations less than 1 ppm of dyes can
give an undesirable highly visible color to water and some dyes, or their degradation
products, may be toxic and carcinogens. For this reason, numerous techniques for water
de-colorization have been developed like coagulation, flocculation, several kinds of
physical, chemical and biological degradations and the use of cation exchange membranes.
Beside these, the adsorption on solid adsorbents is a technique that shows many attractive
features. The advantages of this technology are represented by low costs, simplicity of
design, ease of operation and insensitivity to toxic substances. The cheapness of the method

4
 is mostly dependent on the adsorbent choice, for example by using non-conventional
lowcost adsorbents (active carbon from natural waste sources, i.e., pinewood, rice husk,
tree fern, vine, sugar cane dust, banana pith, corncob, coal sewage sludge, fly ashes ) or
natural materials, such as clays and silica. In order to properly design an adsorption column
for dyes removal, it is necessary to perform an intensive batch investigation on both the
equilibrium and the kinetics of the couple adsorbate/ adsorbent. Some important physical
and chemical properties can be determined with a correct experimentation, such as the
equilibrium dye concentration on the adsorbent, the diffusivity of the adsorbate in both the
external film of the liquid–solid interface, the internal diffusivity and the surface diffusivity
. All the mentioned properties are of crucial importance in design of an adsorption column
and are only measurable univocally by performing batch experiments. In the present work,
a model system has been taken into account, that is the adsorption of methylene blue over
silica. Methylene blue (MB) has been chosen as adsorbate molecule, because it is widely
used in industry for dying cotton, wood and silk and its release in the environment can
generate health disease to human and animals such as eye burns or permanent injuries to
eyes. Even if in the literature there are already some papers dealing with the removal of
MB by adsorption using siliceous adsorbents, the collected data are not enough detailed to
design an adsorption column, because lacking of either the equilibrium or kinetic data. For
this reason, the sorption of methylene blue on raw silica has been explored in this paper,
designing two experimental devices useful to collect adsorption kinetics data and carrying
out a systematic study to explore the effect of stirring rate, mass of adsorbent, dye initial
concentration, solid particle size in batch conditions, and of length of packing and particle
dimensions in continuous conditions. All the collected experimental data have been
interpreted with a dynamic intraparticle model (ADIM) previously developed and validated
for batch systems.

Materials and Methods:

Adsorbent and adsorbate properties
In performing equilibrium and kinetic experiments, raw silica cylindrical pellets
AerolystTM 355 were used as adsorbent material without any type of pre-treatment. A
morphological characterization of the solid was made by physisorption of N2 at 78 K.
Physical properties of the solid are listed in Table 1. The average equivalent particle radius

5
 has been calculated as reported in the literature , that is the radius of a sphere of equal volume
(RP = 6 . VP/SP). This value has been considered as the integration extreme of the mass
balance intraparticle equations. Trihydrate methylene blue powder has been provided by
ICN Biomedicals, Inc. (M.W. = 373.9 g.mol^-1 , CAS: 7220-79-3) and was used to realize
a stock solution at concentration of 1.10^-2 mol.m^-3 then diluted when necessary. Dye
concentration was detected by UV analysis by using a Jasco UV-975 detector. Among the
various peaks characterizing the methylene blue spectrum, the one at the wavelength of 291
nm was chosen for detection, as advised in other literature works.
Experimental devices:

In order to obtain batch kinetic uptake curves, a proper experimental apparatus was installed
(Fig. 1A). Solid particles were put in contact with about 150 cm3 of an MB solution in a 250
cm3 glass jacketed three-necked flask with an impeller providing the stirring of the system

6
 at the desired rotational speed. Using a Jasco 880-PU HPLC pump liquid from the bulk of
solution was continuously withdrawn, pumped at 10 cm3 /min into the UV detector and then
returned to the flask. The absorbance measured by the detector was acquired by a DAQ
system (NI-USB6211) connected to a computer, at an acquisition rate of one value per
second. A thermocouple placed in the bulk solution monitored the temperature that was kept
constant by using a thermostat. In order to collect breakthrough curves data, a lab-scaled
adsorption apparatus has been assembled by filling the column with different amounts of
cylindrical silica pellets (see Fig. 1B). Aqueous methylene blue was continuously withdrawn
from the stock solution and flowed into the column using the already mentioned peristaltic
pump. The column was constituted by a cylindrical stainless steel pipe with length L = 0.4
m and radius R = 0.005 m. The temperature was kept constant at T = 30°C by using a
recirculating thermostat, flowing water in the column jacket. The column temperature was
monitored with a thermocouple. Once flowed through the column, the solution was sent to
UV– VIS detector. The pipelines connecting the pump to the column and the column to the
detector were steel pipes with external diameter of 1/1600 in order to minimize dead
volumes. The column void fraction (Ɛv = 0.4) was easily measured by filling the column
with wet silica pellets and weighting the amount of water that the filled column was still able
to contain. To have rigorous breakthrough curves as output, the dead times due to the
pipelines have been measured and taken into account. At this purpose, methylene blue
aqueous solution was flowed into each pipe as a step-wise fluid dynamic test and the
inflection point of the resulting sigmoid has been considered as the dead time. By working
at a fixed flowrate, the dead volumes can be easily calculated. In this way, the overall dead
volumes (pipelines, connections and HPLC pump internal volume) resulted to be 7.3 cm^3
.

Batch and continuous model equations:

In order to interpret the kinetic experimental data, a dynamic intraparticle model previously
developed and validated has been used [14,15]. According to the mentioned model the
system is conceptually divided into three domains: (i) a bulk liquid phase, (ii) a liquid
intraparticle phase, (iii) a solid intraparticle phase. The dye is transferred from the bulk phase
to the particle through the liquid film by molecular diffusion and then it diffuses along the
particle radius in the pore, in which the mass transfer is divided into the parallel contribution
of liquid porous diffusion, surface diffusion and adsorption [15]. For simplicity, all the
particles have been considered of the same size, with a cylindrical geometry (s = 1). With
these assumptions, the adsorption kinetics can be described by writing the mass balances
constituted by two partial differential equations, one considering the film transfer (Eq. (1))
and one the intraparticle diffusion (Eq. (2)).

7
 Here, the pore diffusivity (DP) can be calculated from the molecular diffusivity (D0), that
can be estimated by using the Wilke–Chang correlation [17], porosity (e) and tortuosity (s)
of the particle, as in Eq. (3), approximation valid for solid characterized by macro and
mesoscopic pores. In particular, the estimated value of methylene blue molecular diffusivity
in water is 6.10^10 m^2 s^-1 , that is in linea with the experimental value reported in the
literature [18]: D0 = 4.6. 10^10 m^2 s^-1 .
The boundary conditions needed to solve the PDE system are: (i) intraparticle local
equilibrium between surface and liquid phases (Eq. (4)) expressed in terms of the adopted
equilibrium isotherm; (ii) spherical symmetry (Eq. (5)); (iii) steady-state on particle surface
(Eq. (6)). The equilibrium between surface and liquid phases has been considered
instantaneous, and this aspect is one of the main approximation of the presented model.

Solving the partial differential equations with the method of lines it is possible to obtain
temporal bulk concentration profiles. In order to adapt the equations listed above to a
continuous system, the mass balance on the bulk phase must be opportunely arranged.
Particularly, it is necessary to consider the motion of the fluid along the packed column

8
 adding terms accounting for the convective flux and dispersion. In this way, the
concentration profiles depend also on further two coordinates, that are the axis and the
radius of the pipe. By considering that the equipment used in the present study has a
L/D=40, it is possible to neglect the radial dispersion, so the concentration profiles depend
only on the axial coordinate (z) and the axial dispersion contribution must be included in
the final bulk phase mass balance (Eq. (7)).

Concerning the intraparticle mass balance, Eq. (2) is still valid. By considering that the
bulk concentration evolves along the axial direction, both CL and CS terms are axial
coordinate dependent, too. All the boundary conditions already defined for the particle
remain valid, but it is necessary to add the boundary conditions related to the column
coordinates. At the column entrance (z = 0), it is considered that no adsorption occurs and
that there is no accumulation. On this basis, it is possible to assume that the axial dispersion
must be equal to the convective term (Eq. (8)). This kind of condition is called Danckwerts
closed boundary condition . For the intraparticle solid and liquid concentrations, conditions
in Eq. (9) are defined at z = 0, while at the column final section (z = L) conditions in Eq.
(10) are valid:

The assumption that the spatial derivatives of the concentrations at the column boundaries
are equal to zero is a reasonable approximation, considering that the concentration
variations between the inlet flow and the first section of the column are typically slight (this
is also valid for the last column section and the outlet flow).

3. Results and discussion:

9
 Adsorption isotherm study

The analysis of the equilibrium isotherm is crucial to solve the mathematical system and
the goodness of the fitting on the kinetic data depends on the correctness of its estimated
parameters, especially in the region of kinetic curves concerning the final plateau. The

adsorption isotherm experiments have been performed at 30 °C, by preparing different MB

solutions with the same concentration but different silica amount. The solutions have been
stirred for about 3 weeks in order to be sure to have reached the equilibrium. The collected
experimental data have been fitted with two classical isotherm equations, the Langmuir
(Eq. (11)) and the Freundlich (Eq. (12)):

where b is called affinity parameter and CS* is the concentration of dye on the solid at
saturation of monolayer while KF and n are Freundlich empirical parameters and,
respectively, rough measures of adsorption capacity and adsorption effectiveness. The
analysis of the R2 value (0.99 for Langmuir isotherm and 0.95 for Freundlich isotherm)
suggested the use of Langmuir equation. In Fig. 2, the fitting curves are shown. Optimized
Langmuir’s parameters are b = 646.2 ± 94.4 m3.mol^-1 and CS* = 140.6 ± 4.17 mol.m^3
sol. 3.2. Batch kinetic study Once equilibrium isotherm parameters were estimated, it is
possible to proceed through the kinetic study. For this purpose, a set of experiments were
performed at the temperature T = 30°C to explore the effect of different operative
conditions, that are listed in Table 2. As already mentioned, the used experimental system
was able to acquire one absorbance (and so concentration) measurement per second. On
the other hand, the UV detector is characterized by an instrumental noise resulting in an
undesired oscillation of uptake data pattern. For this reason, a smoothing operation was
carried out to eliminate the electrical disturbance, by using a Savitzky–Golay of 2nd order
algorithm for the experimental data smoothing operation. Further, only a part of the whole
dataset was reported on pictures for a reading purpose. Fig. 3 provides a clear example of
the explained operation. In order to properly interpret the collected kinetic data, all the
chemical–physical parameters must be known, that are: (i) the external mass transfer
coefficient (km); (ii) tortuosity factor (s); (iii) surface diffusivity (DS). The typical ranges
reported in the literature of the mentioned parameters are: km = 10^-8( –1 m.s^-1 ), s = 1–
10, DS = 10^18(–10^-11) m2.s^-1. By considering that the performed experimentation
covers a wide range of operative conditions, the mentioned coefficients have been
determined by simultaneous parameter estimation analysis on all the collected
experimental data performed at 300 rpm. The obtained parameters are: km = (3.42 ±
0.11).10^-4 m.s^-1 , s = 8.29 ± 0.78, and DS = (4.74 ± 0.09).10^-12 m2 .s^-1 . As it can be

10
 seen, the estimated parameters fall in the mentioned typical ranges reported in the literature.
In Fig. 4, the effect of the adsorbent content on the kinetic curves is reported. The
simulations performed at different solid contents show good agreement. As can been
appreciated, using greater amounts of solid, an increase of the adsorption kinetics can be
observed. In fact, the initial slope of the kinetic curves increases when loading a bigger
amount of silica in the adsorber. This aspect is in linear with the typical experimental
evidences reported in the literature.

In interpreting data obtained at different stirring rate, the mass transfer coefficient has been
estimated on dataset for each experiment. As a matter of fact, by increasing the stirring rate
in a fluid– solid system, the width of the stagnant film surrounding the solid particle gets
thinner. Consequently, the km value gets higher, fact that corresponds to a faster adsorption
rate. This parameter mainly influences the initial slope of the adsorption kinetic curves.
According to this, the parameter estimation process allowed to obtain km values that well
fit the initial slope behavior of adsorption curves. In fact, the greater the stirring rate, the
greater is the absolute value of the slope, clearly indicating that a better mixing condition

11
 enhances the mass transfer through the stagnant liquid film sur rounding the adsorbent
particle. As it can be appreciated in Fig. 5, the maximum value of the mass transfer
coefficient is km = 3.73.10^-4 m.s^-1 and the km versus stirring rate is roughly lin ear in
the investigated stirring rate range. Thus, the importance of the liquid film mass transfer as
rate limiting step of the process have been observed for such a kind of system, in which the
stirring speed has a visible effect on kinetic curves. The reason of the liquid film transfer
limitation can be found in the use of relatively big cylindrical pellets of silica: in fact, it is
largely known that greater particles generates wider liquid films and vice versa. The effect
of initial concentration on adsorption kinetic has been investigated and elaborated. As it
can be seen, the bulk con centration profiles show an increasing initial slope when

12
 increasing the MB initial concentration. The collected data have been interpreted with the
ADIM model and also in this case we obtained a good data interpretation (Fig. 6). Then,
the effect of silica particle size has been investigated. In fact, the particle sizes influence
the adsorption kinetics in two ways: (i) smaller particle present a smaller intraparticle
diffusion path; (ii) smaller particles present a thinner stagnant fluid film

compared to bigger ones, so different km values. Thus, investigating this effect is a crucial
aspect for a complete adsorption kinetics description. To obtain particle with different
dimensions, the original cylindrical pellets were mechanically crushed two times, the first
roughly, the second more accurately. Being the particle relatively big yet, it has been
possible to measure an average particle size with a caliber (first size RP = 1.30 .10^-3 m,
second size RP = 9.25. 10^-4 m). In these cases, particles were considered spherical for
simplicity, as they assumed irregular shapes. The results of the experiments suggested that,
with smaller particles, faster kinetics are achieved. Predicted curves were obtained first by
simulations, using the same parameters of the reference curve. This is not completely exact;
in fact, the particle size influences the thickness of the liquid stagnant film and causes a
variation of the mass transfer coefficient. A further investigation has been carried out
verifying the sensitivity of this parameter. For the first particle size, for which particles
were only slightly smaller respect to integer cylinders, this operation did not have any
appreciable effect while for the second particle size, characterized by significantly smaller
particles, the optimization gave back a better fitting and, as expected, a slightly bigger

value of the mass transfer coefficient (km = 4.29.10^-4 m.s^-1 ). Therefore, being the
particle sizes of the same order of magnitude, the km values are comparable. These results
are shown in Fig. 7. Of course, the sensitivity of the model respect to particle size is
important, being this parameter an integration domain and it was already investigated in a
previous work [15].

3. Continuous kinetic study:

13
 Breakthrough data obtained with the
mentioned continuous
apparatus were smoothed and filtered
as for batch data. First of all, a
fluid-dynamic characterization of
the column has been carried out in
order to evaluate the axial
dispersion coefficient
without adsorption
contribution. The cross sectional
diameter was supposed to be
small enough to neglect any radial
dispersion. The mentioned
coefficient depends on several
factors as bulk fluid physical
characteristics, solute molecular
diffusivity, column void fraction
1Effect of MB initial concentration on the
adsorption kinetics and volumetric flow
rate. In order to carry out the
fluiddynamic characterization, the
column was packed with 3 mm
diameter steel spheres that
reproduced the features of the silica pellets package avoiding the adsorption phenomena (as
steel adsorbs only negligible methylene blue amount). For a packed bed the outlet
concentration can be obtained solving the mass balance reported in Eq. (13)

14
 In the present paper, the results obtained by using Eq. (13) have been compared with the

experimental outlet concentrations data is possible to estimate the value of DZ, as all the
other quantities are known. Three experiments have been performed by vary ing the
volumetric flowrate (Q1 = 4 cm3.min^-1 , Q2 = 7 cm3 .min^-1 and Q3 = 10 cm3 .min^1 ).
By performing a parameter estimation analysis, an average axial dispersion coefficient of
DZ = (5 ± 0.1).10^-4 m2 .s^-1 has been determined, showing to well fit the three
experimental curves, as reported in Fig. 8. In this way, in order to simulate continuous
adsorption tests, all the needed parameters are available except the mass transfer
coefficient, that is expected to be quite different from the one estimated for the stirred batch
system. A list of all the performed continuous experiments, with related experimental

15
 conditions, is reported in Table 3. A first test has been made with the intent to work under
negligible external mass transfer conditions. As it is well known from literature, the
external mass transfer coefficient strictly depends on the average particle dimension. The
correlation reported in Eq. (15) has been used in order to find an adequate particle diameter
value that gives place to a sufficiently high km value that, in agreement with our
preliminary simulations, lead to the possibility to exclude the external mass transfer regime.

In this way, the silica pellets have been mechanically crushed in smaller particles, which
average diameter has been measured with a caliber resulting to be 0.4 10 3 m (see
experimental conditions reported in Table 3). A simulation has been performed by using
the same pore and surface diffusivity values obtained in batch and a non-limiting external
mass transfer value. The results are reported in Fig. 9. As it can be seen, a good fit has been
obtained. Then, four experiments have been carried in the same conditions by using four
different length of the adsorbent bed, corresponding to the package weights reported in
Table 3, but with intact silica pellets, in order to investigate the external mass trans fer
limitation (see Fig. 10). A key aspect of the obtained curves is that, after an increase in
concentration at about 150 s, that corresponds to the average residence time of an inert
adsorption bed, including dead volumes, the system approaches to apparent saturation
values very slowly. A realistic hypothesis to describe the observed phenomena, is that in

16
 the adopted experimental conditions, the liquid–solid film external mass transfer is the rate
determining step and the total adsorption is delayed for the time necessary to the solute to
diffuse in the external liquid film. Thus, the solute starts to exit at the same residence time
as no adsorption occurs but, as this phenomenon occurs, the contribution of the mass
transfer starts to be significant. This cause a variation in the breakthrough curve slope. By
this point the outlet concentration only slightly increases, as in the column adsorption is
occurring more effectively. As shown in Fig. 10, the proposed model is able to predict such
behavior, by using km = (6 ± 0.1).10^-5 m.s^-1 . This value is in good agreement with the
estimation obtained by using Eq. (15), that gives 2. 10^-5 m.s^-1 . By considering that by
using the adopted correlation in its extremes, the km value ranges between 1.3 . 10^-5 and
6.4. 10^5 m.s^-1 , the value obtained in the present paper can be considered acceptable. In
order to properly compare the obtained results by using different silica particle sizes, the
adsorption efficiency is defined as in Eq. (16), in analogy to what is well known for catalyst
effectiveness factor. Here, the total liquid concentration inside the adsorbent particle is
normalized by the surface concentration. Of course, if this value is near to the unity, it
means that the concentration inside the silica pellet is homogeneous and equal to the surface
one (saturated pellet).

In Fig. 11, both the breakthrough profiles, prolonged till saturation, and the adsorption
efficiency obtained in simulating experiments C1 and C2 are reported. As it can be seen,
Fig. 11A shows that the experiment performed by using small silica particles gives to a
very regular breakthrough curve, with a sigmoidal shape. Instead, by using bigger particles,
a profile with two sigmoidal steps can be roughly observed: the first related to the external
mass transfer regime, the second to intraparticle diffusion regime. It is evident by observing
the contour plots reported in Fig. 11B and C that when the external mass transfer is
dominant, the particles are quite empty of methylene blue. So, the first inflection point of

17
 Fig. 11C is related to the methylene blue molecules that exit the adsorption column without
being adsorbed. As time proceeds, the external mass transfer slowly occurs and when the
film starts to be saturated, the intraparticle diffusion become dominant and a second
inflection point in the breakthrough curve can be seen. Although, for smaller particles, the
silica pellets get saturated gradually till the unique inflection point is reached (see Fig.
11B).

It is important to underline that the results obtained from the simulations performed under
external diffusion regime give important information in designing an industrial adsorption
column. As a matter of fact, if an industrial column works in these conditions it could be
possible to reach the desired outlet concentration (about 5% of the feed) with only a
partially full column, so using the sorbent only in part. This fact leads to economic

18
 consequences on the adsorption plant. Moreover, the apparent breakthrough could lead also
to important consequences on the regeneration techniques. These aspects are not
predictable with the adsorption models that are normally used and reported in the literature,
such as pseudo-kinetics 1st and 2nd order, fractal like and simplified diffusion models, that
neglects one or more diffusion paths that are considered in the ADIM model. The power of
the presented model, is that it is possible to predict both the case that have been observed,
so giving the opportunity to correctly design the adsorption column, choosing the right
working conditions.

CONCLUSION:
In conclusion, the design of a continuous adsorber emerges as a pivotal facet in the
landscape of chemical engineering, representing a dynamic solution for the ongoing
purification of fluid streams. The significance of this design lies in its ability to seamlessly
and continuously remove impurities while maintaining operational stability.

A key consideration in this design process is the judicious selection of adsorbent materials.
Careful evaluation of their properties, including surface area, pore size distribution, and
affinity for target molecules, dictates the efficiency and efficacy of the continuous adsorber.
This meticulous selection process ensures optimal performance tailored to the unique
characteristics of the substances targeted for removal.

Efficiency is further pursued through the optimization of operating parameters such as bed
height, flow rate, and temperature. Striking the right balance among these variables

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 maximizes adsorption capacity and minimizes energy consumption, contributing to both
economic viability and operational effectiveness.

Integral to the continuous adsorber design is the phase of regeneration, ensuring the
sustained functionality of the adsorbent. Methods like thermal, pressure swing, or vacuum
regeneration are strategically employed to rejuvenate the adsorbent, extending its
operational life and maintaining cost-effectiveness over time.Safety considerations,
environmental impact, and cost-effectiveness are woven into the fabric of the design
strategy. This holistic approach ensures not only the removal of impurities but also aligns
with sustainability goals and economic feasibility in diverse industrial applications.

In essence, the design of a continuous adsorber encapsulates a synergistic blend of

engineering precision, material science, and environmental responsibility. A well-crafted
design not only safeguards the efficiency of chemical processes but also aligns with the
evolving ethos of sustainable technology. As a perpetual guardian against impurities, the
continuous adsorber design embodies a commitment to excellence, innovation, and
environmental stewardship in the realm of chemical engineering.

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