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The integration of an in-situation separation function within the reactor holds the promise of
increased conversion, higher selectivity and reduced capital investment. The introduction of an
in-situation separation function within the reaction zone leads to complex interactions between
vapour liquid equilibrium, vapour
heterogeneously catalysed processes) and chemical kinetics. Such interactions have been shown
to lead to the phenomenon of multiple steady-states and complex dynamics, which have been
verified in experimental laboratory and pilot plant units. In this paper we have discussed the
Dynamics and Kinetics of four major separation processes namely Distillation; Extraction;
Absorption and Adsorption. Multi-functional reactor is discussed which is often used to embrace
reactive separations technology, which promises reduction in capital costs, increased conversion
and reduced by-product formation.
The design and operation issues for reactive separation systems are considerably more complex
than those involved for either conventional reactors or conventional separation columns. In
heterogeneous reactive separation the problem is exacerbated by the fact that these transfer
processes occur at length scales varying from 1 nm (pore diameter in micro gels) to say a few
meters (column dimensions).The time scales vary from 1 ms (dilution within gels) to say a few
hours (column dynamics). The phenomena at different scales interact with each other. Such
interactions, along with the strong nonlinearities introduced by the coupling between dilution and
chemical kinetics in counter-current contacting, have been shown to lead to the phenomenon of
multiple steady-states and complex dynamics, which have been verified in experimental
laboratory and pilot plant units.
The main underlying principle behind the application of reactive distillation for selectivity
enhancement is to facilitate the separation of selected components and favorably manipulate the
composition profiles in the reactive zone to get desired reaction. Reactive distillation today is a
well established operation that combines reaction and distillation in a single stage which offers
enhancement in the overall performance of the process. While there has been substantial
experimental & theoretical work reported on equilibrium related reactions, its practical
applications and its usage in selectivity engineering has not been well established. The basic
principle behind the application of this process for selectivity engineering is that one can
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favorably manipulate the composition profiles with the aid of distillation attributes to expedite
the desired reaction. A need for such progress has been emphasized here.
Survey has been done on the
emphasising the available alternatives and pointing out obstacles in the way of successful
implementation of this technology.[1]
process industries for having favourable economics of carrying out reaction simultaneously with
separation for certain classes of reacting systems, and many new processes (called reactive
separations) have been invented based on this technology. The most important examples of
reactive separation processes (RSP) are reactive distillation (RD) and reactive absorption (RA.
Chemical process industries have shown increasing interest in the development of reactive
separation processes (RSP) combining reaction and separation mechanisms into a single,
integrated unit. Such processes bring several important advantages among which are increase of
reaction yield and selectivity, overcoming thermodynamic restrictions, e.g. azeotropes, and
considerable reduction in energy, water and solvent consumption. Important examples of reactive
separations are reactive distillation (RD) and reactive absorption (RA). Due to strong interactions
of chemical reaction and heat and mass transfer, the process behavior of RSP tends to be quite
complex.
When considering in-situ separation of product, it is important to stress that often removing only
one of the products of the reaction is sufficient to drive the equilibrium to the right or prevent
unwanted side reactions. There is usually a choice with respect to the product to separate from
the reaction zone.
Fig 1: (a) Conventional 5xed-bed reactor train, with inter-stage sulphur removal by condensation,
for Claus process. (b) Fixed bed reactor, with in-situ sorption of water by zeolite adsorbent.
Adapted from Agar (1999).[1]
effectiveness of online model based applications, such as process control and optimization,
depends strongly on the quality of the available model predictions. When considering in-situ
separation of product, it is important to stress that often removing only one of the products of the
reaction is sufficient to drive the equilibrium to the right or prevent unwanted side reactions.
There is usually a choice with respect to the product to separate from the reaction zone
Compared to reactive distillation, the absence of a reboiler and a condenser makes reactive
absorption a simpler process. However, the drawback is the small number of degrees of freedom
that makes it difficult to set the reactants feed ratio correctly and consequently to avoid
impurities in the products. Reactive absorption offers indeed significant advantages such as
minimal capital investment and operating costs, as well as no catalyst-related waste streams and
no soap formation. However, the controllability of the process is just as important as the capital
and operating savings. Therefore, it is important to note that reactive absorption has less degrees
of freedom and therefore more difficult to control than reactive distillation. Reactive Absorption
is usually dominated by the mass transport kinetics. Besides, in reactive processes, chemical
reactions must be taken into account.
Mass transfer in RA is explained using the two-film theory. The boundary between the gas phase
and the liquid phase is presumed to consist of a gas film adjacent to a liquid film. Flow in both of
these films is assumed to be laminar or stagnant. The main-body gas phase and liquid phase are
assumed to be completely mixed in turbulent flow so that no concentration gradient exists in the
main body of either phase. The solute concentration in the gas film at the interface is assumed to
be in equilibrium with the solute concentration in the liquid film at the interface. There is a solute
concentration gradient across both the gas film and the liquid film.
in the gas phase. Therefore the absorption rate can be estimated by knowing the gas-phase rate
coefficient KG. The liquid-phase rate coefficient K6
+L is strongly affected by fast chemical reactions and generally increased with increasing
reaction rate.
The highest possible absorption rates will occur under conditions in which the liquid phase
resistance is negligible and the equilibrium back pressure of the gas over the solvent is zero. This
condition can be attained if KL is very large. Frequently, even though reaction consumes the
solute as it is dissolving, thereby enhancing both the mass transfer coefficient and the driving
force for absorption, the reaction rate is slow enough that the liquid-phase resistance must be
taken into account.
This may be due to an insufficient supply of a second reagent or to an inherently slow chemical
reaction. What this all boils down to is that the liquid-phase rate coefficient KL in the presence
of a chemical reaction normally is larger than the value found when only physical absorption
occurs. To account for the effects of chemical reaction, the liquid enhancement factor, E is
introduced.
kL
kLo < 1
the equilibrium state can be shifted favorably resulting in enhanced solution capacity.
Most of the RA processes involve reactions in the liquid phase only, in some of them both
liquid and gas reactions occur.
equilibrium.
Most of the RA processes are steady-state operations, either homogeneously catalyzed or
auto-catalyzed.
Pressure Constraints
Reactive absorption is best run at high pressures. The high pressure will force more gas into the
liquid phase and consequently a better reaction conversion will be attained. However, to operate
at high pressures requires the use of a compressor, which is usually the most expensive unit in a
plant design.
Temperature Considerations
In physical absorption it is best to operate at low temperatures to promote the gas to go to the
liquid phase and to avoid solvent losses to the vapor phase. In reactive absorption one would
want to operate at low enough temperatures to allow for absorption of the gas to the liquid, but if
the kinetics governing the reaction is not favorable at this temperature we have to weigh the
possibilities of operating at a higher. The burden is on the engineer to choose a solvent that reacts
with the solute at low enough temperatures.
advantageous because co-current operation eliminates the flooding concerns. We can have very
high flow rates for both the gas and solvent streams and still attain very good separations.
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CO2 Removal.
H2S Removal.
Removal of CO2 and/or H2S.
Removal of CO2H2S mixtures and other impurities.
Several reviews have been published in the last decades which give an excellent introduction and
overview of RD
Reactive distillation is one of the most promising technologies of the integrated reactionseparation concept because its design is simple and can increase the efficiency and profitability
of a process .
In RD, reaction and distillation take place within the same zone of a distillation column.
Reactants are converted to products with simultaneous separation of the products and recycle of
unused reactants. The RD process can be efficient both in size and cost of capital equipment as
well as in energy used to achieve complete conversion of reactants. Since reactor costs are often
less than 10% of the capital investment the combination of a relatively cheap reactor with a
distillation column offers great potential for overall savings. Among suitable RD processes are
etherifications, nitrations, esterifications, transesterifications, condensations and alcylations [12].
Conventional processes use one or more liquid-phase reactors with large excess of one reactant
in order to achieve high conversions of the other. This process requires a large capital
investment, high energy costs and a large inventory of solvents. In RD process the entire process
is carried out in a single column. The RD column represents an entire chemical plant and costs
one-fifth of the capital investment of the conventional process and consumes only one-fifth of
the energy
The successful commercialization of RD technology requires special attention to hardware
design that does not correspond to those for conventional (non-reactive) distillation.
The petroleum industry is a potential candidate for the use of RD technology. Co-current gas
liquid downflow trickle bed reactors are widely applied for hydrodesulphurization (HDS) of
gasoil and heavier oils as shown in figure (a) below. The counter-current reactor shown in figure
(b) is essentially an RD column wherein the H2S is stripped from the liquid phase at the bottom
and carried to the top. The major bottleneck to the implementation of RD technology for countercurrent hydroprocessing in commercial practice relates to hardware limitations. There is a need
to develop improved hardware configurations that allow counter-current contacting of gas and
liquid, in the presence of 11:5 mm catalyst particles, wherein the catalyst loadings are in the
region of 5060%.
12
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Improved conversion: By removing products from the reactive section, the chemical
equilibrium of equilibrium-limited reactions is shifted toward the product side, leading to
improved conversions.
Direct heat integration and avoidance of hot-spots. For exothermic reactions, the heat of
the reaction can be directly used to evaporate components, reducing the amount of total
heat required and avoiding the occurrence of hot-spots.
But even after several advantages it is not used in industries because of several reasons as listed
below:
1. Complexity resulting from non-ideality of components
2. Intricate hydrodynamics
3. Relying on empirical correlations for design and control
4. Difficulty in finding common operation range for T&P for both reaction and separation
5. Proper Boiling Point sequence
6. Optimum residence time
ii.
iii.
Reduced energy consumption via direct heat integra-tion in case of exothermic reactions;
iv.
v.
vi.
a simpler process,
vii.
viii.
ix.
i.
Common operation range for temperature and pressure for distillation and reaction.
ii.
Proper boiling point sequence: the key component should be a top or a bottom product,
undesired side or consecutive products should be medium boiling components.
iii.
3.4 APPLICATIONS:
Biotechnologies
Membrane-assisted Distillation
Organic Chemistry
Extension of Existing application areas.
Homogeneous catalysis
Bio-based processing
Retrofit
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successful scale up to commercial operations.In recent years, reactive extraction processes are
gaining lot of importance in response to extreme economic pressure posed by industries as the
result of emergence of new processes and decline of existing ones, demand of high purity
products with low cost and are environmentally safe . However, commercialization of reactive
separation processes is desired, which can be achieved by the mutual working of chemists and
engineers. Reactive extraction links chemical sources and sink to enhance reaction rates,
conversions and selectivity. Since most of chemical processes are equilibrium driven, removal of
product as soon as it is produced would lead to enhanced reaction rates, increased feed
conversions, reduce reaction severity and provide operation under milder conditions. Mass
transfer and reaction coupling improves catalyst life, since, high mass transfer forces lead to
better catalyst irrigation and surface renewals with transport of catalyst inhibitors away from
catalyst surfaces. Further, in reaction and separation operations, the duo would lead to high local
driving forces for separation, leading to reduction in equipment size, elimination of recyclable
streams and reductions in utility costs. Reactive separators also lead to safer equipments since it
reduces the working inventory of reactive chemicals in the equipment. Lower the hazardous
chemical, lower will be the chance of its leakage, spills and environmental release. Coupling of
reaction and separation also leads to suppression of byproduct reactions which are likely to
exhibit runaway behavior and the reactive separator design will increase the inherent safety in
the unit against severe process upsets. The combination also provides low cost equipment
through the consolidation of multiple pieces of process equipment into single piece and/or
through the elimination of process recycles streams
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1:
Boiling
points
of
pure
components
and
azeotropic
data
at
atm
Fig 5: Reactive distillation column with a membrane separation located in the distillate stream.
Identification of
distillation
processes is as follows:
The description of thermodynamic and physical properties of the
multicomponent System,
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It should be emphasized that no side product (di-n-propyl ether, DPE) was detected by gas
chromatography and no parameter fitting is carried out. Due to an excess of 1-propanol and a
sufficient amount of catalyst, the propionic acid is nearly completely converted in the reactive
section N-propyl propionate leaves the column as a bottom product beside non-converted
propionic acid. At the top of the column, an almost binary mixture consisting of 1-propanol and
water near to azeotropic composition with a small amount of n-propyl propionate is obtained.
The simulation results are displayed with continuous lines. Both the composition profiles and the
temperature profile are predicted with high accuracy.
21
Figure 6: Liquid phase molar fraction (left) and temperature profile of the vapour phase (right.
The solid lines represent the simulation results, the symbols the experimental values
22
Feed, retentate and permeate samples are analysed with the aid of gas
chromatography to determine the mass fraction of the organic component.
The experimental data and operating conditions are summarised in Table.
Table 5: Experimental data for the operating conditions of the vapour
permeation
experiments.
It can be seen that the separation characteristics show a strong dependency on the feed
concentration
5.3Conclusion
The theoretical and experimental investigation shows that the heterogeneously catalysed
synthesis of n-propyl propionate via a hybrid process consisting of reactive distillation and
vapour permeation is feasible The analysis of the hybrid separation process shows high
complexity in comparison to the stand-alone unit-operations, reactive distillation and vapor
permeation. Thus, the presented validated process models for both units are linked together to
enable a theoretical analysis of the hybrid separation process. Both the influence of decisive
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operational parameters, reboiler heat duty and reflux ratio, on the process performance in terms
of product purity and acid conversion and the effect of a variation of the recycle purity are
analyzed [8]
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concentrations (Benson et al., 1954). A rate-based model for the Benson Process based on
effective interfacial area to calculate the mass transfer was also developed by Cents .
Electrolyte System
The given reactive system of weak and strong electrolytes is described by considering the
following reactions with the dissociation constants Kj.
Its contribution to the overall rate of reaction is therefore small and can be neglected .To
calculate the concentrations of molecular and ionic species in solution the chemical equilibria
are expressed with their dissociation constants Kj.
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27
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the reaction and decreases as the reaction progresses. Furthermore, from Table was shown
that the ester yield is low at low catalyst concentration, but the ester concentration in the bulk
methanol is similar at higher and lower concentrations. Hence, inadequate conversion of
triglycerides in the bulk methanol phase is not the cause of the lower extraction
yield. On the other hand, it is likely that at low catalyst concentration, there is insufficient
conversion of triglycerides to ester inside the seed, which reduces the yield of ester.
Table:
Conclusion
The maximum yield of reactive extraction of rapeseeds using methanol is determined
primarily by the methanol to oil molar ratio. Methanol to oil molar ratios greater than 400:1
were required to obtain ester yields higher than 80%. This is a much higher amount of
methanol than that needed for conventional transesterification. In order to make the process
economically viable, more research is needed to identify techniques that can reduce the
solvent consumption. The rate of the process, on the other hand, is mainly controlled by
the catalyst concentration and the seed particle size. Decreasing the catalyst concentration
and increasing the particle size reduces the overall rate of extraction. Temperatures within the
range of 30 to 60 C only affect the initial rate of extraction, but the time to reach the
maximum yield is similar. It appears that the process is not significantly adversely affected
by water when the seed moisture content is less .Hence, the drying step could be removed if
the moisture content does not exceed this level, which should improve the process
economics.[10]
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References
1. R. Krishna Reactive separations: more ways to skin a cat, Chemical Engineering
Science 57 (2002) 14911504.
2. Agar, D. (1999). Multifunctional reactors: Old preconceptions and new dimensions.
Chemical Engineering Science, 54, 12991305.
3. Drioli, E., & Romano, M. (2001). Progress and new perspectives on integrated membrane
operations for sustainable industrial growth. Industrial & Engineering Chemistry
Research, 40, 12771300.
4. C. P. Almeida-Rivera, P. L. J. Swinkels, J. Grievink: Designing reactive distillation
processes: present and future. Computers and Chemical Engineering 28 (2004) 1997
2020.
5. Philip
Lutzea,
Andrzej
Gorak.
Reactive
and
membrane-assisted
distillation:
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