BANSILAL RAMNATH AGARWAL CHARITABLE TRUST’S

VISHWAKARMA INSTITUTE OF TECHNOLOGY PUNE- 411037

(An Autonomous institute Affiliated to University of Pune)

Chemical reaction engineering

Project Report

On

Seminar on reactive absorption

Under The Guidance of
Prof.Amruta Mokashi Mam

Submitted by: TY_CH-B_Group No. 2

 TABLE OF CONTENT

SR.NO TABLE OF CONTENT

1. INTRODUCTION

2. LITERATURE SURVEY

3. FORMULIES

4. CASE STUDY

5. RESULT AND DISCUSSION

6. CONCLUSION

7. REFERENCE
INTRODUCTION

ABSORPTION
Absorption is the process in which a fluid is dissolved by a liquid or a solid (absorbent).
Adsorption is the process in which atoms, ions or molecules from a substance (it could be
gas, liquid or dissolved solid) adhere to a surface of the adsorbent.

TYPES OF ABSORPTION
Absorption is a process that may be chemical (reactive) or physical (non-reactive).

Chemical absorption]
Chemical absorption or reactive absorption is a chemical reaction between the absorbed
and the absorbing substances. Sometimes it combines with physical absorption. This type
of absorption depends upon the of the reaction and the concentration of its reactants. They
may be carried out in different units, with a wide spectrum of phase flow types and
interactions. In most cases, RA is carried out in plate or packed columns

Physical absorption
Water in a solid
Hydrophilic solids, which include many solids of biological origin, can readily absorb
water. Polar interactions between water and the molecules of the solid favor partition of
the water into the solid, which can allow significant absorption of water vapor even in
relatively low humidity.
INTRODUCTION : (REACTIVE ABSORPTION)
The development of reactive separation processes, which combine reaction and separation
into a single, integrated unit, has attracted more attention than ever in the chemical process
sector in recent decades. Reactive separations offer several significant advantages over
conventional techniques, including improved selectivity. and reaction yield, circumventing
thermodynamic constraints, requiring less energy, and consuming significantly less water and
Reactive distillation (RD) and reactive absorption (RA) are the two most significant and well-
known examples of reactive separations. RA qualifies as a process-intensification approach
by combining absorption and chemical reactions into a single operational unit with improved
performance. Similar to reactive distillation, RA is frequently performed in packed or tray
columns; however, unlike reactive distillation, RA does not necessitate a reboiler. The most
typical application of RA as an industrial process is the separation and/or purification of a gas
mixture by the absorption of a portion of the mixture (for example, CO2, H2S, NOx, and
SOx) in a solvent, which is then regenerated. However, RA is also used in the manufacture of
bulk chemicals like sulfuric and nitric acid in addition to gas cleaning More recently,
producing fatty esters used in the synthesis of speciality chemicals and biodiesel has been
made possible by reactive separations (RD and RA) employing solid catalysts. Key
advantages of combining reaction and separation into a single production unit include
streamlined operations, zero waste, lowered capital expenditure, and low operating costs
(Kiss, 2009, 2010, 2011). This chapter gives a case study that is pertinent to the production of
biofuels after introducing the fundamentals of reactive absorption. This article describes a
revolutionary heat-integrated reactive absorption method that removes all traditional catalyst-
related procedures, effectively utilises raw materials, and significantly reduces the amount of
energy required. decreases the energy needed to produce biodiesel—over 85% less energy is
needed compared to RA and foundation cases for RD. On the basis of experimental findings,
thorough simulations were run using Aspen Plus and Aspen Dynamics. Using the effective
control structure suggested in this work, the process is easily controllable despite the high
degree of integration. The primary findings are given for a plant that produces fatty acid
methyl esters (FAME) at a rate of 10 KTPY (10000 tonnes per year) from waste vegetable oil
with a high free fatty acid content and methanol utilising sulfated zirconia as a solid acid
catalyst.
MARKET AND INDUSTRIAL NEEDS

Reactive absorption is, in essence, an established procedure that has been understood since
the beginning of the modern chemical industry. The importance of RA as a fundamental
environmental protection technique has increased dramatically in recent years, and it is now
the most often used reactive separation technique. The current market for reactive absorption
techniques is expanding, mostly as a result of significant efforts in the field of CO2 capture
and storage (Rahimpour and Kashkooli, 2004), as well as new applications being proposed
for the manufacture of biofuels). According to the majority of current research focuses on
creating novel solvents with high capacity and simple regeneration capabilities. The solvent
regeneration has the most room for improvement because it can account for up to 80% to
70% of the operating expenses. To lower the energy requirements, either the current methods
must be improved or new solvents must be investigated. Additionally, the absorption can be
integrated into the entire plant, which could considerably lower the total amount of energy
needed. Reactive separation methods that are more effective, less expensive, sustainable, and
environmentally benign are becoming more and more important to industry as a result of
stricter regulations on greenhouse gas emissions. However, the primary industrial uses of
reactive absorption continue to be the production of bulk chemicals and the purification of
gas streams

• removal of harmful substances (e.g. coke oven gas purification, CO2 and NOx removal)

• retrieval of valuable substances or non-reacted reactants (e.g. solvent regeneration);

• production of chemical products (e.g. sulfuric and nitric acid, formaldehyde synthesis);

• water removal (e.g. water removal from natural gas, air drying);

• conditioning of gas streams (e.g. synthesis gas conditioning);

• separation of substances (e.g. olefin/paraffin separations)..

BASIC PRINCIPLES OF REACTIVE ABSORPTION
Either a physical or a chemical mechanism can result in absorption. A substance included in
one state is moved into the bulk volume of another substance included in a different state
through the process of absorption. This process commonly involves a gas being absorbed in a
liquid. Contrast this with adsorption, which is the chemical's physical adhesion or attaching to
the surface of another substance. The mass transfer that takes place at the gas-liquid interface
and the gas's diffusion into the liquid are both necessary for the physical absorption of a gas
or portion of a gas mixture in a liquid solvent. The solubility of the gases, as well as the
pressure and temperature conditions, affect how readily gases can be absorbed physically in a
liquid solvent. An old one The physical absorption of carbon dioxide (CO2) into water
(H2O), a process well known from the beverage industry, is an example of a gas into a liquid.
Chemical absorption, often referred to as reactive absorption, happens when the substance
being absorbed and the liquid in its entirety undergo a chemical reaction. It is based on the
reaction's stoichiometry and the reactant concentration. The sanitization of natural gas is an
illustration of chemical absorption gas by passing it through an aqueous solution of mono-
ethanolamine (MEA) in which the acid gases (e.g. H2S, CO2) are removed by reacting with
MEA. Note that reactive absorption may be reversible or irreversible, depending on the
reaction type (e.g. equilibrium or irreversible)

APPLICATIONS :
The application of reactive absorption is benefi- cial for processes in which the concentration
of the target component (absorptive) in the gas stream is low. Additionally, reactive
absorption can be applied at lower pres- sures and for limited solubility of the target
component in the solvent.
ADVANTAGES OF REACTIVE ABSORPTION :
1. Enhance reaction rate
2. Enhance reaction selectivity
3. Increased reaction conversion
4. Increased catalyst life
5. Simplified separation
6. Improved product quality
7. Heat integration benefits
8. Reduced operating cost
9. Reduced capital investment
10. Novel equipment designs

DISADVANTAGES OF REACTIVE ABSORPTION :

1. Relatively new technology
2. Limited applications window
3. Complex modeling requirements
4. Significant devlopement cost
5. Increased operational complexity
6. Increased scale-up risks
7. Extensive experimental development.
MODELLING, DESIGN AND SIMULATION
The modelling of reactive absorption received considerable attention, reflected in several
publications The optimal design of reactive absorption processes requires adequate models
covering column hydrodynamics, mass and heat transfer, as well as reaction kinetics. Large-
scale applications are modelled by dividing the columns into smaller segments, called stages.
Each stage corresponds to a single tray or to a segment of packed column. A general
overview of the reactive absorption modelling approaches was given by (2005). Several
models were developed along the history of reactive absorption—the main ones being
described hereafter.

EQUILIBRIUM STAGE MODEL.

This assumes that the gas and liquid streams leaving a stage are in thermodynamic
equilibrium. This simple model was used in the past decades for a variety of applications,
especially for non-reactive systems. However, reactive systems require further extensions for
a proper description. The chemical reactions are taken into consideration using a source term
in the mass and energy balances. Yet, in real absorption processes, the thermodynamic
equilibrium is usually not attained within a stage. For this reason, tray efficiencies or HETP
(height equivalent of a theoretical plate) values were introduced to build a link to real
columns. This method often fails for RA processes, due to the specific features of multi-
component mixtures .
HTU/NTU-CONCEPTS AND ENHANCEMENT FACTORS.

A simple approach to take mass transfer kinetics into account for the determination of
transfer units was developed by Chilton and Colburn (1934). The column height is
determined as a product of the number and height of the transfer units (NTU and HTU,
respectively). The height of the transfer unit is estimated via empirical Sherwood
correlations, whereas the number of transfer units is obtained by numerical or analytical
integration of the inverse of the driving force over the column height. Chemical reactions are
considered via enhancement factors, which are defined as the quotient of mass transfer rate
with reaction and the mass transfer rate without reaction (Danckwerts, 1970). Since the
complexity of the occurring reactions is described using one single parameter, this method
often leads to inaccurate results.

RATE-BASED STAGE MODEL.

The rate-based approach is a method that directly takes into account the multicomponent
mass and heat transfer and the chemical reaction. The mass transfer between the phases can
be described by different theories, such as the two-film model or the penetration/surface
renewal theory. The corresponding model parameters are determined using empirical
correlations. For many applications, the two-film model parameters can be found in the
literature and, therefore, this method is often preferred For the design and simulation of
reactive absorption processes, adequate software tools are
required. Nowadays, the rate-based models are mostly used, being typically implemented in
AspenTech AspenPlus (RATEFRAC or RateSep unit), Aspen Custom Modeller (Kenig et al.,
2003; Kucka et al., 2003), gPROMS (Kiss et al., 2010), Mathworks Matlab (Gabrielsen et al.,
2006), FORTRAN (Thiele et al., 2007), ProTreat or even CFD software (e.g. ANSYS CFX).
Reactive absorption can be performed in a variety of equipment types, which provide a
continuous flow of both contacting phases. Just as reactive distillation, RA is typically carried
out in tray or packed columns. However, RA requires no reboiler or condenser (Kenig and
Seferlis, 2009; Kiss, 2009). The RA process is characterized by independent flow of both gas
and liquid phases, and allows co-current (down-flow and up-flow) and more typical counter-
current operating regimes. Reactive absorption operating units can be

conveniently classified according to which phase is in a continuous or a disperse form. Using

this criterion,

the classification of the reactive absorption equipment can be summarized as:

• both phases in a continuous form: packed columns, thin-film contactors, wetted-wall

columns, contactors with flat surface, laminar jet absorber, disc (sphere) columns;

• a disperse gas phase and a continuous liquid phase: plate columns, plate columns with
packing, bubble

columns, packed bubble columns, mechanically agitated columns, jet absorbers;

• a disperse liquid phase and a continuous gas phase: spray columns, Venturi scrubbers
CASE STUDY:

Catalytic Reactive Absorption For The Manufacture Of Biodiesel

Important chemicals known as fatty esters are mostly employed in the food, cleaning product,
pharmaceutical, and cosmetic industries. However, since the 1990s, large-scale production
has captured the majority of attention.

producing biodiesel, which has increased market need for more creative and effective
methods. With characteristics resembling those of petroleum diesel, biodiesel is a renewable
and biodegradable alternative fuel (Bowman et al., 2006; Balat and Balat, 2008; Knothe,
2010). Biodiesel is made up of fatty acid methyl esters (FAME), not hydrocarbons like
petroleum diesel, which is a mixture of them. According to Encinar et al. (2005) and Kulkarni
and Dalai (2006), it is typically made from environmentally friendly sources such vegetable
oils, animal fat, or even leftover cooking oils from the food sector. the growing interest in the
world.
ECONOMIC IMPORTANCE AND INDUSTRIAL CHALLENGES
Reactive absorption is essentially an established technology, known and used since the
foundation of the chemical industry. Recently, the role of RA as a core environmental
protection process has grown up significantly, and nowadays RA is the most widely applied
reactive separation process. As illustrated by the case study presented in this chapter, reactive
absorption can lead to significantly lower investment and operating costs as compared to
reactive distillation or the rest of conventional processes for biodiesel production. Moreover,
it can also bring significant green advantages such as less waste, lower energy requirements,
cleaner gas emissions and drastically reduced greenhouse gas (GHG) pollution.

Industrial challenges depend mainly on the nature of the process. In the case of CO2
absorption and sour gas treatment, the main room for improvement in the industrially used
RA processes is in the regeneration of the solvent (e.g. amines). Although the RA step is not
energy demanding, solvent recovery by desorption typically requires 70–80% of the total
operating costs. Current research focuses on development of new solvents (e.g. amine
mixtures or hindered amines) with high capacity and easy regeneration properties. In general,
either existing processes or equipment must be improved or different solvents have to be
considered in order to reduce the energy usage. Moreover, absorption can also be integrated
into the total plant, which could significantly reduce the overall energy requirements. For
NOx removal, the latest research activities were dedicated to aqueous alkaline solutions,
since valuable by-products can be obtained (e.g. nitric acid, nitrates and nitrites). Recent
research on SOx removal focuses on investigating wet processes and significant progress was
made (e.g. with limestone technology, Wellman-Lord process, ammonia or seawater
scrubbing). For biodiesel production the main challenges could be the stability of the solid
catalyst (Bildea and Kiss, 2011), the use of various mixtures of fatty acids, and the integration
of esterification and trans-esterification steps.
CONCLUSION FUTURE TRENDS :
The novel heat-integrated reactive absorption process presented here eliminates all
conventional catalystrelated operations, improves efficiency and considerably reduces the
energy requirements for biodiesel production—85% lower as compared to the base case.
Another important result is an efficient control structure that ensures the required reactant
ratio and fulfils operating constraint of having an excess of methanol. This is, in fact,
sufficient for the total conversion of the fatty acids and consequently for prevention of
difficult separations. Remarkable, despite the high degree of integration, this reactive
absorption process is very controllable as illustrated by the results of rigorous dynamic
simulations.

Given tighter legislation, future work will aim to apply integrated RA technologies to the
eco-efficient removal of contaminants from gas streams, as well as the production of biofuels
—for example, biodiesel production by green processing of waste materials with high FFA
content.
REFERENCES