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

Viraj khandagale
Yash wagh

1
 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

2
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.

3
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)..

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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)

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APPLICATIONS :
1.

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 ACKNOWLEDGEMENT

Co-operation is the key of success. Thank you is a very small word to express
our deep gratitude to our respected guide Prof.Satchidanand Satpute who
guided and inspired us as whole heartedly, spending her valuable time and
taking such great part in our project work that is. Study and analysis of Hagen
Poiseuille equation. That is also help us in knowing about so many things.

We are also thankful to all faculty members for their tremendous support help
and guidance towards a successful completion of our project.

Last but not least we would like to express deep gratitude to our friends who
helped us in our project completion.

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 CONTENT

SR.NO TABLE OF CONTENT

8. INTRODUCTION

9. LITERATURE SURVEY

10. FORMULIES

11. CASE STUDY

12. RESULT AND DISCUSSION

13. CONCLUSION

14. REFERENCE

8
 1. INTRODUCTION

Different synthetic chemical dyes are used in numerous industrial processes for
a variety of uses. The production of paper and pulp, textile dyeing, leather
conditioning, printing, etc. are among industries that frequently employ these
chemicals. The majority of used solutions containing these dyes are thrown
away as effluents. because some Since these dyes have a hazardous character,
removing them from industrial effluents is a significant environmental
challenge . Aside from the visual appeal of coloured streams made from dye
waste, some colours in particular might degrade anaerobically to amines that
may be carcinogenic. A study of the relevant literature has shown the value of
using different strategies to manage these wastes. Among them are the enhanced
oxidative, photocatalytic, photolytic, and biodegradation of different dye
solutions. There has also been a significant amount of research on the adsorption
of certain dyes on different adsorbent surfaces, including clays, fly ash,
polymers, and activated carbon, but no similar study has been done on sand
surfaces [11e15]. The goal of this work is to draw attention to the Methylene
Blue (MB) adsorption on local sand, which is a cheap good and readily
available in developing nations. The study was conducted with different ions
present and absent. Maximal adsorption-optimized parameters were assessed.
To determine specific constants relevant to the adsorption phenomenon, the
adsorption data were fitted to various equations.

9
LITERATURE SURVEY

10
Define adsorption

Adsorption is the process of collecting molecules by the internal surface or

external surface of solids or by liquid surface. Adsorption refers to the
collecting of molecules by the external surface or internal surface (walls of
capillaries or crevices) of solids or by the surface of liquids. You may have
confusion with the word adsorption and absorption. Absorption is the process of
penetrating the substance of blocks of amorphous liquids or solids, or into the
actual interior crystals. Sometimes a solid takes up the liquid or gas without
specifying a particular process of absorption or absorption, such process is
called adsorption.

Difference Between Adsorption and Absorption

Most people have confusion between these two terms as they sound similar but
both the processes are different. Adsorption is the surface phenomenon and is
an exothermic process. It depends on temperature and initially, the process will
increase and will decrease gradually. Whereas, absorption is an endothermic
process. Absorption is not affected by temperature and occurs at uniform rates.
Substances penetrate the surface of the material. Absorption is spontaneous
whereas adsorption is not spontaneous. Absorption is unique throughout the
surface area and adsorption is not unique on the surface area. Molecule
interaction is higher in absorption than adsorption.

For the adsorption process, two components are required,

 Adsorbate: Substance that is deposited on the surface of another
substance. For example, H2, N2 and O2 gases.
 Adsorbent: Surface of a substance on which adsorbate adsorbs. For
example, Charcoal, Silica gel, Alumina.
Adsorption Enthalpy
Adsorption constants are basically equilibrium constants. What it means is that
they also follow or obey the van ‘t Hoff equation:
(∂ln⁡K∂1T)θ=−ΔHR.

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In this formula, the variation of K must be isosteric, that is, at constant
coverage.
Starting from BET isotherm and assuming that the entropy change is the same
for liquefaction and adsorption, we obtain
ΔHads=ΔHliq−RTln⁡c
Precisely, we can say that adsorption is more exothermic than liquefaction.

Types of Adsorption
On the basis of interaction forces between adsorbate and adsorbent, adsorption
is of two types.
1. Physical adsorption:
This type of adsorption is also known as physisorption. It is due to weak Van
der Waals forces between adsorbate and adsorbent.
For example, H2 and N2 gases adsorb on coconut charcoal.
2. Chemical adsorption:
This type of adsorption is also known as chemisorption. It is due to strong
chemical forces of bonding type between adsorbate and adsorbent. We can take
the example involving the formation of iron nitride on the surface when the iron
is heated in N2 gas at 623 K.
Adsorption of gas on a solid is a spontaneous exothermic reaction. The amount
of heat liberated when a unit mass of a gas is adsorbed on the surface is called
heat of adsorption.

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 Physical Adsorption and Chemical Adsorption: Difference

Physical Adsorption Chemical Adsorption

The process involves weak or Van Der The process involves covalent or
Waals forces. ionic chemical bonds.

By decreasing pressure and increasing Irreversible process and makes

temperature, physical adsorption can compound when forces applied to
be reversed. free the adsorbed gas.

No activation energy is needed. Activation energy is needed.

A multimolecular layer is formed. The unimolecular layer is formed.

Low heat adsorption High heat adsorption

Physisorption and Chemisorption Adsorption Characteristics

Characteristics of physical adsorption:

1. This type of adsorption is caused by physical forces.

2. Physisorption is a weak phenomenon.
3. This adsorption is a multi-layered process.
4. Physical adsorption is not specific and takes place all over the adsorbant.
5. Surface area, temperature, pressure, nature of adsorbate effects physisorption.
6. Energy for activation is low (20 – 40 kg/mol).

Characteristics of chemical adsorption:

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 1. This type of adsorption is caused by chemical forces.
2. It is a very strong process.
3. This type of adsorption is almost a single-layered phenomenon.
4. Chemisorption is highly specific and takes place at reaction centres on the adsorbant.
5. Surface area, temperature, nature of adsorbate effects chemisorption.
6. Energy of activation is very high 40 – 400 kJ/mol.

There are five primary reactor designs based in theory: batch, semibatch,
continuous-

A. COMBINATION OF TERMS

Any combination of the above classifications can be used to describe a reactor:

for example, a heterogeneous-catalytic-batch reactor.

Primary Reactors

There are five primary reactor designs based in theory: batch, semibatch,
continuous-stirred tank, plug flow, and fluidized bed. The operating
expressions for these reactors are derived from material and energy balances,
and each represents a specific mode of operation.

PLUG FLOW

i) DESCRIPTION.

This reactor has continuous input and output of material through a tube.

Assumptions made for the plug flow reactor (PFR) are material passes through
the reactor in incremental slices (each slice is perfectly mixed radially but has
no forward or backward mixing between slices; each slice can be envisioned as
a miniature CSTR). Composition and conversion vary with residence time and

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can be correlated with reactor volume or reactor length, and the reactor operates
at steady state. The PFR can be imagined as a tube, but not all tubular reactors
respond as PFRs. The assumptions need to be verified with experimental data.

CLASSIFICATION.

The plug flow reactor is the second primary type of ideal flow reactor. It is also
erroneously referred to as a tubular reactor.

DESIGN PARAMETERS. The parameters for PFRs include space time,

concentration, volumetric flow rate, and volume. This reactor follows an
integral reaction expression identical to the batch reactor except that space time
has been substituted for reaction time. In the plug flow reactor, concentration
can be envisioned as having a profile down the reactor. Conversion and
concentration can be directly related to the reactor length, which in turn
corresponds to reactor volume.

APPLICATIONS. For normal reaction kinetics the plug flow reactor is

smaller than the continuous-stirred tank reactor under similar conditions. This
gives the PFR an advantage over CSTR for most reactions. These conditions
are best met for short residence times where velocity profiles in the tubes can be
maintained in the turbulent flow regime. In an empty tube this requires high
flow rates; for packed columns the flow rates need not be as high. Noncatalytic
reactions performed in PFRs include high-pressure polymerization of ethylene
and naphtha conversion to ethylene. A gas-liquid noncatalytic PFR is used for
adipic nitrile production. A gas-solid PFR is a packed-bed reactor (Section IV).
An example of a noncatalytic gas-solid PFR is the convertor for steel
production. Catalytic PFRs are used for sulphur dioxide combustion and
ammonia synthesis.

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ADVANTAGES-DISADVANTAGES.

The advantages of a PFR include

(1) Steady state operation,

(2) Minimum back mixing of product so that concentration remains higher than
in a CSTR for normal reaction kinetics,

(3) Minimum reactor volume in comparison with CSTR (since each incremental
slice of the reactor looks like an individual CSTR, we can operate at an infinite
number of points along the rate curve),

(4) Application of heat transfer in only those sections of the reactor where it is
needed (allowing for temperature profiles to be generated down the reactor),
and

(5) no requirement for agitation and baffling. The plug flow reactor is more
complex than the continuous-stirred tank alternative with regard to operating
conditions. There are a few other disadvantages associated with the PFR. For
the kinetics where rate increases with conversion (rare), an isothermal plug flow
reactor has lower product composition than a CSTR. For highly viscous
reactants, problems can develop due to high-pressure drop through the tubes and
unusual flow profiles.

A. APPROACH, CONSIDERATIONS, AND METHODS

1. Use of the Reaction Coordinate or Molar Extent of Reaction

In chemical reactor design, an understanding of the reactions and mechanisms

involved is required before a reactor can be built. In general, this means the
chemical reaction equilibrium thermodynamics must be known before the
reactor is even conceptualized. Any chemical reaction can be written as

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aA + bB + ... = rR + sS + ...

where A and B are the reactants, R and S the products, and a, b, r, s are defined
as the stoichiometric coefficients. In general, these stoichiometric coefficients
are given a value of vi (stoichiometric numbers). An arbitrary sign convention
is given to the stoichiometric numbers to make them consistent with
thermodynamics: positive signs for products, negative signs for reactants.

In general, the reaction coordinate or molar extent of reaction is a bookkeeping

method. Numerical values of the reaction coordinate depend on how we write
the chemical reaction. When the initial moles are unknown or when
preliminary calculations are done, a basis of one mole of feed is usually
assumed. The numerical value of the reaction coordinate depends on this basis
but cancels out when mole fractions are calculated. Another commonly used
method for determining the extent of reaction is conversion.

Conversion is based on initial and final molar quantities of a reactant. This

molar basis can be written in terms of either total moles of reactant or in terms
of molar flow rate. In equation form, In general, the reaction coordinate or
molar extent of reaction is a bookkeeping method. Numerical values of the
reaction coordinate depend on how we write the chemical reaction. When the
initial moles are unknown or when preliminary calculations are done, a basis of
one mole of feed is usually assumed. The numerical value of the reaction
coordinate depends on this basis but cancels out when mole fractions are
calculated. Another commonly used method for determining the extent of
reaction is conversion. Conversion is based on initial and final molar quantities
of a reactant. This molar basis can be written in terms of either total moles of
reactant or in terms of molar flow rate. In equation form,

N AO−N A
XA = N AO

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Where XA is the conversion of reactant A between 0 and 1, NA0 the initial
moles of reactant A or initial molar flow rate of A, and NA the final number of
moles or outlet molar flow rate of A. For single reactions, fractional conversion
is normally the preferred measure of the extent of reaction. However, for
multiple reactions the reaction coordinate is the method of choice. The
relationship that exists between conversion and the reaction coordinate is

νA ε

XA = -
N AO

2. Rate Expressions

Before designing a chemical reactor, one must know the reaction(s) rate. Rates
of reaction can be written in intrinsic form or in terms of a specific reactant of
interest. An intensive measure, based on a unit volume of fluid, is normally
used for homogeneous reacting systems. Thus, the general definition of
reaction rate can be written as

( )
1 dN
ri = V t dt i

where ri is the number of moles of component i that appear or disappear by

reaction per unit volume and time in kg mol liter -l sec -l, Vt the total volume of
reacting fluid in liters, Ni the number of moles of component i in kg mol, and t
the time in seconds. The rates of formation of products R, S, T,... are related to
the rates of disappearance of reactants A, B,..., by the stoichiometric numbers

r A r B r R rS rT ri
= = = = =
v A v B v R v S v T vi

With the normal sign convention (positive for products, negative for reactants),
a rate is negative for a reactant (-r A) and positive for a product (rR). Rates of
reactions are functions of the thermodynamic state of the system. For a simple

18
system, fixing temperature and composition fixes the rest of the thermodynamic
quantities or the state. Thus, the rate can be written in terms of a temperature-
dependent term called the rate constant k (constant at fixed temperature) and a
concentration term or terms Ci.

-rA =kCA

Rates of reaction vary with changes in temperature or concentration. All

reactions are reversible (i.e., have a forward and a reverse reaction). When the
rate of the forward reaction equals the rate of the reverse reaction, there is no
net change in concentrations of any component, and the system is said to be at
thermodynamic equilibrium. This condition represents a minimum free energy
of the system and determines the limits of conversion. The overall rate of
reaction equals zero at equilibrium. A relationship can be derived between the
forward and reverse rate constants and the overall thermodynamic equilibrium
constant. For example, consider the reaction.

k1
A + B ¿ k 2 >¿ R + S

If the forward rate equals k1CACBand the reverse rate equals k2CR CSthe overall
rate of disappearance of component A is –r A = k1CACB - k2CRCS . At
equilibrium, -rA ≅ 0,

k1 C R C S
= =K C
k2 C A C B

where Kc is defined as the thermodynamic equilibrium constant based on

concentration. Reactions that have very high values of the equilibrium constant
are termed irreversible since the value of k2 must be very small. Without much
loss of accuracy, these equations can be modelled as dependent only on the
forward rate. In this example, if the reaction is essentially irreversible , –rA =
k1CACB .

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 Rate expressions must ultimately come from an analysis of experimental data.
We cannot normally write a rate equation by inspection of the stoichiometric
reaction equation; however, a reaction is termed elementary if the rate
expression can be written by inspection based on the stoichiometric numbers.

Consider the following reversible reaction

k1
A+B ¿ >¿ =2R
k2

Reactions are classified by their order depending on the sum of the

stoichiometric coefficients of each term. Reactions are classified by their order
depending on the sum of the stoichiometric coefficients of each term.

-rA = k zero order

-rA = kCA first-order irreversible

-rA = kC2A second-order irreversible

-rA = k1CA - k2CR first-order reversible

1. Use of Kinetic Data

To design a chemical reactor the rate expression must be known. Assuming the
reaction is known not to be elementary, we must search for a mechanism that
describes the reaction taking place or use experimental data directly.
Mechanisms can be hypothesized as the sum of a series of elementary reactions
with intermediates. Using methods developed by physical chemists, we can
hypothesize whether the proposed mechanism fits the actual experimental
evidence. If no inconsistencies are found, the hypothesized mechanism is
possibly the actual mechanism. However, agreement of the mechanism with the

20
 experimental data does not necessarily mean that the proposed mechanism is
correct, since many mechanisms can be hypothesized to fit such data. An
interpretation of batch or flow reactor data is used to fit an empirical rate
expression. For example, in a simple batch reactor, concentration is measured
as a function of time. Once the experimental data are available, two methods
can be used to fit a rate expression. The first, called the integral method of data
analysis, consists of hypothesizing rate expressions and then testing the data to
see if the hypothesized rate expression fits the experimental data. These types
of graphing approaches are well covered in most textbooks on kinetics or
reactor design. The differential method of analysis of kinetic data deals directly
with the differential rate of reaction. A mechanism is hypothesized to obtain a
rate expression and a concentration-versus-time plot is made. The equation is
smoothed, and the slopes, which are the rates at each composition, are
evaluated. These rates are then plotted versus concentration; and if we obtain a
straight line passing through the origin, the rate equation is consistent with the
data. If not, another equation is tested. Kinetic data can also be taken in flow
reactors and evaluated with the above methods and the reactor design equation.

2. Temperature Dependence of the Rate Constant

On a microscopic scale, atoms and molecules travel faster and, therefore, have
more collisions as the temperature of a system is increased. Since molecular
collisions are the driving force for chemical reactions, more collisions give a
higher rate of reaction. The kinetic theory of gases suggests an exponential
increase in the number of collisions with a rise in temperature. This model fits
an extremely large number of chemical reactions and is called an Arrhenius
temperature dependency, or Arrhenius' law. The general form of this
exponential relationship is

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 k = K0 e −( E| RT)

where k is the rate constant, k0 the frequency factor of pre-exponential, E the

activation energy, R the universal gas constant, and T the absolute temperature.
For most reactions, the activation energy is positive, and the rate constant k
increases with temperature. Some reactions have very little or no temperature
dependence and therefore activation energy values close to zero. A few
complex reactions have a net negative activation energy and actually decrease
with temperature. These reactions are extremely rare. The Arrhenius
temperature dependency for a reaction can be calculated using experimental
data. The procedure is to run a reaction at several different temperatures to get
the rate constant k as a function of absolute temperature. From the previous
equations ln k = ln k0 - E/RT; the natural log of k is then plotted versus the
reciprocal of the absolute temperature. The slope of this line is then -E/R, and
the intercept is the ln k0.

Space Time

It is useful to have a measure of time for a flow reactor even though the major
design variable is reactor or fluid volume. A commonly used quantity in
industrial reactor design is space time. Space time is defined as the time
required
to process one reactor volume of feed, measured at some set of specified
conditions. The normal conditions chosen are the inlet concentration of a
reactant
and inlet molar or volumetric flow rate.
Volumetric flow rate into the reactor is defined as
3. Space Time

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It is useful to have a measure of time for a flow reactor even though the major
design variable is reactor or fluid volume. A commonly used quantity in
industrial reactor design is space time. Space time is defined as the time
required to process one reactor volume of feed, measured at some set of
specified conditions. The normal conditions chosen are the inlet concentration
of a reactant and inlet molar or volumetric flow rate. Volumetric flow rate into
the reactor is defined as

Since time is obtained when total volume is divided by volumetric flow rate, a
quantity r called space time is defined

Since space time is defined for the inlet conditions, it is constant no matter what
happens in the reactor. Our design equations for a CSTR and a PFR can be
modified to reflect this quantity
Since space time is defined for the inlet conditions, it is constant no matter what
happens in the reactor. Our design equations for a CSTR and a PFR can be
modified to reflect this quantity .
C AO X A
CSTR , r = −r
A

XA
dX A
PFR, r=CAO∫
0 −r A

For the special cases of constant density, these equations simplify to

For the special cases of constant density, these equations simplify to
C AO −C A
CSTR , r = −r [constant volume or density]
A

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 CA
dC A
PFR, r= ∫ [constant volume or density]
CA 0 −r A

Reactors in Series and Parallel.

I . PLUG FLOW REACTORS.

Plug flow reactors are unique in the sense that operation in parallel or series
give the same conversion if the space time is held constant. This implies, for
example, that if a 20-m reactor of fixed diameter is required to achieve a given
conversion, the same conversion and capacity can be achieved by running ten 2-
m reactors in series or ten 2-m reactors in parallel. The split of the feed in the
parallel case must be one tenth of the total to keep the same space time. In
industrial applications the geometry chosen is a function of cost of construction,
ease of operation, and pressure drop. Parallel operation is normally preferred to
keep the pressure drop at a minimum.

Reactors in Series and Parallel.

i. PLUG FLOW REACTORS. Plug flow reactors are unique in the sense that
operation in parallel or series give the same conversion if the space time is held
constant. This implies, for example, that if a 20-m reactor of fixed diameter is
required to achieve a given conversion, the same conversion and capacity can
be
achieved by running ten 2-m reactors in series or ten 2-m reactors in parallel.
The
split of the feed in the parallel case must be one tenth of the total to keep the
same
space time. In industrial applications the geometry chosen is a function of cost
of
construction, ease of operation, and pressure drop. Parallel operation is
normally

24
preferred to keep the pressure drop at a minimum.
II . Plug Flow and Stirred Tank Reactors in Series.

When two reactors, a plug flow and a stirred tank are operated in series, which
one should go first for maximum conversion? To solve this problem the
intermediate conversion is calculated, the outlet conversions are determined,
and the best arrangement chosen. Keeping the intermediate conversion as high
as possible results in the maximum conversion. Concentration levels in the feed
do not affect the results of this analysis as long as we have equal molar feed

2. FORMULIES FOR SERIES REACTION IN PFR

A. For calculate Final Concentration :-
The derivations assumed that the feed contained no reaction products R or S.
If we replace reaction time by the space time, these equations apply equally
well for plug flow reactors, thus

Where, CA = final Concentration

CA0 = Initial Concentration
e = exponential factor
k1 and k2 = rate constant
B. The maximum concentration of intermediate and the time at which it
occurs is given by

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 CR, max = Concentration of R maximum
topt = optimum time

This is also the point at which the rate of formation of S is most rapid. Figure,
prepared for various k,lk, values, illustrates how this ratio governs.

26
 3. CASE STUDY
Currently, the production of methanol from methane can be done through the
process of decomposition, partial oxidation and steam reforming. Methanol to
gasoline (MTG) with the catalyst ZSM 5 has been investigated very effective in
converting methanol into gasoline. Merging two single reaction is a new process
innovations used to develop a model reaction biogas into bio gasoline through
pyrolysis in a fixed bed reactor, the main advantage of this reaction process
model does not require oxygen compounds, minimizing unwanted product and
get the process closer to the scale technical industrial applications and allow the
process to work with reactants in the gas to form a more homogeneous.

In line with the above reasons need to develop and transform the role of
catalyst into nanocatalyst in order to improve product quality gasoline. The
development of synthetic material that has a structure of nanometre dimension
has attracted the world of science and stimulate researchers to explore its
application in the industrial, medical, pharmaceutical, food, consumer goods.
Nanoparticles are catalysts that have a size of 1- 100 nm. The reduced
dimensions of the catalyst into nano size would increase the surface area of the
catalyst and consequently increase the specific activity of the catalyst in the
reaction. Society tends to desire to obtain goods at the lowest possible price
with satisfactory quality. This is possible if the product is used in the
manufacturing process at a minimum cost. Methane (biogas) in addition to the
abundant amount, also can be used as an alternative energy source instead of
fuel oil, because it has a lot of similarities between fuel oil with gas. So its use
does not require a drastic change of the infrastructure which is generally used in
fossil fuel use. The process of converting methane into liquid hydrocarbons can
be done in three ways, namely steam reforming, autothermal reforming and
partial oxidation. Methane has a low potential and do not last long so that when
the conversion is done by means of steam methane reforming or autothermal
27
reforming, commercially would be less profitable because it requires expensive
investment. Whereas when converting methane partial oxidation method has a
low selectivity, because there is competition between the reaction of oxygen
with methane gas into methanol and the methanol newly formed gas into CO2
and H2O. So as to obtain high selectivity, oxygen is added to be controlled by
staying. Control of oxygen can be performed by using oxygen ion conductive
membrane. This membrane and beyond merely supplying sufficient oxygen to
convert methane to methanol by using oxygen ions in the crystal lattice of the
membrane material. Thus, the use of oxygen for the conversion of methanol to
be minimized so that the chances of further oxidation reaction of methanol with
oxygen more be lower. Previous research on the sole reaction of methane into
biomethanol has been found that the metal oxide catalysts capable of converting
92% achievement of this conversion is able to eliminate the inert ingredient in
the product. These series of reactions in this study using biogas utilizing the
content of methane (CH4), which is converted into the metal oxide catalysts
biomethanol then simultaneously biomethanol converted into bio gasoline with
synthetic zeolite catalyst ZSM 5. Using serial reaction method can drive the
reaction intermediate reaction route as be bio gasoline, while the others can be
minimized so that it takes a technique that is capable of directing the reaction
series and is able to give the concept of merging a single reaction.

3.1 Catalysts

Material ZnSO4.7H2O mixing as much as 397.67 grams and 3 mmol ascorbic

acid with 197.6 grams of NaOH. The mixture is then in an autoclave at a
temperature of 190oC for 10 hours with agitation. After going through the
autoclave process the mixture is then cooled to room temperature of about 25oC
naturally. White precipitate formed was filtered and then washed with distilled

28
water. After the white precipitate is dried at a temperature of 80 ° C 2.2.
Equipment and Reaction Conditions The reaction equipment used is provided
with an plug flow reactor, which has been conditioned for operating up to 10
bar and 350 °C. The reactor is a vertical hollow cylinder of 10 mm internal
diameter and 64,4 mm length with a volume of 4 cm3 for the catalyst. It is
placed withina stainless-steel chamber heated by an electric resistance, andthe
inside is clad with a 9 mm thick thermal insulator. The equipment is provided
with a temperature controller that actuates on the catalyst bed and on the wall of
thereactor. The molar flowrate of the reactants (CH4, CH3OH, H2, CO, and
CO2) is controlled by Brooks 5850 mass flow meters. The reaction mixture is
passed through several purifiers to eliminate possible traces of oxygen, water,
and iron carbonyl that may deactivatethe catalyst.In order to carry out kinetic
modelling, runs have been carried out under the following reaction conditions:
250-350 °C; 10-20 bar; space time, 1.6-57.0 (g of catalyst) h (mol H2) -1 ; time
on stream, 6 h, which is sufficiently short for deactivation to be insignificant;
(H2 + CO), (CH4 + CH3OH) and (H2 + CO2) feeds, both with a 4:1 molar ratio
between the components biogas to oxygen. These ranges havebeen established
subsequent to a detailed study of the effect of operating conditions.

29
 4. RESULT AND DISCUSION

The results quantified are the yields of methanol, Methane, and hydrocarbons.
The yields of methanol (YMeOH) and CH4 (YCH4) have been calculated as the
percentage of carbon atoms that convert to methanol or CH4 from CO or CO2
in the feed. Reaction engineering models of biogas into bioethanol is an
alternative design that can be applied in series reaction kinetic models.
Reactions to convert methane into methanol, CO2 and water. Levels of
methane, methanol, CO2 and water are calculated as mole percentage.

2 CH 4 K 1 CH 3 OH K 2 CO 2+2 H 2O
→ →

Design parameters :

Rate Constant

K1 = 0.1795 min^-1

K2 = 0.1147 min^-1

t = 6 min

CA0 =1.25 mol/min

Simulation of PFR

30
Fig. 1 Dwsim PFR

31
 Fig. 2 Input stream

Fig. 3Conversion data

Table No. 1

Temperature Conversion

150 88.7606

175 87.0713

200 85.29

225 83.55

250 81.84

275 80.16

300 78.53

325 76.5

350 75.39

375 73.84

400 72.44

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 Temperature vs Conversion
100
90
80
70
conversion %

60
50
40
30
20
10
0
100 150 200 250 300 350 400 450
temperature ℃

Fig. 4 Conversion Rate

Table No. 2

Temperature Residence time in min

150 2.77597

175 2.61021

200 2.46408

225 2.33414

250 2.21774

275 2.1128

300 2.01765

325 1.93094

33
 350 1.85157

375 1.77862

400 1.71133

Fig. 5 T

5. CONCLUSION

Model significant reaction biogas into bio gasoline was successfully run in
DwSim software. Reaction of biogas into biogas line series follows the pattern
of first-order reaction value of the reaction rate constants for the two reactions
are relatively similar.We find maximum conversion up to 75% at 350 ℃ and
residence time of 6 min.The reaction conversion is increases as we decreasegas
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
hat reactive absorption may be reversible or irreversible, depending on the
reaction type (e.g. equilibrium or irreversible)REFERENCE

1.

34