Study of product distribution in Seies reaction in plug flow

BANSILAL RAMNATH AGARWAL CHARITABLE TRUST’S

VISHWAKARMA INSTITUTE OF TECHNOLOGY PUNE- 411037
(An Autonomous institute Affiliated to University of Pune)

CHEMICAL REACTION ENGINEERING

Course Project Report
On

Study of product distribution in Series reaction in

plug flow.

Under The Guidance of

Prof. (SMT). Gayatri Gawande
Submitted by: TY_CH-B_Group No. 8
12120071 34 Dhananjay Bhagat
12120153 47 Tejas Kale
12120186 49 Aishwarya Karangale
12120268 51 Umesh Khade
12120232 52 Sanket Kumavat

ABSTRACT

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For irreversible First order reaction A ----> R ----> S the values of rate constant
K1 and K2 are 0.17 (min)-1 & 0.11 (min)-1 respectively time = 6 min calculate.
1) the time at which concentration of R is maximum if CAo =1.25 mol/lit. 2)
find CR and CS.

Design model proposed in this study is a single reaction kinetic model of Series
of the irreversible first order series reaction. The design of chemical reactors
encompasses at least three fields of chemical engineering: thermodynamics,
kinetics, and heat transfer. The reaction equipment used is provided with an
plug flow reactor, which has been conditioned for operating up to 10 bar and
350 °C. These parallel reactions biomethanol and biogas into CO2 gas in this
study id designed in DwSim software at different operating temperatures. In this
study we find the maximum conversion upto 75% at 350 ℃ and residence time
of 1.85157 hour.

Keywords:- DwSim, PFR, kinetic, parallel reactions.

ACKNOWLEDGEMENT

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Co-operation is the key of success. Thank you is a very small word to express
our deep gratitude to our respected guide Prof. (SMT). Gayatri Gawande 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.

CONTENT

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SR.NO TABLE OF CONTENT PAGE NO

1. INTRODUCTION 5
2. LITERATURE SURVEY 6
3. FORMULIES 10
4. CASE STUDY 12
5. RESULT AND DISCUSSION 15
6. CONCLUSION 22
7. REFERENCE 22

1. INTRODUCTION
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A chemical reactor is any type of vessel used in transforming raw materials to

desired products. The vessels themselves can be simple mixing tanks or
complex flow reactors. In all cases, a reactor must provide enough time for
chemical reaction to take place. The design of chemical reactors encompasses at
least three fields of chemical engineering: thermodynamics, kinetics, and heat
transfer. For example, if a reaction is run in a typical batch reactor, a simple
mixing vessel, what is the maximum conversion expected? This is a
thermodynamic question answered with knowledge of chemical equilibrium.
Also, we might like to know how long the reaction should proceed to achieve a
desired conversion. This is a kinetic question. We must know not only the
stoichiometry of the reaction but also the rates of the forward and the reverse
reactions. We might also wish to know how much heat must be transferred to
or from the reactor to maintain isothermal conditions. This is a heat transfer
problem in combination with a thermodynamic problem. We must know
whether the reaction is endothermic or exothermic. After chemical reaction a
series of physical treatment steps is usually required to purify the product and
perhaps recycle unreacted material back to the reactor. The quantity of material
to be processed is a key factor in determining what type of reactor should be
used. For small-lot quantities, a batch reactor is commonly used in industry.
For large, high-volume reactions, such as in the petroleum industry, flow
reactors are common.

2. LITERATURE SURVEY
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Reactors may be classified by several different methods depending on the

variables of interest. There is no single clear cut procedure for reactor
classification. As a result, several of the more common classification schemes
are presented here.

A. OPERATION TYPE
The operational configuration for the reactor can be a primary method of
classification.
1. Batch:- Batch reactors are operated with all the material placed in the
reactor prior to the start of reaction, and all the material is removed after the
reaction has been completed. There is no addition or withdrawal of material
during the reaction process.
2. Semi batch:- The semibatch reactor combines attributes of the batch and the
continuous-stirred tank. The reactor is essentially batch but has either a
continuous input or output stream during operation.
3. Continuous Flow Reactors:- Continuous flow reactors represent the largest
group of reactor types by operational classification. Several continuous flow
reactors are used industrially.
A. The continuous-stirred tank reactor (CSTR) involves feeding reactants into a
well mixed tank with simultaneous product removal.
B. The plug flow reactor (PFR) consists of a long pipe or tube. The reacting
mixture moves down the tube resulting in a change in concentration down the
length of the reactor.
C. In the recycle reactor part of the outlet stream is returned to the inlet of the
reactor. Although not a typical reactor classification by type, the recycle reactor
allows for continuous operation in regimes between CSTR and PFR conditions.

B. NUMBER OF PHASES

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Reactors can also be classified by the number of phases present in the reactor at
any time.

1. Homogeneous
Homogeneous reactors contain only one phase throughout the reactor.
2. Heterogeneous
Heterogeneous reactors contain more than one phase. Several heterogeneous
reactor types are available due to various combinations of phases.
a. Gas-liquid
b. Gas-solid
c. Liquid-solid
d. Gas-liquid-solid

Multiphase reactor configurations are strongly influenced by mass transfer

operations. Any of the reactor types presented above can be operated as
multiphase reactors.

C. REACTION TYPES

Classification of reactors can also be made by reaction type.

1. Catalytic

Reactions that require the presence of a catalyst to obtain the rate conditions necessary
for that particular reactor design.

2. Noncatalytic

Reactions that do not include either a homogeneous or heterogeneous catalyst.

3. Autocatalytic

Reaction scheme whereby one of the products increases the overall rate of reaction.

4. Biological

Reactions that involve living cells (enzymes, bacteria, or yeast), parts of cells, or
products from cells required for the reaction scheme.

5. Polymerization

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Reactions that involve formation of molecular chains, whether on a solid support or in

solution
C. REACTION TYPES
Classification of reactors can also be made by reaction type.
1. Catalytic: Reactions that require the presence of a catalyst to obtain the rate
conditions necessary for that particular reactor design.
2. Noncatalytic: Reactions that do not include either a homogeneous or
heterogeneous catalyst.
3. Autocatalytic: Reaction scheme whereby one of the products increases the
overall rate of reaction.
4. Biological: Reactions that involve living cells (enzymes, bacteria, or yeast),
parts of cells, or products from cells required for the reaction scheme.
5. Polymerization: Reactions that involve formation of molecular chains,
whether on a solid support or in solution.

D. COMBINATION OF TERMS

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

for
example, a heterogeneous-catalytic-batch reactor.

II. 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
D. 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

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There are five primary reactor designs based in theory: batch, semi batch,
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
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.

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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.

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
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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

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
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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

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

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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
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

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If the forward rate equals k1CACB and the reverse rate equals k2 CR CS the 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 .

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

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3. 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
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.

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4. 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

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

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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
5. 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

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
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C AO −C A
CSTR , r = −r [constant volume or density]
A

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

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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

3. 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

CR, max = Concentration of R maximum

topt = optimum time
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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.

4. 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
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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 nano catalyst 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
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

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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
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 with in a stainless-steel chamber heated by an electric resistance, and the
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
the reactor. The molar flowrate of the reactants (CH4, CH3OH, H2, CO, and
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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 deactivate the 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 have been established
subsequent to a detailed study of the effect of operating conditions.

5. 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.

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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

Fig. 1 Dwsim PFR

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Fig. 2 Input stream

Fig. 3 Conversion data

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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

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

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Table No. 2

Residence time in
Temperature 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
350 1.85157
375 1.77862
400 1.71133

Temp Vs Residence time

3

2.5
Residence time in hr

1.5

0.5

0
100 150 200 250 300 350 400 450
temperature ℃

Fig. 5 Temp Vs Residence time

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6. 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 decrease the
temperature up to certain extent. The residence time is increases for lower
temperature.

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7. REFERENCE

1. Chumaidi, Achmad & Murdani, Anggit & Hendrawati, Nanik. (2015). Parallel
Reaction Kinetic Modelling Of Biogas To Biomethanol With Zno/Sio 2
Nanoparticles. International Journal of Engineering Research and Development.
11. 2278-800.
2. Levenspiel, Octave. Chemical Reaction Engineering. Design for Parallel
Reactions. New York: Wiley, 1999.
3. Buren (2009) , Catalytic conversion of Methanol to Gasoline Range
Hydrocarbons, Catalysis Today. 96 (2004) 155-160.
4. Dube and Carlson (2011) , Transformation of Methanol to Gasoline Range
Hydrocarbons using copper oxide impregnated HZSM-5 Catalysts. Korean J.
Chem. Engg. 22 (3) (2005) 353-357.

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