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Reactive Distillation In Process Industries

Technical Report · May 2015

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 A

SEMINAR REPORT

ON

REACTIVE DISTILLATION IN PROCESS

INDUSTRIES

Submitted By: Guided By:

BINOY H SHAH Dr. PARIN D SHAH
13BCH159 Associate Professor

CHEMICAL ENGINEERING DEPARTMENT

INSTITUTE OF TECHNOLOGY
NIRMA UNIVERSITY
 CERTIFICATE

This is to certify that Mr. Binoy H Shah (13BCH159), student of Chemical

Engineering, VI semester, of Nirma University, has satisfactorily completed the
seminar on REACTIVE DISTILLATION IN PROCESS INDUSTRIES as a partial
fulfillment towards the degree of B. Tech. in Chemical Engineering.

Date:
Place:

Name of Guide Dr. S. S. Patel

Designation of Guide Head of Department
 Acknowledgement
I would like to express my sincere gratitude to Dr. Sanjay Patel (Head of CH/PL
Department, Institute of Technology, NIRMA UNIVERSITY) for providing me
the opportunity for this seminar.

I am very thankful to Associate Professor Dr. Parin Shah for his immense help in
guiding me throughout the duration of my seminar.

I remain greatly indebted to many publications for their permission to use their
material.

I would especially like to thank Dr. Anton A. Kiss (AkzoNobel – Research,

Development and Innovation, 6824 BM Arnhem, The Netherlands) and Dr. Kiran
D Patil (Professor in Chemical Engineering, MIT Pune) for their special inputs,
material and contribution throughout the duration of this seminar.

I’d also like to thank colleagues who provided comments and helped in reviewing
the seminar.
 CONTENT TABLE
Chapter Title Page No.
No.
1. Introduction To Reactive Separation Technology 1-3
2. Introduction To Reactive Distillation 4-6
3. Characteristics Of Reactive Distillation 7-15
3.1 Explanation Of Reactive Distillation 7-10
3.2 Ideal Reactive Distillation System 11-15
4. Reactive Distillation As Front-Runner Of Industrial Process 16-25
Intensfication
4.1 Reactive Distillation Processes In Commercial 16-17
Operation
4.2 Operation Experiences 17
4.3 Economic And Environmental Advantages 19
4.4 Social Acceptance 19
4.5 Available Commercial Catalytic Packing’s And 20-21
Homogeneous Internals
4.6 Multi-Function Integrated Design 22
4.7 Process Development In Pilot Plants 23
4.8 Barriers To Commercial Implementation 23-25
5. Design Of Reactive Distillation 26-41
5.1 Methods For Conceptual Design Of RD Columns 27-31
5.1.1 Graphical Methods 27-30
5.1.1.1 Statics Analysis 27-30
5.1.2 Optimization-Based Methods 30
5.1.2.1 Mixed-Integer Non-Linear 30
Programming
5.1.2.2 Orthogonal Collocation On Finite 30
Elements
5.1.3 Evolutionary/Heuristic Methods 31-33
 5.2 Multistage Approach To Design 34-35
5.3 Effects Of Feed Tray Locations To The Design 36
Of Reactive Distillation And Its Implication To
Control
5.4 Internal Heat Integration In Design Of 37
Reactive Distillation Columns
5.5 Seeking Further Internal Heat Integration 38-40
Within Reactive Distillation Columns
5.6 Concluding Remarks On The Design Scope 41
And Future Of Reactive Distillation
6. Modelling Reactive Distillation 41-50
6.1 Equilibrium (EQ) Stage Models 46
6.2 Non-Equilibrium (NEQ) Stage Modelling 47
6.3 NEQ Cell Model 49
6.4 Future And Scope Of Modelling Of Reactive Distillation 50
7. Case Studies 50-55
7.1 Case Study 1:- A Reactive Distillation Process For Deep 52
Hydrodesulfurization Of Diesel
7.1.1 Introduction 52
7.1.2 Conceptual Design Of The Reactive Distillation 53-54
Column
7.1.3 Result 55
7.2 Case Study 2:- A Detailed Discussion On Using Heat- 56-61
Integrated Reactive Distillation Process For The
Synthesis Of Fatty Esters
7.2.1 Introduction 56
7.2.2 Problem Statement 57
7.2.3 Heat-Integrated Design 57-59
7.2.4 Plantwide Control: -An Important 59-60
Enhancement Of Using Reactive Distillation
 7.2.5 Conclusions 61
7.2.6 Advantage Of Using RD Over RA In This 61
Process
8. Future Scope Of Reactive Distillation 59
9. Summary 60
10. References 61-63
 List Of Figures
Sr. No Figure Name Page No
No
1 1.1 Multi-functional Reactor 3
2 3.1 Processing schemes for a reaction sequence 8
3 3.2 Schematic of an Ideal RD column 12
4 3.3 Schematic of ideal RD column with salient design 14
parameters and operating conditions
5 4.1 Packing types in a reactive distillation column 21
6 4.2 Principles of equipment choice reactor and distillation 22
7 5.1 Method of statics analysis 28
8 5.2 Multiple stage approach: tools and decisions 34
9 5.3 Multiple stage approach: interstage flow of 35
information
10 5.4 Two methods of seeking further internal heat 39
integration within a reactive distillation column
11 6.1 Counter-current vapor-liquid contacting in trayed 42
columns
12 6.2 Counter-current vapor liquid contacting in packed 43
columns
13 6.3 Flow regimes on trays 43
14 6.4 Different modelling approaches available to describe 44
mass transfer, chemical reactions and hydrodynamics
in a reactive distillation process
15 6.5 a) The equilibrium stage. (b) Multi-stage distillation 45
column
16 6.6 The non-equilibrium cell model 48
17 7.1 Reactive distillation column configuration for ultra-low 54
sulfur diesel production
18 7.2 Synthesis of fatty esters by reactive distillation 58
19 7.3 Composite curve and yearly cost vs minimum delta T 59
20 7.4 Plantwide control structure of the heat-integrated RD 60
process
 LIST OF TABLES
Sr No. Table Page No.
1 Catalytic distillation in commercial operation in 2006, licensed from 17
CDTECH
2 CDTECH reactive distillations 18

NOMENCLATURE TABLE
Sr.No Abbrivation Full
1. RSP Reactive Separation Processes
2. RD Reactive Distillation
3. RA Reactive Absorption
4. MINLP Mixed-integer non-linear programming
5. OCFE Orthogonal collocation on finite elements
6. EQ Equilibrium stage
7. NEQ Non Equilibrium stage
 ABSTRACT
In the past few years chemical process industries have shown keen interest in the development of
Reactive Separation Processes (RSP), which combines reaction and separation mechanisms into
a single, integrated unit. This process brings important advantages such as increase of reaction
yield and selectivity, overcoming thermodynamic restrictions, e.g. azeotropes, and considerable
reduction in energy, water and solvent consumption. The integration of an in-situation separation
function within the reactor holds the promise of increased conversion, higher selectivity and
reduced capital investment. The introduction of an in-situation separation function within the
reaction zone leads to complex interactions between vapour liquid equilibrium, vapour liquid
mass transfer, intra-catalyst dilution (for heterogeneously catalysed processes) and chemical
kinetics. Such interactions have been shown to lead to the phenomenon of multiple steady-states
and complex dynamics, which have been verified in experimental laboratory and pilot plant
units. Reactive distillation (RD) is a unit operation comprising of distillation of many volatile
components with simultaneous chemical reactions within a single apparatus. During RD process,
reactants are reacted and after the completion of the reaction, the components are distilled away;
all of which occurs in same apparatus only. The role of RD as front runner of industrial process
intensification has increased. Nowadays, this technology belongs to the most important
separation methods in the chemical process industry for production of different chemical
compounds. In this report attempts have been made to describe the RD field of application in
process industries.

Keywords: reactive distillation, reactive separation processes, reactive distillation applications,

 Chapter 1: INTRODUCTION TO REACTIVE SEPARATION
TECHNOLOGY

The traditional flow sheet of a chemical process consists of a reactor followed by a separation
unit to remove the unconverted reactants from the desired product and recycle these to the
reactor. This is done to maximize the conversion of reactants and improve selectivity to the
desired product, thereby reducing the costs associated with the separation step.

Strategies for arriving at the “ideal” reactor configuration have been discussed in the literature.
In recent years there has been considerable academic and industrial interest in the area of
reactive separations wherein the separation function is integrated within the reactor; a variety of
separation principles and concepts can be incorporated into the reactor. The term multi-
functional reactor is often used to embrace reactive separations technology, which promises
reduction in capital costs, increased conversion and reduced by-product formation [1].

When chemical reactions and physical separations have some overlapping operating conditions
the combination ofthese tasks in a single process unit can offer significant benefits.These
benefits could involve: avoidance of reaction equilibrium restrictions, higher conversion,
selectivity and yield, removal of side reactions and recycling streams, circumvention of non-
reactive azeotropes and last but not least reduction of number of units (investment cost) and
energydemands (heat integration) [8].

Nowadays, the focus of the chemical and process industry has shifted towards the development
and application of integrated processes. This trend is motivated by benefits such as a reduction in
equipment and plant size and improvement of process efficiency and safety, and hence a better
process economy.

Reactive distillation and Reactive Absorption is an important example of a reactive separation

process. Especially for equilibrium reactions like esterifications, ester hydrolysis and

Page 1 of 66
etherifications, the combination of reaction and separation within one zone is a well-known
alternative to conventional processes with sequential reaction and separation steps [5][6].

Chemical manufacturing companies produce materials based on chemical reactions between

selected feed stocks. In many cases the completion of the chemical reactions is limited by the
equilibrium between feed and product. The process must then include the separation of this
equilibrium mixture and recycling of the reactants. Usually reaction and separation stages are
carried out in discrete equipment units, and thus equipment and energy costs are added up from
these major steps. In recent decades, a combination of separation and reaction inside a single unit
has become more and more popular.

This combination has been recognised by the chemical process industries for having favourable
economics of carrying out reaction simultaneously with separation for certain classes of reacting
systems, and many new processes (called reactive separations) have been invented based on this
technology. The most important examples of reactive separation processes (RSP) are reactive
distillation (RD) and reactive absorption (RA)[2].

Chemical process industries have shown increasing interest in the development of reactive
separation processes (RSP) combining reaction and separation mechanisms into a single,
integrated unit. Such processes bring several important advantages among which are increase of
reaction yield and selectivity, overcoming thermodynamic restrictions, e.g. azeotropes, and
considerable reduction in energy, water and solvent consumption. Important examples of
reactive separations are reactive distillation (RD) and reactive absorption (RA). Due to strong
interactions of chemical reaction and heat and mass transfer, the process behavior of RSP tends
to be quite complex [2].

Page 2 of 66
 Figure 1.1:- Multi-functional Reactor

The term multi-functional reactor is often used to embrace reactive separations technology,
which promises reduction in capital costs, increased conversion and reduced by-product
formation as shown in Figure 1.1

Page 3 of 66
 Chapter 2: INTRODUCTION TO REACTIVE DISTILLATION

“The versatility of the fractionating column in the dual role of continuous reactor and separator
as applied to chemical processing is well established.”- Berman, Isbenjian, Sedo and Othmer
(1948)

Reactive distillation is the integration of reaction and distillation within the same compartment of
space and time of one column. Reactive distillation integrates reaction and distillation within one
apparatus. Hence, both phenomena occur at the same time and place. Identifying a common
operating window between the reaction and separation that provides acceptable and controllable
reaction rates and appropriate volatilities to ensure high concentrations of reactants and low
concentrations of products in the reactive zone is difficult [4].

There are many reasons as to which Reactive Distillation has became a successful Technology

i. Improved conversion: By removing products from the reactive section, the chemical
equilibrium of equilibrium-limited reactions is shifted toward the product side,
leading to improved conversions.
ii. Circumventing/overcoming of azeotropes. For chemical systems that tend to form
azeotropes, reactive distillation avoids azeotropic mixtures by “reacting away”
participating components.
iii. Reduced side-product formation. Consecutive reactions are reduced by removing
products from the liquid reaction phase, thereby maintaining low product concentrations
in the reaction zone/phase.
iv. Direct heat integration and avoidance of hot-spots. For exothermic reactions, the heat of
the reaction can be directly used to evaporate components, reducing the amount of total
heat required and avoiding the occurrence of hot-spots.
v. Capital savings: Removal of components due to reactions resulting in the simplified
downstream processing of reactants and products.
vi. Decreased catalyst amount. Reduced amount of catalyst for a comparable conversion of
the reactants.

Page 4 of 66
Reactive distillation, offers several advantages over conventional reactor–separator
configurations, such as higher conversion in equilibrium limited reversible reaction, a more
profitable product distribution of multiple reaction system, breaking of distillation
azeotropes, significant capital saving, and so on. The world has witnessed a flurry of research and
application of reactive distillation in the last decades.

However, our cognition to the reactive distillation process is far from enough due to its
complexity resulting from the non-ideality of components and the interaction between them, and
the intricate hydrodynamics and transport phenomena in the column. Until now, the design,
control and simulation of the reactive distillation highly rely on empirical correlations for lack of
comprehensive understanding to the process [5].

It is also called catalytic distillation, and can be considered as reaction and distillation combined
into one new unit operation. Distillation itself is here considered in the wide sense, i.e. the
separation by use of vapor–liquid composition difference. So it includes distillation columns,
flashers, strippers and condensers. The reactions in reactive distillation considered include
heterogeneous catalysis reactions, homogeneous catalysis reactions, and thermal (non catalyst)
reactions. In nearly all cases reactions take place in the liquid phase, but reactions taking place in
the gas phase and locate the catalyst in the vapor phase of the column is conceivable.

Reactive distillation combines reaction with distillation in a single column. Reactive distillation
was known and sporadically applied in the chemical process industry as early as 1951, but in the
last few years the number of commercial implementations has grown rapidly to over 150. The
reasons for this rapidimplementation are the business drivers capital cost and energysavings,
while the hurdles for implementation are low. The individual elements, column, heat exchangers,
gas/liquid separator are all conventional, only the catalytic packing is novel [6].Most industrial
scale reactive distillations, operated worldwide today at capacities of 100–3000 ktonnes/y. Most
of these plants started up less than 15 years ago.

Page 5 of 66
The business drivers are

i. Economical (prosperity): variable cost, capital expenditure and energy requirement

reduction. In all cases these are reduced by 20% or more, when compared to the classic
set-up of a reactor followed by distillation.
ii. Environmental (planet): lower emissions to the environment. In all cases carbon dioxide
and diffusive emissions are reduced and
iii. Social (people): improvements on safely, health and society impact are obtained by lower
reactive content, lower run away sensitivity and lower space occupation.

These industrial reactive distillation systems comprise homogeneous and heterogeneous

catalysed, irreversible and reversible reactions, covering large ranges of reactions, notably
hydrogenations, hydrodesulfurisation, esterifications and etherification. Various commercial
methods for packing heterogeneous catalyst in columns are now available. The systems comprise
amongst others: multiple catalyst systems, gas and liquid internal recycle traffic over these
catalyst systems, separation, mass flow, and enthalpy exchange. These are integrated optimally in
a single vessel, a characteristic feature of process intensification [6].

Reactive Catalytic Distillation is also being used nowadays. In this case, the multi-functional
reactor is a distillation column filled with catalytically active packing. In the column, chemicals
are converted on the catalyst while reaction products are continuously separated by fractionation
(thus overcoming equilibrium limitations). The catalyst used for heterogeneous reactive
distillation is usually incorporated into a fiber-glass and wire-mesh supporting structure, which
also provides liquid redistribution and disengagement of vapor. Structured catalysts, such as
Sulzer’s KATAPAK-S, are also employed. The group of industrial technologies, in which
reactive distillation has already been implemented or is offered for commercialization, has
expanded in the last 20 years.

Page 6 of 66
 Chapter 3: CHARACTERISTICS OF REACTIVE
DISTILLATION

In the previous chapter, an introduction to RD system was shown. Here an overview of the
characteristics of RD system is described. Introductory the concept of RD is shown, while
comparing it with the traditional process. Then schematics of an ideal RD column are shown in
detail. Also physical and chemical data of an ideal RD column are shown

3.1 Explanation of Reactive Distillation

Let us begin by considering a reversible reaction scheme: A+B C+D where the boiling
points of the components follow the sequence A, C, D and B.

The traditional flow-sheet for this process consists of a reactor followed by a sequence of
distillation columns; see Figure 3.1(a). The mixture of A and B is fed to the reactor, where the
reaction takes place in the presence of a catalyst and reaches equilibrium. A distillation train is
required to produce pure products C and D. The un-reacted components, A and B, are recycled
back to the reactor [21].

In practice the distillation train could be much more complex than the one portrayed in Fig.
3.1(a) if one or more azeotropes are formed in the mixture.

The alternativeRDconfiguration is shown in Figure 3.1(b).

 The RD column consists of a reactive section in the middle with nonreactive rectifying
and stripping sections at the top and bottom.
 The task of the rectifying section is to recover reactant B from the product stream C. In
the stripping section, the reactant A is stripped from the product stream D.
 In the reactive section the products are separated in situ, driving the equilibrium to the
right and preventing any undesired side reactions between the reactants A (or B) with the
product C (or D). For a properly designed RD column, virtually 100% conversion can be
achieved [21].

Page 7 of 66
 Figure 3.1:- Processing schemes for a reaction sequence where C and D are both desired
products. (a) Typical configuration ofa conventional process consisting of a reactor followed by
a distillation train. (b) The reactive distillation configuration. The components A, C, D andB
have increasing boiling points. The reactive sections are indicated by grid lines. [Adapted from
Stichlmair and Frey (1999)].

Page 8 of 66
The reactive distillation combines both chemical reaction and multicomponent separation into a
single unit. It offers significant economic advantages in some systems, particularly when
reactions are reversible or when the presence of azeotropes makes conventional separation
systems complex and expensive.

The reactive distillation differs from the conventional distillation in that a tubular type of reactor,
the reactive flash cascades to be specificaded with separation units. From this perspective, the
composition profile inside the reactive zone becomes important for an effective operation of
the reactive flash cascades.Moreover, typical distillation columns follow certain temperature
profile. That is, the temperature increases as one-steps down the column [7].

The thermodynamic efficiency of a reactive distillation column involving reactions with a highly
thermal effect could sometimes be improved substantially through seeking further internal heat
integration between the reaction operation and separation operation. Prudent arrangement of the
reactive section and deliberate determination of feed location are the two effective methods that
can complement internal heat integration within a reactive distillation column. The reactive
section is suggested to properly superimpose onto both the stripping section for exothermic
reactions and the rectifying section for endothermic reactions. Feed location should be
determined so that the effect of internal heat integration can be maximized between the reaction
and separation operations.

Reactive distillation can be effectively used to improve the selectivity of a reaction especially
when an intermediate product is desired in the series or combination of series and parallel
reactions. Removing one of the products from the reaction mixture or maintaining low
concentration of one of the reactants can lead to reduction in the rates of side reactions. Itis
showed that RD can be used as a promising tool to improvethe selectivity of the desired product
in a single reactant system [8].

For a non-azeotropic reacting system with series (A → B → C)and series-parallel (2A → B; A

+ B → C) reactions, Damkohler number can be manipulated such that maximum
possibleselectivity close to 100% can be achieved at any conversion.As a general rule, for a non-
azeotropic system, it has beenrecommended that if the reactant (A) is more volatile than the
desired product then the reactive section of RD should be placed in the rectifying zone of the

Page 9 of 66
reactive distillation column and if it is less volatile than the desired product the reactive
section should be placed in the stripping section.

Being a front runner in industrial process intensification, there are many characteristics of RD
which still are in the stages of only conceptual understanding. Employing latest techniques in has
helped in getting a model through which RD can be analyzed.

Reactive distillation systems are known to be highly non-linear processes exhibiting phenomena
such as steady-state multiplicities and non-monotonic temperature profiles, unlike typical
ordinary distillation systems. The high nonlinearity coupled with fewer valves for regulating
both the reaction and the separation makes the design of an effective control system challenging.
The application of advanced model based and traditional decentralized control systems has been
reported in the RD control literature. A variety of systems with different reaction chemistries,
feed configurations and varying degrees of non-ideality in the VLE relation have thus been
studied [9].

The choice of a suitable RD configuration is based on a parameter called selectivity factor, which
is defined as the rate of desired reaction to the rate of undesired reaction. Considering the
volatilities of the components and the expression of the selectivity factor we can decide whether
to conduct the reaction in the rectifying section or in the stripping section of a RD column.
However, in the case of few complex reaction schemes selectivity factor alone cannot form a
basis for this analysis. The complexity may arise through the reaction kinetics or throughthe
vapor–liquid equilibrium. There is no systematic method available to obtain the attainable region
in such case; and ongoing research is being carried out for that [10].

Page 10 of 66
3.2 Ideal Reactive Distillation System

A schematic of the ideal RD column consisting of rectifying, reactive and stripping sections is
shown in Figure3.2. The reaction A+B↔C+D occurs on the reactive trays.

The component relative volatilities are in the order αC >αA>αB >αD so that the reactants are
intermediate boiling. The heavy reactant B is fed above the light reactant A to achieve high
reactant concentration (and hence reaction rate) in the reactive section.

The distillate is mainly product C and the bottoms stream is mainly product D. The relative
volatility order is such that the rectifying and stripping sections push the reactants back into the
reactive section.

Important column design and base-case operating conditions are shown in the following
schematic Figure 3.3 of another ideal reactive distillation column. The column consists of 5
rectifying, 13 reactive and 5 stripping stages with 550 kg catalyst on each reactive tray. The
reaction A + B ↔ C + D occurs on the reactive trays.

The relative volatilities are in the order αC(8)> αA(4)> αB(2)> αD(1), hence the reactants are
intermediate boiling. Pure fresh feeds FB and FA at 100 kmol/h are fed immediately above and
below the reactive section, respectively.

The light product C leaves as the distillate and the heavy product D leaves as the bottoms. The
distillate rate is fixed at 100 kmol/h and the reflux ratio is adjusted till the distillate and bottoms
are 95 mol% C and D, respectively [22].

Page 11 of 66
Figure 3.2:- Schematic of an Ideal RD column

Page 12 of 66
The reaction kinetic parameters, Antoine constants and constant heats of vaporization and
reaction are reported below.

Physical and chemical data for the proposed ideal RD column

i. Reaction data (kf, kmol/h/kg catalyst)

ii. rC or rD=Mcatkf (xAxB−xCxD/Keq)
iii. kf= 187434 ×exp(−6287/T ),Keq = 2 ×exp(782/T )
iv. Heat of reaction (cal/mol) −6935.8
v. Latent heat of vaporization (cal/mol) 5948.3
vi. Vapor pressure constantsa

B A D C

K1 15.6983 16.3905 15.0042 17.0830

K2 5619 5619 5619 5619

a {lnPS,j= K1,j −K2,j /T ; T in K and PS in bar.}

The proposed base-case column design is in the kinetic regime. Thiscan be inferred from the
product compositions where the two reactants are in noticeable amounts in both the product
streams. In contrast, for a column in the equilibrium regime, the principal impurity in the
distillate would be the heavy reactants B while the principal impurity in the bottoms would be
the light reactant A [22].

Page 13 of 66
Figure 3.3:- Schematic of ideal RD column with salient design parameters and operating
conditions. Adapted from [22]

Page 14 of 66
Compared to the many advantages that reactive distillation offers it is not explicitly implemented
in the process industries due to the many hurdles that come along in its implementation along-
with several constraints and foreseen difficulties

i. Volatility constraints. The reagents and products must have suitable volatility to
maintain high concentrations of reactants and low concentrations of products in the
reaction zone.
ii. Residence time requirement. If the residence time for the reaction is long, a large
column size and large tray hold-ups will be needed and it may be more economic to use a
reactor-separator arrangement.
iii. Scale up to large flows. It is dificult to design RD processes for very large #ow rates
because of liquid distribution problems in packed RD columns.
iv. Process conditions mismatch. In some processes the optimum conditions of temperature
and pressure for distillation may be far from optimal for reaction and vice versa [19].

Page 15 of 66
CHAPTER 4: REACTIVE DISTILLATION AS FRONT-RUNNER
OF INDUSTRIAL PROCESS INTENSFICATION

Considered to be as the Standard of Process Intensification in Industry by many, RD employs the

advanced techniques for its commercial application. Technology providers such as CDTECH and
Sulzer Chemtech have used these scale-up methods successfully. Barriers perceived and real
have also been removed by these companies. Chemical manufacturing companies have also
developed their own specific reactive distillations by their own research and development. These
companies, both on their own and in consortia have also developed heuristic process synthesis
rules and expert software to identify the attractiveness and technical feasibility of reactive
distillation. Academic research also produced design methods to identify the feasibility of
reactive distillation, to determine the feed locations, to select packing types, to sequence columns
optimally and also produced methods to design, optimise and control the columns with steady
state and dynamic simulation models. The rapid commercial scale implementation of reactive
distillation by co-operation of partners in research, scale-up, design and reliable operation can
also be seen as a model for rapid implementation of other process intensification techniques in
the chemical industry [6].

4.1 Reactive distillation processes in commercial operation

CDTECH, the major commercial process technology provider, licensed up to now over 200
commercial scale processes. Of these 146 are in commercial operation at the end of 2006. The
process applications are shown in Table 4.1 Below.

 Eastman’s first methyl acetate reactive distillation tower started up in 1980. It is more
than 80 m tall with a diameter of about 4 m.
 The process (including condenser and reboiler) ismade of five different materials of
construction (ranging to zirconium).
 It has an annual capacity significantly in excess of 200,000 metric tonnes per year methyl
acetate.

Page 16 of 66
 Table 4.1
Catalytic distillation in commercial operation in 2006, licensed from CDTECH

Process Number
Ethers: MTBE, TAME, ETBE 69
Hydrogenation of aromatics and 50
light sulfur
Hydrodesulfurisation 21
Isobutylene production from C4 3
stream
Ethyl benzene production 3
Total 146

 It contains five functions in one column resulting in capital expenditure and energy
reductions by a factor 5 relative toconventional unit operation design.
 Combining the reported commercial applications with these the total number of
commercial applications exceeds 150.
 The second plant, built 7 years later with the benefit of operating experience, is virtually
identical (geometry, staging, dimensions, capacity) except for some sieve tray detail in
the upper non-reactive zones.

Table 4.2 shows the process applications CDTECH presently offers for licensing.

4.2 Operation experiences

No major operational problems are reported on these processes. Giventhe complex phenomena
occurring in the columns this can be considered remarkable. The designers, knowing the
complexity, were paying extra attention to all critical details, to ensure robust controllable
operation. For instance in the Eastman methyl acetate process the reactants flows are exactly
controlled on stoichiometry. If this would not be precisely controlled either methanol will
contaminate the product or acetic acid will contaminate the co-product water. The process has no
back-up ability to recover from these kinds of errors.

Page 17 of 66
Table 4.2 CDTECH reactive distillations

CDHydro ® Selective hydrogenation using catalytic distillation:

• MAPD reduction in mixed C3s
• C4 diolefins reduction in mixed C4s (hydroisomerisation option)
• C4 acetylenes reduction in mixed C4s
• C5 diolefins reduction in mixed C5s (hydroisomerisation option)
• C6 diolefins reduction in mixed C6s
• Benzene reduction in LSR and reformate streams
• Mercaptan reduction in C4/C5/C6 olefinic streams
• Hydrogenation of benzene to produce cyclohexane
CDHDS® and Desulfurisation using catalytic distillation
CDHDS+® • FCC gasoline
• Jet fuel/kerosene
HDSelect® Selective desulfurisation of mid catalytic naphtha
CDSelectSM Low cost desulfurisation of low sulfur catalytic naphtha
CDAlkySM Sulfuric acid alkylation of olefins
CDMtbe® MTBE production from mixed C4s and methanol
CDEtbe® ETBE production from mixed C4s and ethanol
CDTame® TAME production from mixed C5s and methanol
CDTaee® TAEE production from mixed C5s and ethanol
CDEthers® Co-production of ethers from mixed C4–C7s andmethanol
CDEtherol® Selective hydrogenation of diolefins within ether processes above
ISOMPLUS® Isomerisation of n-olefins to iso-olefins
DimerSM8 Dimerisation of iso-olefins in C4 streams
CDCumene® Alkylation of benzene with propylene
CDIB® Decomposition of MTBE to high-purity isobutylene
CDTECH EB® Alkylation of benzene with ethylene
BASF SELOP Selective hydrogenation of C4s and C5s for diolefin reduction
CDAcrylamideSM Hydration of acrylonitrile to acrylamide
Sulzer Butene-1 Superfractionation of mixed C4s to produce high-purity butene-1

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4.3 Economic and Environmental advantages

Present reactive distillation applications in general are showing large savings in capital cost and
energy over conventionalset-ups between 15 and 80%. Moreover, industrialpresenters often
mention the higher reliability of the system, dueto less rotating equipment in particular and due
to less equipmentin general, requiring less maintenance.

For hydrogenations the following specific advantagesappeared:

i. Lower capital expenditure due to no recycle compressor H2.

ii. Lower capital expenditure due to integrated heat removal.
iii. Lower capital expenditure due to lower H2 pressure (5–15 bar i.s.o. 25–40 bar).
iv. Lower feedstock cost due to higher selectivity by product to vapor by lower temperature
across reaction zone.
v. Longer catalyst life due to (a) washing with cleans reflux, (b) reduced oligomer
formation, because dimer goes to bottom none-reacting zone.

Environmental advantages: -Because reactive distillation reduces the number of equipment and
the number of connections between equipment it willhave less diffusive gas emissions. Because
it requires less energyit will also reduce carbon dioxide emissions.

4.4 Social acceptance

In reactive distillation the heat of reaction is removed byevaporation. A higher reaction rate
means a higher evaporationrate, but the reaction temperature changes very little.
Runawaybehavior of a reactive distillation is therefore in general less severe than a conventional
reactor. This means thatreactivedistillations in general require less safety precaution measures.
Safety of chemical processes is the key critical factor for socialacceptance; so reactive
distillation implementation is likely to help in achieving social acceptance.

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4.5 Available commercial catalytic packing’s and homogeneous internals

Catalyst particles as such cannot be used directly as distillation packing because they form too
compact a mass for the upward flow of the vapor and downward flow of liquid. Therefore, the
catalyst particles are placed in various ways in the column as shown in Figure 4 below.

In bale packing the catalyst particles are placed in pockets ina cloth belt and these are supported
in a distillation column reactor with the help of open mesh knitted stainless steel wire so that the
requisite flow of the vapor and liquid can be ensured.

This widely used swelling of the catalyst particles and it also prevents the breakage of the
catalyst particles due to mechanical attrition. This packing structure was the first commercially
used packing for reactive distillation applications for MTBE production. The cloth containers
that hold the catalyst particle should be inert tothe reactants and products and to the conditions in
the reactionsystem. Cotton, polyester, nylon and the like can be used for the cloth containers, but
fiber-glass has been reported to be the mostwidely used.

Homogeneous reaction column internals

For homogeneous reactions taking place in the liquid phasemulti-tray columns are commercially
used, because the liquid hold-up can be adjusted to achieve the required residence time for
reaction. In the methyl acetate column of Eastman for instance trays with bubble caps of 25 cm
high are used. In cases of fast reactions packing’s could be used.

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Figure 4.1- Packing types in a reactive distillation column.

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4.6 Multi-function integrated design

Processing companies have developed their own methods forquickly assessing the feasibility and
attractiveness for particularcases. BASF for instance provides a rapid way of identifyingreactive
distillation as a feasible and attractive option is by usinga qualitative graphical method provided
by Schoenmakers and shown in Figure 4.2

Figure 4.2:- Principles of equipment choice reactor and distillation

For rapidly assessing the economic attractiveness and technical feasibility of cases the author has
developed a set of 15 guidelines for Shell. Here are a few ofthose rules. Reactive distillation is
attractive if -

i. If the reaction is so exothermic that cooling in the conventionalreactor is required.

ii. If there is un-undesired consecutive reaction and the productis a light boiler.
iii. If the conventional separation is expensive due to azeotropeformation and by reaction the
azeotrope is prevented

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4.7 Process development in pilot plants

CDTECH is a very successful developer of reactive distillation technologies. Their first

commercial implementation was aMTBE plant at Charter Oil, Houston, TX USA in 1981.
Sincethen they have implemented 123 commercial units. This rapid development and reliable
commercial implementation is probably due to their large pilot plant facilities and their
connection with the engineering contractor ABB/Lummus

SulzerChemtech has pilot plant facilities for testing and contractor engineering capability for
commercial scale design. As part of the European consortium project INTINT
comprehensivetesting of reactive packing’s was carried out and for the study twoprocesses pilot
plants were build. Currently more than 20industrial processes are in pilot testing phase. So far all
companies seem to use pilot plants tovalidatetheir designs. Eastman has several reactive
distillation pilot plants in operation.

BASF has a reactive distillation pilot plant facilityobtained from SulzerChemtech in

Ludwigshaven with SulzerKatapak-S packing. Shell Global Solutions has currently developed
their first methyl acetate plant without the benefit of commercial reactive distillation codes at that
time (1980). Internal dynamic simulation software and piloting at several scales (up to 20-cm
diameter) were then used to prove the concept.

4.8 Barriers to commercial implementation

The barriers (real and perceived) are:

i. Complex design.
ii. Complex control design with less degrees of freedom.
iii. Expensive pilot plant development is needed.
iv. Validated scale-up knowledge is needed.
v. Difficult to start-up and to operate.

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A brief discussion of these barriers and way’s (includingresearch) to reduce them are given here
[6].

Reactive distillations are more complex to design than a reactor or a distillation column.
However, methods and software facilitating the design are becoming increasingly more
sophisticated. The large number of commercial applications shows that the design problems have
been solved. For irreversible reactions no methods and little information are available in the open
literature for conceptual design. Academic research in this area would be very useful.

Reactive distillations have indeed less degrees of freedom,but for all cases reported so far
sufficient variables for control appear to be available. The design of the control is, according to
CDTECH Lummus/ABB in their commercial applications, not complex. In other cases this may
be the case and dynamic simulation to determine a feasible control design is needed. However, if
the column design and the control design are done in an integral way, additional cost savings and
increased robustness are achievable.

Extensive pilot plant development appeared to be needed forthe Eastman process developed in
the nineteen seventies. However, this is about the most complex process (five functionsin one
column) imaginable and at that time no comprehensive simulation packages were available.
Presently pilot plants of modest sizes and scale-up knowledge on mass transfer and pressure drop
are sufficient to reduce the risk to normal levels. In general the pilot plants applied by CDTECH,
Sulzer Chemtech and others have a small diameter of typically 5 cm, so small feed flows. So
pilot plant cost are low [11].

Validated scale-up knowledge is needed. However, the scale-up methods, as indicated by the
author, are available and also many commercial scale applications, whose results can be used for
validation of models.

Difficult start-up and operations are not reported. From myown experience at a manufacturing
site operation of the three- phase reactive distillation column was not particularly difficult. It is
likely that the increased attention and focus in the designphase in fact reduces the operational
difficulty, by a robust controllable design.

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Reactive distillation for many different processes has been rapidly implemented in more than
150 commercial operationsof the petrochemical and chemical industry.These implementations
show large capital and energy costreductions, a lower environmental impact and safe and reliable
operation.

Reliable scale-up from to pilot plant facilities without inter mediate demonstration scale seems to
have been obtained in all cases. In most cases the scale-up is carried out by the major
technology providers CDTECH and Sulzer Chemtech.

Academic research has lead to methods and tools to identifydesign and optimize new
applications, however all for reversible reactions only.The present status seems to warrant the
conclusion that reactive distillation is now an established unit operation in process technology
and that is what makes it a front runner of process intensification.

Process synthesis heuristics on feasibility and attractiveness are typically recommended to be

developed for irreversible reactions in reactive distillation. As a future scope Scale-up based on
pilot plants with the brute force or by model validation method are recommended for process
intensification technologies in general.

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 Chapter 5: DESIGN OF REACTIVE DISTILLATION

The aim of chemical process design has conventionally been considered as finding equipment
sizes, configuration’s and operating conditions that will allow for the economical, safe and
environmental responsible conversion of specific feed stream(s) into specific product(s). This
task is in principle carried out only by specifying the state of the feeds and the targets on the
output streams of a system [12].

Frequently, however, the design activity turns to be severely complicated by the difficulty of
identifying feasible equipment configurations and ranges of suitable operating conditions. This
situation can be explained by the fact that the design of chemical process units is only a
constitutive part of a larger scale and therefore more complex problem: the joint consideration of
process unit development and design.

In the case of RD, design issues are by far more complex than those involved in conventional
distillation and may differ significantly from case to case. For instance, the design variables for
conventional distillation include the number of trays, the feed tray location and the reflux ratio
for a constant molar overflow (CMO) system with single-feed tray. In contrast, in a RD column
the liquid hold-up is the major design parameter that determines the extent of reaction, the feed
might be distributed within the unit and a CMO cannot be assumed unless the reaction is
thermally neutral and stoichiometrically balanced. All these facts have led to a smaller number of
RD applications inthe chemical industry, than could be expectedgiven the economic benefits that
this combined process offers. Dueto this intricate feature all the endeavours of the RD
scientificcommunity have resulted in the development of designalgorithms mostly based upon
equilibrium models applied to systems with simplified thermodynamics and reactionskinetics
[13].

Lately, however, non-equilibrium (NEQ) models have been developedto assist in the accurate
modelling of RD units,accounting for mass transfer limitations and considering itsinteraction
with chemical reaction

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5.1 Methods for conceptual design of RD columns

The available approaches for the design of RD may be categorized into three main groups: those
based upon graphical/topological considerations, those based upon optimization techniques and
those derived from heuristic/evolutionary considerations.

5.1.1 Graphical methods

The graphical methods are called so, because the decisions are made upon the basis of graphical
information. This information is often generated by means of models. These approaches rely
upon the behavior of residue curves or distillation lines and may be classified into two well-
defined trends: (a) methods based upon thermodynamic-topological analysis of distillation lines;
and (b) methods based upon composition transformations.

5.1.1.1 Statics analysis

The design method based upon statics analysis in RD units involves finding the complete set of
steady-state modes and the set of corresponding operating parameters. Since separation is by far
the most costly task, the prime purpose of statics analysis method is the synthesis of RD
processes with reduced separation costs and with improved reaction parameters. For this
purpose, severalapproaches are proposed, which are in general terms based upon
thermodynamic-topological analysis of distillation diagrams.

Assumptions:-

i. The vapour and liquid flow rates in the column are infinitely large;
ii. The capacity of the reaction part in the column is large enough to carry out a given
conversion rate;
iii. The plant is operated at steady-state and theoretical stages are chosen; and
iv. One reversible equilibrium reaction is considered.

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Figure 5.1:- Method of statics analysis (Giessler et al., 1999): (a) schematic representation of RD
sequence; (b) distillation lines for A + B C

This method considers that compositionchange due to reaction is negligible on each stage and
thatRD is a succession of reaction and distillation operationswhere the feed is firstly converted
toa pseudo-initial mixture—with composition X∗assuming certain extent of reaction ε—which
is then separated in adistillation column (Figure 5.1a). For that pseudo-initial mixturefeasible
steady states occur when: the composition X∗andthe product compositions satisfy the mass
balance and apart of the distillation line lies inside the forward reactionrate region [14].

The number of theoretical and reactive stages is determinedfrom the distillation line and from the
intersectionof the distillation line and CEM (i.e. chemical equilibriummanifold and represents
the boundary of the forward andbackward reactions) [14]. Since there aremultiple pairs of X∗and
product composition that satisfythe mass balance, the method sets one of the product
composition as reference point and solves for the other two (fora three-component system) by
using material balance expressions.Thus, two of the components’ compositions andX∗ lie on the
same line—referred to as line of mass balance(LMB)—in the diagram and allow the estimation
ofthe ratio D/B at a certain reboil ratio only by exploringthe ratio of the line segments (Figure 5.2
b).

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After fixing thereference point, all the compositions of LMB are exploredto estimate the degree
of conversion required in the reactionstep. The highest conversion value is found by
iterationamong the feasible degrees of conversion and defines the limiting steady state—LSS—
i.e. condition of maximumconversion for a certain reactant [15]. Atthis condition, the location
and the length of the reactivezone in the RD column are estimated by counting all reactivestages
present in the forward reaction section. Attainingthe LSS can proceed by several limiting paths,
dependingon the nature of the stability of the fixed point from whichthe distillation lines start or
end. IfLSS is not convenient, the composition of the initialmixture, the structure of the phase
equilibrium diagramand the reactions conditions (P, T) have to be changed andthe iteration loop
is performed again. The proposed methodstresses the importance of identifying all feed
compositionregions, since they lead to the complete set of column configurations.Thus, the entire
feed region is classified into severalsub-regions, each of which has the same characteristicswith
respect to the product configurations [16].

Advantages:

i. This method gives a straight forward solution to the question whether or not a reaction
should be performed in a RD column;
ii. Allows one to synthesize flowsheets qualitatively (e.g. maximum degree of conversion,
reactive zone location and length and column sequencing);
iii. Forits application this method requires little data (i.e. feed composition, phase
equilibrium model parameters, chemical equilibrium model parameters and reaction
stoichiometry);
iv. Providesan effective tool for the study of strongly non-ideal mixtures with multiple
chemical reactions and number of components;
v. Allowsthe selection of the appropriate steady states from their complete set;
vi. Simplifiestroublesome calculations (including expensive full-scale experiments) reducing
dramatically computational time (up to five times);
vii. Representsa general method that does not depend on the concrete column structure;
viii. Doesnot require that product compositions, extent of reaction and number of stages are
fixed a priori.

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 ix. Allows one to determine the stability of various product regimes and derive the possible
product compositions and the column structure for not only one fixed feed composition
but for the entire feed region

Limitations:

i. This method assumes infinite separation efficiency

ii. Matchingthe operating lines with the assumed product composition can be sometimes
troublesome

5.1.2Optimization-based methods

This second group of design methods is composed of those methodologies, which are supported
by the power of computational subroutines and take into account important elements of an
overall design strategy (e.g. types of phase equilibrium, number of components, occurrence or
not of chemical reaction on a given stage)

5.1.2.1 Mixed-integer non-linear programming (MINLP)

This method is particularly helpful to find fully or partially optimised solutions for RD design
variables. The objective function for the RD problem is commonly composed of two basic terms:
annual operating cost (e.g. consumption of raw materials, steam and cooling water) and the
annualised investment (i.e. column, internals, reboiler and condenser). The constraints are
formed from the MESH equations on each tray, material balances at the top and bottom of the
column, kinetic and thermodynamic relationships, and logical relationships between process
variables and the number of trays.

5.1.2.2 Orthogonal collocation on finite elements (OCFE)

MINLP has been found to be troublesome for units with large number of trays and for the
simultaneous design of more than one distillation unit due to the considerable computationaltime
required for attaining the solution. Furthermore, special attention must be paid in the MINLP
model formulation and initial guesses outside the feasibility domain may lead into convergence
difficulties. OCFE techniques is suggested for the design and optimization of staged RD

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columns. This approach transforms the discrete number of stages in the column into a continuous
variable and treats the composition and temperature as functions of the position.

5.1.3 Evolutionary/heuristic methods

A third trend of conceptual design approaches maybeidentified from the evolution of RD as a

derivation fromconventional distillation processes.The proposed guidelines involve the following
issues [17].

i. Use of a pre-reactor:- Incorporating a pre-reactor could profitably enhance the conversion

of equilibrium-limited reactions, especially when it handles a substantial part of the
reaction duty (rule of thumb: use a pre-reactor when reaction rate at 80% conversion is
more than half the initial rate).
ii. Operating pressure: -The column pressure ranges from the condenser pressure
(determined by the condenser coolant temperature) to the reboiler pressure (fixed by the
heating medium temperature and the column pressure drop).
iii. Reactive zone location: - This parameter represents the best trade-off between conversion
and product purity. Thus,the reactive zone section should be located where the
concentration of at least one reactant (preferably the limiting reactant) is the maximum.
For instance, when the limiting reactant is the most volatile component and the product is
the heaviest component, the reactive zone is located towards the top of the column. For
high purity requirements, stripping or rectifying sections must be incorporated below or
above the reaction zone.
iv. Feed location: - A right choice of feed location guarantees high concentrations of
reactants in the reactive zone. The following considerations should be taken into account:
 if the reactants are the most volatile components, then the feed should be introduced at
the bottom of the reactive zone;
 if the volatilities of the reactants are very different, an additional feed location may be
required to ensure stoichiometric reactant quantities;
 a pre-reacted product-containing feed enters the column at some distance from the
reactive zone, ensuring thereby that separation between reactants and products takes
place on stages between the feed point and the reactive zone.

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 v. Reactant ratio: - Reactants’ requirements can be calculated from product specifications,
desired conversion and azeotropic compositions at different operating pressures.
vi. Catalyst mass: - The minimum catalyst requirements are determined by simulating a
series of isothermal PFR’s and ideal separators in series. The feed to the first PFR
contains the necessary quantity of unconverted reactants; the partially reacted effluent is
fed to an ideal separator that completely separates reactants from products. This
procedure is repeated for different temperatures until the desired conversion is reached,
where the operating temperature defines the minimum amount of catalyst. Since there is a
relevant influence of operating temperature upon catalyst life, chemical equilibrium and
column pressure, the adopted operation temperature value differs from the highest
possible value. In order to account for the non-isothermal operation and for the, imperfect
separation on each stage, the mass of catalyst should be 20–30% greater than the
estimated value. Additionally, inadequate catalyst volume reduces residence time and
gives poor conversion.
vii. Number of theoretical stages: - the number of stages may be estimated to a certain extend
by shortcut methods (e.g. Fenske Underwood), especially for the non-reactive zones
(stripping and rectifying). A procedure may be adopted to estimate the number of stages
in the stripping and rectifying sections. According to Solokhin and Blagov (1996), there
is an optimum number of reactive stages which allows one to obtain the highest reaction
extent for given vapour flow and column height.
viii. Reactive zone height and column diameter: - The diameter of the column is determined
by the flooding velocity, vapour–liquid traffic, pressure drop and packing catalyst
density; the reactive zone height, on the other hand, depends upon the catalyst mass,
packing catalyst density and column diameter.
ix. Reflux ratio: - In RD columns, the rate and ratio of reflux play an important role in
reaction and separation phenomena. For equilibrium-controlled systems, a high reflux
rate increases the separation of products from reactants, thereby increasing the reaction
driving force. Excessive reflux leads to operating problems and insufficient reaction hold-
up, leading to incomplete conversion (rule of thumb: use a factor of 1.2–1.4 × the
minimum ratio). Shortcut methods derived from conventional distillation have been

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 found to be inappropriate for the estimation of reflux ratio for reactive case and new
approaches have been adopted. Methods derived from the boundary value approach allow
the determination of the minimum and real reflux ratio, which are key factors in the
determination of vapour and liquid velocities. The reflux ratio can be calculated by means
of an iterative procedure.
x. Reboil ratio: - The feasibility of RD processes has been closely related to the minimum
reboil ratio (smin), at which the composition of the rectifying fixed point equals the
composition of the stripping fixed point. The reboil ratio normally ranges from 3 to 8 and
reaches a minimum when plotted versus the total number of stages.
xi. Actual trays/packed height: - For the stripping and rectifying sections experimental tray
efficiency or packing HETP should be used, whereas for the reactive section masstransfer
coefficients should be calculated from experimental data at the operating conditions of
the system. In the event that thermophysical data, transport phenomena data and
hydraulic models are available, non-equilibrium design approaches are found to provide a
better agreement between experimentation and simulation.

The proposed approach may be extended by incorporating hydraulic models which account for
the column capacity in terms of pressure drop and percent flood, and for masstransferefficiency
estimations in terms of liquid hold-up, mass-transfer coefficients and interfacial area.

Advantages: - This method estimates easily several equipment and/or operational variables.

Limitations: - This method is basically a post-design algorithmand as such it requires an already

defined process structure.

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5.2 Multistage Approach to Design

A multi-stage design strategy will be required. It allows the designer to combine in a systematic
way the capabilities and complementary strengths of the available graphical and optimisation-
based methods. As a step towards such an integrated design approach, Almeida-Rivera and
Grievink (2001) propose a methodology, supported by a decomposition in a hierarchy of
imbedded design spaces of increasing refinement. As a design progresses the level of design
resolution can be increased, while constraints on the physical feasibility of structures and
operating conditions derived from first principles analysis can be propagated to limit the searches
in the expanded design space. The general design paradigm of Siirola (1996a, Chapter 23,
1996b) is taken as the backbone of this multi-stage approach. As depicted in Figures 5.2 and
9\5.3, different decisions are made at the different levels, supported by specific design tools.
Furthermore, all the levels are inter-related by the flow of information originated at lower levels.
As one steps up the design pyramid, the scope of design is decreased whereas the information
flow is incremented.

Figure 5.2:- Multiple stage approach: tools and decisions

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 Figure 5.3:- Multiple stage approach: interstage flow of information

The successful application of the integrated design methodology relies upon considering the
output of the graphical methods as initial structure for the optimization drivendesign approaches.
In this way, the optimised design is likely to be embedded within the feasible space and the
computational effort becomes less demanding due to the reduced number of design variables.
This approach intends toreduce the complexity of the design problem, and it shouldnot be
considered as a mechanistic recipe.

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5.3 Effects of feed tray locations to the design of reactive distillation and its
implication to control

The reactive distillation differs from the conventional distillation in that a tubular type of reactor,
the reactive flash cascades to be specific, is cascaded with separation units. From this
perspective, the composition profile inside the reactive zone becomes important for an effective
operation of the reactive flash cascades. Moreover, typical distillation columns follow certain
temperature profile. That is, the temperature increases as one steps down the column. The
composition as well as the temperature effects shouldplay some role for the performance of a
reactive distillation column. The reactant feed location is an obvious design degree of freedom to
locate optimal composition andtemperatures profiles inside the column. Itthen becomes obvious
that the feedtray location shouldbeincluded as a design variable.

On-going analyses clearly indicate that the feed locations are important design parameters, and
significant energy saving (ranging from 7% to 47%) will result if we place the feed trays
optimally. As for the specific feed locations, the following heuristics are useful.

i. Heuristic H2: - Place the light and heavy reactant’s feed location close to each other
when the relative volatility between the reactants is small. Similarly, move the feed tray
locations away from each other when the relative volatility between the reactants is large.
ii. Heuristic H3: - When the relative volatility between the light reactant and the light
product is large, move the feed locations upward (i.e., to the upper reactive zone;).
Similarly, when the relative volatility between the heavy reactant and the heavy product
is large, move the feed locations downward (i.e., to the lower reactive zone; e.g.,). These
were observed not only for systems with base case kinetics, but also for processes with
temperature less sensitive kinetics. Also note that the terms “small” and“large” used are
in a relative sense.

Because the temperature andcomposition profiles play a vital role for theeffective utilization of
the reactive section, the optimal feed locations are essential to obtain improved performance.
Qualitatively, heuristics can also be given to place the feeds at the vicinity of optimal locations.
Quantitatively, a systematic procedure can be proposed to find the right feed trays.

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5.4 Internal heat integration in design of reactive distillation columns

The thermodynamic efficiency of a reactive distillation column involving reactions with a highly
thermal effect could sometimes be improvedsubstantially through seeking further internal heat
integration between the reaction operation andseparationoperation. Prudent arrangement of the
reactive section and deliberate determination of feed location are the two effective methods that
can complement internal heat integration within a reactive distillation column. The reactive
section is suggested to properly superimpose onto both the stripping section for exothermic
reactions and the rectifying section for endothermic reactions. Feed location should be
determined so that the effect of internal heat integration can be maximized between the reaction
and separation operations [18].

Although a reactive distillation column may offer a convenient way to incorporate heat of
reaction to separation operation, the effectiveness of internal heat integration between the
reaction operation andseparationoperation depends heavily upon the detailed process design, for
instance, the arrangement of the reactive section and determination of feedlocation. For an
exothermic reaction with a highlythermal effect, if a reactive distillation column is designed with
its reactive section in between the rectifying and stripping sections, most of the heat of reaction
is simply drawn off from the top condenser and failed to drive effectively the separation
operation in the stripping section. In the worst situation, it is even found that the reactive section
was superimposed entirely onto the rectifying section in someprocess designs reported in the
open literature [18].

For a reactive distillation column involving reactions with a highly thermal effect,the
improvement of thermodynamic efficiency sometimes appears still possible by seeking further
internal heat integration between the reaction operation andseparation operation. The heat of
reaction can be used effectively as either a heat source (in case of exothermic reactions) or a heat
sink (in case of endothermic reactions) to drive the separationoperation in either the stripping
section or the rectifyingsection [18].

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5.5 Seeking further internal heat integration within reactive distillation
columns

For effectively conducting the process design for a reactive distillation column involving
reactions with a highly thermal effect, it is frequently necessary to consider internal heat
integration between the reaction operation andseparationoperation through deliberately
distributing the reactive section within the process. More specifically, the reactive section
shouldbesuperimposed properly onto the stripping section for an exothermic reaction andonto the
rectifying section for an endothermic reaction.

Generally speaking, the higher the degree of superimposition, the larger the improvement in
system performance, and the ideal situation is to completely accommodate the reactive section
with either the rectifying section including top condenser or the stripping section including
bottom reboiler. Although it might be infeasible to reach that ideal situation in practice because
of, for instance, the complicated thermodynamic properties, the existence of side reactions, the
strong dependence of reaction kinetics upon temperature, and so forth, a substantial reduction in
energy consumption can still be expected for some reaction systems through partial internal heat
integration between the reaction operation and separation operation.

By means of internal heat integration between the reaction operation andseparation operation,
not only could the degree of conversion for a reversible reaction be enhanced, but also the
irreversibility associated with the separation operation be reduced, both of which contribute
actually to the improvement of system performance. In the former situation, lower energy
consumption can result from the recycle of less reactants unconverted back to the reactive
section, and in the latter situation, smaller reboil and reflux ratios can achieve a specified
separation. The improvement in system performance can permit further reduction in capital
investment and therefore lead to a more compact process design, which is one of the main
features of process intensification.

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Figure 5.4:-Two methods of seeking further internal heat integration within a reactive distillation
column: (a) Superimposition of the reactive section onto the rectifying section or stripping
section, (b) determination of feedlocation.

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Although reactive distillation columns have frequently been quotedas effective in integrating
heat of reaction to the separation operation, they are generally inefficient from the viewpoint of
the second law of thermodynamics. By seeking further internal heat integration between the
reaction operation andseparationoperation, the thermodynamic efficiency of a reactive
distillation column can frequently be improved in addition to a further reduction of capital
investment. Designating appropriately feedlocation within the reactive section andsuperimposing
properly reactive stages onto either the rectifying section (in the case of endothermic reactions)
or the stripping section (in the case of exothermic reactions) can be effective in two ways for the
reinforcement of internalheat integration. Combinatorial utilization of these two methods could
frequently provide more benefits and higher flexibility than either of them.

The effectiveness of internal heat integration between the reaction operation andseparation
operation is closely dependent on the thermodynamic properties of reacting mixtures and the
operating conditions of reactive distillation columns. Fortunately, it has been foundthrough
sensitivity analysis that even under some stringent circumstances, it can still guarantee a
substantial improvement in thermodynamic efficiency, demonstrating the high applicability to
design of reactive distillation columns.

Although seeking further internal heat integration betweenthe reaction operation and separation
operation can enhance the thermodynamic efficiency of a reactive distillation column,its
influences to system dynamics and operation remain to be a matter of special concern. As the
combination of reaction operation and separation operation already makes a reactive distillation
column more difficult to control than a conventional distillation column, it will certainly perplex
process designers if seeking further internal heat integration results in very complicated process
dynamics and potential operation difficulties. Therefore, future work should be directed towards
investigation of process dynamics and operation as well as their relations with the supplementary
internal heat integration between the reaction operation and separation operation.

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5.6 Concluding Remarks on the design scope and future of Reactive
Distillation

Both the graphical and optimization-based design methodshave already proven their potential in
RD process design but have also shown some significant limitations. Graphical methods are
fairly flexible in generating alternative designs at various design parameters, allowing the
designer to define realistic bounds on them. Furthermore, the graphical nature of the methods
clarifies the understanding of those fundamental issues in RD, which might be disguised by other
approaches (e.g. reactive azeotropes). On the other hand, graphical methods are strongly limited
by their graphical nature (i.e. (nc − nrx) ≤ 3). Optimization-based methods overcome the last
limitation and have successfully solved design problems, where multi-component mixtures,
multiple chemical reactions and multiple units are involved. However, additional caution is
required in the problem formulation and inappropriate initial guesses of the optimization
variables may lead into convergence difficulties [13].

The multi-stage approach conjugates the strengths of both graphical and optimization-based
methods, aimingat an integrated and generalized methodology. Economic, controllability-related
and environmental issues have been included as evaluation criteria and special attention has been
paid to the definition of rigorous building blocks (dynamic models for the involved units and
physical/chemical properties estimation). This approach proposes a decomposition of the design
problem in a hierarchy of design spaces ofincreasing refinement.

The challenges in the design of RD are numerous and foreseen to be exciting. The drive for
process intensification and more sustainable plant operations can lead to more intricate geometric
structures (e.g. packings, dividing walls, distributed heat exchange) and to more refined models
which couple mass and energy transfer in a more realistic way. Finally, incorporating supply
chain motivated temporal featureswithin the design task (e.g. switching modes) mightincrease
tremendously the degrees of freedom and the problemcomplexity [13].

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 Chapter 6: Modelling reactive distillation

The design and operation issues for RD systems are considerably more complex than those
involved for either conventional reactors or conventional distillation columns. The introduction
of an in situ separation function within the reaction zone leads to complex interactions between
vapor liquid equilibrium, vaporliquidmass transfer, intra-catalyst diffusion (for heterogeneously
catalyzed processes) and chemical kinetics [19].

Before modelling aspects can be considered, careful attention needs to be paid to

hardware design aspects. Towler and Frey (2000) have presented an excellent summary of
hardware design aspects of RD columns. Some of the important issues are discussed below.

For homogeneous RD processes, counter-current vapor liquid contacting, with sufficient degree
of staging in the vapor and liquid-phases, can be achieved in a multi- tray column (Figure 9)or a
column with random or structured packing’s (Figure 10). The hardware design information can
be found in the standard sources for conventional distillation design. The Hatta number for most
RD applications is expected to be smaller than about unity and thefrothregime is usually to be
preferred on the trays (Figure 11)because of the desire to maintain high liquid hold-up onthe
trays. High liquid hold-ups could be realised by use of bubble caps, reverse flow trays with
additional sumpstoprovide ample tray residence time. In the Eastman process for methyl acetate
manufacture specially designed high liquid hold-up trays areused.

Figure6.1: -Counter-current vapor-liquid contacting in trayed columns

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Figure: - 6.2 Counter-current vapor liquid contacting in packed columns

Figure: - 6.3 Flow regimes on trays

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 Figure 6.4:- Different modelling approaches available to describe mass transfer, chemical
reactions and hydrodynamics in a reactive distillation process. Adapted from Noeres et al.
(2003).

As shown in Figure 6.4, there are many ways to combine the different modelling approaches
with respect to mass transfer, reaction kinetics and hydrodynamics. In general, however, the
different combinations are classified either as equilibrium-stage or non equilibrium-stage
models, depending on how the mass transfer between the vapour and liquid phase is described.
The accuracy of the simulation results strongly depends on the quality of the applied model
parameters. The more complex the model, themoremodel parameters are required. Consequently,
the highest modelling depth is not always the best choice because the accessibility of the model
parameters and the possible costs for the determination of the missing parameters must be
considered in the determination of the optimal modelling depth.

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6.1 Equilibrium (EQ) stage models

The development and application of the EQ stage model for conventional (i.e. non-reactive)
distillation has been described in several textbooks. Here we are concerned with the extension of
this standard model to distillation accompanied by chemical reaction(s).

A schematic diagram of an equilibrium stage is shown in Fig. 6.5(a). Vapor from the stage below
and liquid from the stage above are brought into contact on the stage together with any fresh or
recycle feeds. The vapor and liquid streams leaving the stage are assumed to be in equilibrium
with each other. A complete separation process is modelled as a sequence of s of these
equilibrium stages (Fig. 6.5 (b)).

Figure 6.5:- (a) The equilibrium stage. (b) Multi-stage distillation column

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Grosser, Doherty and Malone (1987) use a dynamic model based on the following assumptions:

i. The mixture reaches reaction and phase equilibriuminstantaneously on each tray;

ii. The solutions are dilute (thus the temperature changecan be ignored);
iii. The liquid hold-up is constant on each tray (the vapor holdup is ignored);
iv. Constant molar overflow (modified somewhat) relates the flows from stage to stage.

6.2 Non-equilibrium (NEQ) stage modelling

Building an NEQ model of a reactive separation process is not as straightforward as it is for the
EQ stage model in which we simply (or not so simply) add a termto account for reaction to the
liquid-phase material balances.For a reactive separation process, we first need toknow whether
the reaction is heterogeneous or homogeneous.For homogeneous systems the component molar
balancefor the liquid-phase becomes

Where Rm,jis the rate of reaction m on stage j. li,m represents the stoichiometric coefficient of
component i in reaction m and εj represents the reaction volume on stage j. For homogeneous
reactions this is given by the total liquid hold-up on stage j and, in an NEQ model, is obtained
directly from the column internals specifications and appropriate hydrodynamic correlations. If it
is sufficiently rapid, the reaction will also take place in the liquid film adjacent to the phase
interface,and very fast reactions may occur only in the film. Ineither case the continuity
equations for the film are requiredfor taking into account the effect of the reactionon the
interphase mass transfer rates. The combined setof MS and continuity equations usually must be
solvednumerically.

The phase equilibrium equations for the interface may need to be modified for the influence of
additional species on the thermodynamic properties at the interface. Amine based gas treating
again provides a case in point where reactions in the liquid phase create additional species
(including ions) that affect the interfacial equilibrium.

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For a heterogeneous reaction, there are two optionsfor the description of the reaction term. The
simplestapproach is to treat the reaction pseudo-homogeneously, whereby catalyst diffusion and
reaction is lumped into anoverall reaction term. For heterogeneous reactions thatare modelled in
this way the liquid-phase material balance is as given above and ej is given by the total amount
of catalyst present on the stage under consideration. In this case, one only needs to specify
catalyst mass and activity.A more rigorous approach would involve the use of the dusty fluid
model discussed above if the catalyst is porous, or reaction at the surface if not. In this case one
also needs information about the catalyst geometry (surface area, mean pore diameter, etc). In
either case it isunnecessary to allow for reaction in the vapor-liquid film and the vapor-liquid
transport equations are exactly as given above.

6.3 NEQ cell model

An issue that is not adequately addressed by most NEQ models is that of vapor and liquid flow
patterns on distillation trays or maldistribution in packed columns. Since reaction rates and
chemical equilibrium constants are dependent on the local concentrations and temperature,they
may vary along the flow path of liquid on a tray, or from side to side of a packed column. For
suchsystems the residence time distribution could be very important, as well as a proper
description of mass transfer.On distillation trays, vapor will rise in plug-flow through a layer of
froth. The froth will pass through theliquid more or less in plug-flow, with some axial dispersion
due to the vapor jets and bubbles. In packed sections, maldistribution of internal vapor and liquid
flowsover the cross-sectional area of the column can lead toloss of interfacial area. This is known
to be one of themain reasons for inadequate performance of packed columns.

To deal with this shortcoming of earlier models NEQ cell model. The distinguishing feature of
this model is thatstages are divided into a number of contacting cells, as shown in Figure 6.6.
These cells describe just a small sectionof the tray or packing, and by choosing an
appropriateconnection pattern, one can very easily study the influence of flow patterns and
maldistribution on the distillation process.

Flow patterns on distillation trays are modelled bychoosing an appropriate number of cells in
each flowdirection. A column of cells can model plug-flow in thevapor phase, and multiple
columns of cells can modelplug-flow in the liquid-phase. Back-mixing may also be taken into

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account by using anappropriate number of cells. This may be derived fromcalculating an
equivalent number of cells from eddydiffusion models. Flow patterns in packed columns
areevaluated by means of a natural flow model. The flowsare split up according to the ratio of
the cell surface areasbetween the cells. Various flow patterns may be approximatedusing
different flow splitting policies.

Figure 6.6:-The non-equilibrium cell model of Higler, Krishna and Taylor (1999).

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6.4 Future and Scope of Modelling of Reactive Distillation

Belck (1955) concludes his paper describing a hand calculation method for RD columns with the
following words:

“as the complexity of the system increases, the calculation becomes increasingly difficult..the
uncertainty inherent in the experimental determination of reaction rate constants and liquid-vapor
diagrams also tends to make the value of such calculations questionable. Whether or not the
experimental work and calculation time -for a detailed computation of such a process in a system
with four or more components-can be justified or not will then ultimately depend upon the
economic importance of the products”.

There remains more than a grain of truth to these remarks even today, when the computer, which
would make its mark in chemical engineering soon after these words were written, has largely
rendered moot the issue of computational cost.

There are a variety of models now available in the literature for screening, analysis, design and
optimization of RD columns. Each model has its place in the process development cycle.
Residue curve maps are invaluable for initial screening and flow-sheet development. EQ models
have their place for preliminary designs. However, recent NEQ modelling works have exposed
the limitations of EQ models for final design and for the development of control strategies. NEQ
models have been used for commercial RD plant design and simulation.Column hardware choice
can have a significant influence on the conversion and selectivity; such aspects can be properly
described only by the NEQ cell model. It is insufficiently realised in the literature that say for
tray RD columns, the tray design can be deliberately chosen to improve conversion and
selectivity. Even less appreciated is the fact that the design methodology for RD tray columns is
fundamentally different from that of conventional trays [19].

Liquid residence time and residence time distributions are more important in RD. The froth
regime is to be preferred to the spray regime for RD applications; this is opposite to the design
wisdom normally adopted for conventional distillation. Though the phenomena of MSS
havereceived considerable attention in the literature, it is possible that not all of the steady-states
can be realised in practice due to hydraulic aspects, which are taken into account in the NEQ

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model. For relatively fast reactions, it is essential to properly model intra-particle diffusion
effects.

Pseudo-homogeneousreaction models may be inadequate for fast reactions. RD columns using

dumped (random) packing’s are susceptible to maldistribution and there is a case to be made for
choosing regular structured packings. For proper description of the column dynamics, it is
essential to adopt the NEQ model.

Though sophisticated NEQ design models are available already, detailed information on the
hydrodynamics and mass transfer parameters for the various hardware configurations is woefully
lacking in the open literature. Paradoxically, such information has vital consequences for the
conversion and selectivity of RD columns. There is a crying need for research in this area. It is
perhaps worth noting here that modern tools of computational fluid dynamics could be
invaluable in developing better insights into hydrodynamics and mass transfer in RD columns
[19].

Besides more research on hydrodynamics and mass transfer, there is need for more experimental
work with the express purpose of model validation. In such process studies, parameters need to
be measured along the height of RD columns. Too often measurements are confined to feed and
product stream conditions. Such data cannot serve as a reliable discriminant of computer-based
process models.

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 Chapter 7:- CASE STUDIES

Process integration and intensification is increasingly applied in the production of many day-to-
day chemicals, as shown by recent research papers. Here case studies are provided better
understanding of reactive distillation from an industrial perspective.

First case study is use of RD for deep hydro desulfurization of diesel, which forms an important
process in the petrochemical industry. Here a novel structure is shown which can be applied for
DHSD. It incorporates many features of conventional techniques while adding features of the
reactive separation.

Second case study is of Heat-Integrated Reactive Distillation Process for the Synthesis of Fatty
Esters. Here the applied technology is being compared with another one of the reactive
separation technique, namely Reactive Absorption which was discussed in previous seminar.
Certain features show that RD can be a better process for production of fatty esters compared to
RA. An important feature shown in the case study is that of plant wide control and its
implications.

By providing such case studies the author has managed to describe the commercial applications
of a novel technology which shows increasing aspects of becoming the front runner on industrial
process intensification.

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7.1 Case Study 1:- A REACTIVE DISTILLATION PROCESS FOR
DEEP HYDRODESULFURIZATION OF DIESEL

Conventional hydro-treating is a commercially proven refiningprocess that passes a mixture of

heated feedstock and hydrogen(H2) through a catalytic reactor to remove sulfur and
otherundesirable impurities. A review of the technologies for producingultra-low sulfur diesel
(ULSD) fuel reveals that current technologiescan be modified to produce diesel with less than 10
parts per million(ppm) of sulfur.

Nevertheless, only a small number of refineries currentlyproduce diesel with sulfur in the 10ppm
range on a limitedbasis. The existence of the required technology does not ensure thatall
refineries will have that technology in place and in time tomeetthe new ULSD standards because
these plants are characterized bya wide range of size, complexity, and quality of crude oil inputs.

7.1.1 Introduction

Here a systematic study of the operating conditions and parameter sensibility is shown under
which MSS may occur, and to assess their influence on a RDC for the deep HDS of diesel.The
multiplicity analysis is performed for two feed case scenarios, showing its implication on the
design and operation of the RDC. Effectofthe operating conditions and parameter sensibility over
the main, variables to monitor or control hereinafter: the recalcitrantorgano-sulfur compounds
conversion and the product purity is described.

Moreover, an important parameter which is being described here is of the conceptual design by
considering the thermodynamic considerations.

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7.1.2 Conceptual design of the reactive distillation column

Development of a conceptual design of a RDC for deep HDS of diesel through a thermodynamic
analysis considering the following aspects:

i. the volatility of the organo-sulfur compounds;

ii. the different reactivities of the organo-sulfur compounds;
iii. the computation of non-reactive and reactive residue curve maps for DBT elimination.

An equilibrium stage model considering homogeneous liquid chemical reactions was used. The
validation of such model has previously been discussed. Recently it is shown that the equilibrium
model predicts consistently experimental values (Broderick & Gates, 1981) when only the
hydrogenolysis reaction pathway of DBT is considered.

The non-idealities of the vapor and liquid phases are calculated through the Peng–Robinson
equation of state with the appropriate binary interaction parameters. The missing critical
properties and acentric factors for DBT and 4,6-DMDBT as well as its respective hydrogenolysis
and hydrogenation reaction products, were estimated using the Joback and Reid method which
has proven to be versatile here in many ways which can be described in lierature.

The RDC configuration obtained consisted of 14 stages with two reactive zones and three non-
reactive zones (Fig. 15). Target conversion of 99% for the DBT and 4,6-DMDBT and complete
elimination of Th and BT were assumed as part of the design specifications. Anoperating
pressure of 30 atm and a H2 to hydrocarbon (HC) feed ratio of 3 wasthe optimal values in a
simple reactive batch distillation process toreach deep HDS of diesel [20].

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Figure 7.1:- Reactive distillation column configuration for ultra-low sulfur diesel production.

Page 54 of 66
7.1.3 Result

It could be established that the absence of H2 in the reactive zones implies operating conditions
similar to those of conventional (non-reactive) distillation columns with their respective MSS.
On the other hand, when an excess of H2 is present in the reaction zones, the behavior of the
RDC is very likely to a HDS conventional catalytic reactor. Therefore, it may be concluded that
the multiplicities found in this work are highly related to the specific phenomena (reaction-
separation) involved. As an overall conclusion, under optimal design and operating conditions,
reactive distillation could be considered as a viable technological alternative to produce ULSD.

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 7.2 Case Study 2:- A DETAILED DISCUSSION ON USING
HEAT-INTEGRATED REACTIVE DISTILLATION
PROCESS FOR THE SYNTHESIS OF FATTY ESTERS

7.2.1 Introduction

Fatty esters are key products of the chemical process industry, involved not only in the
production of biodiesel but also in specialty chemicals. However, the main interest has shifted
nowadays to the larger scale production of biodiesel — hence the strong market drive for more
innovative and efficient processes. Biodiesel is an alternative renewable and biodegradable fuel
with properties similar to petroleum diesel. It is produced mainly from green sources such as
vegetable oils, animal fat or even waste cooking-oils from the food industry. At present,
employing waste and non-edible raw materials is mandatory to comply with the ecological and
ethical requirements for biofuels. However, waste raw materials can contain a substantial amount
of free fatty acids (FFA), up to 100%. Accordingly, the development of an efficient continuous
process for fatty esters manufacturing is required, in which the use of a solid catalyst is
especially wanted in order to suppress the costly chemical processing steps and waste treatment.
Moreover, the ‘food versus fuel’ competition can be avoided when the raw materials used are
waste vegetable oils or non-food crops such as Jatropha and Mahua , or castor oil [23].

As a non-petroleum-based diesel fuel, biodiesel consists of fatty acid methyl esters (FAME),
currently produced by acid/base catalyzed trans-esterification, followed by several neutralization
and purification steps. Nonetheless, all conventional methods suffer from problems associated
with the use of homogeneous catalysts, leading to severe economical and environmental
penalties. This has to change in view of the massive growth of overall biodiesel production and
consumption scale [24].

Nowadays, the most widespread manufacturing technologies usehomogeneous catalysts, in batch

or continuous processes where bothreaction and separation steps can create bottlenecks.

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 7.2.2 Problem Statement

Biodiesel is an attractive but still costly alternative fuel. The common problem of all
conventional processes is the use of liquid catalysts that require neutralization and an expensive
multi-step separation that generates salt waste streams. To solve these problems, a process is
described here that makes use of solid acids applied in an esterification process based on
catalytic reactive distillation. Such an integrated process is able to shift the chemical equilibrium
to completion and preserve the solid catalyst activity by continuously removing the products.
Moreover, the investment and operating costs are lower, as compared to conventional processes.
However, the market pressure demands further reduction ofthe operating costs by replacing the
raw materials with inexpensivewaste oils with high FFA content, and reducing the energy
requirements per ton of product.Moreover; several reactive separationprocesses based on fatty
acids esterification are reported recently,aiming at high performance and productivity, as well as
low energyrequirements:

i. Reactive distillation: 191.2 kW h/ton biodiesel [25]

ii. Dual reactive distillation: 166.8 kW h/ton biodiesel [27]
iii. Reactive absorption: 138.4 kW h/ton biodiesel [26].
7.2.3 Heat-integrated design

The conceptual design of the process is based on a reactive distillation column (RDC) that
integrates the reaction and separation steps into a single operating unit. By combining reaction
and separation, one can shift the reaction equilibrium towards products formation by continuous
removal of reaction products, instead of using an excess of reactant. An additional flash and a
decanter are used to guarantee the high purity of the products. RDC consists of a core reactive
zone completed by rectifying and stripping separation sections, whose extent depends on the
separation behavior of the reaction mixture. Since methanol and water are much more volatile
than the fatty ester and acid, these will separate easily in the top. Fig. 1. (top) presents the
flowsheet of this biodiesel process based on conventional reactive distillation, as reported in
previous seminar work.

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The reference flow-sheet presented in Fig. 7.2. (top) is relatively simple, with just a fewoperating
units, two cold streams that need to be pre-heated (fatty acid and alcohol) and two hot streams
that have to be cooled down (top water and bottomfatty esters).

Therefore the heat-integration was performed by applying previously reported heuristic rules.
Consequently, a feed-effluent heat exchanger (FEHE) should replace each of the two heat
exchangers HEX1 and HEX2. Fig. 7.2. (bottom) illustrates the improved process design
including heat-integration around the reactive distillation column. The hot bottom product of the
column, a mixture of fatty esters, is used to pre-heat both reactants: the fatty acid and alcohol
feed streams. Fig.7.3 shows the composite curve and the cost as function of theminimum delta T.
This confirms the heuristics findings, as there is no longer need for an external hot utility to pre-
heat the reactants feed streams.

Figure 7.2:-Synthesis of fatty esters by reactive distillation: base case flowsheet (top) and heat-
integrated RD flowsheet (bottom).

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 Figure 7.3:- Composite curve (left) and yearly cost versus minimum delta T (right).

7.2.4 Plantwide control:-An important Enhancement of using Reactive

Distillation

Heat-integrated reactive distillation offers indeed major advantages such as reduced capital
investment and operating costs, as well as no catalyst-related waste streams and no soap
formation. However, the controllability of the process is just as important as the capital and
operating costs savings. In processes based on reactive separations, feeding the reactants
according to their stoichiometric ratio is essential to achieve high products purity. It is important
to remark that this constraint must be fulfilled not only during the normal operation, but also
during the transitory regimes arising due to planned production rate changes or unexpected
disturbances. It is experimentally proved by [27] that, in spite of the high degree of integration
this heat-integrated reactive distillation process is very well controllable. A key result of this
study is an efficient control structure that can ensure the reactants ratio required for the total
conversion of the fatty acids and for the prevention of the difficult separations (e.g. fatty acid–
fatty ester).

Fig. [19] presents a plant-wide control structure. The production rate is set by the flow rate of the
Acid stream (controller FC1). The setpoint of the Alcohol feed flow controller FC2 is set, in a
feed forward manner, by multiplying the Acid flow rate by the desired Alcohol:Acid ratio. It
should be noted that setting the flow rates such that the stoichiometric ratio is fulfilled is not

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possible using only the flow controllers FC1 and FC2 because of unavoidable measurement or
control implementation errors. For this reason, an additional concentration controller is
necessary. An excess of Alcohol will have as result the complete consumption of Acid and a
drop of the Acid concentration at the bottom of the column. On the other hand, large quantities
of Acid will be present when this reactant is in excess.

It can be concluded that the imbalance in the Alcohol:Acid ratio can be detected by measuring
the concentration of Acid in the bottom outlet of the column (e.g. pH meter). Therefore, the
concentration controller CC1 is used to give, in cascade manner, the Alcohol:Acid ratio. In this
way, when production rate changes are implemented by changing the Acid flow rate, the correct
ratio between reactant is achieved. The control of the distillation column is achieved by the
pressure (PC1) and level (LC1 and LC4) control loops. The reflux rate is kept constant because
of its small value, while the reboiler duty is ratio-ed to the Acid feed rate. The inventory of the
two liquid phases in the decanter and the level and pressure in the flash are also controlled by
standard loops (LC2, LC3 and LC5, PC2, respectively).

Figure 7.4:- Plantwide control structure of the heat-integrated RD process. Concentration of acid
in bottom stream is controlled by manipulating the alcohol flow rate

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7.2.5 Conclusions

The heat-integrated design shown here is based on catalytic reactive distillation, powered by
sulfated zirconia as solid acid catalyst for fatty acids esterification. While maintaining the same
capital investment costs, significant energy savings (lower operating costs) of ~45% are possible
by adding heat integration to the conventional RD setup.

Another important result is an efficient control structure that ensures the reactants ratio required
for the total conversion of the fatty acids and for prevention of difficult separations. Remarkably,
in spite of the high degree of integration this reactive distillation process is very well controllable
as is supported by various rigorous simulation. The steady-state model developed in Aspen Plus
and its corresponding dynamic model built in Aspen Dynamics can be further used for other
controllability studies as well as a starting point for the development of other control relevant
models— such as model predictive control (MPC).

7.2.6 Advantage of using RD over RA in this process

An integrated RD alternative offers significant benefits over conventional biodiesel processes:

i. Elimination of all conventional catalyst-related operations such as: catalyst neutralization,

separation and disposal of waste salts, waste water treatment.
ii. Efficient use of the raw materials and equipment: stoichiometric reactants ratio, complete
conversion, significantly high unit productivity.
iii. Multifunctional plant suitable for a large range of feedstock with very high FFA content,
such as palm fatty acid distillate, frying oils, animal tallow and waste vegetable oil (wvo).
iv. Reduced capital and operating costs. Compared to the base case, the heating and cooling
requirements of this process are significantly decreased, by 43% and 47% respectively.

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 Chapter 8:- FUTURE SCOPE OF REACTIVE DISTILLATION

The integration of an in-situ separation function within the reactor holds the promise of increased
conversion, higher selectivity and reduced capital costs. Reactive separations have therefore
attracted the attention of academic researchers and industrial practitioners alike. While surveying
the highlights of recent developments, the following major points for future scope emerge:

i. The in-situ separation function could be incorporated into the heterogeneous catalyst by
altering the catalyst morphology and design.
ii. Separately feeding the reactants to the reaction zone could be beneficial in many cases.
iii. For successful commercial implementation of reactive distillation technology, increased
attention needs to be paid to the development of the proper hardware.
iv. The use of membrane reactor technology is already being commercially used in the
biotechnology area. Its use in the mainstream chemical industry is imminent.
v. New developments in materials technology such as solid oxides and nano-porous
materials (zeolites, carbon molecular sieves, nano-porous carbon) have opened new
separation-with-reaction avenues, hitherto not possible [1].

Theeffects of feed locations to the design of reactive distillation were explored in the design part
and ideal reactive distillation systems are used to illustrate the advantage of feedtrays
optimization. The results from all system studied indicated a 6% to 47% energy saving, which
can be achieved by simply rearrange the feedlocations.

Process synthesis heuristics on feasibility and attractivenessare typically recommended to be

developed for irreversible reactionsin reactive distillation.Scale-up based on pilot plants with the
brute force or by modelvalidation method are recommended for process
intensificationtechnologies in general [6].

Compared to conventional internals forheterogeneous catalytic distillations the multi-channel

packinghas advantages due to low packing costs, easy catalystreplacement, and a high hydraulic
flexibility. A first applicationof the multi-channel packing on production scale has showed good
results and more research is needed in this area [28].

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 SUMMARY

Reactive distillation, catalytic reactive distillation and membrane-assisted distillation

areimportant candidates to be integrated into future, more efficient, flexible and more sustainable
production processes.Over the last decades, research in the area of reactive distillation has been
multifaceted with respect to the identification of potential application areas and the experimental
testing of thesetechniques at the pilot plant and industrial scales. Thedevelopment of conceptual
and detailed models has helpedto improve the understanding of transport processes andenabled
scale-up. Together with the developed design methods that handle the complexity of such
integration, the useof a set of important performance criteria, such as energyconsumption and
costs, has been a considerable step towardevaluating both technologies.

Although research on reactivedistillation and has proventhat both are promising technologies to
build more sustainable and more economic processes, their implementation inindustry is still
scarce. This scarcity may be remedied bythe provision of more detailed models and design tools
thatcan handle multi-component and multi-reaction systems aswell as manage the complexity
given by the large number ofpotential process configurations and large sets of potentialsolvent–
membrane candidates.

We can say that in the coming years due to energy savings and intensification of plants; RD is
going to gain more importance. A plethora of literature is available were many reviews and
experimental validation are shown. It all suggests that this process is truly the front runner of
industrial process intensification. As always with new technologies there are many hurdles in its
commercial implementation; but which are being solved; thanks to newest software’s and
computational tools available. One hopes that the research intensifies and the barriers to it’s
implementation are broken so that RD can become the new standard for process industries
aiming for economic and environmental success.

In conclusion, the authorbelievesthat reactive distillation is an important building block for

future production processes.

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 REFERENCES

[1] R. Krishna, Reactive separations: more ways to skin a cat, Chemical Engineering Science
57 (2002) 1491 – 1504.
[2] C. Noeres, E.Y. Kenig , A. Gorak, Modelling of reactive separation processes: reactive
absorption and reactive distillation, Chemical Engineering and Processing 42 (2003)
157/178
[3] W.J. Hatcher, Reaction and mass transport in two-phase reactors, in: N.P. Cheremisinoff
(Ed.), Handbook of Heat and Mass Transfer, vol. 2, Gulf Publ Comp Book Division,
Houston, 1986, pp. 837/868.
[4] Sundmacher, K., Kienle, A., 2003. Reactive Distillation – Status
and Future Directions, first ed. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
[5] R. Krishnamurthy, R. Taylor, A nonequilibrium stage model of multicomponent
separation processes. The influence of unequal component-efficiencies in process design-
problems, AIChE J. 31 (1985) 1973–1985.
[6] G.J. Harmsen, Reactive distillation: the frontrunner of industrial process intensification:
a full review of commercial applications, research, scale-up, design and operation,
Chem. Eng. Process. 46 (9) (2007) 774–780.
[7] Doherty, M.F., Malone, M.F., 2001. Conceptual Design of Distillation Systems.
McGraw-Hill, New York.
[8] SumanThotla, Sanjay M. Mahajani; Conceptual design of reactive distillation for
selectivity improvement in multiple reactant systems; Department of Chemical
Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India
[9] M.V. Pavan Kumar, NitinKaistha; Decentralized control of a kinetically controlled ideal
reactive distillation column; Department of Chemical Engineering, Indian Institute of
Technology Kanpur, Kanpur 208016, India
[10] VinayAmte, SriharshaNistala, Ranjan Malik, SanjajMahajani; Attainable regions of
reactive distillation—Part III. Complex reaction scheme: Van de Vusse reaction;
Department of Chemical Engineering, Indian Institute of Technology, Bombay, Powai,
Mumbai 400 076, India

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[11] C.P. Almeida-Rivera, Simultaneous optimisation of process control structures in reactive
distillation, in: H.A. Akse (Ed.), OSPT Process Technology Hesselink of Shell Global
Solutions for reviewing the paper. Ph.D.-projects in Miniposters.
[12] Buzad, G., & Doherty, M. (1994). Design of three-component kinetically controlled
reactive distillation columns using fixed-point methods. Chemical Engineering Science,
49(12), 1947–1963.
[13] C. P. Almeida-Rivera, P. L. J. Swinkels, J. Grievink; Designing reactive distillation
processes: present and future; Process Systems Engineering Group, DelftChemTech,
Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
[14] Giessler, S., Danilov, R. Y., Pisarenko, R. Y., Serafimov, L. A., Hasebe, S., &
Hashimoto, I. (1998). Feasibility study of reactive distillation using the analysis of the
statics. Industrial and Engineering Chemistry Research, 37, 4375–4382.
[15] Giessler, S., Danilov, R. Y., Serafimov, L. A., Hasebe, S., & Hashimoto, I. (1999).
Feasible separation modes for various reactive distillation systems. Industrial and
Engineering Chemistry Research, 38, 4060– 4067.
[16] Giessler, S., Danilov, R. Y., Pisarenko, R. Y., Serafimov, L. A., Hasebe, S., &
Hashimoto, I. (2001). Systematic structure generation for reactive distillation processes.
Computers and Chemical Engineering, 25, 49– 60.
[17] Subawalla, H., & Fair, J. (1999). Design guidelines for solid-catalyzed reactive
distillation systems. Industrial and Engineering Chemistry Research, 38(10), 3696–3709.
[18] Kejin Huang, Koichi Iwakabe, Masaru Nakaiwa, Atsushi Tsutsumi; Towards further
internal heat integration in design of reactive distillation columns—part I: The design
principle; Chemical Engineering Science 60 (2005) 4901 – 4
[19] R. Taylor, R. Krishna; Modelling reactive distillation; Chemical Engineering Science 55
(2000) 5183-5229
[20] J. Carlos Cardenas-Guerra, Teresa Lopez-Arenas, Ricardo Lobo-Oehmichen, Eduardo S.
Perez-Cisneros; A reactive distillation process for deep hydrodesulfurization of diesel:
Multiplicity and operation aspects; Computers and Chemical Engineering 34 (2010) 196–
209
[21] Siirola, J. J. (1995). An industrial perspective on process synthesis. A.I.Ch.E. Symposium
Series No. 304, Vol. 91 (pp. 222-233).

Page 65 of 66
 [22] M.V. Pavan Kumar, NitinKaistha;Decentralized control of a kinetically controlled ideal
reactive distillation column; Chemical Engineering Science 63 (2008) 228 – 243
[23] Anton A. Kiss; Heat-integrated reactive distillation process for synthesis of fatty esters;
Fuel Processing Technology 92 (2011) 1288–1296
[24] A.A. Kiss, Novel process for biodiesel by reactive absorption, Separation & Purification
Technology 69 (2009) 280–287.
[25] A.A. Kiss, A.C. Dimian, G. Rothenberg, Biodiesel by reactive distillation powered by
metal oxides, Energy & Fuels 22 (2008) 598–604.
[26] A.A. Kiss, Novel process for biodiesel by reactive absorption, Separation & Purification
Technology 69 (2009) 280–287.
[27] A.C. Dimian, C.S. Bildea, F. Omota, A.A. Kiss, Innovative process for fatty acid esters
by dual reactive distillation, Computers & Chemical Engineering 33 (2009) 743–750
[28] C. Miller, G. Kaibel; Packings for fixed bed reactors and reactive distillation; Chemical
Engineering Science 59 (2004) 5373 – 5379

Page 66 of 66

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