KINGDOM OF SAUDI ARABIA

KING SAUD UNIVERSITY

COLLEGE OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

MODELING AND SIMULATION OF A REACTIVE

DISTILLATION UNIT FOR PRODUCTION OF MTBE

SUBMITTED BY

FAHAD S. AL-HARTHI
424121504

SUPERVISED BY

PROF. DR. AHMED E. ABASAEED

PROF. DR. IBRAHIM S. AL-MUTAZ

A Thesis submitted in partial fulfillment of the requirements for the

degree of Master of Science in Chemical Engineering

2nd Semester 1428-1429 AH

JUNE 2008
KINGDOM OF SAUDI ARABIA
KING SAUD UNIVERSITY
COLLEGE OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

MODELING AND SIMULATION OF A REACTIVE

DISTILLATION UNIT FOR PRODUCTION OF MTBE

Submitted by:

Eng. Fahad Al-Harthi

424121504

Supervised by:

Prof. Dr. Ahmed E. Abasaeed

Prof. Dr. Ibrahim S. Al-Mutaz

Examination Committee Members

Prof. Ahmed E. Abasaeed

Prof. Ibrahim S. Al-Mutaz
Prof. Kamil M. Wagialla
Prof. Mohammed Asif
Prof. Khalid I. Al-Humaizi

A thesis submitted in partial fulfillment of the requirements for the degree of

Master of Science in Chemical Engineering

2nd Semester 1428-1429 AH

JUNE 2008


)(MTBE
:
/

:

:

June 2008
 TABLE OF CONTENTS
Table of contents .. i
List of Figures. iii
List of Tables.. v
Nomenclature vi
Dedication viii
Acknowledgments. ix
Abstract .. xi

CHAPTER 1 : INTRODUCTION .. 1

1.1 Properties of MTBE 2

1.2 Chemistry of MTBE 3
1.3 Demand of MTBE.. 3
1.4 Commercial Technology of MTBE.. 5
(a) lsobutylene from Steam Crackers. 6
(b) Isobutylene from Refineries 6
(c) Isobutylene by dehydrogenation lsobutane.. 7
(d) Isobutylene from TBA.. 7
1.5 Introduction to Conventional Process.... 8
1.6 Concept of Reactive Distillation Process.. 9
1.7 Production of MTBE by Reactive Distillation. 10
1.7.1 ABB LUMMUS Process...... 11
1.7.2 UOP Process ...... 12
1.7.3 Huntsman TBA/PO Process... 14
1.8 Thesis outline and Work Methodology.. 15
1.8.1 Research Outline15
1.8.2 Research Methodology.....15

CHAPTER 2 : REACTIVE DISTILLATION

2.1 Introduction to Reactive Distillation. 17

2.2 Basics and Advantages of Reactive Distillation... 17
2.2.1 Importance of RD 18
2.2.2 Constraints and Difficulties in RD implementation.... 23
2.2.3 The complexity of RD. 24
2.2.4 Model Available for design of RD columns.... 25

i
CHAPTER 3 : LITERATURE SURVEY

3.1 Overall Review....... 28

3.2 Computational Methods...... 30

CHAPTER 4 : MODELING & SIMULATION OF MTBE PROCESS

4.1 MTBE Production by PRO/II 40

4.1.1 Introduction 40
4.1.2 Process description .. 40
Catalyst used43
MTBE Recovery section.43
Methanol Recovery section44
4.2 Modeling and Simulation of MTBE RD unit....... 45
4.3 Thermodynamics Data............ 46
4.4 MTBE Reaction Kinetics.......... 48
4.5 Modeling Procedure.......... 51
4.5.1 Model Equations for a single Stage............. 53
4.6 Modeling and simulation framework........... 54

CHAPTER 5 : RESULTS AND DISCUSSION

5.1 Results of the simulation work........................ 57

5.2 Results discussion......................... 62
5.3 Cases studies (Optimization)................... 62

CHAPTER 6 : CONCLUSIONS AND RECOMMENDATIONS

6.1 Conclusions.. 69
6.2 Recommendations ..... 71

REFERENCES...... 73

APPENDIXES
APP (A) : Reaction model code. .. 76
APP (B) : MTBE Process Simulation Procedure using PRO/II software. .. 80
APP (C) : Process Input-File used in PRO/II software. .... 98

ii
 LIST OF FIGURES
Figure No Page

Figure 1.1 : Publications and Patents on Reactive Distillation (1973-2003)..... 1

Figure 1.2 : MTBE Global Demand Distribution. 5

Figure 1.3 : MTBE Production Processes...... 6

Figure 1.4 : MTBE Production via conventional Processes .............. 9

Figure 1.5 : CDTECH Process Flow Diagram.............. 12

Figure 1.6 : ETHERMAX MTBE Process Flow Diagram......... 13

Figure: 2.1 Simple Reactive Distillation sketch..................................... 18

Figure 2.2: Processing schemes for a reaction sequence A +B <==> C+ D ...... 19

Figure 2.3: Processing schemes for the esterification reaction MeOH + AcOH<==>MeOAc + H2O 20

Figure 2.4: (a) Reactive distillation concept for synthesis of MTBE from the acid catalysed reaction
between MeOH and iso-butene. The butene feed is a mixture of reactive iso- butene and non-
reactive n-butene. (b) Reactive distillation concept for the hydration of ethylene oxide to ethylene glycol.
(c) Reactive distillation concept for reaction between benzene and propene to form cumene. (d)
Reactive distillation concept for reaction production of propylene oxide from propylene chlorohydrin
and lime. The reactive sections are indicated by grid line... 21

Figure 2.5: Hydrodesulphurisation of gas oil carried out in (a) co-current trickle bed reactor and (b)
counter-current RD unit...... 22

Figure 2.6: Transport processes in RD. (a) homogeneous liquid phase reaction, and (b) heterogeneous
catalyzed reactions.......... 25

Figure 2.7 : Length and time scales in RD.......... 25

Figure 3.1: Ternary LLE diagram for Acetone-water-MIBK system at 5atm. ..33

Figure 3.2: RD Column Configuration............ 34

Figure 3.3: Liquid Composition profile in RD Column............ 34

Figure 3.4 Nonreactive residue curve map for the system IBTE+ MeOH MTBE at 101.32 kPa 36

Figure 3.5 Reactive residue curve map for the system IBTE+ MeOH MTBE at 101.32 kPa. 37

Figure 3.6 Reactive phase diagram for the system IBTE/ MeOH /MTBE at 101.32 kPa. 37

Figure 3.7 Reactive phase diagram for the system IBTE/ MeOH /MTBE at 810.56 kPa. 38

Figure 4.1: MTBE Plant Flowsheet................41

Figure 4.2: Thermodynamic Data of PRO/II software.........47

Figure 4.3: A schematic representation of a catalytic distillation column........52

iii
Figure 4.4: Representation of a generic equilibrium stage............52

Figure 4.5: MTBE Process Flowsheet PRO/II..........55

Figure 5.1: Feed and products concentration profile among column trays.........57

Figure 5.2: Temp Profile of column T-1...............58

Figure 5.3: Rates Profile of column T-1... 58

Figure 5.4: Density Profile of column T-1....59

Figure 5.5: Viscosity Profile of column T-1......59

Figure 5.6: Temp Profile of column T-2.......59

Figure 5.7: Rates Profile of column T-2...59

Figure 5.8: Density Profile of column T-2.....60

Figure 5.9: Viscosity Profile of column T-2..... 60

Figure 5.10: Temp Profile of column T-3.....60

Figure 5.11: Rates Profile of column T-3.....60

Figure 5.12: Density Profile of column T-3......61

Figure 5.13: Viscosity Profile of column T-3........61

Figure 5.14: Results of changing the MeOH/IBTE ratio.......63

Figure 5.15: Results of changing the number of trays of RD column.....64

Figure 5.16: Results of changing the location of feed stream into RD column 65

Figure 5.17: Results of changing the Reflux Ratio........66

Figure 5.18 Results of changing the location of reaction zone ........67

iv
 LIST OF TABLES
Table page

Table 1.1: Typical Properties of Oxygenates............... 2

Table 1.2 : MTBE competitive strengths and weaknesses................ 3

Table 1.3 : Global MTBE demand (thousand tons per year) ................ 5

Table 1.4: Typical isomer distribution in C4 product stream (volume %)................. 7

Table 4.1: Reactor Feed Data.................... 42

Table 4.2: Reaction Stoichiometry.................... 43

Table 4.3: Approximate Catalyst Properties of Amberlyst 15.................. 43

Table 4.4: Binary Interaction Parameters for SRKM_VLE................. 46

Table 5.1: Summary Table................. 57

Table 5.2: Summary of MTBE column T-1.................... 58

Table 5.3: Summary of water wash column T-2................... 59

Table 5.4: Summary of Methanol Recovery column T-3..................... 60

Table 5.5: Overall Report...................... 61

v
 NOMENCLATURE
Notations
a,b,c Order of reaction of species A,B and C respectively
HA Heat of adsorption of methanol, J/mol
HC Heat of adsorption of MTBE, J/mol
aij The mixing rule
Xi Mole fraction of component i
Xj Mole fraction of component j
Kij Binary interaction parameter
Ks Surface reaction rate constant, (gmole/g catalyst)
KA Equilibrium adsorption constant for A, g cat/gmole
KC Equilibrium adsorption constant for C, g cat/gmole
K Equilibrium constant for the overall reaction
KAO , KCO, KSO Preexponential factor
rs Rate of surface reaction, (mol/gcat)/h
CA IBTE concentration, mole/l
CB MEOH concentration, mole/l
CC MTBE concentration, mole/l
R Gas constant, 8.314 J/mol.K
T Temperature, K
E1 Activation Energy of the forward reaction, J/mol
KX Mole fraction Equilibrium ratio
K Ratio of activity coeffiecients at equilibrium
Xk,i The mole fraction of liquid phase for species j in stage k.
Yk,i The mole fraction of vapor phase for species i leaving stage k
Lk The molar liquid flow rate leaving stage k.
Vk The molar vapor flow rate leaving stage k.
Fk The feed flow rate to stage k.
hk The molar enthalpy of liquid phase in stage k.
HK The molar enthalpy of vapor phase in stage k.
Hjk The heat of reaction in stage k.
Qk The heat duty in stage k.
k,i The activity coefficient of component i in stage k.
Kk,i The vapor-liquid equilibrium constant.
k The molar density of the liquid on stage k.
vk The volumetric hold-up of liquid on stage k
P Pressure, bar
NC Number of components
NT Number of trays

vi
 u,w Constants, typically integers

Subscripts:
i Tray index
j Component index
Superscripts:
F refers to a feed
D refers to a draw
L refers to a liquid property
V refers to a vapor property

vii
 DEDICATION

To my mother, who will be always my inspiration. This work is also dedicated to the ones that
encourage me, my wife , my daughter Lujain, and my brothers.

viii
 ACKNOWLEDGMENT
Firstly, I thank Allah almighty for His blessings and providing me with the
strength and power to succeed.
This research compiles the upmost results of a 2-year period of intense and
challenging work. Independently on the nature of their contribution (intellectual or/and
emotional), many people have pushed toward the completion of this work. To all of
them I am deeply and sincerely indebted.
My first words of thanks go, sincerely, to my promoter, Prof. Ibrahim Al-Mutaz.
I thank him for his continuous guidance and scientific insight during these 2+ years
and, on top of this, for his admirable kindness and politeness. I fully enjoyed the long
hours we spent together, discussing a wide range of topics. Also. I would like to thank
my advisor Prof. Ahmed Abasaeed for his support and I am very much thankful for
allocating time in your tight agenda to discuss and repeatedly correct all the thesis
chapters. Really, Without all your comments and suggestions this thesis probably
would have remained as a bunch of unconnected manuscripts.
Additionally, I would like to thank all the people who supported my research
and me during the past two years. Foremost have been my wife who has always
encouraged me to work hard and to continue this work.
Moreover, my thanks also extended to my family members, relatives and
colleagues for supporting me throughout my research period.

ix


:
) ( ) (MTBE

) (

. MTBE

.
MTBE

.
MTBE
60-45 .
) (MTBE
.
MTBE 1980
MTBE
MTBE Reactive Distillation Process
:

.

MTBE
.
PRO/II
MTBE %99.2
.%99.7

x
 ABSTRACT
Methyl tertiary butyl ether (MTBE) is primarily used in gasoline blending as an octane
enhancer to improve hydrocarbon combustion efficiency. Of all the oxygenates, MTBE is
attractive for a variety of technical reasons. It has a low vapor pressure. It can be blended with
other fuels without phase separation. It has the desirable octane characteristics.
MTBE is produced via direct addition of methanol to isobutylene using sulphonated ion
exchange resin as catalysts. There are two ways to produce MTBE, one is the conventional
process which is mainly a reactor and separate distillation column with conversion range 87-
92%. Another method for the production of MTBE is newly established and date back to the
way in 1980 as the scientist Smith recorded the first patent for the production of MTBE
through this method, this method called Reactive Distillation Process, and there are a lot of
features that makes this process attractive and practical with a conversion reached 99.2%.
The main objectives from this research are developing a mathematical model for the
MTBE production via reactive distillation column at steady state, coding and embedding the
model into simulation software (PRO/II) and using the developed model to assess the effect of
some critical design and operating parameters on column performance and doing some case
studies.
PRO/II software has the capabilities of solving Reactive Distillation Processes
utilizing Chemdist Algorithm provided by the software, but it requires knowledge of Material
and Energy balances equations as well as Thermodynamics and kinetics of reaction.
In this work, we have made an extensive literature survey for the previous research
done in this area to study this technology and then we have developed a mathematical model
that simulates the production of MTBE in a reactive distillation unit and that model was used
to study the impact of operational factors and different design parameters by doing several case
studies "Optimization".
The main conclusion of this work is that the higher conversion of IBTE to MTBE can
be obtained by applying Reactive Distillation approach, we have obtained 99.2 % IBTE
conversion and high selectivity for MTBE with 99.7%. Moreover, the optimum
Methanol/Isobutylene ratio was found equal to 1.0 and the optimum number of trays for
Reactive Distillation column is 30 trays.

xi
 CHAPTER -1-

INTRODUCTION
 CHAPTER -1-

INTRODUCTION

Methyl tertiary butyl ether (MTBE) is primarily used in gasoline blending as an

octane enhancer to improve hydrocarbon combustion efficiency. Of all the
oxygenates, MTBE is attractive for a variety of technical reasons. It has a low vapor
pressure. It can be blended with other fuels without phase separation. It has the
desirable octane characteristics and is becoming increasingly important as stricter air
pollution control measures are implemented.
MTBE can be produced by addition of methanol to isobutylene in the liquid
phase over an acidic catalyst consisting of sulfonated macroporous ion exchange
resins.
In 1980, Smith registered a patent to process MTBE for Chemical Research
and Licensing Company. He used a reactive distillation system, containing catalytic
packing. The pilot plant was 3 inches in diameter and it was used to predict the
operation variables of a large commercial plant [1].
Due to its potential for improved process design and the success of its
commercial applications, reactive distillation gained the interest of both academics
and industry toward its use and application in commercial processes. Figures 1.1
show the growing interest in reactive distillation in recent years. These data were
compiled from the ACS databases CAPLUS, CHEMCATS and CHEMLIST. Some 400
publications were taken into consideration for the period of 1973 to May 2003 [2].

Figure 1.1 Publications and Patents on RD -Historical Trends (1973-2003).

-1-
1.1 PROPERTIES OF MTBE

Oxygenates are hydrocarbons that contain one or more oxygen atoms.

The primary oxygenates are alcohols and ethers, including: fuel ethanol, methyl
tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), and tertiary amyl
methyl ether (TAME). The physical properties for these components are shown
in Table 1.1.
The 1977 Clean Air Act amendments set requirements for "substantially
similar gasoline," which requires that oxygenates be approved by the U.S. EPA
before they are allowed to be used in gasoline. In 1981 the EPA allowed the
blending of MTBE up to 11 volume %, and extended the limit to 15 volume % in
1988.
Oxygenates are added to motor vehicle fuels to make them burn more
cleanly, thereby reducing toxic tailpipe pollution, particularly carbon monoxide.
Oxygenates are favored not only for their vehicle emission benefits but also
their blending properties in motor gasoline (e.g., octane).

Table 1.1: Typical Properties of Oxygenates.

Ethanol MTBE ETBE TAME

Chemical formula CH3CH2OH CH3OC(CH3)3 CH3CH2OC(CH3)3 (CH)3CCH2OCH3

Oxygen content, %
34.73 18.15 15.66 15.66
by weight
Octane, (R+M)/2 115 110 111 105
Blending vapor
18 8 4 1.5
pressure, RVP

Source: National Petroleum Council, U.S. Petroleum Refining: Meeting Requirements for Cleaner Fuels
and Refineries (Washington, DC, August 1993) Appendix L.

There is an increasing demand for MTBE as a gasoline additive.

Currently, the worldwide consumption of MTBE reached 6.6 billion gallons of
which 65% is consumed in the United States [3].
Methyl tertiary-butyl ether is an excellent gasoline blending component
because it is a high octane enhancer and has low volatility. It has blending
properties similar to gasolines, but do not exhibit undesirable properties such
as azeoptrope formation, water pick-up, or phase separation. Gasoline

-2-
 containing MTBE is accepted for transport on common carrier pipelines in the
United States and by major and independent refiners.
Table 1.2 summarizes the relative strengths and weaknesses of MTBE
compared to other octane enhancers. MTBE is a widely accepted octane
enhancer and enjoys several significant strengths compared to competing
octane enhancers. Its major weakness is that one of its key feedstocks,
isobutylene, is limited by petrochemical and refinery operations.

Table 1.2 : MTBE competitive strengths and weaknesses

Strengths Weaknesses
- High octane - Availability of economical
- Low volatility isobutylene feedstocks is
- Blending characteristics similar to gasoline limited
- Widely accepted in marketplace by - Possible methanol
consumers and refiners supply constraints
- Reduces carbon monoxide and exhaust - Health hazard
- hydrocarbon emissions

Although MTBE has a density less than that of water, when dissolved in
water, MTBE responds to localized groundwater gradients and aquifer
recharge. A growing number of studies have detected MTBE in ground water in
United State; in some instances these contaminated waters are sources of
drinking water. Low levels of MTBE can make drinking water supplies
undrinkable due to its offensive taste and odor. Therefore, the jurisdiction of the
U.S. Department of Transportation (DOT) has set some restricted Regulation to
minimize releases from gasoline pipelines or another potential source of leaks.
MTBE is believed to have entered the water supply from leaking
underground storage tank systems including underground lines that contained
gasoline and/or from surface spills at gas stations. Once in the ground, MTBE
behaves differently from other gasoline constituents such as benzene . Unlike
petroleum hydrocarbons, it is highly water soluble, not easily absorbed into soil,
and is more resistant to biodegradation. Thus, with widespread use, MTBE
has the potential to occur in high concentrations in groundwater, travel far from
leak sources, and accumulate to become a concern for the entire region.

-3-
1.2 CHEMISTRY OF MTBE

Methyl tertiary-butyl ether (MTBE) can be formed by the addition of

methyl alcohol to the highly reactive double bond in isobutylene, as shown in
the following equation:

CH 3 OH + (CH 3 )2 C = CH 2 (CH 3 )3 C O CH 3
Methanol Isobutylene MTBE

MTBE synthesis occurs in the liquid phase at 40C-100C and 100-150

psig as an exothermic reaction (HR= -16,060 Btu/lb-mole). In the presence of
a small amount of acidic cation exchange resin catalyst the reaction proceeds
quantitatively. Indeed, there are few reactions in industrial chemistry that
demonstrate such high selectivity. Several processes, as will be discussed
later, have been devised for carrying out this reaction efficiently on the
isobutylene contained in the so-called raffinate-I that results when butadiene is
removed from the C4 fraction obtained either from steam or catalytic cracking.
The C4 fraction from the former source is preferred because of its higher
isobutylene concentration. This fraction contains, in addition to isobutylene,
butene-I, and butane-2. The removal of isobutylene from raffinate-I provides a
mixture of the normal butenes known as raffinate-Il [2].

1.3 DEMAND OF MTBE

The importance of MTBE is increasing from year to year since the global
demand for MTBE is expected to grow at 4.0% annually from 1994 to 2010, as
shown in Table I.3. In the 2000-2010 period, however, growth will slow to 1.7 %
annually from 8.1 % from 1994-2000 as shown in Fig 1.3 [4].

-4-
 Table 1.3 : Global MTBE demand (thousand tons per year). Adapted from CHEM
SYSTEM.

Figure 1.2 : MTBE Global Demand Distribution

1-4 COMMERCIAL TECHNOLOGIES OF MTBE

Methyl tertiary-butyl ether (MTBE) is produced through the reaction of

isobutylene with methanol. The MTBE reaction is equilibrium limited. Higher
temperatures increase the reaction rate, but the conversion level is lower.
Lower temperatures shift the equilibrium toward ether production, but more
catalyst inventory is required. Therefore, conventional MTBE units are
designed with two reactors in series. Most of the etherification reaction is
achieved at an elevated temperature in the first reactor and then finished at a
thermodynamically favorable lower temperature in the second reactor [2].
Figure 1.3 shows the different routes to obtain IC4 for MTBE production, which
vary largely due to the different isobutylene feedstock sources. As shown in the
figure, isobutylene can be produced as a:
Byproduct of ethylene manufacture in steam cracker units

-5-
 Byproduct of fluid catalytic cracking operations.
Main product of an isobutane dehydrogenation unit
Coproduct (via tertiary-butyl alcohol-TBA) of propylene oxide manufacture,
as operated by ARCO Chemical and Texaco Chemical Company

Figure 1.3 : MTBE Production Processes

These various supply sources for isobutylene are briefly reviewed below.
(a) lsobutylene from Steam Crackers
The mixed butylene stream produced from ethylene plants has a
relatively high isobutylene content. Depending on the feedstock, operating
conditions, plant configuration, and other factors, the isobutylene content can
vary from 35 to 50 vol%, with about 44 % considered typical. One benefit of
MTBE manufacture from steam cracker sourced mixed butylenes is that it
provides an easy way to separate butylene isomers [2].

(b) Isobutylene from Refineries

Isobutylene is also produced as a byproduct of fluid catalytic cracking
(FCC) operations in refineries. The isobutylene concentration is much lower in
this mixed butylene stream compared to the steam cracker mixed C4s stream.
Table 1.4 shows the relative butane/butylene isomer distribution for typical FCC
and steam cracker C4 streams [2].
The higher isobutylene concentration in steam cracker mixed butylene
streams reduces the capital and operating costs compared to feeding FCC
mixed butylenes.

-6-
Table 1.4: Typical isomer distribution in C4 product stream (volume %)

(c) Isobutylene by dehydrogenation lsobutane

One possibility in alleviating the potential problem of insufficient
isobutylene is to dehydrogenate isobutane. lsobutane may, in turn, be made by
the isomerization of n-butane, a reaction well established, for isobutane is
prepared in large volumes for alkylation reactions in the refinery. Another
approach involves the skeletal isomerization of butene-1.
These reactions are shown in the following equations:

(d) Isobutylene from TBA

High capital costs are involved in the isomerization and dehydrogenation
reactions. tertiary-Butyl alcohol (TBA), made by ARCO and Texaco as a
coproduct of propylene oxide production, is another source of isobutylene. This
involves dehydration to isobutylene, as shown in the following equation [2].

-7-
 A number of companies have technology for MTBE manufacturing: all
the routes are based on liquid phase etherification of isobutylene with
methanol. Selected technology holders and licensers are: ARCO, CDTECH
(ABB Lummus Crest and Chemical Research & Licensing), Snamprogetti,
Phillips Petroleum, HuelslUOP, Sumitomo Chemical, Erdoelchemie, IFP.

Description of some commercial conventional Processes are given below:

1.5 A TYPICAL CONVENTIONAL PROCESS

As mentioned in the previous section, MTBE is produced via direct
addition of methanol to isobutylene using sulphonated ion exchange resin as
catalysts. The technology features a two-stage reactor system of which the first
reactor is operated in a recycle mode. With this method, a slight expansion of
the catalyst bed is achieved which ensures very uniform concentration profiles
within the reactor and, most importantly, avoids hot spot formation. Undesired
side reactions, such as the formation of dimethyl ether (DME), are minimized.
The reactor inlet temperature ranges from 45C at start-of-run to about 60C at
end-of-run conditions. The catalyst used in this process is a cation-exchange
resin. Isobutylene conversions of 97% are typical for FCC feedstocks. Higher
conversions are attainable when processing steam-cracker C4 cuts that
contain isobutylene concentrations of 25% as illustrated in figure 1.4 [2].
MTBE is recovered as the bottoms product of a distillation unit. The
methanol-rich C4 distillate is sent to the methanol-recovery section. Water is
used to extract excess methanol and recycle it back to process. The isobutylene-
depleted C4 stream may be sent to a raffinate stripper or to a molsieve-based
unit to remove other oxygenates such as DME, MTBE, methanol and tert-
butanol.

-8-
 Figure 1.4 : MTBE Production via Conventional Processes

An alternative to the conventional process is Reactive Distillation process.

1.6 CONCEPT OF REACTIVE DISTILLATION PROCESS

Reactive distillation is a process where simultaneous chemical reaction

and vapor-liquid phase separation take place in the presence of a
heterogeneous catalyst. This represents an exciting alternative to traditional
liquid phase chemical reaction processing. In reactive distillation separation of
product(s) from unconverted reactants allows for greater conversion, because
product removal displaces equilibrium and forces the reaction to completion [4].

Both reaction and distillation acting simultaneously offers certain

advantages that cannot be matched by conventional processing. The
advantages of reactive distillation are specific to each system. However, the
followings are some of the significant advantages of reactive distillation:[4]

-9-
 Effecting distillation and reaction simultaneously reduces the capital
costs and includes benefits such as reduction of recycle, optimization of
separation, lower requirements of pumps, instrumentation and piping.
An equilibrium reaction can be driven to completion by separation of the
products from the reacting mixture.
Elimination of possible side reactions by removal of the products from
the reaction zone. This can serve to increase selectivity.
Savings associated with energy costs, through use of the energy
released by exothermic reactions for vaporization. This reduces the
reboiler heat duty for boil-up that is supplied normally by steam.
Non-reactive azeotropes may disappear under reactive distillation
conditions.
Improved materials use. With reactive distillation, material proper usage
is attained through removal of the reaction product(s) from the reaction
phase. Also, elimination of by-products formation may allow use of
lesser quantities of reactants.
Reduction of hot spots, because the liquid vaporization provides a sink
for thermal energy.

Synthesis of chemicals through reactive distillation has been mainly

applied to processes such as esterifications, hydrolysis reactions, trans-
esterifications, and etherifications. A detailed list of reactions where reactive
distillation is advantageous is cited by Doherty and Malone in 2001 [5]. While
the use of reactive distillation is well established in the chemical process
industry, very little is known regarding the importance of mass transfer
resistances in limiting catalyst effectiveness in MTBE synthesis [6].

1.7 PRODUCTION OF MTBE BY REACTIVE DISTILLATION UNIT

Most of the new commercial MTBE plants utilize reactive distillation

technology in which chemical reaction and fractionation of products are
combined into a single unit operation.

- 10 -
 In the production of MTBE in reactive distillation process, a pre-reactor
and a reactive distillation column replaced the conventional process. The
reactive column completes the exothermic reaction and simultaneously
conducts the separation. It is also possible to incorporate the pre-reactor into
the reactive column thereby lowering capital costs and improving energy
integration [7]. The reaction between methanol and isobutylene to form MTBE
is equilibrium limited and the feed to a conventional reactor requires a relatively
low methanol/isobutylene feed ratio in the feed.
Maintaining the methanol/isobutylene ratio below 1.05 allows recovery of
the product MTBE as the bottoms product from a distillation tower with the
overhead product being at the azeotropic composition of methanol and
isobutylene. Feeding a higher methanol/isobutylene ratio results in recovery of
the MTBE from the bottoms at the methanol/MTBE azeotropic composition
[8,9]. Use of reactive distillation allows more economical recovery of the MTBE
product. Typical Reactive Distillation processes are:

1.7.1 ABB LUMMUS Process

The process of production of MTBE using ABB LUMMUS process

consists of three basic steps as listed below [2]:
Isomerization of n-butanes to isobutane.
Dehydrogenation of isobutane to isobutylene (CATOFIN Process).
Etherification of isobutylene with methanol to MTBE (CDTech
Process).
MTBE is formed by the catalytic etherification of isobutylene with
methanol, as shown in Figure 1.5 Isobutylene-rich feedstock from the
dehydrogenation unit is combined with fresh methanol from offsite storage and
recycle methanol from the methanol recovery of the MTBE unit and fed to the
primary fixed bed reactor. The CDTech process is based on a two step reactor
design, consisting of a fixed bed reaction followed by final conversion in a
catalytic distillation column [2].
After reaction in the primary reactor, the partly reacted mixture is cooled
to the bubble point and pumped to the catalytic distillation reaction column that

- 11 -
 combines reaction and fractionation sections. The reaction is continued in the
column and the MTBE product is separated from the un-reacted C4s. The
column allows a high conversion (99 %) of isobutylene.
Methanol and C4s form a minimum boiling azeotrope, so that the
methanol is carried into the catalyst packing where the reaction proceeds. As
MTBE is formed, it is removed from the reaction zone by distillation, which
allows the reaction to proceed well beyond the limit set by chemical equilibrium
for a conventional reactor system. MTBE leaves the reaction column as the
bottoms product together with a small amount of reaction byproducts. All
byproducts formed in the MTBE reaction are gasoline compatible components.
They include TBA (formed by the reaction of isobutylene and water) and
diisobutylene (formed by the dimerization of isobutylene). Any residual
methanol distills overhead with the unreacted C4s and is routed to the
methanol extraction column. The recovered methanol (methanol column
overhead) is recycled to the MTBE reactor feed. The methanol column bottoms
product (water) is recycled to the methanol extraction column.

Figure 1.5 : CDTECH Process Flow Diagram

1.7.2 UOP Process
The process of production of MTBE using UOP Process consists of three
basic steps as listed below [2]:
Butane isomerization (Butamer Process).
Isobutane dehydrogenation (Oleflex Process).

- 12 -
 Isobutylene Etherification (Ethermax Process).

In the Ethermax process isobutylene reacts selectively with methanol to

yield MTBE. The reaction proceeds in the liquid phase at mild conditions in the
presence of a sulfonic acid ion exchange resin. A simplified flow diagram of the
process is shown in Figure 1.6. The reaction of isobutylene with methanol is
conducted in the presence of a small excess of methanol relative to that
required for the stoichiometric reaction of the isobutylene contained in the C4
feed.

Figure 1.6 : ETHERMAX MTBE Process Flow Diagram

The reaction is virtually 100 % selective except for minor side reactions
owing to the presence of certain impurities in the feed. Thus, feed water will
give rise to equivalent amounts of tertiary-butyl alcohol (TBA) in the product,
whereas feed isoamylene will yield tertiary-amyl methyl ether (TAME). These
byproducts are usually unimportant, since they can be used equally as gasoline
blending agents and need not be separated from the MTBE product.
The Ethermax process combines the fixed bed reactor technology
(originally developed by Huels) with Koch Engineerings RWD reaction with
distillation technology to overcome equilibrium limitations found with
conventional fixed bed technologies. The methanol and C4 streams are
combined, heated, and charged to a fixed bed reactor. In the reactor,

- 13 -
 condensation of isobutylene and methanol takes place under relatively mild
conditions. Although a tubular reactor can be used, UOP has opted for an
adiabatic packed bed reactor for the large flow rates associated with Oleflex-
based units.
The catalytic section of the RWD column uses a structured packing that
contains catalyst to overcome reaction equilibrium constraints by continuously
fractionating the product from unreacted components. The key to success with
this type of technology is proper distribution of liquid and vapor in the reaction
zone; efficient contact of reactants with catalyst; and instantaneous
fractionation of products. Thus, the KataMax structured packing, developed by
Koch Engineering provides an efficient mass and heat transfer between vapor,
liquid, and solid catalyst, and exhibits a high hydraulic capacity.
MTBE is taken off as RWD bottoms and C4 raffinate is recovered in the
overhead fraction. Residual methanol in the raffinate stream is recovered and
recycled with a water wash system to reduce methanol consumption to about
stoichiometric levels.

1.7.3 Huntsman TBA/PO Process

Huntsman has a 181,000 metric ton per year propylene oxide plant in
Port Neches, Texas, which started up in 1994. The plant, originally built by
Texaco was designed with Texaco technology. The byproduct TBA is
converted to 14,000 barrels per day of MTBE (560,000 metric tons). The
Texaco/Huntsman process is believed to be essentially similar to Lyondell's
propylene oxide production process. However, MTBE is produced directly from
TBA with no intermediate production of isobutylene as in the Lyondell process,
according to patent information.
The Texaco/Huntsman process route consists of the well-known steps of
peroxidation of isobutane to TBHP and TBA; epoxidation of propylene with
TBHP to propylene oxide and TBA; and the reaction of TBA with methanol to
form MTBE, although this has not been previously practiced as a one step
reaction.

- 14 -
1.8 THESIS OUTLINE AND WORK METHODOLOGY

1.8-1 Research Objectives

The main aim of this work is to develop a mathematical model for the
production of MTBE in a reactive distillation unit at steady state operation. The
model will incorporate rate data, thermodynamics properties and vapor-liquid
non-idealities. A suitable coding language (FORTRAN) will be used to code the
relevant model equations into used simulation software. The coded equations
will be embedded into PROII software using UAS feature "User Added
Subroutine". The simulation package will be used to assess the effects of some
important design and operating variables on RD column performance.

1.8-2 Research Methodology

The methodology that will be approached to achieve the objectives of this

research topic can be summarized as follows:

Collect and choose the required data for the RD unit (thermodynamics,
kinetics, operating parametersetc).
Formulate a mathematical model for the RD unit.
Code the relevant model equations using a suitable coding language.
Embed the coded equations using a suitable embedding technique such as
User Added Subroutines (UAS), Excel Visual Basic for Applications (VBA)
or CapeOpen interface into a simulation package whenever it is possible.
Use a suitable simulation software (PROII, Aspen Plus) to solve the model
equations.
Perform sensitivity analysis on the effect of some important design,
operating and kinetics parameters on column performance.

- 15 -
 CHAPTER -2-

REACTIVE DISTILLATION

- 16 -
 CHAPTER -2-

2.1 INTRODUCTION TO REACTIVE DISTILLATION

Currently there is considerable academic and industrial interest in multi-
functional reactors, involving in-situ separation of products from the reactants
[10]. Reactive distillation is one of the most common means of in-situ product
removal and has been receiving increasing attention in recent years as an
alternative to the conventional reaction-followed-by-distillation processes [11].
Doherty and Buzad in 1992 have placed this subject in historical perspective
and list references to show that the advantages of reactive distillation were
recognized as early as in 1921. [12]
Reactive distillation is potentially attractive whenever a liquid phase
reaction must be carried out with a large excess of one reactant. Under such
circumstances, conventional processes incur large recycle costs for excess
reactant. Reactive distillation, on the other hand can be carried out closer to
stoichiometric feed conditions, thereby eliminating recycle costs. Both
homogeneous and heterogeneous catalysed chemical reactions can be carried
out in a reactive distillation column.
Process development, design and operation of RD processes are highly
complex tasks. The potential benefits of this intensified process come with
significant complexity in process development and design. The nonlinear
coupling of reactions, transport phenomena and phase equilibrium can give
rise to highly system-dependent features, possibly leading to the presence of
reactive azeotropes and/or the occurrence of steady-state multiplicities
Furthermore, the number of design decision variables for such an integrated
unit is much higher than the overall design degrees of freedom of separate
reaction and separation units [13].

2.2 BASICS AND ADVANTAGES OF REACTIVE DISTILLATION

Reactive distillation is an old concept that combines chemical reaction

and physical separation in the same unit. It is a unit operation that combines a
reactor as an integral part of the distillation column as depicted in Figure 2.1. It

- 17 -
can be utilized for either equilibrium reactions or non-equilibrium (irreversible)
reactions. In the first case, the withdrawal of products as they are formed
results in an increase in the conversion that can be achieved. This increase is
achieved through a shift in the equilibrium, based on Le Chateliers principle. In
the second case, it is generally applied to systems where products may react
with reactants, causing a decrease in product yield in conventional reactors.
The term catalytic distillation is also used for such systems where a
catalyst (homogeneous or heterogeneous) is used to accelerate the reaction. In
this thesis we use the generic name reactive distillation, with the acronym RD,
to cover both catalyzed or unanalyzed reactions systems.

Figure 2.1 Simple Reactive Distillation sketch.

2.2-1 Importance of RD

Consider the 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 2.2 (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 unreacted components, A and B, are recycled back to the reactor.

- 18 -
In practice the distillation train could be much more complex than the one
portrayed in Figure 2.2 (a) if one or more azeotropes are formed in the
mixture. The alternative RD configuration is shown in Figure 2.2 (b). The RD
column consists of a reactive section in the middle with non-reactive 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.[14]

Figure 2.2 Processing schemes for a reaction sequence A+ B C+ D where C and D are
both desired products. (a) Typical configuration of a conventional process consisting of a
reactor followed by a distillation train. (b) The reactive distillation configuration. The
components A, C, D and B have increasing boiling points. The reactive sections are indicated
by grid lines.

The most spectacular example of the benefits of RD is in the production

of methyl acetate. The acid catalyzed reaction MeOH + AcOH MeOAc +
H2O was traditionally carried out using the processing scheme shown in Figure
2.3 (a), which consists of one reactor and a train of nine distillation columns. In
the RD implementation (see Figure 2.3 (b)) only one column is required and
nearly 100 % conversion of the reactant is achieved. The capital and operating
costs are significantly reduced.

- 19 -
 Figure 2.3 Processing schemes for the esterification reaction MeOH + AcOH
MeOAc + H2O (a) Conventional processing scheme consisting of one reactor followed
by nine distillation columns. (b) The reactive distillation configuration. The reactive
sections are indicated by grid lines.

For the acid catalyzed reaction between iso-butene and methanol to

form methyl tert-butyl ether, isobutylene + MeOH MTBE , the traditional
reactor-followed-by-distillation concept is particularly complex because the
reaction mixture leaving the reactor forms three minimum boiling azeotropes.
The RD implementation requires only one column to which the butenes feed
(consisting of a mixture of n-butene, which is non-reactive, and iso- butene
which is reactive) and methanol are fed near the bottom of the reactive
section.[13]
The RD concept shown in Figure 2.4 (a) is capable of achieving close to
100% conversion of iso-butene and methanol, along with suppression of the
formation of the unwanted dimethyl ether. Also, some of the azeotropes in the
mixture are reacted away.[11]

For the hydration of ethylene oxide to mono-ethylene glycol:

EO + H2O EG, the RD concept, shown in Figure 2.4 (b) is advantageous for
two reasons [15].
Firstly, the side reaction EO+EG DEG is suppressed because the
concentration of EO in the liquid phase is kept low because of its high volatility.

- 20 -
 Secondly, the high heat of reaction is utilized to vaporize the liquid
phase mixtures on the trays. To achieve the same selectivity to EG in a
conventional liquid phase plug flow reactor would require the use of 60%
excess water Similar benefits are also realized for the hydration of iso-butene
to tert-butanol [16] and hydration of 2-methyl-2-butene to tert-amyl alcohol
[17].

Figure 2.4 (a) Reactive distillation concept for synthesis of MTBE from the acid catalysed
reaction between MeOH and iso-butene. The butene feed is a mixture of reactive iso- butene
and non-reactive n-butene. (b) Reactive distillation concept for the hydration of ethylene oxide
to ethylene glycol. (c) Reactive distillation concept for reaction between benzene and propene
to form cumene. (d) Reactive distillation concept for reaction production of propylene oxide
from propylene chlorohydrin and lime. The reactive sections are indicated by grid lines.

Several alkylation reactions, Aromatic + Olefin Alkylaromatic, are best

carried out using the RD concept not only because of the shift in the reaction
equilibrium due to in-situ Separation but also due to the fact that the
undesirable side reaction, Alkyl Aromatic+Olefin dialkyl aromatic , is
suppressed. The reaction of propene with benzene to form cumene,
Benzene+Propene Cumene ([18]; see Figure 2.4 (c)), is advantageously
carried out in a RD column because not only is the formation of the undesirable
di-isopropylbenzene suppressed, but also the problems posed by high
exothermicity of the reaction for operation in a conventional packed bed reactor
are avoided. Hot spots and runaway problems are alleviated in the RD concept
where liquid vaporisation acts as a thermal flywheel. The alkylation of
isobutane to isooctane, isobutene+ n-butane isooctane , is another reaction
that benefits from a RD implementation because in-situ separation of the
product prevents further alkylation: isooctane + n-butene C12H24 [18].

- 21 -
 The reaction between propylene chlorohydrin (PCH) and Ca(OH)2 to
produce propylene oxide (PO) is best implemented in an RD column, see
Figure 2.4 (d). Here the desired product PO is stripped from the liquid phase by
use of live steam, suppressing hydrolysis to propylene glycol [19].
Co-current gas-liquid down flow trickle bed reactors are widely applied
for hydroprocessing of heavy oils. This co-current mode of operation is
disadvantageous in most hydroprocesses [11], and counter-current flow of gas
and liquid would be much more desirable as shown in Figure 2.5. The counter-
current reactor shown in Figure 2.5 (b) is essentially a RD column wherein the
H2S is stripped from the liquid phase at the bottom and carried to the top. The
quantitative advantages of the RD implementation for hydroprocessing are
brought out in a design study carried out by Van Hasselt in 1999. For a 20,000
bbl/day hydrodesulphurisation unit with a target conversion of 98% conversion
of sulphur compounds, the catalyst volume required for a conventional trickle
bed reactor is about 600 m3. For counter-current RD implementation the
catalyst volume is reduced to about 450 m3.

Figure 2.5 Hydrodesulphurisation of gas oil carried out in (a) co-

current trickle bed reactor and (b) counter-current RD unit

From the foregoing examples, the benefits of RD can be summarized as

follows:

a) Simplification or elimination of the separation system can lead to

significant capital savings.

b) Improved conversion of reactant approaching 100 %. This increase in

conversion gives a benefit in reduced recycle costs.

- 22 -
 c) Improved selectivity. Removing one of the products from the reaction
mixture or maintaining a low concentration of one of the reagents can
lead to reduction of the rates of side reactions and hence improved
selectivity for the desired products.

d) Significantly reduced catalyst requirement for the same degree of

conversion.

e) Avoidance of azeotropes. RD is particularly advantageous when the

reactor product is a mixture of species that can form several azeotropes
with each other. RD conditions can allow the azeotropes to be reacted
away in a single vessel.

f) Reduced by-product formation.

g) Heat integration benefits. If the reaction is exothermic, the heat of

reaction can be used to provide the heat of vaporization and reduce the
reboiler duty.

h) Avoidance of hot spots and runaways using liquid vaporization as

thermal fly wheel.

2.2-2 Constraints and Difficulties in RD implementation

Against the above mentioned advantages of RD, there are several

constraints and foreseen difficulties [20].
1. 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.
2. 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.
3. Scale up to large flows. It is difficult to design RD processes for very
large flow rates because of liquid distribution problems in packed RD
columns.
4. 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.

- 23 -
2.2-3 The complexity of RD

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 vapour-liquid equilibrium,
vapour-liquid mass transfer, intra-catalyst diffusion (for heterogeneously
catalysed processes) and chemical kinetics. Figure 2.6 shows the various
transfer processes in homogeneous and heterogeneous RD.
In heterogeneous RD the problem is exacerbated by the fact that these
transfer processes occur at length scales varying from 1 nm (pore diameter in
gels, say) to say a few meters (column dimensions); see Figure 2.7. The time
scales vary from 1 ms (diffusion within gels) to say a few hours (column
dynamics). The phenomena at different scales interact with each other. Such
interactions, along with the strong non-linearities introduced by the coupling
between diffusion and chemical kinetics in counter-current contacting, have
been shown to lead to the phenomenon of multiple steady states and complex
dynamics, which have been verified in experimental laboratory and pilot plant
units [36]. Successful commercialization of RD technology requires careful
attention to the modelling aspects, including column dynamics, even at the
conceptual design stage [12].
In some cases the reactor and distillation paradigms do not translate
easily to RD. The potential advantages of RD could be nullified by improper
choice of feed stage, reflux, amount of catalyst, boilup rate, etc. Thus, it is
possible to decrease conversion by increasing the amount of catalyst under
certain circumstances. Increased separation capability could decrease process
performance [21].

- 24 -
 Figure 2.6 Transport processes in RD. (a) homogeneous liquid phase reaction,
and (b) heterogeneous catalyzed reactions.

Figure 2.7 Length and time scales in RD.

2.2-4 Models available for design of RD columns

A variety of models exist in the literature for design of RD columns. They
can be classified in the following manner.

1. Steady-state equilibrium (EQ) stage model

2. Dynamic EQ stage model
3. Steady-state EQ stage model with stage efficiencies

- 25 -
 4. Dynamic EQ stage model with stage efficiencies
5. Steady-state nonequilibrium (NEQ) stage model, where the interphase
mass transfer is described by rigorous Maxwell-Stefan diffusion
equations
6. Dynamic NEQ stage model
7. Steady-state NEQ cell model, developed by Higler in 1999, in order to
account for staging of the vapour and liquid phases during cross-current
contacting on a distillation tray [22].

The equilibrium stage model assumes that the vapor and liquid streams
leaving a given stage are in thermodynamic equilibrium with one another.
These models can be coupled with the assumption of chemical equilibrium at
each stage or the kinetics can be described using an nth order kinetic reaction
model.
The column is described by a group of equations that model the
equilibrium stages in a column configuration. These are known as the MESH
equations. MESH stands for:

M: Material balance equations for each component and total mass.

E: Equilibrium equations.
S: Summation equations or composition constraints.
H: Heat or energy balance equations.

- 26 -
 CHAPTER -3-

LITERATURE SURVEY

- 27 -
 CHAPTER -3-
3.1 OVERALL REVIEW

The combination of chemical reaction with distillation in only one unit is

called reactive distillation. The performance of reaction with separation in one
piece of equipment offers distinct advantages over the conventional, sequential
approach [7]. In reactive distillation (RD) chemical reactions occur within the
distillation column to achieve specific goals, such as to obtain high conversions
and high purity products as well to minimize side reactions. Currently RD has
various applications, such as the production of methyl tertiary -butyl ether
(MTBE) and ethylene oxide (EO) and others.
Reactive distillation is being used in industrial applications with more
frequency because of increasing research and development of this technology,
a result of commercial and academic experience and success. Examples of
commercialized technologies are the Ethermax process from UOP-Huls and
Koch Engineering that uses the KataMax structured packing from Koch and
Catacol, a low cost reactive distillation technology for etherification from IFPs
Industrial Division [22].
So far, there is no generally accepted method for the design of
distillation with reaction. Most of the systematic methods available possess
limitations because of their simplified assumptions. Moreover, these methods
have rarely been proven with a variety of reactive distillation processes and
they do not consider the design in detail [12].
In spite of the advances in separation with reaction processes, reactive
distillation still relies on intuition and expertise. A reactive distillation problem
can be studied using different approaches including: feasibility, simulation,
modeling, design and experimental studies in the laboratory and the pilot plant.
A combination of all of these methods gives rise to the most accurate
solution to the problem. One very important aspect of predicting the behavior in
these systems is the model used to design and simulate the reactive distillation
process. In the literature, the most common models that have been developed
and proven are the equilibrium stage model and the non-equilibrium stage

- 28 -
model. The equilibrium stage model is based on the conventional equilibrium-
stage model of a distillation column with the addition of the reaction terms in
the mass and energy balances. The non-equilibrium stage model for reactive
distillation, also known as the rate-based model, is an extension of the
conventional rate based model for distillation. In this chapter, a discussion of
the important aspects of modeling, simulation, design and analysis of reactive
distillation is provided.
Matthias et al, [24] presented a conceptual design methodology for the
reactive distillation columns, the method assesses feasibility of a proposed
reactive distillation, designs the column and allows evaluation of the design for
both fully reactive and "hybrid" column configurations. Stage composition lines
are used to represent all possible liquid compositions in a column section for
specified product compositions and for all reflux or reboil ratios. Reaction
equilibrium is assumed on each reactive stage, and vapor-liquid equilibrium is
assumed on all stages. The methodology is illustrated by application to an ideal
reactive system and for MTBE production. They developed a new graphical
design methodology to assess feasibility and design columns for proposed
reactive distillation processes. Also, they concluded that the methodology is
restricted to systems with a single-feed two-product columns. It is assumed that
equilibrium reaction take place in the liquid phase only.
A simulation study of the impact of various process configuration
catalyst types and catalyst loading on the production rate and separation of the
MTBE product was carried by Shah et al, [25]. They mentioned in their paper
the advantages and disadvantages of each configurations. For reactive
distillation, the catalyst distribution on a range of trays and the feed location is
considered for the optimal production/separation scenario. They also studied
an approach, based purely on steady state analyses, for synthesizing effective
control structures for reactive distillation (RD) columns [26]. The main idea was
to analyze the steady-state relationships between the manipulated (input)
variables and potential controlled (output) variables to identify input-output (IO)
pairings that are sensitive and avoid steady state multiplicities providing a large
range of nearly linear operating region around the base case design. The
MTBE case study shows that input and output multiplicity in the IO relation

- 29 -
 occurs in the steady-state relationships. It also shows that the occurrence of
multiplicity depends on the control strategy implemented.
Rivera and Johan [27] considered the residue curve mapping technique
(RCM) a powerful tool for the flow-sheet development and preliminary design of
conventional multi-component separation processes. An RCM-based feasibility
analysis has been applied to the homogeneous RD synthesis of MTBE at 11
atm from methanol and isobutylene and in the presence of n-butane. The
reaction space, defined in terms of transformed composition variables, has
been divided into sub-regions characterized by separation boundaries. A
feasibility analysis of the RD process has been performed based upon the
location of the reacting mixture, defined initial separation sequences have been
generated according to the feed transformed-composition. In the generated
sequence, high purity MTBE has been obtained as a product, due to the
appearance of a pseudo reactive azeotrope, which imposes limitation to the
separation task.
The progress in chemical engineering unit operations which laid out the
catalytic distillation column is a significant advancement in chemical
engineering technology. Some of the equilibrium-limited reactions show an
improving yield due to the continuous removal of the products from the reaction
zone. A substantial research work, mainly experimental has been done for this
combined unit operation, most of which have appeared in patents [28 & 29].
However, essential research aspects of the reactive distillation process
mathematical modeling, design, optimization and control have been covered
yet. Also, little attention has been paid to plate efficiency when reaction occurs.
Research and development work on reactive distillation has focused on:
Computational methods to solve the simulations chemical reaction and
vapor-liquid equilibrium equations.
Chemical equilibrium aspects in reactive systems (e.g. thermodynamic
models).

3.2 COMPUTATIONAL METHODS

The Computational methods used for reactive distillation are extensions
to the algorithms developed for the solution of the equations for conventional

- 30 -
distillation. The first attempts to model reactive distillation were by using the
simplified plate-to-plate calculations. Rigorous mathematical models for
computer simulation were not developed until the 1970's. Since that time,
various techniques have been developed that allow the rigorous solution of the
equations. These techniques include equation partitioning methods, and
Newton-Raphson based methods.
Nelson in 1971 modified the Tierny-Bruno algorithm based on tray-by-
tray calculation, by taking into consideration the non-ideal vapor liquid
equilibrium. Which represented in material balance equations no longer linear
in composition [30].
Suzuki et al. in 1971 applied the successive iteration method to reactive
distillation problems, and concluded that it converges rapidly and it is stable.
However, difficulties with convergence arise for systems with non-ideal
solutions, because of non linearity of the equations. In addition, successive
iteration methods have the disadvantage that as the solution is approached,
the progress of iteration calculations decelerates [31].
Murthy in 1984 considered an extension of the Newton-Raphson
algorithm to columns in which chemical reactions occur, while Venkataraman et
al. in 1990 were developed an extension of the " inside-out" approach
proposed by Boston that combines the advantages of Newton's method with
those of the inside-out strategy very effectively [32].
Jelinek and Hlavacek in 1976 applied the relaxation method to solve
steady state countercurrent equilibrium stage separation with chemical reaction
problems. They confirmed the suitability of this method where an azeotrpoe
exists [33].
Teirney and Riquelme in 1982 proposed a correction algorithm which
gives quadratic convergence near the solution. Its use was demonstrated on a
sample problem of the separation of meta-and para-xylene using experimental
results from an earlier study done by Satio et al. in 1971. They found that their
solution agree well with the numerical solution obtained by Satio et al, but not
with Saito's experimental data. Teirney and Riquelme in 1982 claimed the
equilibrium in the reaction is not satisfied in each stage. This contradicts the
experimental results of Satio et al. in 1971, showing that the equilibrium

- 31 -
constant is almost constant in the range of operating temperature between (50-
100 C) [34].
The reactive distillation column has no reboiler, although it has to be
used in conjunction with the gas/liquid polymer reactor. The model was based
on the material balance equations describing the system, and the simulation
was carried out by using a fourth-order Runge-Kutta method. The usefulness of
the model was limited because of the number of assumptions and
simplifications that were made in development of the model, such as:
neglecting enthalpy balances, neglecting tray hydraulics [34].
Reactive Distillation (RD) is state-of-the-art multifunctional reactor
concept that integrates reaction and distillation in a single process unit. Some
recent reactions that have been proposed to utilize RD technology involve non-
condensable species like hydrogen which proposed by Kamath et al in 2005.
Reactions involving liquid phase splitting have also been examined in RD .
Very little research has been done for such complex cases and the potential of
RD for such reactive systems has not been thoroughly investigated [36].
This work focuses on the presence of both non-condensables and liquid
phase splitting in RD using the one-step synthesis of methyl isobutyl ketone
(MIBK) from acetone as a case study. Traditionally, MIBK is produced in three
steps by the condensation of acetone to diacetone alcohol followed by its
dehydration to mesityl oxide (MO) and then its hydrogenation to MIBK. The first
two reactions are reversible and limited by thermodynamic equilibrium. But the
third reaction (MO to MIBK) is fast and irreversible and hence the overall
reaction (acetone to MIBK) is expected to be an irreversible reaction. However,
the presence of water as a product inhibits the reaction rate considerably
leading to pseudo-equilibrium [36].
The work employs the RD technology to minimize the amount of water in
the reactive zone by simultaneous distillation and thereby increase the overall
conversion of acetone. The hydrogenation reaction results in the appearance of
a non-condensable species in the RD column while the ternary acetone-water-
MIBK system results in liquid-liquid phase splitting (Figure 3.1).

- 32 -
 Figure 3.1 Ternary LLE diagram for Acetone-water-MIBK system at 5atm.

A potential RD configuration for the synthesis of MIBK was developed as

shown in Figure 3.2. The column configuration is capable of achieving a very
high conversion of around 95% by employing a very high reflux ratio (defined
as ratio of the liquid refluxed to the liquid distillate). The liquid phase
composition profile in the column is shown in Figure 3.3. The simultaneous
distillation in the reactive zone keeps the water concentration below 35% which
would not have been possible in a conventional reactor. Because of the
presence of a binary acetone-water azeotrope at higher pressures, a large
number of stages may be required to reduce the water concentration in the top.
As expected, phase-splitting is observed in the stripping section. However, the
presence of sufficiently large amount of acetone in the reactive zone ensures a
homogenous liquid phase [35].

- 33 -
 Figure 3.2 RD Column Configuration.

Figure 3.3 Liquid Composition profile in RD Column.

It was concluded from the above work that there is a further scope for
improvement of the proposed RD configuration. The column performance is
very sensitive to the feed locations and their flow rates. The presence of non-
condensable hydrogen poses additional complexities in the VLLE
computations. A successful RD process is not only capable of achieving a
much higher conversion as compared to the conventional route but also leads
to process intensification and compactness.

- 34 -
 An approach, based purely on steady-state analyses, for synthesizing
effective control structures for reactive distillation (RD) columns . The main idea
is to analyze the steady-state relationships between the manipulated (input)
variables and the potential controlled (output) variables to identify inputoutput
(IO) pairings that are sensitive and avoid steady-state multiplicities providing a
large range of nearly linear operating region around the base case design.
Traditional SISO control loops are then implemented using these IO pairings to
obtain control structures that maintain the column near the design product
purity and conversion for the anticipated primary disturbances. The Niederlinski
Index is used to eliminate dynamically unstable pairings in control structures
with multiple loops. The approach is demonstrated on an example MTBE RD
column. The impact of steady-state multiplicities on control structure design is
highlighted. [25]
This work illustrates the systematic analysis of the steady-state IO
relationships for synthesizing effective control structures for RD columns. Such
control structures are necessary to provide robust, stable, safe and economical
column operation to tide over disturbances entering the column. Effective
control structures can be obtained by identifying IO pairings that avoid
multiplicities and allow a sizeable nearly linear operating region around the
base case. The MTBE case study shows that input and output multiplicity in the
IO relations occurs in the steady-state relationships. It also shows that the
occurrence of multiplicity depends on the control strategy implemented.
For the MTBE example, a control structure that uses the reboiler duty to
control Tray 11 temperature in the stripping section and the butene feed to
control Tray 10 isobutylene composition in the reactive section is found
suitable. Proper choice of the manipulated variables and the tray locations for
the measurements in the two loops is especially critical for effective column
regulation. At a more general level, the results show that maintaining the
stoichiometric balance of the fresh feeds is needed for the effective control of
double feed RD columns.

M. H. M. Reis et al in 2006, presented a novel approach for establishing

the route for process intensification through the application of two developed

- 35 -
softwares to characterize reactive mixtures is presented. A robust algorithm
was developed to build up reactive phase diagrams and to predict the
existence and the location of reactive azeotropes. The proposed algorithm
does not depend on initial estimates and is able to compute all reactive
azeotropes present in the mixture. It also allows verifying if there are no
azeotropes, which are the major troubles in this kind of programming. An
additional software was developed in order to calculate reactive residue curve
maps. Results obtained with the developed program were compared with the
published in the literature for several mixtures, showing the efficiency and
robustness of the developed software's. [40]
Figure 3.4 shows the nonreactive residue curve map for the system
under consideration. The binary azeotrope between methanol and tert-butyl
methyl ether (MTBE) is a saddle point and between isobutylene and methanol
an unstable node appears, leading to the occurrence of a distillation boundary.
This distillation boundary splits the diagram in two different regions of
distillation, making the separation of the ternary mixture impossible. [40]

Figure 3.4 Nonreactive residue curve map for the system IBTE+ MeOH MTBE at
101.32 kPa.
Figure 3.5 shows the reactive residue curve map for this system, where
it can be seen that, under atmospheric pressure, this reactive mixture does not
present any azeotrope, showing how the chemical equilibrium influences the
phase equilibrium. This conclusion is in agreement with the results of Barbosa

- 36 -
and Doherty (1988b). Figure 3.6 shows the reactive phase diagram for
isobutylene/methanol/MTBE at 101.3 kPa, confirming that this reactive system
is zeotropic.

Figure 3.5 Reactive residue curve map for the system IBTE+ MeOH MTBE at
101.32 kPa.

Figure 3.6 Reactive phase diagram for the system IBTE/ MeOH /MTBE at 101.32
kPa.
Maier et al. (2000) studied this same system at 810.56 kPa (8 atm) and
with different constant values for the equilibrium constant (Kr). Similar results
were obtained in this work. When Kr is equal to 49.0, the mixture forms two
azeotropes at different compositions. Figure 3.7 shows the reactive phase
equilibrium diagram for this case. [40]

- 37 -
 Figure 3.7 Reactive phase diagram for the system IBTE/ MeOH /MTBE at 810.56
kPa.

In actual processes to produce MTBE through reactive distillation, the

source of iC4 consists of C4 cuts available from steam or catalytic crackers. In
order to analyze this multicomponent system, it is considered that C4 stream
consists, basically, of isobutylene and n-butenes, being n-butenes inert
components in the reaction.
For this quaternary system (ethanol/isobutylene/MTBE/n-butene) the
search of azeotropes were carried out at pressures of 1013.2, 2026.4 and
4052.8 kPa (10, 20, and 40 atm). Although in this high pressure it is not correct
to consider the vapor as an ideal mixture, this assumption will be still
considered, in order to compare the obtained results with those published by
Maier et al. (2000). [40]

- 38 -
 CHAPTER -4-
MODELING AND SIMULATION
OF MTBE PROCESS

- 39 -
 CHAPTER -4-

4.1 MTBE PRODUCTION BY PROII

4.1-1 Introduction

This section will demonstrate the use of PRO/II in the simulation of the
synthesis of methyl tert-butyl ether (MTBE), also the simulated process for
MTBE production will be depicted and each unit in the process will be
elaborated. A PRO/II simulation model of a typical MTBE plant is presented
here. The process plant includes a reactor along with an azeotropic distillation
column for separation of the MTBE product.
A reactive distillation section is added to the MTBE azeotropic column in
order to increase the overall conversion to MTBE. This is followed by the
methanol recovery section which includes a liquid-liquid extractor. The
thermodynamics successfully predicts the azeotropic removal of methanol from
the MTBE product stream.

4.1-2 Process Description

There are several variations on MTBE plant designs. In general, an

MTBE plant is comprised of the three sections, a reactor section, a MTBE
recovery section, and a methanol recovery section. For the Ethermax process,
the MTBE recovery section includes a second reaction zone in the distillation
column. The complete process flow diagram for the MTBE reactive distillation
plant model used in this simulation is given in Figure 4.1.

- 40 -
 Figure 4.1 MTBE Plant Flowsheet.

MTBE is manufactured by catalytically reacting isobutylene and

methanol in a fixed-bed reactor at a moderate temperature and pressure. The
reaction is exothermic and reversible, and is carried out in the liquid phase over
a fixed bed of ion-exchange resin-type catalyst. It is highly selective since
methanol reacts preferentially with the tertiary olefin.

In the Ethermax MTBE process, modeled here, an isobutylene-rich

mixed C4 stream is mixed with fresh methanol along with a small amount of
recycle methanol and fed to the reactor section. The reactors are cooled to
under 200 F to prolong catalyst life and to minimize the undesirable side
reactions such as dimerization of isobutylene.

The methanol-to-isobutylene ratio in the reactor feed is kept low to

minimize the costs of recovering unreacted methanol, and to facilitate the
operation of the MTBE column which will be discussed later. Generally, this
ratio is maintained close to 1:1. Table 4.1 contains the reactor feed composition
used in this model.

- 41 -
Table 4.1 Reactor Feed data
Stream Name C4 Feed Methanol Feed Methanol Recycle
Stream Number 2 1 20
Flowrate (kg-mol/hr) 850 277.5 4.3
Temperature (C ) 16 16 44
Pressure (kPa) 1620 1620 1724
Component Mole %
N-butane 9.0 0.0 0.0
Isobutane 41.0 0.0 0.0
1-butene 7.0 0.0 0.0
Cis 2-butene 4.0 0.0 0.0
Trans 2-butene 6.0 0.0 0.0
Isobutylene (IBTE) 33.0 0.0 0.0
MTBE 0.0 0.0 0.0
Tert-butanol (TBA) 0.0 0.0 0.0
Water 0.19 0.0 6.98
Di-isobutylene (DIB) 0.0 0.0 0.0
Methanol (MEOH) 0.0 100 93.02

An isobutylene conversion to MTBE of 90 to 93% is easily achieved in

the reactor. Overall isobutylene conversions higher than those obtained in the
standard process can be achieved by either recycling a portion of the MTBE
column overhead product, or by providing a second reactor unit and MTBE
column downstream of the first MTBE column. The cost-effectiveness of these
options vary from plant to plant, but both require greater capital expenditure. In
the reactive distillation process, no major increase in capital expenditure is
required and overall isobutylene conversions of over 99% are easily obtained.

Any water in the reactor feed (from recycle methanol) is instantly

converted to t-butanol. Another impurity, di-isobutylene, is formed by the
dimerization of isobutylene. While the formation of di-isobutylene and t-butanol
should be minimized, their presence in small concentrations in the MTBE
product is acceptable since these byproducts also have very high octane
numbers. Table 4.2 shows the three main reactions used in the stoichiometric

- 42 -
reactor model. The base component and the fraction converted are also
shown.

Table 4.2 Reaction Stoichiometry

Reaction Base Component Conversion %
2 (IBTE) = DIB IBTE 0.25
H O + IBTE = TBA H0 100.00
2 2
IBTE + MEOH = MTBE MEOH 93.0

Catalyst Used
A common catalyst for the MTBE synthesis process is the Amberlyst 15
polymeric catalyst developed by Rohm and Haas. Approximate properties of
the commercial form of this catalyst, along with suggested operating conditions
are provided below in Table 4.3.

Table 4.3 Approximate Catalyst Properties of Amberlyst 15

Physical form Spherical beads
Ionic form Hydrogen
Acid site concentration 1.8 meg/ml (4.9 meg/g)
Moisture content 53%
Apparent density 770 g/l
Particle size 0.35-1.2 mm
Shrinkage: Wet to methanol 4%
Wet to MTBE 12%
Porosity 0.30 cc/g
Average pore diameter 250 A
2
Surface area 45 m /g
3
Bulk density 48 lb/ft
Maximum operating temperature 120 C
Minimum bed depth 0.61 m
-1
Flowrate, LHSV 1-5 hr

MTBE Recovery Section

In the Hls process, the reactor products are processed in the MTBE column
where MTBE, along with t-butanol, dimerized butylene, and a trace amount of
methanol, are removed as the bottoms product. In the Ethermax process,
further reaction of the isobutylene to MTBE takes place in a section of the
distillation column containing the catalyst resin in tower packing. The MTBE is

- 43 -
removed as the bottoms product in a manner similar to the standard process.
The MTBE product is greater than 99.5% pure and requires no further
purification.
The key to operating the MTBE column is to have a sufficient amount of
C4s in the column feed to form azeotropes with the methanol in the feed.
Conversely, if a proportionately large amount of methanol is present in the
column feed, it may result in breakthrough of methanol with the MTBE bottoms
product. Therefore, suitable azeotrope formation is possible only when a limited
excess of methanol is used in the reactor feed. In this manner, unreacted
methanol, which has a higher boiling point than MTBE, is fractionated away
from the MTBE bottoms. The overhead product containing non-reactive linear
butenes, iso and normal butanes, and unreacted methanol and isobutylene, is
sent to the methanol recovery section.

Methanol Recovery Section

In the methanol recovery section, the MTBE column overhead product is

water washed to extract methanol. This unit is simulated as a liquid-liquid
extraction column. The raffinate, which contains less than 10 ppm methanol, is
suitable for recovering high purity C4 isomers, or as a feed to an alkylation unit.
The extract phase which contains water, methanol and small amounts of
dissolved hydrocarbons is warmed and flashed to remove the hydrocarbons.
The resultant methanol-water mixture is fractionated to recover methanol as
the overhead product. The methanol (with a trace of water) is recycled to the
MTBE reactor. The wash water stream from the bottoms, along with a small
amount of makeup water, is returned to the water wash column.

- 44 -
4.2 MODELING AND SIMULATION OF MTBE PROCESS USING PRO/II

PRO/II software has the capabilities of solving Reactive Distillation Processes

utilizing Chemdist Algorithm provided by the software, but it requires knowledge of
Material and Energy balances equations as well as Thermodynamics and kinetics of
reaction.
The Chemdist algorithm in PRO/II is a Newton based method which is suited to
solving non-ideal distillation problems involving a smaller number (10 vs. 100) of
chemical species. These conditions are generally encountered in chemical distillations
as opposed to crude fractionation where the I/O algorithm would be a better choice.
Chemdist is designed to handle both vapor-liquid and vapor-liquid-liquid equilibrium
problems as well as chemical reactions.
All derivatives for the Jacobian matrix are calculated analytically. User-added
thermodynamic options that are used by Chemdist must provide partial derivatives
with respect to component mole fractions and temperature. Chemdist uses the chain
rule to convert these to the needed form.
PRO/II automatically generates numerical estimates for the reaction rate
derivatives. In many cases, this is sufficient. However, certain reactions require the
use of more accurate analytical derivatives that provide better solutions. Reactions
requiring these more accurate analytical derivatives include: reversible reactions,
exothermic reactions, and/or reactions where the equilibrium is sensitive to
temperature. There are some assumption will be considered to simplify the simulation
work which can be listed as :

1. The reactor is operated under steady state conditions.

2. The reactor is isothermal operating condition (55 C), it is maintained by
circulating a coolant.
3. The pressure drop across reactor is specified with 69 kpa.
4. One dimensional homogeneous model is considered.
5. Dispersion of mass and energy terms are negligible and a plug flow
reactor model is assumed.
6. Complete mixing of gases entering the collection chamber before the
catalyst beds. No reaction takes place inside the chamber, the reaction

- 45 -
 is only in the liquid phase.
7. Physical properties are considered as a function of temperature and
pressure, and SRKM thermodynamic method is used.

4.3 THERMODYNAMIC DATA

The VLE fractionators are simulated well with PRO/II's modified Soave-
Redlich-Kwong (SRKM) equation of state method. For this method, PRO/II
contains extensive, built-in databanks that encompass binary interaction
parameter data for the majority of component pairs present in this simulation.
However, binary interaction data (Kijs) are directly supplied for 8 component
pairs to improve the accuracy of the separations in the columns as
demonstrated in Figure 4.2. The binary interaction parameters are listed below
in Table 4.4. The thermodynamic set used for VLE thermodynamics is referred
to as SRKM_VLE. The used components and their abbreviation are as follows:

Table 4.4 Binary Interaction Parameters for SRKM_VLE

Comp I NC4 1BUT BTC2 BTT2 IBTE MEOH TBA MTBE
n-butane 1-butene Cis2-butene Trans2- Isobutylene Methanol Tert-
butene Butanol
Comp j TBA MEOH MEOH MEOH MEOH TBA H20 DIB
kija 0.0469 0.136 0.136 0.136 0.13553 - -0.145 0.05785
0.07397
kjia 0.1260 -0.0323 -0.0323 -0.0323 -0.0322 - -0.253 -0.0093
0.05522
kijb 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -10.144
kjib 0.0 0.0 0.0 0.0 0.0 0.0 0.0 6.17
UOM K K K K K K K K

- 46 -
 Figure 4.2 Thermodynamic Data of PRO/II software.

Transport properties are needed in order to use the rigorous heat

exchanger model in the MEOH recovery section. Transport property
calculations are set to pure-component averages by default and can be
modified by modifying the thermodynamic method of choice.
The liquid extraction unit is simulated using the SRKM method for VLLE
thermodynamics with binary interaction data again supplied as part of the input.
The thermodynamic set used for VLLE thermodynamics is referred to as
SRKM_VLLE. The L1KEY component (i.e., the predominant component in the
L1 liquid phase) is specified as n-butane. The L2KEY component is specified to
be water. Explicitly specifying the key components eliminates the need for
PRO/II to find an appropriate immiscible pair, reducing the computation time.
All the azeotropes are properly predicted. The form of SRKM is presented as:

1
aij = (ai a j ) [(1 kij ) + (kij k ji )( X i /( X i + X j )) ij ]
2 c
..(4.1)

Where :
Xi= Mole fraction of component i
Xj= Mole fraction of component j
Kij= Kji = Binary interaction parameter
aij= The mixing rule, Cij= constant

- 47 -
 The accuracy of correlating vapor-liquid equilibrium data using a cubic equation
of state can be improved further by choosing an appropriate mixing rule. The
original mixing rule was derived from the van der Waals one-fluid
approximation:

P = RT /(v b) a (T ) /(v 2 + ubv + wb 2 ) ......(4.2)

where:
P = the pressure
T = the absolute temperature
v = the molar volume
u,w = constants, typically integers

a = xi x j aij ......(4.3)
i j

b = xi bi ................................................(4.4)
i

where:
Xi = mole fraction of component i.
The binary interaction parameter, kij, is introduced into the mixing rule to
correct the geometric mean rule of parameter a in the general cubic equation of
state (4.2):
The original mixing rule is capable of representing vapor-liquid equilibria
for nonpolar and/or slightly polar systems using only one (possibly
temperature-dependent) binary interaction parameter.

4.4 MTBE REACTION KINETICS

The algorithm used for the reactive distillation column model is a

Newtonian-based algorithm. Therefore, in order to accurately model the MTBE
reaction in the distillation column, we need to determine not only the reaction
rate of the reaction, but also the temperature and composition derivatives of the
rate. These derivatives may be generated numerically by an estimation
method, or analytically by an expression based on the reaction rate equation.
The MTBE reactions fit all three of the reaction types, requiring the use
of analytical derivatives. The reaction rate expression and its analytical
derivatives can be easily and readily entered by the user in the Procedure Data

- 48 -
category of input. The MTBE reaction rate expression used in this simulation
model is based on the rate expression described in a paper by Al-Jarallah [38].
First, in the Reaction Data category of input, the stoichiometry of the
forward reaction is given (IBTE + MEOH = MTBE). The kinetic data will be
provided later on in the Procedure Data category of input using FORTRAN-like
language as the procedure named ALJD. The procedure data used in the
reactive distillation column model is entered in the Kinetic Procedure data entry
window shown in App (A).
The MTBE synthesis reaction can be represented by:
A + B C .....(4.5)

Where, A, B and C denote methanol, isobutylene and MTBE

respectively, In general, the forward reaction is order a in A and order b in B,
and the reverse reaction is order c in C.
The rate of surface reaction, rs, is assumed to be the rate controlling
step, as there were no mass transfer limitations. There are two possible
mechanisms by which this surface reaction takes place:
1. Reaction between adsorbed molecules of both A and B on adjacent
active centers, and
2. Reaction between one adsorbed reactant and the other reactant in
solution [37].
The first mechanism is the Langmuir-Hinshelwood mechanism and the
second one is the Rideal-Eley mechanism as discussed by Smith in 1981 and
Satterfield in 1980. In these references the reaction is assumed to be a simple
reaction, that is, the reaction is first order in all species. The following rate
equations were derived for general orders of reaction a, b and c. For a
Langmuir-Hinshelwood model, the rate of reaction can be represented by the
following equation [37]:

C Aa C Bb C Cc / k
rs = k s k k
a b
a +b
....(4.6)
(1 + K A C A + K B C B + K C C C )
A B

For the case of the Rideal-Eley mechanism, there are two possibilities in which
either one of the two reactants is adsorbed on the catalyst and then reacts with

- 49 -
the other reactant in solution. For the case when the methanol (A) is adsorbed
and reacted with the isobutylene (B) in solution, the final rate equation is:
C Aa C Bb C Cc / k
rs = k s k Aa a
.....(4.7)
(1 + K A C A + K C C C )

For the case when isobutylene is absorbed and reacted with methanol in
solution, the final rate equation is:

C Aa C Bb C Cc / k
rs = k s k Bb b
.....(4.8)
(1 + K B C B + K C C C )

For a given set of a, b and c the unknown parameters in Equation (4.6), (4.7)
and (4.8) are the surface reaction rate constant, Ks the equilibrium adsorption
constants KA, KB and KC and the thermodynamic equilibrium constant, K. This
equilibrium constant can be calculated from experimental concentration data in
which concentration equilibrium has been reached [37].

Since

K = Kx K ..(4.9)

The dependence of the rate constant, Ks, on temperature was determined from
the Arrhenius equation,

Ks = Kso exp (-E1 / RT)......(4.10)

The values of Kso and E1 were found from the least squares fit of Equation
(4.10) Thus:

13
Ks = 1.2 x 10 exp (-87,900/RT)..(4.11)

The dependence of the adsorption constants, KA and KC, was

determined from the vant Hoff equation,

KA = KAo exp (HA / RT)..........(4.12)

- 50 -
 KC = KCo exp (HC / RT).......(4.13)

The values of KAO, KCO, HA and HC where obtained from the least
squares fit of the above two equations. Thus:

KA = 5.1 x 10-13 exp (97,500/RT).(4.14)

and
KC = 1.6 x10-16 exp (119,000/RT)...(4.15)

The reaction rate equation described by Al-Jarallah takes into account

the forward and the reverse reaction. We have modified Al-Jarallah's rate
equation for MTBE process to simulate the effect of catalyst loading on the
reaction rate. This was achieved by removing the catalyst terms from the
concentration terms. The modified reaction rate is given by:

C Aa C Bb C Cc / k
rs = k s k A a +b
..(4.16)
(1 + K A C A + K B C B )
where:
Ks: surface reaction rate constant= 1.2x1013 exp(-87900/RT) in (gmole/g catalyst)
KA: equilibrium adsorption constant = 5.1x10-13 exp(97500/RT) in g catalyst/gmole
KC : equilibrium adsorption constant = 1.6x10-16 exp(119000/RT) in g catalyst/gmole
K : equilibrium constant
CA : IBTE concentration in mole/l
CB : MEOH concentration in mole/l
CC : MTBE concentration in mole/l

4.5 MODELING PROCEDURE

In modeling this process, the Steady-state equilibrium stage model, will all its
underlined assumptions has been used. The main feature of the model is the
assumption that the vapor and liquid streams leaving a given stage are in a
thermodynamic equilibrium.
The reaction kinetics in the reaction zone was assumed to follow Al-Jarallah
kinetics [37]. A typical schematic diagram of a catalytic distillation column is shown in
Figure 4.3.

- 51 -
 Figure 4.3 A schematic representation of a catalytic distillation column.

A schematic diagram of an equilibrium tray is shown in Figure 4.4. It is

assumed that the tray has one feed stream Fk one vapor side streams SV one liquid
side stream SL and coolings Q occurs.

V
Lk+1 k
Feed SVk

Fk Stage K Qk

HEAT DUTY
T k , Pk Rk, Mk
SLk
V
Lk k-1

Figure 4.4 Representation of a generic equilibrium stage.

- 52 -
4.5-1 Model equations for a single stage
The model equations for a generic stage k and component i are presented
based on the commonly used distillation column, with incorporation of the
reaction terms, they may be expressed as follows:
1. Component material balance on stage k:
r
Lk+1 X k+1,i + Vk 1Yk1,i (Lk + SLk ) X k ,i (Vk + SVk )Yk ,i + Fk Zk ,i Rjk,i = 0 ..(4.17)
j =1

Where;
Xk,j is the mole fraction of liquid phase for species i in stage k.
Yk,i is the mole fraction of vapor phase for species i leaving stage k
(Lk+SLk) is the molar liquid flow rate leaving stage k.
(Vk+SVk) is the molar vapor flow rate leaving stage k.
Fk is the feed flow rate to stage k.
R jk,i is the rate of disappearance of component i due to reaction j on stage k
(i.e. when the sign is negative).

2. Total material balance on stage k:

Lk +1 + Vk 1 ( Lk + SLk ) (Vk + SVk ) + Fk + Rk = 0 ..(4.18)

3. Energy balance on stage k:

r
Lk +1hk +1 + Vk 1 H k 1 ( Lk + SL k ) hk (Vk + SV k ) H k + Fk h fk Q k + R jk H jk = 0 ..(4.19)
j =1

Where;
hk denotes the molar enthalpy of liquid phase in stage k.
HK denoted the molar enthalpy of vapor phase in stage k.
Hj,k is the heat of reaction in stage k.
Qk is the heat duty in stage k.

For stages without feed or side streams or no reaction, these terms are
assigned a value of zero in Equations (4.17-4.19).

4. Component equilibrium relationship on stage k:

Yk,i = k,i Kk,i X k,i ........(4.20)

Where;
k,i denotes the activity coefficient of component i in stage k.
Kk,i denotes the vapor-liquid equilibrium constant.

- 53 -
 5. Constraint equations:

Y
i
k ,i 1 = 0 ...(4.21)

X
i
k ,i 1 = 0 .....(4.22)

The unknowns, alternatively referred to as iteration or primitive variables:

(X, Y, L, V)i , where i= 1, NT are solved for directly using an augmented Newton-
Raphson method. Specification equations involving the iteration variables are
added directly to the above equations and solved simultaneously.

4.6 MODELING AND SIMULATION FRAMEWORK

It has been assumed in this work that the production of MTBE using
PRO/II is a steady-state process. Therefore, the necessary process flowsheet
for production of MTBE by Reactive Distillation has been built and developed
using PRO/II as shown in Figure 4.5 , the detailed procedure is described step
by step in App. (B). All required files (Model file and process input file) are
given in App. (A) and App. (C), respectively.

- 54 -
Figure 4.5 MTBE Process Flowsheet PRO/II .
55
 CHAPTER -5-

RESULTS AND DISCUSSION

56
 CHAPTER -5-

5.1 RESULTS OF THE SIMULATION WORK

In this section, the outcome of simulation work will be presented for each
equipment with some demonstrated graphs. The used software which is PRO/II
can extract the results on excel file after running the model as shown below.

Table 5.1 Summary Table

Stream Name 1 2 3 5 6 7
Stream Description MEOH FEED OLEFINS T-1 OVHD

Phase Liquid Liquid Liquid Liquid Liquid Liquid

Temperature (C?) 16.0000000 16.0000000 43.5000000 72.0000000 43.5000000 129.0753174

Pressure, bar 16.2000008 16.2000008 15.8549995 14.8199997 6.2100000 6.9749999

Flowrate, Kgmol/hr 277.5000000 850.0000000 1131.8957520 869.3738403 575.9934692 278.0000000

Composition
NC4 0.0000000 0.0900000 0.0675875 0.0879966 0.1328171 0.0000005
IC4 0.0000000 0.4100000 0.3078933 0.4008669 0.6050468 0.0000001
1BUTENE 0.0000000 0.0700000 0.0525667 0.0684401 0.1032997 0.0000002
BTC2 0.0000000 0.0400000 0.0300382 0.0391087 0.0590279 0.0000014
BTT2 0.0000000 0.0600000 0.0450572 0.0586630 0.0885424 0.0000007
IBTE 0.0000000 0.3300000 0.2478143 0.0202760 0.0039012 0.0000000
MTBE 0.0000000 0.0000000 0.0000000 0.3013479 0.0000071 0.9976990
MEOH 1.0000000 0.0000000 0.2488773 0.0226821 0.0073578 0.0003628
TBA 0.0000000 0.0000000 0.0000000 0.0002155 0.0000000 0.0006739
H2O 0.0000000 0.0000000 0.0001655 0.0000000 0.0000000 0.0000000
DIB 0.0000000 0.0000000 0.0000000 0.0004033 0.0000000 0.0012612

COLUMN T-1
1.00

Liquid Fraction of IBTE

Liquid Fraction of MEOH
Liquid Fraction of MTBE

0.80 Liquid Fraction of NC4

0.60
Fraction

0.40

0.20

0
0 6.0 12.0 18.0 24.0 30.0
Tray Number

Figure 5.1 Feed and products concentration profile among column trays.

57
 Table 5.2 Summary of MTBE column T-1
Column T-1 Summary
Net Flow Rates
Tray Temp. Pressure Liquid Vapor Feed Product Duties
C BAR KG-MOL/HR M*KJ/HR
1 43.5 6.21 633.6 576.0 -23.6655
2 50.6 6.21 661.6 1209.5
3 51.3 6.24 659.7 1237.6
4 51.7 6.26 658.5 1235.7
5 52.1 6.29 657.3 1234.4
6 52.4 6.32 655.6 1233.3
7 52.8 6.35 651.6 1231.5
8 53.5 6.37 636.0 1227.6
9 54.5 6.40 614.4 1214.5
10 56.2 6.43 582.6 1195.5
11 59.1 6.46 539.7 1166.4
12 63.5 6.48 494.3 1126.8
13 68.7 6.51 462.8 1084.6
14 73.4 6.54 445.4 1054.2
15 76.9 6.57 1206.9 1036.7 869.4
16 91.0 6.59 1180.5 928.9
17 105.5 6.62 1202.3 902.5
18 115.4 6.65 1237.5 924.3
19 121.0 6.67 1264.7 959.5
20 123.9 6.70 1281.9 986.7
21 125.5 6.73 1292.5 1003.9
22 126.5 6.76 1299.2 1014.5
23 127.1 6.78 1303.8 1021.2
24 127.5 6.81 1307.2 1025.8
25 127.9 6.84 1309.8 1029.2
26 128.2 6.87 1311.9 1031.8
27 128.4 6.89 1313.8 1033.9
28 128.6 6.92 1315.4 1035.8
29 128.8 6.95 1316.9 1037.4
30 129.1 6.97 1038.9 278.0 23.7889

Tem perature, C
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 Vapor Rate, KG-MOL/HR
1 0.0 200.0 400.0 600.0 800.0 1000.0 1200.0 1400.0
3 1
5 3
5
7
7
9 9
11 11
13
13
Tray

15
15 17
Tray

19
17 21
19 23
25
21
27
23 29
25
0.0 200.0 400.0 600.0 800.0 1000.0 1200.0 1400.0
27
Vapor Liquid Rate, KG-MOL/HR
29
Liquid

Figure 5.2 Temp Profile of column T-1 Figure 5.3 Rates Profile of column T-1

58
 Vapor Density, KG/M3 Vapor Viscosity, PAS
0.000 5.000 10.000 15.000 20.000 25.000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
1 1
3 3
5 5
7 7
9 9
11 11
13 13
Tray

Tray
15 15
17 17
19 19
21 21
23 23
25 25
27 27
29 29

520.000 540.000 560.000 580.000 600.000 620.000 0.0001 0.0001 0.0001 0.0001 0.0002 0.0002 0.0002
Vapor Liquid Density, KG/M3 Vapor Liquid Viscosity, PAS
Liquid Liquid

Figure 5.4 Density Profile of column T-1 Figure 5.5 Viscosity Profile of column T-1

Table 5.3 Summary of water wash column T-2

Column T-2 Summary
Net Flow Rates
Tray Temp. Pressure Liquid Vapor Feed Product Duties
C BAR KG-MOL/HR M*KJ/HR
1 38.2 7.92 947.2 375.0 572.1
2 38.2 7.92 947.2 0.0
3 38.2 7.92 947.3 0.0
4 38.2 7.92 948.1 0.0
5 38.2 7.92 0.0 576.0 378.8

Tem perature, C
38.2 38.2 38.2 38.2 38.2 38.3 Vapor Rate, KG-MOL/HR
1 0.0 0.2 0.4 0.6 0.8 1.0
1

2 2
Tray

3
Tray

4
5
947.0 947.2 947.4 947.6 947.8 948.0 948.2
Vapor Liquid Rate, KG-MOL/HR
5 Liquid

Figure 5.6 Temp Profile of column T-2 Figure 5.7 Rates Profile of column T-2

59
 Vapor Density, KG/M3 Vapor Viscosity, PAS
0.000 0.200 0.400 0.600 0.800 1.000 0.0000 0.2000 0.4000 0.6000 0.8000 1.0000
1 1

2 2
Tray

Tray
3 3

4 4

5 5
603.700 603.800 603.900 604.000 604.100 604.200 604.300 604.400 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003
Vapor Liquid Density, KG/M3 Vapor Liquid Viscosity, PAS
Liquid Liquid

Figure 5.8 Density Profile of column T-2 Figure 5.9 Viscosity Profile of column T-2

Table 5.4 Summary of Methanol Recovery column T-3

Column T-3 Summary
Net Flow Rates
Tray Temp. Pressure Liquid Vapor Feed Product Duties
C BAR KG-MOL/HR M*KJ/HR
1 30.0 1.03 96.9 4.4 -4.0730
2 74.1 1.38 105.9 101.3
3 76.5 1.40 103.7 110.3
4 81.7 1.42 99.4 108.1
5 92.8 1.44 95.8 103.8
6 104.6 1.46 95.9 100.2
7 108.8 1.48 96.2 100.3
8 109.9 1.50 96.3 100.6
9 110.4 1.51 96.4 100.7
10 110.8 1.53 483.1 100.7 378.8
11 111.6 1.55 483.6 108.7
12 112.2 1.57 484.0 109.2
13 112.8 1.59 484.4 109.6
14 113.3 1.61 484.8 110.0
15 113.7 1.63 485.1 110.4
16 114.2 1.65 485.5 110.7
17 114.6 1.67 485.8 111.0
18 114.9 1.69 486.1 111.3
19 115.3 1.71 486.4 111.6
20 115.7 1.73 111.9 374.4 4.5077

Tem perature, C
0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 Vapor Rate, KG-MOL/HR
1 98.0 100.0 102.0 104.0 106.0 108.0 110.0 112.0 114.0
3 1
3
5 5
7 7
9
Tray

9
11
Tray

11 13
15
13
17
15 19

17 0.0 100.0 200.0 300.0 400.0 500.0 600.0

19 Vapor Liquid Rate, KG-MOL/HR

Liquid

Figure 5.10 Temp Profile of column T-3 Figure 5.11 Rates Profile of column T-3

60
 Vapor Density, KG/M3 Vapor Viscosity, PAS
0.000 0.500 1.000 1.500 2.000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
1 1
3 3
5 5
7 7
9 9
Tray

Tray
11 11
13 13
15 15
17 17
19 19

0.000 200.000 400.000 600.000 800.000 1000.000 0.0000 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006
Vapor Liquid Density, KG/M3 Vapor Liquid Viscosity, PAS
Liquid Liquid

Figure 5.12 Density Profile of column T-3 Figure 5.13 Viscosity Profile of column T-3

Table 5.5 Overall Report

Stream (Summary) UOM 1 10 11 12 13 14
Name 1 10 11 12 13 14
Description MEOH FEED 10 C4'S 12 13 14
Phase Liquid Liquid Liquid Liquid Mixed Mixed
Thermodynamic System S1 S1 S1 S1 S1 S1
Total Molar Rate kg-mol / hr 277.5 375.0209471 572.136588 378.87777 378.87777 378.87777
Total Mass Rate kg / hr 8891.699411 6756.40571 32942.70972 6886.158242 6886.158242 6886.158242
Temperature C 15.9999939 37.9999939 38.1693034 38.1787967 98.9999939 99.0980516
Pressure bar 16.2 7.93 7.92 7.92 7.575 2.41
Total Molecular Weight 32.04216003 18.01607554 57.57840072 18.17514456 18.17514456 18.17514456
Total Specific Enthalpy kJ / kg 23.45157451 169.3191479 92.15106329 166.9490502 422.8609698 422.8609697
Total Cp J/kg-K 2454.101878 4366.688375 2503.383034 4341.893717 0 0
Total Molar Component Rates kg-mol / hr
NC4 0 0 76.4962078 0.005569965 0.005569965 0.005569965
IC4 0 0 348.4874116 0.015603494 0.015603494 0.015603494
1BUTENE 0 0 59.49979477 0.000171456 0.000171456 0.000171456
BTC2 0 0 33.99945592 0.000241614 0.000241614 0.000241614
BTT2 0 0 50.99964646 0.000192594 0.000192594 0.000192594
IBTE 0 0 2.247034765 5.202E-06 5.202E-06 5.202E-06
MTBE 0 1.68576E-18 0.004041775 2.16251E-05 2.16251E-05 2.16251E-05
MEOH 277.5 0.021275489 0.003515716 4.255771777 4.255771777 4.255771777
TBA 0 3.14002E-36 2.8833E-10 2.73157E-13 2.73157E-13 2.73157E-13
H2O 0 374.9996714 0.399479196 374.6001924 374.6001924 374.6001924
DIB 0 0 1.03273E-11 1.28821E-23 1.28821E-23 1.28821E-23
Total Molar Component Fractions fraction
NC4 0 0 0.133702702 1.47012E-05 1.47012E-05 1.47012E-05
IC4 0 0 0.60909828 4.11835E-05 4.11835E-05 4.11835E-05
1BUTENE 0 0 0.103995787 4.52538E-07 4.52538E-07 4.52538E-07
BTC2 0 0 0.059425418 6.3771E-07 6.3771E-07 6.3771E-07
BTT2 0 0 0.089138936 5.08327E-07 5.08327E-07 5.08327E-07
IBTE 0 0 0.003927445 1.373E-08 1.373E-08 1.373E-08
MTBE 0 4.49511E-21 7.06435E-06 5.70768E-08 5.70768E-08 5.70768E-08
MEOH 1 5.67315E-05 6.14489E-06 0.011232572 0.011232572 0.011232572
TBA 0 8.37292E-39 5.03954E-13 7.20964E-16 7.20964E-16 7.20964E-16
H2O 0 0.999943269 0.000698223 0.988709874 0.988709874 0.988709874
DIB 0 0 1.80503E-14 3.40006E-26 3.40006E-26 3.40006E-26
Vapor Molar Rate kg-mol / hr N/A N/A N/A N/A 0.000577937 0.029560113
Vapor Mass Rate kg / hr N/A N/A N/A N/A 0.030431601 1.20838919
Vapor Molecular Weight N/A N/A N/A N/A 52.65556269 40.87904483
Vapor Mole Fraction fraction N/A N/A N/A N/A 1.52539E-06 7.80202E-05
Vapor Specific Enthalpy kJ / kg N/A N/A N/A N/A 629.8510681 950.3195163
Vapor CP J/kg-K N/A N/A N/A N/A 2096.037884 2012.784279
Vapor Composition fraction
NC4 N/A N/A N/A N/A 0.13081499 0.122759833
IC4 N/A N/A N/A N/A 0.711658135 0.422089572
1BUTENE N/A N/A N/A N/A 0.007379891 0.004578206
BTC2 N/A N/A N/A N/A 0.004576501 0.005051828
BTT2 N/A N/A N/A N/A 0.006164664 0.004781536
IBTE N/A N/A N/A N/A 0.000268759 0.000144091
MTBE N/A N/A N/A N/A 8.803E-07 2.36786E-06
MEOH N/A N/A N/A N/A 0.010672162 0.032527184
TBA N/A N/A N/A N/A 7.31467E-14 1.93873E-13
H2O N/A N/A N/A N/A 0.128464018 0.408065382
DIB N/A N/A N/A N/A 2.18059E-20 4.35717E-22
Vapor Component Rate kg-mol / hr
NC4 N/A N/A N/A N/A 7.56028E-05 0.003628795
IC4 N/A N/A N/A N/A 0.000411294 0.012477015
1BUTENE N/A N/A N/A N/A 4.26511E-06 0.000135332
BTC2 N/A N/A N/A N/A 2.64493E-06 0.000149333
BTT2 N/A N/A N/A N/A 3.56279E-06 0.000141343
IBTE N/A N/A N/A N/A 1.55326E-07 4.25934E-06
MTBE N/A N/A N/A N/A 5.08758E-10 6.99943E-08
MEOH N/A N/A N/A N/A 6.16784E-06 0.000961507
TBA N/A N/A N/A N/A 4.22742E-17 5.7309E-15
H2O N/A N/A N/A N/A 7.42441E-05 0.012062459
DIB N/A N/A N/A N/A 1.26024E-23 1.28798E-23
Liquid Molar Rate kg-mol / hr 277.5 375.0209471 572.136588 378.87777 378.8771922 378.84821
Liquid Mass Rate kg / hr 8891.699411 6756.40571 32942.70972 6886.158242 6886.127812 6884.949852
Liquid Molecular Weight 32.04216003 18.01607554 57.57840072 18.17514456 18.17509196 18.17337306
Liquid Mole Fraction fraction 1 1 1 1 0.999998475 0.99992198
Liquid Specific Enthalpy kJ / kg 23.45157451 169.3191479 92.15106329 166.9490502 422.860055 422.7683945
Liquid CP J/kg-K 2454.101878 4366.688375 2503.383034 4341.893717 4133.847462 4134.720639
Liquid Composition fraction
NC4 0 0 0.133702702 1.47012E-05 1.45017E-05 5.12388E-06

61
5.2 RESULTS DISCUSSION

The results of this simulation shown in previous section indicate that the
overall conversion of IBTE is 99.2%, the conversion can be calculated as
following:
(IBTE) inlet - (IBTE) outlet
Conv. (%) = 100
(IBTE) inlet
280.5 - 2.32
Conv. (%) = 100
280.5
Conv. (%) = 99.2 %

Also with a selectivity to MTBE of 99.7%. In the reactive distillation

column itself, 87.2% of the IBTE fed to the column is converted to MTBE. The
MTBE product is 99.77% pure and needs no further purification.
There are a number of factors that affect the overall conversion rate of
IBTE. Some of these are:
MeOH to IBTE ratio.
Number of reaction trays.
Type of catalyst used.
Reflux ratio

Note, however, that while the IBTE conversion in the conversion reactors
increases as the MEOH:IBTE ratio is increased, the overall IBTE conversion
reaches a maximum, then decreases as the MEOH:IBTE ratio is increased.
This is due to the fact that more MTBE product is carried upward through the
column stripping section into the reaction trays. This promotes the reverse
reaction of MTBE to methanol and IBTE, thus reducing the overall conversion
of IBTE.

5.3 CASE STUDIES

The validated MTBE primary reactor and reactive distillation column models
were used to develop new process flow diagrams for the MTBE unit.
Concerning the evaluation of plant performance, there are some parameters
were taken into account for the plant optimization as follows:

62
 o MeOH to IBTE ratio.
o Number of trays.
o Location of feeds into RD column.
o Reflux ratio of RD column.
o Number of reaction trays.

Case Title: Case-1: Changing the Methanol/ Isobutylene Ratio

Case Clarifications:

R1 = 0.90 ==> (MeOH)Feed= 252.5 kgmol/hr

R2 = 0.95 ==> (MeOH)Feed= 266.5 kgmol/hr
R3 = 0.98 ==> (MeOH)Feed= 277.5 kgmol/hr
R4 = 1.0 ==> (MeOH)Feed= 280.5 kgmol/hr (Base case)
R5 = 1.05 ==> (MeOH)Feed= 294.5 kgmol/hr

MeOH/IBTE Ratio 0.900 0.950 0.980 1.000 1.050

Conversion(%) 87.500 92.300 96.970 99.200 96.970
MTBE Purity(wt%) 87.900 92.700 99.600 99.700 99.600

Case Observations and Comments:

- The overall conversion of IBTE into MTBE is increased when the

Methanol/Isobutylene ratio increased but it dropped when the ratio exceed 1.0 as
shown in the figure 5.14.
- The purity of MTBE is increased when the Methanol/Isobutylene ratio increased as
shown in the figure 5.14. The last two runs are showing almost stable purity.
- The optimum Methanol/Isobutylene ratio is 1.0 as demonstrated in figure 5.14.

Figure 5.14 Results of changing the MeOH/IBTE ratio

63
Case Title: Case-2: Changing the Number of trays for RD column

Case Clarifications:

R1 = The RD column consists of 20 trays

R2 = The RD column consists of 25 trays
R3 = The RD column consists of 30 trays (Base case)
R4 = The RD column consists of 32 trays
R5 = The RD column consists of 35 trays
R6 = The RD column consists of 40 trays

RD Trays 20 25 30 32 35 40
Conversion(%) 97.00 98.00 99.20 99.20 99.20 99.20
MTBE Purity(wt%) 97.20 99.20 99.70 99.70 99.80 99.80

Case Observations and Comments:

- The overall conversion of IBTE to MTBE is increased when the number of trays
increased as shown in the figure 5.15.
- The purity of MTBE is increased when the number of trays increased as shown in
the figure 5.15. The last three runs are showing almost stable purity.
- The last two runs are almost comparable which indicates that the both parameters
will get stable.
- The optimum number of trays are 30 (The max limit to have the desired results).

Figure 5.15 Results of changing the number of trays of RD column

64
Case Title: Case-3: Changing the Location of feed stream into RD column

Case Clarifications:

R1 = The feed stream entered the RD column at tray # 8

R2 = The feed stream entered the RD column at tray # 10
R3 = The feed stream entered the RD column at tray #12
R4 = The feed stream entered the RD column at tray #15 (Base case)
R5 = The feed stream entered the RD column at tray #17

Note:- The Reaction zone applied in this case is from 11-13 trays of RD column

Feed stream to tray 8 10 12 15 17

Conversion(%) 94.50 95.30 97.91 99.20 99.20
MTBE Purity(wt%) 94.50 95.80 98.40 99.70 99.70

Case Observations and Comments:

- The overall conversion of IBTE to MTBE is increased when the location of feed
stream changed to the next tray as shown in the figure 5.16.
- The purity of MTBE is increased when the location of feed stream changed to the
next tray as shown in the figure 5.16.
- The last two runs are almost comparable which indicates that the both parameters
will get stable.
- The optimum location for the feed stream is tray 15 (The middle of the column).

Figure 5.16 Results of changing the location of feed stream into RD column

65
Case Title: Case-4: Changing the Reflux Ratio for RD column

Case Clarifications:

R1 = The Reflux Ratio is equal to 0.8

R2 = The Reflux Ratio is equal to 0.9
R3 = The Reflux Ratio is equal to 1.0
R4 = The Reflux Ratio is equal to 1.1 (Base case)
R5 = The Reflux Ratio is equal to 1.2

Reflux Ratio 0.8 0.9 1.0 1.1 1.2

Conversion(%) 98.33 98.75 99.16 99.20 99.20
MTBE Purity(wt%) 98.80 99.30 99.60 99.70 99.80

Case Observations and Comments:

- The overall conversion of IBTE to MTBE is increased when the Reflux Ratio
increased as shown in the figure 5.17.
- The purity of MTBE is increased when the Reflux Ratio increased as shown in the
figure 5.17.
- The overall conversion of IBTE into MTBE is getting stable for the last three runs at
the value 99.2 %.

Case-4: Changing the Reflux Ratio for RD column

Conversion(%) MTBE Puirty(wt%)

100.00

99.80

99.60

99.40

99.20

99.00

98.80

98.60

98.40

98.20
0.6 0.7 0.7 0.8 0.8 0.9 0.9 1.0 1.0 1.1 1.1 1.2 1.2 1.3

Reflux Ratio

Figure 5.17 Results of changing the Reflux Ratio

66
Case Title: Case-5: Changing the Location of reaction zone in RD column

Case Clarifications:

R1 = The Reaction zone from 9-13 trays

R2 = The Reaction zone from 10-13 trays
R3 = The Reaction zone from 11-13 trays (Base case)
R4= The Reaction zone from 12-13 trays
R5 = The Reaction zone only tray # 13

Reaction zone 9-13 10-13 11-13 12-13 13

Conversion(%) 99.20 99.20 99.20 99.17 98.50
MTBE Purity(wt%) 99.80 99.80 99.70 99.70 99.20

Case Observations and Comments:

- The overall conversion of IBTE to MTBE is decreased when the location of reaction
zone get changed as shown in the figure 5.18.
- The purity of MTBE is stable then decreased when the reaction zone get small (only
one tray) as shown in the figure 5.18.
- The optimum location for the reaction zone is tray 11-13 (The middle of the packing
bed).

Case-5: Changing the Location of reaction zone in RD column

Conversion(%) MTBE Puirty(wt%)

100.00

99.80

99.60

99.40

99.20

99.00

98.80

98.60

98.40
0 1 2 3 4 5 6

Reaction Zone

Figure 5.18 Results of changing the location of reaction zone

67
 CHAPTER -6-

CONCLUSIONS AND RECOMMENDATIONS

68
6.1 CONCLUSIONS

The combination of reaction and distillation helps in achieving products of

higher purity and higher conversion of reactants as compared to old
conventional processes.
As shown in this study it is possible to obtain an overall conversion of IBTE
around 99.2% with purity of MTBE almost 99.7%.
The mathematical model developed has shown satisfactory results in
simulating a reactive distillation column for the etherification of methanol and
isobutylene to form MTBE.
The model and computational technique has also been successful in
determining the effect of various design variables namely reflux ratio, feed plate
location, reaction zone, Methanol/Isobutylene molar ratio.
The selectivity of IBTE to MTBE is 99.7%. In the reactive distillation column
itself, 87.2% of the IBTE fed to the column is converted to MTBE. The MTBE
product is 99.77% pure and needs no further purification.
The overall conversion of IBTE to MTBE is increased when the
Methanol/Isobutylene ratio increased but it dropped when the ratio exceed 1.0
as shown in the figure 5.14.
The purity of MTBE is increased when the Methanol/Isobutylene ratio
increased as shown in the figure 5.14. The last two runs are showing almost
stable purity.
The overall conversion of IBTE to MTBE is increased when the number of trays
increased as shown in the figure 5.15.
The purity of MTBE is increased when the number of trays increased as shown
in the figure 5.15. The last three runs are showing almost stable purity.
The optimum number of trays are 30 (The max limit to have the desired
results).
The overall conversion of IBTE to MTBE is increased when the location of feed
stream changed to the next tray as shown in the figure 5.16.
The purity of MTBE is increased when the location of feed stream changed to
the next tray as shown in the figure 5.16. but the last two runs are almost
comparable which indicates that the both parameters will get stable.

69
 The optimum location for the feed stream is tray 15 (The middle of the
column).
The overall conversion of IBTE to MTBE is increased when the Reflux Ratio
increased as shown in the figure 5.17.
The purity of MTBE is increased when the Reflux Ratio increased as shown in
the figure 5.17.
The overall conversion of IBTE to MTBE is decreased when the location of
reaction zone get changed as shown in the figure 5.18.
The purity of MTBE is stable then decreased when the reaction zone get small
(only one tray) as shown in the figure 5.18.
The optimum location for the reaction zone is tray 11-13 (The middle of the
packing bed).
It is not recommended to exceed the MEOH/IBTE ratio more than 1.0 to
achieve the desired conversion as well as the MTBE purity, this due to
limitation observed from the simulation results.
It is not recommended to increase the number of trays more than 30 trays
since the conversion of IBTE and purity of MTBE were not increased much
when the trays increased up to 40. this will also maintain the capital cost.
It is recommended to keep the feed stream into RD column at stage no. 15
which represents the middle of the column.
It is recommended to keep the reflux ration equal to 1.1 since the conversion
and purity of MTBE were no effected when it increased more than 1.1.
It is recommended to keep the location of the reaction zone in the space of tray
11-13 (The middle of the packing bed).
It is recommended to keep close monitoring system on the recycled methanol
to the reactor to monitor the moisture content in the stream to avoid forming
impurities such as t-butanol.
It is recommended to maintain a sufficient amount of C4s in the column feed to
have smooth operation for the MTBE RD column. Also to form azeotropes with
the methanol in the feed.

70
6.2 RECOMMENDATIONS

It is recommended to perform an Economic Evaluation study for RD process

against the conventional process.
It is recommended also, to perform a dynamic study.
It is recommended to validate the results by using another data or another
simulation software.
It is recommended to perform an effective control study on control structures
for RD column to have effective system to control the critical parameters.
It is recommended to study the possibility of having quality performance system
for the feed and recycled streams to avoid forming undesired products.
It is recommended to use this model as a tool for design, optimization and
control of Reactive Distillation processes.

71
BIBLIOGRAPHY

72
 REFERENCES
1- J. H. Gregor, S.T. Bakas, and M. A. Ulowetz, "Converting field butanes into MTBE",
Seventy-First Annual Convention Gas Processors Association, Anaheim, California,
1992, sku P1992.36.
2- Sandra Viviana, " Computer Simulation Studies for the production of 7-Tertadecene by
Reactive Distillation", Mississippi State University , USA, 2 August 2003.
3- D. N. Nakamura, HP in Processing, Hydrocarbon Processing, Vol. 77(1), 15, 1998.
4- CHEM System Inc, "Methyl tertiary-Butyl Ether (MTBE)", PERP 94/95-4, 1996.
5- M. F. Doherty, and M. F. Malone, "Conceptual Design of Distillation Systems",
McGraw Hill, New York, 2001
6- E. J. Chang and S. M. Leiby, Ethers Help Gasoline Quality, Hydrocarbon Processing,
Vol. 71(2), 4144, 1992.
7- J. D. Seader, "Separation Process Principles", John Wiley and Sons, Inc., New York,
1998.
8- J. L. DeGmo, V. N. Pdekar, and V. Pinjala, "Consider Reactive Distillation," Chem
Eng. Prog. 88, 43-50, 1992.
9- R. K. Toghiani, H. Toghiani, and G. Venkateswarlu, "Vapor-liquid Equilibria for methyl
ter-butyl ether+methanol and ter-amyl methyl ether+methanol", Fluid Phase Equilibria
122, 157-168, 1996.
10- A. Tuchlenski, A. Beckmann, D. Reusch, R. Dussel, U. Weidlich, and R. Janowsky,
"Reactive Distillation-Industrial Applications, Process Design and Scale-up", Chemical
Engineering Science 56, 387-394, 2001.
11- Krishna, R. and Sie, S.T. "Strategies for Multiphase Reactor Selection", Chem.Engng
Sci., 49, 4029-4065, 1994.
12- Agreda, V.H., Partin, L.R. and Heise, W.H. "High-purity methyl acetate via reactive
distillation", Chem. Eng. Progress, 2, 40 46, 1990.
13- Doherty, M.F. and G. Buzad, "Reactive Distillation by Design", Chem. Eng. Res& .
Design., Trans I.Chem.E., Part A, 70, 448-458, 1992.
14- Siirola, J.J., "An Industrial Perspective on Process Synthesis", A.I.Ch.E. Symposium
Series No. 304, 91,222 233, 1995.
15- Stichlmair, J.G. and Frey, T., "Reactive distillation processes", Chemical and
Engineering Technology, 22, 95-103, 1999.
16- Ciric, A.R., and D. Gu., "Synthesis of nonequilibrium reactive distillation by MINLP
optimization", A.I.Ch.E.J., 40, 1479 1487,1994

73
17- Gonzalez, J. C., & Fair, J. R., "Preparation of tertiary amyl alcohol in a reactive
distillation column.1 Reaction kinetics, chemical equilibrium, and mass transfer
issues". Industrial and Engineering chemistry Research, 36, 3833-3844,1997.
18- Velo, E., Puigianer, L. & Recasens, F., "Inhibition by product in the liquid-phase
hydration of iso-butane to tert-butyl alcohol kinetics & equilibrium studies", Industrial
and Engineering chemistry Research, 27, 2224-2231, 1988.
19- Shoemaker, J.D. and E.M. Jones, "Cumene by catalytic distillation", Hydrocarbon
Processing, June 1987, 57 58, 1987.
20- Subawalla, H., Gonzalez, J.C., Seibert, A.F., and Fair, J.R., "Capacity and Efficiency
of Reactive Distillation Bale Packing: Modeling and Experimental Validation", Ind. Eng.
Chem. Res., 36, 3821-3832, 1997
21- Van Gulijk, C. , "Using computational fluid dynamics to calculate transversal dispersion
in a structured packed bed", Comput. Chem. Eng., 22, S767-S770, 1998.
22- Higler, A., Krishna, R., Ellenberger, J. and Taylor, R., "Counter-current operation of a
structured Catalytically Packed Bed Reactor: Liquid phase mixing and mass transfer",
Chem. Eng. Sci., in press, 1999c.
23- Frey, S. J., Ozmen, S. M., Hamm, D. A., Pinjala, V., & DeGarmo, J. L. , "Advanced
ether technology commercialized". Paper presented at the world conference on clean
fuels and air quality control, Washington, DC, 1993.
24- G. Matthias, M. Ramona, Dragomir and J. Megan, "Conceptual design of reactive
distillation columns using stage composition lines", Chemical Engineering Science 60,
5049-5068, 2005.
25- V. B. Shah, D. Bluck, J. W. Kovach III, "The sensitivity of the design and operability of
the MTBE processes with respect to changes in reaction parameters and process
configurations", Refining LNG and Petrochmasia 1994.
26- P. S. Bhanu, S. Ram, M.V Pavan, and K. Nitin, "Steady state analysis for reactive
distillation control: An MTBE case study", Journal of Loss Prevention in the process
Industries 18, 283-292, 2005.
27- C. A. Rivera and G. Johan, "Feasibility of Equilibrium controlled reactive distillation
process: application of residue curve mapping", Computers and Chemical Engineering
28, 17-25, 2004.
28- Smith Jr., L.A. " U.S. Patent 4443559", Catalytic distillation structure, 1984.
29- Johnson, K.H. , "U.S. Patent 5189001", Catalytic distillation structure,1993.
30- Nelson, P. A., "Countercurrent equilibrium stage separation with reaction". American
Institute of chemical Engineers Jornal, 17, 1043-1049, 1971.

74
31- Suzuki, I., Yagi, H., Komatsu, H., and Hirata, M., " Calculation of multicomponent
distillation accompanied by chemical reaction", J. Chem. Eng. Jap., 4, 26-33, 1971.
32- Venkataraman, S., Chan, W. K., & Boston, J. F., "Reactive distillation using ASPEN
PLUS". Chemical Engineering Process, 86(8), 45-54, 1990.
33- Jelink, J., & Halvacek, V., "Steady state Countercurrent equilibrium stage separation
with chemical reaction by relaxation method". Chemical Engineering
communications,2, 79-85, 1976.
34- Saito, S., Michishita, T., & Maeda, S. , " Separation of meta- and para-xylene mixture
by distillation accompanied by chemical reaction". Journal of Chemical Engineering
Japan, 4, 37-43, 1971.
35- Grosser, J.H., Doherty, M.F. and Malone, M.F., "Modeling of reactive distillation
systems", Ind. Chem. Eng. Res., 26, 983-989, 1987.
36- Kamath R., Qi Z., Sundmacher K., Aghalayam P., Mahajani S., "Modelling and
Optimization for Energy Saving and Pollution Reduction", 8th conference on Process
Integration, The Italian Association of Chemical Engineering (AIDIC) 309, 2005.
37- Al-Jarallah, A. M., M. A. B. Siddiqui and A. K. K. Lee, Kinetics of Methyl Tertiary Butyl
Ether Synthesis Catalyzed by Ion Exchange Resin, Canadian J. Chem. Eng. , 66,
802-7, 1988.
38- A. Abufares, and P.L. Douglas, "Mathematical Modeling and Simulation of an MTBE
Catalytic Distillation Process using Speedup and Aspenplus", Chemical Engineering
Research and Design 79 (A1), 3-12, 1995.
39- J. M. Bader, S. Guesneux, Axens, "Increase MTBE plant productivity", Hydrocarbon
Processing, October 2005.
40- M. H. M. Reis; L. F. S. Mascolo; M. R. Wolf-Maciel, " Development of a robust
algorithm to compute reactive azeotropes ", Brazilian Journal of Chemical
Engineering, vol.23 no.3 , July/Sept. 2006.

75
 APPENDIX (A)
REACTION MODEL CODE

76
APPENDIX (A) : MTBE Reaction Model Code

In this section the entire code of reaction kinetics will be shown below along with a
description of purpose. The first portion of the defines real and integer variables

REAL KS , KA , KC , KALJ , KREH1 , KREH2 , KIZQ , KEQREF

INTEGER IBTE , MEOH , MTBE

Next, the indices for the components are set, a value is given for the gas constant in
J/gm-mole K, and the basis for the temperature values in the procedure is set to an
absolute basis. In addition, the temperature and composition rate derivatives are
initially set equal to zero.
$
$ INITIALIZE DATA:
$ SET INDEXES FOR COMPONENTS
$ DEFINE GAS CONSTANT IN JOULES/GM-MOLE K
$ NOTE: R COULD HAVE BEEN RETRIEVED IN INPUT UNITS BY R=RGAS.
$ HOWEVER, SINCE THE REACTION BASIS WON'T CHANGE, AND
$ RGAS WILL CHANGE WITH THE DEFAULT UNITS, THIS
$ ELIMINATES ONE POSSIBLE SOURCE OF ERROR.
$ INITIALIZE THE LOCAL VARIABLE TK TO THE ABSOLUTE TEMPERATURE.
$ NOTE: THE TEMPERATURE BASIS FOR THE FLOWSHET MUST BE C OR K.
$ SET TEMPERATURE AND COMPOSITION DERIVATIVES TO ZERO.
$
IBTE = 6
MTBE = 7
MEOH = 8
$
R = 8.314
$
TK = RTABS
$
DO 1000 I1 = 1,NOR
DRDT(I1) = 0.0
DO 1000 I2 = 1,NOC
1000 DRDX(I2,I1) = 0.0

The surface reaction rate constant, ks, and the equilibrium adsorption constants, K ,
A

and K , are calculated using the expressions given previously as (1a), (1b), and (1c).
B

$ CALCULATE THE SURFACE REACTION RATE CONSTANT, KS, AND THE

$ EQUILIBRIUM ADSORPTION CONSTANTS KA AND KB. THE ACTIVATION
$ ENERGY IS IN J/GM-MOLE.
$ UNITS: KS - (GM-MOLE / GM CATALYST)**1.5 /HOUR
$ KA - GM-CATALYST / MOLE
$ KC - GM-CATALYST / MOLE
$
KS = 1.2E+13*EXP(-87900.0/(R*TK))
KA = 5.1E-13*EXP( 97500.0/(R*TK))
KC = 1.6E-16*EXP(119000.0/(R*TK))

77
 Next, the derivatives of these constants are computed and are used later on in
calculating the rate derivatives.

$
DKSDT = KS * 87900.0 / R / (TK*TK)
DKADT = KA * (-1.0) * 97500.0 / R / (TK*TK)
DKCDT = KC * (-1.0) * 119000.0 / R / (TK*TK)

Then the bulk concentration of components A, B, and C per gram of catalyst

(RHOA, RHOB, and RHOC) are determined from the liquid mole fractions of the
components (XLIQ), the density of the liquid, and the catalyst loading (GCAT) in g/l.
Note that the liquid density, DENS, obtained directly from PRO/II using the predefined
3
variables, RLMRAT and RLVRAT, is in the user-specified units of kg-moles/m (SI
units). Our basis for calculations is gm-moles/l and the conversion factor between
3
these kg-moles/m and gm-moles/l is 1.0. Also, note that the value of GCAT used here
is 12.4 g/l. This value is used because it is the catalyst loading at which data for the Al-
Jarallah rate equation was collected.

$ ---- CALCULATE THE EQUILIBRIUM CONSTANT.

$
$ UNITS - (GM-MOLES/GM-CATALYST)/HOUR
$ PHASE - LIQUID PHASE REACTION
$ CATALYST - ION EXCHANGE RESIN AMBERLYST 15,
$ THE EQUILIBRIUM SHOULD BE INDEPENDANT OF THE CATALYST

Expressions for the equilibrium constant and its derivative as functions of temperature
are provided based on equilibrium data published by Al-Jarallah et al.
$
KALJ = EXP(-17.31715+(7196.776/TK))
$
DKALJDT = - KALJ * 7196.776 / (TK*TK)

Then the reaction rate and rate derivatives with respect to temperature and
composition are determined.

$ BULK CONCENRATIONS OF COMPONENTS PER GRAM OF CATALYST, XLCONC IS

$ IN MOLES/FLOW VOLUME. XLCONC WILL BE PASSED TO THE PROCEDURE
$ IN USER INPUT UNITS. INTERNALLY TO PRO/II, IT IS IN SI UNITS
$ (KG-MOLE/CUBIC METER). THE BASIS FOR THESE REACTION EQUATIONS
$ IS GM-MOLES/LITER. THE CONVERSION FACTOR FROM INPUT UNITS OF
$ KG-MOLES/CUBIC METER TO THE REACTION BASIS OF GM-MOLES/LITER
$ IS ONE. THEREFORE, XLCONC CAN BE USED WITH NO CONVERSION.
$ RHOA=(XLCONC(MEOH)/GCAT) |-THIS SHOULD BE EQUIVALENT TO BELOW.
$ RHOB=(XLCONC(IBTE)/GCAT) | IT HAS BEEN WRITTEN EXPLICITLY BELOW
$ RHOC=(XLCONC(MTBE)/GCAT) | TO MAKE IT OBVIOUS HOW TO DO THE
$ ANALYTICAL DERIVATIVES.

78
$ CALCULATE DENSITY IN MOLES / VOLUME
$
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)
$ ---- CALCULATE REACTION RATE AND DERIVATIVES BY TERMS
$ ---- UNITS - RATE - GRAM-MOLE / GRAM CATALYST / HR.
$
$ DENOMINATOR & DERIVATIVES.
$
RDEN = 1.0 + ( KA*RHOA ) + 0.0 + ( KC*RHOC )
DRDDT = RHOA*DKADT + 0.0 + RHOC*DKCDT
DRDDME = KA/GCATX*DENS
DRDDIB = 0.0
DRDDMT = KC/GCATX*DENS
$
$ FIRST FACTOR IN RATE EQUATION.
FACT1 = KS *KA/RDEN
DFAC1DT = DKSDT*KA/RDEN + KS*DKADT/RDEN - KS*KA/RDEN**2 * DRDDT
$
$ SECOND FACTOR IN RATE EQUATION.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$ COMBINE TERMS TO CALCULATE RATE AND DERIVATIVES.
$ -- RATE EQUATION (RATE PER ONE GRAM OF CATALYSIS).
RATE = FACT1 * FACT2
$ -- RATE TEMPERATURE DERIVATIVE.
DRDT(1) = DFAC1DT * FACT2 &
+ FACT1 * DFAC2DT

$ -- RATE COMPOSITION DERIVATIVES.

DRDX(MEOH,1) = -KS*KA/RDEN**2 * DRDDME * FACT2 &
+ FACT1 * (RHOB**0.5/GCATX*DENS)
DRDX(IBTE,1) = -KS*KA/RDEN**2 * DRDDIB * FACT2 &
+ FACT1 * (RHOA/2.0/RHOB**0.5/GCATX*DENS)
DRDX(MTBE,1) = -KS*KA/RDEN**2 * DRDDMT * FACT2 &
- FACT1 * (1.5* RHOC**0.5/GCATX/KALJ*DENS)
It is important to note, however, that the rate and rate derivatives calculated above are
computed on a basis of 1 gram of catalyst. The reactive distillation algorithm requires
that these values (RRATES, DRDT, and DRDX) be supplied on a unit reaction
volume basis. Therefore, the rate and rate derivatives are multiplied by the grams of
catalyst per unit volume, GCAT.
$ ---- CONVERT RATE EQUATION AND DERIVATIVES TO A STRAIGHT VOLUME BASIS
$ ---- BY MULTIPLING THE BASE RATE BY THE GRAMS OF CATALYST/UNIT VOLUME.
$ ---- THE RATE IS RETURNED IN INPUT UNITS, KG-MOLES/CUBIC METER/HOUR.
$
RRATES(1) = GCAT * RXFACT * RATE
DRDT(1) = GCAT * RXFACT * DRDT(1)
DRDX(MEOH,1) = GCAT * RXFACT * DRDX(MEOH,1)
DRDX(IBTE,1) = GCAT * RXFACT * DRDX(IBTE,1)
DRDX(MTBE,1) = GCAT * RXFACT * DRDX(MTBE,1)

RETURN

79
 APPENDIX (B)
MTBE PROCESS SIMULATION
PROCEDURE USING PRO/II

80
APPENDIX (B) : MTBE Process Simulation Procedure using PRO/II

Process Simulation
General Data
SI units are used in this simulation. The total calculation sequence is specified. The
calculator CAL0 is processed before the MTBE column in order to set the reaction factor
equal to 1.0 on the first pass through the flowsheet.

In order to check the overall material balance, PRO/II is instructed to print out an overall
flowsheet mass balance in the Miscellaneous Report Options menu.

81
Component Data
All the components in the simulation are available in the PRO/II databank.

Thermodynamic Data
The VLE fractionators are simulated well with PRO/II's modified Soave-Redlich-Kwong
(SRKM) equation of state method. For this method, PRO/II contains extensive, built-in
databanks that encompass binary interaction parameter data for the majority of component
pairs present in this simulation. In this case, however, binary interaction data (kijs) are directly
supplied for 8 component pairs to improve the accuracy of the separations in the columns.
The binary interaction parameters are listed below in Table 1. The thermodynamic set used
for VLE thermodynamics is referred to as SRKM_VLE.

Table 1. Binary Interaction Parameters for SRKM_VLE

Comp I NC4 1BUTENE BTC2 BTT2 IBTE MEOH TBA MTBE
Comp j TBA MEOH MEOH MEOH MEOH TBA H20 DIB
kija 0.0469 0.136 0.136 0.136 0.13553 -0.07397 -0.145 0.05785
kjia 0.1260 -0.0323 -0.0323 -0.0323 -0.0322 -0.05522 -0.253 -0.0093
kijb 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -10.144
kjib 0.0 0.0 0.0 0.0 0.0 0.0 0.0 6.17
UOM K K K K K K K K

Transport properties are needed in order to use the rigorous heat exchanger model in
the MEOH recovery section. Transport property calculations are set to pure-component

82
averages by default and can be modified by modifying the thermodynamic method of choice.
Modification is not required in this simulation, as pure-component averages should be used.

The liquid extraction unit is simulated using the SRKM method for VLLE thermodynamics with
binary interaction data again supplied as part of the input. The thermodynamic set used for
VLE thermodynamics is referred to as SRKM_VLLE. Note that the L1KEY component (i.e.,
the predominant component in the L1 liquid phase) is specified as n-butane. The L2KEY
component is specified to be water. Explicitly specifying the key components eliminates the
need for PRO/II to find an appropriate immiscible pair, reducing the computation time. All the
azeotropes are properly predicted.

Stream Data
Feed Stream
The mixed C4 feed stream, and the methanol feed stream are specified in the normal
manner, using the compositions and stream conditions given in Table 2.

Recycle Stream
The composition of the recycle methanol-water stream from the MEOH recovery
section is estimated initially for the first run through the flowsheet (see Table 2).

83
 The amount of wash water in stream 10 (the feed to column T-2) is provided. The
temperature and pressure of the cooling water stream (CW) for the condenser for column T-3
is provided, along with an estimate of the flowrate. An estimated value is given for the flowrate
of the make-up water stream, MKUP.

Unit Operations
MTBE Reaction
The MTBE reaction section of the plant is shown in Figure 2 below.

84
 Figure 2. MTBE Reaction Section

With reference to the previous figure, mixed C4s (stream 2) are combined with fresh
methanol (stream 1) and recycle methanol (stream 20) and pre-heated in a heat exchanger
(HX-1) to 43.5 C. The heated feed (stream 3) is then sent to a conversion reactor (RX-1)
which is maintained at 55 C by circulating a coolant. A pressure drop of 69 KPa through the
reactor is also specified.

Since this is a conversion reactor. The three reactions defined in Table 3 take place in this
reactor at the specified conversion levels. The extent of reaction are defined based on the
values in Table 3.

85
The stoichiometries of the major and minor reactions in the MTBE process are provided in the
reaction definitions data entry window.

MTBE Distillation and Recovery

The MTBE distillation and recovery section of the plant is shown in Figure 3 below.

FIGURE 3. MTBE Distillation and Recovery Section

86
 The reactor product (stream 4) exchanges heat with the MTBE column bottoms
product in exchanger HX-2. Normally, this would create a thermal calculation loop. However,
since the temperature of stream 5 is known, this process is modeled by two separate heat
exchangers, HX-2A and HX-2B as shown in Figure 3. Stream 4 from the reactors is heated to
72 C in HX-2A to produce stream 5. The product of column T-1, stream 7, is cooled in
exchanger HX2-B to produce the MTBE product stream 8. The duty of exchanger HX-2B is
defined to be equal to the duty in HX-2A. This approach avoids an unnecessary calculation
loop since the temperature of stream 5 is fixed at 72 C.

The heated stream 5 is fed to tray 15 of the 30 tray MTBE column (T-1). The MTBE
column is simulated with the CHEMDIST algorithm using the SIMPLE initial estimate
generator (IEG). A top pressure of 621 KPa and a column pressure drop of 76.5 KPa are
given. The condenser is operated at a fixed temperature of 43.5 C and pressure of 621 KPa.
The control specifications are a bottoms flowrate of 278 kgmoles/hr and a reflux ratio of 1.1.
The condenser and reboiler duties are varied to achieve these specifications.

87
The next step is to provide all the information required for specifying the reaction trays in the
distillation column.

Implementing Reactive Distillation

You can visualize the reaction zone of a distillation column as a series of boiling pot
reactors. On each reaction tray sits a bed of solid catalyst. Each tray is connected to the next
in the forward direction (down the column) by the flow of liquid from one tray to the next, and
in the reverse direction by the vapor flow moving up from one tray to the previous tray.
For the reactive distillation process, the reaction zone (trays 8 through 13) is specified
in the column data entry window.

88
Note that the liquid volume of each of the reaction trays is also specified using the Reaction
Volumes button in the Options section of the data entry window, and that the concentration of
the dry catalyst (GCAT, in g/l) is specified using a DEFINE statement specified using the
Subroutine/Procedure Data button in the Options section of the data entry window.

89
A value of 360 g/l is given for GCAT to represent commercial catalyst loadings (corresponding
to a wet catalyst density of 770 g/l at 53% moisture content see Table 1). The reaction
factor, RXFACT, is used to demonstrate how the reaction rate in the simulation model can be
varied to match data from an actual plant. For this case, RXFACT is set equal to 1.0,
indicating that the reaction rate has not been adjusted.

MTBE Kinetic Model

The algorithm used for the reactive distillation column model is a Newtonian-based
algorithm. Therefore, in order to accurately model the MTBE reaction in the distillation column,
we need to determine not only the reaction rate of the reaction, but also the temperature and
composition derivatives of the rate. These derivatives may be generated numerically by an
estimation method, or analytically by an expression based on the reaction rate equation.
PRO/II automatically generates numerical estimates for the reaction rate derivatives.
In many cases, this is sufficient. However, certain reactions require the use of more accurate
analytical derivatives that provide better solutions. Reactions requiring these more accutate
analytical derivatives include: reversible reactions, exothermic reactions, and/or reactions
where the equilibrium is sensitive to temperature .
The MTBE reactions fit all three of the reaction types, requiring the use of analytical
derivatives. The reaction rate expression and its analytical derivatives can be easily and
readily entered by the user in the Procedure Data category of input. The MTBE reaction rate
expression used in this simulation model is based on the rate expression described in a paper
by Al-Jarallah. In this case, we will detail how to enter the reaction rate and the associated

90
analytical derivatives for the MTBE reaction.
First, in the Reaction Data category of input, the stoichiometry of the forward reaction
is given (IBTE + MEOH = MTBE). The kinetic data will be provided later on in the Procedure
Data category of input using FORTRAN-like language as the procedure named ALJD.

The reaction rate equation described by Al-Jarallah takes into account the forward and
the reverse reaction. We have modified Al-Jarallah's rate equation for this case to simulate
the effect of catalyst loading on the reaction rate. This was achieved by removing the catalyst
terms from the concentration terms. The modified reaction rate is given by:

C Aa C Bb C Cc / k
rs = k s k A a +b
(1 + K A C A + K B C B )
where:
13
k = surface reaction rate constant = 1.2x10 exp(- 87900/RT) in (gmole/g catalyst)
s
-13
(1a) K = equilibrium adsorption constant = 5.1x10 exp(97500/RT) in g catalyst/gmole
a
-16
(1b) K = equilibrium adsorption constant = 1.6x10 exp(119000/RT) in g catalyst/gmole
C
(1c) K = equilibrium constant
eq
C = IBTE concentration in mole/l
A
C = MEOH concentration in mole/l and C = MTBE concentration in mole/l
B C

Kinetic Data
The procedure data used in the reactive distillation column model is entered in the Kinetic
Procedure data entry window shown below.

91
 Once the column is converged, the top and bottom product compositions are known.
Exchanger (HX-2B) is now simulated for heat exchange between the column feed (see HX-
2A) and the bottom product (stream 7). The duty in this exchanger is set equal to the duty in
exchanger HX-2A. The cooled hot side fluid is the MTBE product (stream8).
Pump P-1 pumps the liquid distillate (stream 6) at a pressure of 827 KPa to the
methanol recovery section.
A calculator (CONVERSION) is set up to compute the conversions of IBTE and MEOH
to MTBE in the reactive distillation column itself.

92
Methanol Recovery
The methanol recovery section of the process is shown in Figure 4.

FIGURE 4. MTBE Distillation and Recovery Section

The methanol-C4s azeotrope (stream 6P) is delivered by pump P-1 to heat exchanger
HX-3 where it is cooled to 38 C against cooling water (CW). The exchanger also calculates
the utility (CW) requirement given a CW delivery temperature of 16 C and a return
temperature of 32 C. The cooled process stream is fed to the bottom of the water wash
column (T-2).
Column T-2 is simulated as a liquid-liquid extractor with 5 theoretical trays.
Recirculating wash water is fed to the top of the column. A top pressure specification of 792
KPa is given. This column uses the VLLE SRK thermodynamic set (SRKM_VLLE) defined
previously in the Thermodynamic Data Category of the input file.
The raffinate leaves the top of the column (stream 11) and contains the unreacted and
non- reactive C4s. The extract phase (stream 12) exits at the bottom. It enters the cold side
(HX4A) of the feed-bottoms heat exchanger where it is warmed to 99 C against the recycle

93
wash water (stream 21) which in turn is cooled (in unit HX-4B described later on).

Valve V-1 drops the pressure of the heated methanol-water stream (13) to 241 KPa
generating a mixed phase stream (14) which is adiabatically flashed in unit D-1. The vapor
phase (stream 15) containing the dissolved hydrocarbons which have been released is vented
as a flare gas; the liquid phase (stream 16) is pumped (P-2) to the methanol column to
recover methanol.
The methanol column (T-3) is simulated with 20 theoretical trays. The feed (stream 17)
enters on tray 10. The column top pressure is 138 KPa; the pressure drop through the column
is 34.5 KPa. A Subcooled, Fixed Temperature condenser type operating at 30 C and 103.5
KPa is specified. The separation of methanol from water is readily solved using the I/O
algorithm and conventional IEG. The performance specifications are 99.5% recovery of
methanol in the overhead product and 99.95% recovery of water in the bottoms product. Tray
rating calculations are done for this column for 610 mm diameter sieve trays throughout the
column.

94
 A calculator (CAL1) computes the total loss of water as a result of carry over with the
C4s (stream 11), the vent gas (stream 15) and by consumption in the reactor. This total
quantity is the amount of make-up water required. The flowrate of the make-up water stream
(MKUP) is established through a procedure call to the PRO/II stream function SRXSTR.

95
 Pump P-4 pumps the recovered wash water from the methanol column bottoms
combined with make-up water as stream 21 to heat exchanger HX4B. This unit represents the
hot side of the exchanger HX-4 (see HX-4A described previously) and calculates the exit
temperature for stream 22.
Trim cooler (HX-5) further cools the wash water (stream 22) to the desired
temperature of 38 C before it (stream 10) goes back to the water wash column. At this stage,
the first recycle loop between unit T-2 (water wash column) and HX-5 (trim cooler) is closed.
The second recycle loop between unit HX-1 (feed heater) and P-3 (recycle pump) is closed
when the pump P-3 recycles the overhead (stream 19) from the top of the methanol column
(T-3) to the reactor section.
Then, as an illustrative example, a rigorous heat exchanger (RC-1) is used to
rigorously rate the methanol column condenser. This rigorous heat exchanger is modeled as
an attached heat exchanger to column T-3. This unit takes as its input the exchanger's
mechanical data such as shell and tube dimensions, tube layout pattern, the baffle cut and
2
shell and tube side nozzle sizes. A fouling factor of 0.00035 m -K/kW is used for the
condenser cooling water side. The ZONES option is selected to determine where phase
changes occur in the exchanger. An extended data sheet is printed in the output.

96
97
 APPENDIX (C)
PROCESS INPUT FILE USED IN PRO/II

98
Appendix (C): Process Input-File used in PRO/II

$ Generated by PRO/II Keyword Generation System <version 8.0>

$ Generated on: Thu Jan 24 01:49:16 2008
TITLE PROJECT=MasterThises, PROBLEM=MTBE PLANT, USER=Fahad Harthi, &
DATE=Dec 2007
PRINT INPUT=ALL, STREAM=ALL, RATE=M, MBALANCE
DIMENSION SI, TEMP=C, PRES=BAR
SEQUENCE DEFINED=CONVERSION,HX-1,RX-1,HX-2A,CAL0,T-1,HX-2B,P-1, &
HX-3,T-2,HX4A,V-1,D-1,P-2,T-3,CAL1,P-4,HX4B,HX-5,P-3,RC-1
COMPONENT DATA
LIBID 1,NC4/2,IC4/3,1BUTENE/4,BTC2/5,BTT2/6,IBTE/7,MTBE/8,MEOH/ &
9,TBA/10,H2O/11,244TM1P,,DIB
THERMODYNAMIC DATA
METHOD SYSTEM=SRKM, SET=S1, DEFAULT
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
METHOD SYSTEM(VLLE)=SRKM, L1KEY=1, L2KEY=10, SET=S2
KVAL(VLE)
SRKM 1,9,0.046973,0.126027,0,0,0,0,1,1
SRKM 3,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 4,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 5,8,0.136,-0.0323,0,0,0,0,1,1
SRKM 6,8,0.135525,-0.032271,0,0,0,0,1,1
SRKM 8,9,-0.073971,-0.055222,0,0,0,0,1,1
SRKM 9,10,-0.145,-0.253,0,0,0,0,1,1
SRKM 7,11,0.05785,-0.0093,-10.144,6.17,0,0,1,1
STREAM DATA
PROPERTY STREAM=1, TEMPERATURE=16, PRESSURE=16.2, PHASE=M, &
COMPOSITION(M,KGM/H)=8,277.5
PROPERTY STREAM=2, TEMPERATURE=16, PRESSURE=16.2, PHASE=M, &
RATE(M)=850, COMPOSITION(M)=1,9/2,41/3,7/4,4/5,6/6,33, &
NORMALIZE
PROPERTY STREAM=10, TEMPERATURE=38, PRESSURE=7.93, PHASE=M, &
COMPOSITION(M,KGM/H)=10,375
PROPERTY STREAM=20, TEMPERATURE=44, PRESSURE=17.24, PHASE=M, &
COMPOSITION(M,KGM/H)=8,4/10,0.3
PROPERTY STREAM=CW, TEMPERATURE=21, PRESSURE=6.9, PHASE=M, &
RATE(LV)=175, COMPOSITION(M)=10,100
PROPERTY STREAM=MKUP, TEMPERATURE=38, PRESSURE=3.5, PHASE=M, &
COMPOSITION(M,KGM/H)=10,500
NAME 1,MEOH FEED/2,OLEFINS/20,MEOH RECYC/MKUP,MKUP WATER/ &
6,T-1 OVHD/8,MTBE/11,C4'S/15,FLARE GAS
RXDATA
RXSET ID=ST1

99
 REACTION ID=1
STOICHIOMETRY 6,-2/11,1
REACTION ID=2
STOICHIOMETRY 6,-1/9,1/10,-1
REACTION ID=3
STOICHIOMETRY 6,-1/7,1/8,-1
RXSET ID=ALJX
REACTION ID=ALJ0
STOICHIOMETRY 6,-1/7,1/8,-1
PROCEDURE DATA
PROCEDURE(KINETIC) ID=ALJD, NAME=MTBE Process
PDATA GCAT,RXFACT
CODE
REAL KS , KA , KC , KALJ , KREH1 , KREH2 , KIZQ , KEQREF
INTEGER IBTE , MEOH , MTBE
$
$ INITIALIZE DATA:
$ SET INDEXES FOR COMPONENTS
$ DEFINE GAS CONSTANT IN JOULES/GM-MOLE K
$ NOTE: R COULD HAVE BEEN RETRIEVED IN INPUT UNITS BY R=RGAS.
$ HOWEVER, SINCE THE REACTION BASIS WON'T CHANGE, AND
$ RGAS WILL CHANGE WITH THE DEFAULT UNITS, THIS
$ ELIMINATES ONE POSSIBLE SOURCE OF ERROR..
$ INITIALIZE THE LOCAL VARIABLE TK TO THE ABSOLUTE TEMPERATURE.
$ NOTE: THE TEMPERATURE BASIS FOR THE FLOWSHET MUST BE CENTIGRADE
$ OR KELVIN.
$ SET TEMPERATURE AND COMPOSITION DERIVATIVES TO ZERO.
$
IBTE = 6
MTBE = 7
MEOH = 8
$
R = 8.314
$
TK = RTABS
$
DO 1000 I1 = 1,NOR
DRDT(I1) = 0.0
DO 1000 I2 = 1,NOC
1000 DRDX(I2,I1) = 0.0
$
$ CALCULATE THE SURFACE REACTION RATE CONSTANT, KS, AND THE
$ EQUILIBRIUM ADSORPTION CONSTANTS KA AND KB. THE ACTIVATION
$ ENERGY IS IN J/GM-MOLE.
$ UNITS: KS - (GM-MOLE / GM CATALYST)**1.5 /HOUR
$ KA - GM-CATALYST / MOLE
$ KC - GM-CATALYST / MOLE
$
KS = 1.2E+13*EXP(-87900.0/(R*TK))
KA = 5.1E-13*EXP( 97500.0/(R*TK))
KC = 1.6E-16*EXP(119000.0/(R*TK))
$

100
 DKSDT = KS * 87900.0 / R / (TK*TK)
DKADT = KA * (-1.0) * 97500.0 / R / (TK*TK)
DKCDT = KC * (-1.0) * 119000.0 / R / (TK*TK)
$
$ ---- CALCULATE THE EQUILIBRIUM CONSTANT.
$
$ UNITS - (GM-MOLES/GM-CATALYST)/HOUR
$ PHASE - LIQUID PHASE REACTION
$ CATALYST - ION EXCHANGE RESIN AMBERLYST 15,
$ THE EQUILIBRIUM SHOULD BE INDEPENDANT OF THE CATALYST
$
$
KALJ = EXP(-17.31715+(7196.776/TK))
$
DKALJDT = - KALJ * 7196.776 / (TK*TK)

$
$ BULK CONCENRATIONS OF COMPONENTS PER GRAM OF CATALYST, XLCONC IS
$ IN MOLES/FLOW VOLUME. XLCONC WILL BE PASSED TO THE PROCEDURE
$ IN USER INPUT UNITS. INTERNALLY TO PRO/II, IT IS IN SI UNITS
$ (KG-MOLE/CUBIC METER). THE BASIS FOR THESE REACTION EQUATIONS
$ IS GM-MOLES/LITER. THE CONVERSION FACTOR FROM INPUT UNITS OF
$ KG-MOLES/CUBIC METER TO THE REACTION BASIS OF GM-MOLES/LITER
$ IS ONE. THEREFORE, XLCONC CAN BE USED WITH NO CONVERSION.
$
$
$ RHOA=(XLCONC(MEOH)/GCAT) |-THIS SHOULD BE EQUIVALENT TO BELOW.
$ RHOB=(XLCONC(IBTE)/GCAT) | IT HAS BEEN WRITTEN EXPLICITLY BELOW
$ RHOC=(XLCONC(MTBE)/GCAT) | TO MAKE IT OBVIOUS HOW TO DO THE
$ ANALYTICAL DERIVATIVES.
$
$ CALCULATE DENSITY IN MOLES / VOLUME
$
GCATX = 12.4
DENS=RLMRAT/RLVRAT
RHOA=(XLIQ(MEOH)*DENS/GCATX)
RHOB=(XLIQ(IBTE)*DENS/GCATX)
RHOC=(XLIQ(MTBE)*DENS/GCATX)

$
$ ---- CALCULATE REACTION RATE AND DERIVATIVES BY TERMS
$ ---- UNITS - RATE - GRAM-MOLE / GRAM CATALYST / HR.
$
$ DENOMINATOR & DERIVATIVES.
$
RDEN = 1.0 + ( KA*RHOA ) + 0.0 + ( KC*RHOC )
DRDDT = RHOA*DKADT + 0.0 + RHOC*DKCDT
DRDDME = KA/GCATX*DENS
DRDDIB = 0.0
DRDDMT = KC/GCATX*DENS
$
$ FIRST FACTOR IN RATE EQUATION.

101
 FACT1 = KS *KA/RDEN
DFAC1DT = DKSDT*KA/RDEN + KS*DKADT/RDEN - KS*KA/RDEN**2 * DRDDT
$
$ SECOND FACTOR IN RATE EQUATION.
FACT2 = RHOA*RHOB**0.5 - RHOC**1.5/KALJ
DFAC2DT = 0.0 + RHOC**1.5/KALJ**2 * DKALJDT
$
$ COMBINE TERMS TO CALCULATE RATE AND DERIVATIVES.
$ -- RATE EQUATION (RATE PER ONE GRAM OF CATALYSIS).
RATE = FACT1 * FACT2
$
$ -- RATE TEMPERATURE DERIVATIVE.
DRDT(1) = DFAC1DT * FACT2 &
+ FACT1 * DFAC2DT

$ -- RATE COMPOSITION DERIVATIVES.

DRDX(MEOH,1) = -KS*KA/RDEN**2 * DRDDME * FACT2 &
+ FACT1 * (RHOB**0.5/GCATX*DENS)
DRDX(IBTE,1) = -KS*KA/RDEN**2 * DRDDIB * FACT2 &
+ FACT1 * (RHOA/2.0/RHOB**0.5/GCATX*DENS)
DRDX(MTBE,1) = -KS*KA/RDEN**2 * DRDDMT * FACT2 &
- FACT1 * (1.5* RHOC**0.5/GCATX/KALJ*DENS)
$
$ ---- CONVERT RATE EQUATION AND DERIVATIVES TO A STRAIGHT VOLUME BASIS
$ ---- BY MULTIPLING THE BASE RATE BY THE GRAMS OF CATALYST/UNIT VOLUME.
$ ---- THE RATE IS RETURNED IN INPUT UNITS, KG-MOLES/CUBIC METER/HOUR.
$
RRATES(1) = GCAT * RXFACT * RATE
$
DRDT(1) = GCAT * RXFACT * DRDT(1)
$
DRDX(MEOH,1) = GCAT * RXFACT * DRDX(MEOH,1)
DRDX(IBTE,1) = GCAT * RXFACT * DRDX(IBTE,1)
DRDX(MTBE,1) = GCAT * RXFACT * DRDX(MTBE,1)

RETURN
UNIT OPERATIONS
CALCULATOR UID=CONVERSION, NAME=CONVERSION OF IBTE-MEOH TO MTBE
RESULT 1,IN - MEOH/2,IN - IBTE/3,IN - MTBE/4,OUT - MEOH/ &
5,OUT - IBTE/6,OUT - MTBE/20,IBTE CONV/21,MEOH CONV
DEFINE P(1) AS STREAM=4, RATE(KGM/H), COMP=8,WET
DEFINE P(2) AS STREAM=4, RATE(KGM/H), COMP=6,WET
DEFINE P(3) AS STREAM=4, RATE(KGM/H), COMP=7,WET
DEFINE P(4) AS STREAM=6, RATE(KGM/H), COMP=8,WET
DEFINE P(5) AS STREAM=6, RATE(KGM/H), COMP=6,WET
DEFINE P(6) AS STREAM=6, RATE(KGM/H), COMP=7,WET
DEFINE P(7) AS STREAM=7, RATE(KGM/H), COMP=8,WET
DEFINE P(8) AS STREAM=7, RATE(KGM/H), COMP=6,WET
DEFINE P(9) AS STREAM=7, RATE(KGM/H), COMP=7,WET
PROCEDURE
$ --- LOAD RATES
R( 1) = P( 1)

102
 R( 2) = P( 2)
R( 3) = P( 3)
R( 4) = P( 4) + P( 7)
R( 5) = P( 5) + P( 8)
R( 6) = P( 6) + P( 9)
$ --- CALCULATE CONVERSION
R(20) = ( R(2) - R(5) ) / R(2)
R(21) = ( R(1) - R(4) ) / R(1)
$ --- DISPLAY RESULTS
DISPLAY R( 1: 9 )
DISPLAY R( 20:21 )
RETURN
HX UID=HX-1, NAME=FEED HEAT
COLD FEED=1,2,20, L=3, DP=0.345
OPER CTEMP=43.5
CONREACTOR UID=RX-1, NAME=REACTORS
FEED 3
PRODUCT L=4
OPERATION ISOTHERMAL, TEMPERATURE=55, DP=0.69
RXCALCULATION MODEL=STOIC
RXSTOIC RXSET=ST1
REACTION 1
BASE COMPONENT=6
CONVERSION 0.0025
REACTION 2
BASE COMPONENT=10
CONVERSION 1
REACTION 3
BASE COMPONENT=8
CONVERSION 0.93
HX UID=HX-2A, NAME=FEED-BTMS-A
COLD FEED=4, L=5, DP=0.345
OPER CTEMP=72
CALCULATOR UID=CAL0, NAME=COPY RXFACT
PROCEDURE
IF (R(2) .NE. 1.0) R(1) = 1.0 $Set RXFACT TO 1 on first call.
R(2) = 1.0
RETURN
COLUMN UID=T-1, NAME=MTBE COLUMN
PARAMETER TRAY=30,CHEMDIST=35
FEED 5,15, SEPARATE
PRODUCT OVHD(M)=6, BTMS(M)=7,280, SUPERSEDE=ON
CONDENSER TYPE=TFIX, PRESSURE=6.21, TEMPERATURE=43.5
DUTY 1,1,,CONDENSER
DUTY 2,30,,SIDEHC2
PSPEC PTOP=6.21, DPCOLUMN=0.765
PRINT COMPOSITION=M, PROPTABLE=ALL
ESTIMATE MODEL=SIMPLE, RRATIO(L)=1.1
SPEC ID=COL1SPEC1, STREAM=7, RATE(KGM/H),TOTAL,WET, VALUE=278
SPEC ID=COL1SPEC2, RRATIO, PHASE=L, VALUE=1.1
DEFINE GCAT AS 360
DEFINE RXFACT AS 1

103
 VARY DNAME=CONDENSER,SIDEHC2
PLOT LOG, XCOMPONENT=6,6/8,8/7,7/1,1
TSIZE SECTION(1)=2,29,VALVE, DMIN=381, FF=80, DPCALC=0
VLLECHECK CHECK=OFF
LVOL 8,5/9,5/10,5/11,5/12,5/13,5
RXTRAY REFERENCE=ALJX, LOCAL=L_ALJX, KPROCEDURE=ALJD, TRAY=8, &
13
RXSET LOCAL=L_ALJX
REACTION ID=ALJ0, COPTION=KINETICS
KINETICS PEXP(C,KG,M3,KPA,HR)
HX UID=HX-2B, NAME=FEED-BTMS-B
HOT FEED=7, L=8, DP=0.345
DEFINE DUTY(KJ/HR) AS HX=HX-2A, DUTY(KJ/HR)
PUMP UID=P-1, NAME=T-1 OVHD
FEED 6
PRODUCT L=6P
OPERATION EFF=65, PRESSURE=8.27
HX UID=HX-3, NAME=COOLER
HOT FEED=6P, L=9, DP=0.345
UTILITY WATER, TIN=16, TEMPERATURE=32
CONFIGURE COUNTER
OPER HTEMP=38
COLUMN UID=T-2, NAME=WATER WASH
PARAMETER TRAY=5,LLEX=25
FEED 9,5/10,1
PRODUCT OVHD(L1,M)=11, BTMS(M)=12,185, SUPERSEDE=ON
PSPEC PTOP=7.92
PRINT PROPTABLE=PART
ESTIMATE MODEL=SIMPLE
METHOD SET=S2
HX UID=HX4A, NAME=FEED-BTMS
COLD FEED=12, L=13, DP=0.345
OPER CTEMP=99
VALVE UID=V-1, NAME=VALVE
FEED 13
PRODUCT M=14
OPERATION PRESSURE=2.41
FLASH UID=D-1, NAME=SEPARATOR
FEED 14
PRODUCT V=15, L=16
ADIABATIC
PUMP UID=P-2, NAME=FEED PUMP
FEED 16
PRODUCT L=17
OPERATION EFF=65, PRESSURE=6.9
COLUMN UID=T-3, NAME=MEOH COLUMN
PARAMETER TRAY=20,IO=10
FEED 17,10
PRODUCT OVHD(M)=19, BTMS(M)=18,182, SUPERSEDE=ON
CONDENSER TYPE=TFIX, PRESSURE=1.035, TEMPERATURE=30
DUTY 1,1,,CONDENSER
DUTY 2,20,,SIDEHC2

104
 PSPEC PTOP=1.38, DPCOLUMN=0.345
PRINT PROPTABLE=PART
ESTIMATE MODEL=CONVENTIONAL, RRATIO=10
SPEC ID=COL3SPEC1, STREAM=19, RATE(KGM/H), COMP=8,WET, DIVIDE, &
STREAM=17, RATE(KGM/H), COMP=8,WET, VALUE=0.995
SPEC ID=COL3SPEC2, STREAM=18, RATE(KGM/H), COMP=10,WET, DIVIDE, &
STREAM=17, RATE(KGM/H), COMP=10,WET, VALUE=0.9995
VARY DNAME=CONDENSER,SIDEHC2
TRATE SECTION(1)=2,19,SIEVE, PASSES=1, DIAMETER(TRAY)=610, &
DIAMETER(SIEVEHOLE,IN)=0.5, WEIR=50.8, DCC=38.1
CALCULATOR UID=CAL1, NAME=MAKEUP
SEQUENCE STREAM=MKUP
DEFINE P(1) AS STREAM=11, RATE(KGM/H), COMP=10,WET
DEFINE P(2) AS STREAM=15, RATE(KGM/H), COMP=10,WET
DEFINE P(3) AS STREAM=19, RATE(KGM/H), COMP=10,WET
PROCEDURE
R(1) = P(1) + P(2) + P(3)
CALL SRXSTR(SMR,R(1),MKUP)
RETURN
PUMP UID=P-4, NAME=WATER PUMP
FEED 18,MKUP
PRODUCT L=21
OPERATION EFF=65, PRESSURE=8.62
HX UID=HX4B, NAME=FEED-BOTS
HOT FEED=21, L=22, DP=0.345
DEFINE DUTY(KJ/HR) AS HX=HX4A, DUTY(KJ/HR)
HX UID=HX-5, NAME=COOLER
HOT FEED=22, L=10, DP=0.345
OPER HTEMP=38
PUMP UID=P-3, NAME=RECYCLE PUMP
FEED 19
PRODUCT L=20
OPERATION EFF=65, PRESSURE=17.24
HXRIG UID=RC-1, NAME=T-3 COND
TYPE TEMA=AES
TUBES FEED=CW, L=WOUT, LENGTH=5.75, OD=19, BWG=14, PASS=2, &
PATTERN=90, PITCH=25.4, FOUL=0.00035, METHOD=S1
SHELL DPUNIT=0.49244, METHOD=S1, ID=381
BAFFLE CUT=0.18
SNOZZLE TYPE=CONV, ID=152,102
TNOZZLE ID=102,102
PRINT EXTENDED, ZONE
ATTACH COLUMN=T-3, TYPE=CONDENSER
RECYCLE DATA
ACCELERATION TYPE=WEGSTEIN
LOOP NUMBER=1, START=T-2, END=HX-5,WEGSTEIN
LOOP NUMBER=2, START=HX-1, END=P-3,WEGSTEIN
CASESTUDY OLDCASE=BASECASE, NEWCASE=CS1
PARAMETER ID=MTBE, COLUMN=T-1, SPEC(1),STEP(ACT)=0, CYCLES =1,1
RESULT ID=RESULT1, STREAM=15,FRACTION, COMP=1,WET
END

105