CHAPTER 2

Literature Survey

14
 CHAPTER 2
Literature Survey

2.1 Introduction to PI

Process Intensification (PI) has led to modify/retrofit the existing technologies for the

purpose of environment, energy and economy (EEE) concerns. Modified

technologies/structures and new design like multifunctional reactors are implemented

with the aim of reducing these EEE concerns in the industry and therefore increase

productivity, selectivity, reduce toxic losses and facilitate separations. Chemical

industries are directed to follow inherently Safer Design Principles (ISD) for clean and

safer throughput.

ISD proposes five design principles (Garcia-Serna et al., 2007)

1) Intensification: Use of minimal amounts of hazardous materials assures that a

major emergency is not created even if all the contents are released. The changes

in the design procedures going from scale up to scale down.

2) Substitution: Use of non- hazardous compounds.

3) Alternative reaction routes: In addition to using safer chemicals, it is possible to

reduce the risk associated with the manufacturing by making changes in the

reaction route.

4) Modify storage arrangements: It has been summarized as, ‘what you don’t have

can’t leak’

5) Energy limitations: Limiting the amount of energy available in the manufacturing

process also limits the possibility of a runaway process in case of failure.

15
Every technology should follow ISD rule to work towards sustainable and safer

processes and meet PI goals.

In recent years, due to increasing awareness of environmental concerns, the existing

routes of synthesis are attempted to be modified in order to achieve emaciated profit

margins. Reactive distillation is one such integrated technology which combines

reaction and separation together in a single unit. It has subjugated over a conventional

reactor and a separation train for various chemical commodities. The popularity of this

technology due to its extra ordinary advantages (Chapter 1) have grown the increasing

interest in attempting newer applications.

2.2 Reactions

Various phenomenal chemical reactions are a history of RD technology. Applications

are from alcohol, petroleum, fragrance, pharmaceuticals, fine chemicals, biochemical

and paint industry etc. A vast number of reactions like esterification, etherification,

transesterification, acetalisation, hydrogenation, dehydrogenation, hydration,

dehydration, alkylation, isomerization etc. were studied in RD (Sharma and Mahajani,

2002 and Hiwale et al., 2004).

Since the RD literature has contributed sufficient inputs to the database of this

technology, we are adhering to only one class of reactions viz esterification reactions

which are applicable to our proposed work. A number of successful esterification

reactions are studied in RD and achieved remarkable attainments in the industry. A

brief review is provided for C1 to C6 alcohols esterification reactions studied.

Esterification: This is the most favorable type of reversible reaction applicable in RD.

Reaction of alcohol with organic acids in presence of a catalyst produces esters. Esters

are having wide application in process industry, as a raw material for production of

16
many chemicals and as solvents in ink, paint, coatings, adhesives, pharma industries,

specialty chemicals, flavoring industries, ink removers, perfumes etc. (Tau et al.,

1994). These equilibrium limited reactions achieved remarkable achievements in

conversion, cost and energy. A range of esters of different alcohols from C1 to C6 are

studied individually in different studies.

Methyl acetate -After the success of methyl acetate synthesis using homogeneous

catalyst in Eastman Kodak process wherein a multi-unit process was replaced by a

single RD column. The potential of RD came into existence and the research continued

for this acetate. Researchers further intensified the process by the use of heterogeneous

catalyst in a RD column. Bessling et al. (1998) performed experimental investigation

and revealed reflux ratio to be an important parameter for achieving maximum

conversion (97%). Later on experimental as well as simulation study was done for

synthesis of this acetate by Popken et al. (2000, 2001). Two different configurations

were studied, a single feed fully reactive column and double feed hybrid column

consisting of reactive and non-reactive stages. Methanol conversion of 97.1% and

purity of methyl acetate 97.5% was achieved in this study. Huss et al. (2003) studied

the same reaction with simulation approach, hierarchy of methods and models were

used for designing a RD column.

Zuo et al. (2014) used two novel acidic ion exchange catalyst NKC-9 and D072 for

the synthesis of methyl acetate in batch experiments. A kinetic model was estimated

and used for simulation study of this ester. The applicability of this catalyst for good

conversion and selectivity for longer exposure time was studied.

Ethyl acetate – Applicability of RD process for the synthesis of this acetate was

investigated by Kenig et al. (2001). A glass column with 80 bubble cap trays with 50

mm diameter and homogeneous catalyst sulfuric acid was used for the study. A

17
maximum conversion of 86% was obtained by varying operational parameters.

Simulation was done with the help of rate based tool DESIGNER and was found to be

in good agreement with the experimental values. Kloker et al. (2004) studied the use

of heterogeneous catalyst and structured packing KATAPAK, MULTIPAK for ethyl

acetate synthesis. Feasible operating conditions, influence of packings and catalytic

internals on conversion and purity were investigated. Calvar et al. (2007) used both

homogeneous and heterogeneous catalysts for the synthesis study. The operational

conditions like feed conditions, reflux ratio and operating pressure were studied to

obtain pure ethyl acetate. Lai et al. (2008) gave emphasis on the initial startup and

hold up in RD column as important factors to obtain highly pure ethyl acetate. A pre-

reactor followed by a RD column was insisted for the synthesis of ethyl acetate by

Smejkal et al. (2009). A heterogeneously catalyzed pilot plant RD study was done by

Fernandez et al. (2013). They studied the transient behavior of the column and

collected the continuous data of the same. Singh et al. (2014) performed industrial

scale studies with use of homogeneous catalyst pTSA and presented actual plant study

of 60 TPD capacity.

Propyl acetate - Brehelin et al. (2007) studied feasibility of RD for the synthesis of n

propyl acetate. Experimental and simulation studies were given emphasis to find the

best possible column configurations, in order to achieve high purity of ethyl acetate.

Addition of stripping section to pilot plant enhanced conversion of reaction and purity

of this ester. The synthesis of isopropyl acetate was studied by Qi and Malone (2011)

using semi batch reactive distillation with a stripper and decanter assembly. Whereas

Lee et al. (2012) proved from the simulation performance that the use of thermally

coupled RD column can drastically reduce the cost due to energy integration.

18
Butyl acetate- Esters of butanol were extensively studied in the literature.

Venimadhavan et al. (1999) studied the synthesis of butyl acetate in a batch reactive

distillation and explored the presence of heterogeneous azeotrope in butanol, butyl

acetate and water. Hanika et al. (1999) proposed a continuous reactive distillation

study and observed that a pre-reactor for heating the reactants before introducing in

the distillation column helps to achieve high conversion of acetic acid. Steinigeweg

and Gmehling (2002) have done the systematic study for the synthesis of n butyl

acetate, right from reaction kinetics, thermodynamic study, experimental RD to

simulation using RADFRAC. Equilibrium stage model was found to fit the

experimental data and was used for further simulation study. n-butanol conversion of

98.5% and n-butyl acetate purity of 96.9% were achieved using equimolar feed.

Further operational parameters were studied by simulation and a prereactor with RD

column was suggested as best process alternative. This reaction was studied in a

continuous RD column by Singh et al. (2005). Various parameter study and

composition profile missing in literature were attempted to optimize the best possible

configurations. The detail study for formation of the side product dibutyl ether, due to

excess of butanol was reported. This study revealed the conversion close to 100% and

selectivity 99% with acid free pure butyl acetate in the bottom stream. Effect of various

operational parameters were studied and found the reaction to be equilibrium

controlled. He et al. (2010) studied the synthesis of butyl acetate by trans esterification

of methyl acetate with butanol. Different gauze packing and cation exchange resin

NKC_9 as catalyst were used. Different operational parameters were studied and a

steady state non equilibrium stage model was found to be accurate and reliable for

further simulation studies. Tian et al. (2012) performed n-butyl acetate synthesis

studies by experimental and simulation method. Equilibrium stage model was found

19
to fit the data well. Variation in operational parameters led to n- butanol conversion

and n –butyl acetate purity to reach above 96%.

Amyl acetate- Reaction of acetic acid from the aqueous stream containing 30%

aqueous acetic acid solution with higher alcohols such as butanol and amyl alcohol for

the recovery were studied in a RD column by Saha et al. (2000). The study of different

operational parameters and column configurations were done to yield 58% conversion

of acetic acid. Chiang et al. (2002) has performed a comparative study between reactor

+ column assembly and a RD column for esterification reaction and found the RD

column to be efficient. Saha et al. (2005) studied reaction of isoamyl alcohol with

acetic acid in catalytic distillation column. Batch mode experimentation revealed only

18.2 % conversion for aqueous acetic acid whereas the same reaction in RD mode

increased the conversion level to 69.5%. Lee et al. (2009) studied reaction of acetic

acid with a mixture of butanol and amyl alcohol in RD. Two process alternatives were

attempted, separation of mixture into pure alcohols first and then esterification in RD

column and second method of esterification of alcohol mixture in RD column first and

then separation into pure esters. Out of these two methods, first method was found to

be more economical.

Hexyl acetate – It was synthesized in lab scale, semi industrial scale and with different

catalytic packings. The detail kinetic, phase equilibrium and simulation studies were

done. Predicted results from simulation using the stage model ensured the feasibility

of reaction in RD column. Extension of the same work was done in pilot plant studies

with modified column internals. The simulation study was found to be in good

agreement with the experimental study. RD experiments revealed the presence of

byproducts, 1-hexene and dihexyl ether (Schmitt et al., 2004 and 2005). Later on, the

same reaction was studied in a D + R tray which is claimed to be the novel laboratory

20
equipment which facilitates fast and flexible investigation of heterogeneously

catalyzed RD processes. High conversion and purity could be achieved with the help

of this configuration (Von Harbou et.al. 2011).

Mix alcohol - Certain industries are facing problem of alcohol separation from its

waste stream, especially waste of fermentation processes which contains C2-C5

alcohol mixture. This mixture, popularly known as fusel oil is of potential use to

industry when obtained in its pure form or in the form of its acetates. An effort was

done to study this mixture in RD column. A complete set of kinetic data was developed

using Amberlyst 15 as a catalyst and the vapor liquid equilibrium data was collected

from literature and some required data was generated from experiments. The mixture

of alcohols is reacted with acetic acid in the laboratory RD column. Simulation studies

were performed to obtain the best alternatives for the esterification reaction. Cost-

effective alternatives were suggested based on energy consumption (Patidar and

Mahajani 2012, 2013)

2.3 RD & PI

The broad classification of PI factors for RD are as follows 1) based on unexplored

reaction study 2) Structural modification of RD column 3) Applying various strategies

like vacuum/ membrane/ microwave/side stream/entrainer etc. A chart for the same is

given in Figure 2.1.

21
 Reactive Distillation and
Process Intensification
(RD &PI)

Unexplored
reaction

Column Structures Operational

Auxiliary inventory/
Parameters addition of chemicals

Side stream Entrainer

Petlyuk Divided Feed Position Reboiler addition
duty
HIGEE /HIDiC
Micro wave Miscellaneous
heating /column
Input flow rate Reflux ratio internal

Catalyst loading No. of stages

Conversion/Selectivity/Energy/ Cost

Figure 2.1 Flow Chart of Reactive Distillation and PI factors

22
2.3.1 Unexplored reactions

Although every reaction is not possible in RD, many are attempted and then gradually

intensified with the use of above stated PI factors. The basic identification of any

reaction to be applicable to RD requires the detail study of kinetics, thermodynamics

and conceptual design study of the system components. Literature witnesses these

studies since 1990 and exploring applicability of new candidates in RD is ceaseless.

However, the general trend is to perform kinetic and vapor liquid equilibrium (VLE)

experiments and utilize this data to perform the RD study with the help of simulators.

The column considered for exploring new reactions is either a continuous RD or batch

RD column.

2.3.2 Structural modification

Intensification has led to develop many structural modifications for reaction and

separation assembly. Some of the major modifications addressed are heat-integrated

distillation column (HIDiC), petlyuk column, divided wall column, HIGEE column

etc. Olujic et al. (2009) have compiled recent improvements in distillation equipments

and reported some of the above mentioned equipments in the article.

i) HIDic column:

In this configuration, heat required to evaporate the liquid in the stripping section is

obtained from the rectifying section. The latent heat released due to condensation of

vapors in rectifying section is utilized to heat the liquid in stripping section, thereby

decreasing the heat load on reboiler and reducing the total energy demand of the

process. This type of clubbing has reduced the energy demand drastically for certain

system study. In case of benzene toluene separation, benefit of this heat integration

23
has reduced the energy demand by 60 % as compared to the conventional distillation

(Nakaiwa et al., 1997). A review article on HIDiC discusses the advantages and future

prospects related to this type of structural modification (Nakaiwa et al., 2003; Kiss

and Olujic, 2014). Further modifications were done by placing a reactive section in

HIDIC column to check its feasibility for reactive systems. The synthesis of high

purity ethyl acetate by this strategy helped in significant reduction of capital cost,

operating cost and 20% energy savings as compared to the conventional RD system

(Mali and Jana, 2009).

A typical structure of HIDiC column is shown in Figure 2.2 where heat is transferred

from rectifying section to stripping section and decreases the energy requirement of

the whole process. The stripping section may/may not contain the reactive section. If

the reactive section is not present, then only separation takes place and if the reactive

section is present then reactive distillation takes place and equipment is noted as r-

HIDiC. Pulido et al. (2011) reported simulation study for TAME synthesis in reactive

HIDiC column. The reaction took place in the stripping section and the heat transfer

from the rectifying section reduced the power consumption required by the reboiler.

Total energy reduction was found to be 8% less when compared to conventional RD

column. Wang et al. (2011) performed the control study over this column for

transesterification reaction of methyl acetate and n-butanol. Simulation results

indicated thermally coupled processes to be more energy efficient than conventional

columns. This concentric structure provided the best energy efficiency.

24
 Figure 2.2 Schematic of r-HIDiC. Pulido et al. (2011)

A K Jana (2016) proposed a new divided wall heat integrated distillation column for

a batch process. In this the cylindrical shell is divided by a metal wall into two semi

cylinders. The divided wall, transfers the heat from high pressure side to low pressure

side of the column. This configuration was claimed to be simpler than traditional

HIDiC.

ii) Petlyuk and Divided wall column:

Typical thermally coupled columns are shown in Figure 2.3. Petlyuk column consist

of two columns, a prefractionator along with a conventional column with only one

reboiler and a condenser. The integration of two columns had led to minimize the

energy significantly. However, a slight modification in this structure with the removal

of prefractionator and inserting a vertical wall inside the column, separating the feed

25
from the products and thus dividing the whole section of the column is called as

divided wall column (DWC).

a) b)

Figure 2.3 Thermally coupled columns a) Petlyuk column b) Divided wall

Column Kiss et al. (2009)

In both the structures the middle boiling component is removed from the middle of

the column. However DWC has an advantage over petlyuk column of separating three

or more components in a single column. Brugma (1937) laid the fundamentals of what

is popularly known as thermally coupled distillation columns today. However the

credit of recognition of its energy potential, goes to Felix Petlyuk, who along with his

co-workers published a paper that happened to be a milestone in the development of

this technology (Petlyuk 1965). A dividing wall column (DWC) is the most daring

variation of the so-called Petlyuk column. These thermally coupled distillation

columns and their design were addressed by Christiansen et al. (1997). The practical

26
implementation of DWC was made by BASF in 1985 for separating three component

system into almost pure components (Olujic et al., 2009). Sander et al. (2007) reported

the methyl acetate hydrolysis in reactive DWC- one experiment each in mini plant at

BASF and in industrial scale at Sulzer Chemtech. The first reported industrial

application of reactive DWC/ RDWC was studied to find 35% savings in the capital

cost and 15% savings in energy cost as compared to conventional column (Kiss et al.,

2009). In the last decade, researchers have initiated work on this structure. Many of

them have done simulations and control studies (Mueller and Kenig, 2007; Gomez-

Castro et al., 2008; Wang et al., 2008; Salvodar et al., 2009, 2010) for proving the

energy efficiency of this technology. However, the experimental data is very rare for

the same in the open literature. One more attempt for experimentation in a reactive

divided wall column was done by performing esterification of ethanol with acetic acid.

The experimental and simulation studies were comparable (Delgado et al., 2012). An

exclusive work was presented by Ehlers et al. (2017) on comparison of experimental

and simulation work for a complex reaction with non-negligible side reactions in

RDWC. The reaction was transesterification of n-butyl acetate with n hexanol forming

n butanol and hexyl acetate. An experiment for reactive as well as non-reactive DWC

with the same experimental set up and same reaction study was performed. The results

from this work claimed to be a good basis for doing steady state design of reactive

DWC.

iii) HIGEE technology

This integrated structure consists of a cylindrical column with rotating packed bed

inside it. Gas flows inside the column and passes through the packings and comes out

from the center of the rotor. Liquid is introduced in the middle hub of the rotor where,

27
it flows in thin film over the packing due to high centrifugal force developed. This

raises the liquid mass transfer coefficient and hence the separation is achieved.

Schematic of HIGEE unit is shown in Figure 2.4.

Figure 2.4 Schematic of HIGEE unit (Nascimento et al., 2009)

This concept was first developed by Ramshaw et al. (1981). The volume of this

column is 2-3 order less than the conventional column (Rao et al., 2004). The

centrifugal force developed in this structure is 1000 times greater than gravitational

force in the packed bed, due to this enhanced driving force, as compared to that in

packed column, we could achieve enriched throughput and mass transfer efficiency.

Some of the advantages of HIGEE are: i) lower liquid hold up ii) high vapor and liquid

flows iii) quick achievement of steady state iv) ability to process dangerous operation

v) ability to process lower inventories of corrosive, toxic or inflammable material vi)

reduced risk of fire or explosion vii) convenient synthesis of heat sensitive materials.

28
A detail study for finding the effect of rotational speed on the mass transfer coefficient

was done by Nascimento et al. (2009). Application of this technology was efficiently

used in the synthesis of petroleum sulfonate surfactant (Zhang et al., 2010). Recently,

D P Rao (2015) has compiled an article specifically on HIGEE technology covering

all the required aspects and revolutions in the appearance and performance of this

equipment.

All the above mentioned structural modifications proved to be beneficial in terms of

energy reduction, cost reduction, miniaturization of column, efficient gas-liquid

contact, net decrease in volume etc. Continuous efforts are made to attempt different

reactions and achieve the PI ends.

2.3.3 Adding auxiliary inventories / chemical solvents.

Though the traditional reactive distillation is undoubtedly booming, many ancillary

aids are clubbed to improve the process outputs. Some of them are side

stream/vacuum/membrane/ entrainer/ microwave heating etc.

i) Side draw

To enhance the product purity and reduce undesired downstream separation of

components, various strategies were implemented. Side draw is one such strategy to

enhance the product purity. In some reactions where the product is, as compared to

other components, of intermediate volatility may give rise to, unfavorable conditions

in the RD column. In these circumstances, effective removal of product is necessary.

Hence removal of such product from side draws rather than usual top/bottom ends

enhances the conversion and selectivity drastically. In case of lactic acid esterification

with methanol, implementation of side draw enhanced conversion and reduced the

29
ester hydrolysis which would otherwise polymerise and affect the thermal stability of

the column (Thotla and Mahajani, 2009). In an industrial example for the production

of dimethyl ether, the conventional method was energy and cost intensive. Methanol

being one of the reactants was used in excess and the conversion achieved was only

50 % in this reaction. Implementation of reactive divided wall column with side stream

for methanol removal in the middle of the column decreased operation cost and energy

requirement (Kiss et al., 2013). In synthesis of isopropyl acetate, conventional RD

system could not make proper separation of acetate and water due to the presence of

ternary azeotrope. Water is therefore carried in an organic reflux thereby demanding

more energy and hence an entrainer is added and azeotrope thus formed with water is

removed from the middle of column by side draw. Such a policy has helped to reduce

energy requirement of the process by 27.5% (Zhang et al., 2013). Recently conceptual

design algorithm was developed for the complex system with a single and multi-side

draw in the reactive distillation (Hasan et al., 2014 and 2015).

ii) Vacuum

It is generally applied in case of high boiling components to decrease the boiling point

of components and vaporize them at low temperatures, or to avoid some side reactions

that may occur at high temperatures. In case of production of cyclohexanol a two-step

process is involved, viz hydrogenation of benzene to cyclohexane and then oxidation

by air to form cyclohexanol. This synthesis method involves a large amount of energy

and a high risk of operation. Steyer et al. (2008) and Kumar et al. (2011) proposed a

novel process which includes esterification of cyclohexene with formic acid a reactive

entrainer to obtain cyclohexyl formate in the first RD column and then hydrolysis of

cyclohexyl formate to obtain cyclohexanol in the second RD column. In order to avoid

decomposition of formic acid experiments were carried out at a reduced pressure.

30
Operating the column at reduced pressure avoids the formation of side product. The

conversion achieved by this method was found to be 90% of cyclohexene. The use of

reactive entrainer formic acid with indirect hydration method in RD overcame all the

disadvantages of this reaction. This method exhibited good results, made reaction rates

fast, required less amount of catalyst, formed negligible amount of side products and

exhibited good productivity. Wei et al. (2012) has proposed a novel method of

entrainer intensified vacuum reactive distillation to separate 5HMF from the

dehydrated solution of carbohydrates. The reaction is catalyzed by metal chloride ionic

liquid catalyst and nitrogen while other organic vapors are added as entrainers. The

reaction is carried under vacuum to accelerate the evaporation of 5 HMF. The furfural

is unstable at 150 ºC and 180 ºC. However addition of ionic liquid decreases its

degradation by 5% for heating less than 30 minutes. The addition of nitrogen as an

entrainer recovered up to 95.5% and 94.7% of HMF in 30 minutes at 150 ºC and in 10

minutes at 180 ºC respectively. The recovery of 5HMF from fructose and glucose

were around 93% and 88% respectively.

iii) Microwave heating

This is one more mode of an intensification implemented for achieving the PI

objectives. An application of this technology was made earlier by chemists and

physicists but engineering aspect of this methodology was missing in literature. In

case of microwave heating the interaction of electromagnetic waves with components,

catalyst, and column material should be considered. Properties related to electric field

of the electromagnetic spectra (complex permittivity) and those related to the magnetic

field (complex permeability) are considered. In the RD study, magnetic field is not

involved and hence only the complex permittivity is considered which depends upon

the temperature and frequency. It is directly related to a dielectric loss which is the
31
ability of material to absorb microwave and dissipate heat. Applying microwave

heating for propyl propionate synthesis, no significant effect on conversion was

observed. This is mainly due to the reason that microwave reached to the bulk phase

of liquid before they interacted with zeolite catalyst (Altman et al., 2010). Micro wave

assisted evaporation of pure components take place due to super heating of liquid

phase, and boiling of liquid phase is related to the dielectric property of the

components. The extent of superheating depends upon the shape of microwave

equipment, microwave field strength and power. No significant change in the

conversion and selectivity was observed for transesterification reaction of DMC with

ethanol in the RD study (Werth et al., 2015). However in case of ethyl acetate

production, this technology proved to be beneficial (Ding et al., 2016). In general,

application of microwave is not successful in each case, but it depends on various

factors such as, dielectric property of components, shape of the microwave equipment,

strength and power of electric field and ability of microwave to reach the catalyst

surface.

iv) Membrane assisted RD

The fundamental reason behind clubbing the membrane with RD is to separate one

component easily from the reaction and favor forward reaction. The sole purpose of it

is to reduce the energy requirement, enhance the product purity, increase conversion

and selectivity with the aid of hybrid configurations in one column instead of

employing a junky multi- unit system. The use of membrane for selective separation

is not new, types of membrane in use for the separation are hydrophilic and organo

philic in operations. They are mostly used in case of systems where azeotropes are

formed, typically where water is forms an azeotrope with one of the components or

where solvents have to be recovered from waste streams. Membranes are usually
32
located in the distillate section or sometimes placed in the decanter for effective

removal of water/ organic solvents. The combination of this hybrid configuration can

be traced back for the production of MTBE, ETBE in 1990’s (Matouq et al., 1994 and

Yang and Goto, 1997). An example of placing zeolite membrane in distillate section

was in the synthesis of tert amyl ethyl ether where water forms azeotrope with

components of the reaction mixture bringing down the conversion. Applying this

hybrid configuration of RD + membrane led efficient removal of water (99.9 %) in

permeate and hiked the yield of reaction by 10% (Aiouache et al., 2003). An

investigation of a reactive hybrid process concept in the transesterification of methyl

acetate and butanol to butyl acetate and methanol by the combination of reactive

distillation and pervaporation, is examined by Steinigeweg and Gmehling (2004). Liu

et al. (2005) reported the use of poly membrane for the separation of organic

compounds from the aqueous stream in case of butyl acetate esterification reaction.

The heterogeneously catalyzed esterification of propionic acid with 1-propanol to n-

propyl propionate and water in presence of hydrophilic membrane in the distillate is

investigated by Buchaly et al. (2007).The selective separation using commercial

membranes for methanol-nbutyl acetate mixture by pervaporation is reported by Luis

et al. (2013). Recently the production of dimethyl carbonate and propylene glycol from

the transesterification of propylene carbonate using a membrane was reported wherein

the equilibrium limitation and the presence of azeotrope between methanol - DMC

made the process to be energy intensive. The introduction of a membrane intensifies

the process outputs significantly (Holtbruegge et al., 2014).

v) Double reactive section

In certain reactions like consecutive parallel reactions such as reaction of adipic acid

and glutaric acid, we cannot achieve high conversion and selectivity in a RD column
33
with single reactive sections. A column with a double reactive section increases the

effective exposure of the catalyst surface and thereby enhances the conversion for such

reactions. Hence a novel configuration of the RD column with double reactive section

was proposed for such reactions. The reactive sections are generally placed at the top

and bottom of the column. Yu et al. (2014) studied this type of column for two

examples, one hypothetical and the other of transesterification of dimethyl carbonate

with ethanol. The comparative study of single reactive section and double reactive

section for these reactions proved this novel configuration to be beneficial. Additional

degree of freedom and synergy of mass integration and energy integration in sections

proved double reactive section to be superior to the single reactive section. Similar

observation was made by Chen et al., 2016 in the esterification of lactic acid with

methanol and palmitic acid with isopropanol. The double reactive section with feed

splitting and external recycle strategy was successful for the separation of components

having exceptional relative volatility order.

Various clubbing and modification in RD have hiked numerous applications

and is a part of this matured technology. Addition of entrainer is yet another method

for intensifying the conventional RD system. The current research work also uses this

method of intensification and hence is discussed below in detail.

2.4 Entrainer enhanced RD

The formation of azeotrope in the reaction mixture leads to complex situations in

separation of these components. Maintaining purity of product streams in RD becomes

challenging in these cases. The addition of mass separating agent for the separation of

components of such reaction mixtures has proven to be efficient method since last two

34
decades. While applying a mass transfer agent/entrainer, certain rules are defined for

achieving the desired separation tasks.

Rules/heuristics for entrainer selection in case of alcohol forming azeotrope with water

(de Jong et al. 2010) are as follows.

 Increase the relative volatility of water compared to alcohol, such that water can be

removed over the top.

 Have an immiscibility region with water, such that the distillate can be separated in

two immiscible liquid phases by decanting.

 Have a low solubility of the entrainer in water, such that no further purification is

necessary.

 Have a low solubility of water in the entrainer, such that the entrainer can be used

as a recycle.

 Should be acceptable as impurity in products

Though screening of suitable entrainer is more important, the phase equilibrium

behavior study of the system with the addition of entrainer is required for minimizing

energy and maintaining purity of the products in the process. Accordingly the entrainer

should i) form a minimum boiling heterogeneous azeotrope with alcohol among the

system components ii) carry more amount of water with it such that no water remains

in the reactive section of the RD column. A varied list of entrainers is proposed

suitable for water removal and is presented in Table 2.1

35
 Table 2.1 List of entrainers for water removal (Kurum et al. 1995)

mutual solubility (25

℃)
x
Tb,azeo
Component Tb (℃) H2O,azeo organic in
(℃) H2O in H2O
(wt %)
organic
(% mol)

diethyl ether 34.5 1.26 34.15 5.22 1.55

methylene chloride 43.5 1.5 38.1 0.784 0.417

Methyl tert-butyl ether 55 4 52.6 6.7a 1.05

methyl acetate 57.1 2.6 55.8 34.6 7.65

Chloroform 61 2.8 56.1 0.586 0.119

Hexane 68.7 5.6 61.6 0.06 2.8 × 10-4

diisopropyl ether 69 4.5 62.2 4.37a 0.16

vinyl acetate 72.7 7.3 66 4.96a 0.16

tetra chloromethaneb 76.75 4.1 66 0.0801 0.0092

ethyl acetate 77.15 8.47 70.38 13a 1.7

methyl ethyl ketone 79.6 11.3 73.4 34.2 7.63

Benzene 80 8.83 69.25 0.3 0.045

Cyclohexaneb 80.8 8.4 69.5 0.058 1.2 × 10-3

propyl formate 80.9 2.3 71.6 5.8 0.553

ethylene dichloride 82.3 8.2 71.6 0.784 0.159

tri chloroethylene 86.2 7.02 73.4 0.055

isopropyl acetate 90.8 10.6 76.6 11.3 0.395

Heptaneb 98.4 12.9 79.2 7.03 5 × 10-3

36
 Table Continued

Dioxane 101.3 17.6 89.8

n-propyl acetate 101.6 14 82.4 8.35 0.33

methyl propyl ketone 101.7 19.5 83.3 14.7 1.2

diethyl ketone 102 14 82.9 7.59 1.05

Tolueneb 110.7 13.5 84.1 0.237 0.0106

methyl isobutyl ketone 115.8 24.3 87.9 10 0.343

butyl alcohol 117.4 42.5 92.7 51.2 1.92

n-butyl acetate 125 28.7 90.2 10 0.1

Octane 125.75 25.5 89.6 0.081 1.1 × 10-5

4-methyl,2-pentanol 131.8 43.3 94.3 23.5 0.286

ethyl benzene 136.2 33 92 0.252 2.8 × 10-3

isoamyl acetate 142 36.3 93.8

butyl ether 142.6 33 92.9

b-forms azeotrope with acetic acid

Brief Review
Literature studies have reported many examples of entrainer enhanced reactive

distillation, most of them are for water and are compiled below

Dimian et al. (2004) discussed that an elegant separation of water in a distillate phase

can be achieved by the use of an entrainer for higher boiling esters. The reaction

considered was the esterification of lauric acid with n propanol in presence of

sulphated zirconia to give n propyl laurate and water as end products. The

conventional reactive distillation faced two key problems: 1) homogeneous organic

phase due to alcohol-water azeotrope 2) presence of water in the reactive section. The

37
boiling temperature order for the reaction components are ester > acid > water >

alcohol. Ester being of high temperature, column has to be operated under vacuum.

The addition of suitable entrainer would suppress the formation of homo azeotrope

and form hetero azeotrope with water. Since propyl acetate is one of the byproduct of

the reaction, it was selected as a suitable entrainer for this reaction. The addition of

entrainer overcame the limitations of the reaction and improved the process

remarkably. Water was efficiently removed from the reactive section and alcohol

concentration increased thereby enhancing the reaction rate and hence the conversion.

The catalyst loading was found to be reduced to nearly 50 %, while an optimum

entrainer /reactant ratio was found to be 1.3 and the limits of entrainer ratio was

defined for an efficient separation.

Thotla et al. (2009) studied the esterification reaction of ethylene glycol with acetic

acid, a two-step reaction with formation of monoester and diester. Amberlyst 36 was

used as a catalyst and ethylene dichloride (EDC) as a suitable entrainer in this reaction.

The role of entrainer in this reaction system is to enhance conversion and improve

selectivity towards diacetate at stoichiometric ratio of reactants. The selection of

entrainer was based upon the reaction temperature, azeotrope temperature and mutual

solubility of heterogeneous azeotrope components. The selected entrainer is very low

soluble in water and hence a complete entrainer recycle is possible. Two types of

studies were performed, a semi batch reactive distillation and a continuous RD. The

addition of entrainer in both the cases gave encouraging results and helped to bring

down the temperature of the reactive section. Also, the addition of entrainer prevents

acetic acid loss from the aqueous phase of distillate. An introduction of a reflux split

exhibited improved performance of the continuous reactive distillation process. Thus

38
by both the type of column study, the purpose of adding entrainer was useful for this

reaction.

de Jong et al. (2010) reported two entrainers, cyclohexane and isopropyl acetate for

the isopropanol-water separation. They claimed that the principles of azeotropic

distillation can be applied for the entrainer based reactive distillation. The simulation

studies for esterification reaction of myristic acid with n-propanol and isopropanol

were studied with cyclohexane and isopropyl acetate as an entrainer. Cyclohexane

revealed an absence of water in an organic phase but the presence of alcohol and

entrainer in aqueous phase. When isopropyl acetate was used, aqueous phase was pure

but the organic phase contained a significant amount of water. Simulation results

indicated that both the entrainers can be utilized for achieving 99% conversion in a

single RD column for the case of n propanol esterification. Among the two entrainers

cyclohexane can be preferred due to its non-polar nature. However, they found that

the entrainer based reactive distillation was strongly influenced by kinetics of the

reaction.

Hasabnis and Mahajani (2010) studied the entrainer enhanced esterification of

glycerol with acetic acid. This series –parallel reaction led to the formation of mono,

di, and triesters as the products. Triacetin being the desired product for this study, due

to reaction constraint, conventional studies reported limited selectivity and conversion

for this reaction. The use of EDC as an entrainer resolves this problem and also

maintains the temperature of the column within the thermal stability limit of the

catalyst. Experiments with the semi-batch reactive distillation were performed to

assess the feasibility of RD. Various parametric studies revealed EDC as a suitable

entrainer for continuous reactive distillation of this reaction. High concentration of

diacetin and acetic acid in reactive zone, efficient water removal and high temperature
39
were desired factors for high triacetin selectivity. The reflux split introduction was

found to be effective for obtaining 100% selectivity towards triacetin.

Wang and Huang (2011) reported esterification reaction for the synthesis of butyl

cellosolve acetate from butyl cellosolve and acetic acid in RD column. The pinch

between acetic acid and water led to losses of acetic acid in aqueous phase and

consumed more energy. The entrainer enhanced RD was studied for the economic as

well as energy concerns for this reaction. Three entrainers- cyclohexane, toluene and

octane were selected for the simulation studies and based on mutual solubility of

entrainers in both the phases, total annual cost and minimum energy required for

synthesis, octane was proposed to be the suitable entrainer.

Hu et al. (2011) have explored the entrainer enhanced synthesis of ethyl acetate by the

reactive distillation. The azeotrope between ethyl acetate and water is heterogeneous

in nature but the immiscibility region formed is not sufficient to carry all the water

produced in the reaction to the distillate. Water thus remains in the reaction, decreasing

the product formation and results in high reflux ratio thereby consuming excess

amount of energy. Overall, this process seems to be energy intensive in the

conventional RD system. To overcome this difficulty entrainer-butyl acetate was

added to the process. The azeotrope thus formed was removed from the middle of the

column where maximum percentile of water can be fetched instead of usual top of the

column. Butyl acetate carries 5.18 times water than ethyl acetate. Hence, 32% energy

savings are possible as compared to the conventional RD process.

Patidar & Mahajani (2012) reported an esterification of 2 ethyl-hexanol with acetic

acid in RD column. The conventional method used pTSA homogeneous catalyst for

synthesis. The required kinetics was not available in literature and experiments were

40
performed to generate data. The process was intensified by the use of Amberlyst 15

catalyst and toluene as an entrainer. Addition of toluene led to maintain the reaction

temperature and ensured the complete water removal from the reactive section. The

addition of entrainer confirmed energy savings and decrement in cost as compared to

the conventional route of synthesis.

Hasabnis and Mahajani (2014) described an acetalisation of glycerol with

formaldehyde in the RD column. In direct acetalisation route of synthesis,

formaldehyde which is one of the reactants and unstable in nature is available in form

of an aqueous solution. Hence presence of water in the reaction is excess and in such

a case removal of water becomes vital to proceed the reaction in forward direction.

Toluene entrainer is added to the reaction system for effective water removal. Effect

of toluene on conversion was studied for this reaction. A comparison on the basis of

energy consumed proved the direct acetalisation of glycerol in RD with toluene

entrainer to be superior to conventional method of synthesis.

Cho et al. (2014) explored the reaction of butyl acetate synthesis in RD system. In an

esterification of butanol with acetic acid, butyl acetate as the product of the reaction is

forming azeotrope with water and also acts as an entrainer for this reaction. However

the reaction yield was poor due to the reaction constraint. This reaction was studied

by the novel approach of using extraneous entrainer cyclohexane to enhance the

conversion. An addition of cyclohexane entrainer proved to be beneficial over the

internal entrainer system in terms of energy and capital cost.

41
2.5 Findings from literature survey

After overviewing the literature available on the RD technology we find various

intensification factors right from exploring new reactions, structural modifications,

adding auxiliary aids like solvents, heating media, membrane etc. playing an

important role in the process improvement. An entrainer addition has proved as a boon

to the conventional RD systems. They are mostly added to esterification reactions in

which water is one of the products and forms azeotrope with reactants or desired

products creating separation barriers leading to impure product phases in usual

process. Heterogeneous azeotropes can make the separation easy without the need of

external mass transfer agent whereas the system with the presence of homogeneous

azeotrope needs a suitable entrainer to surpass the thermodynamic limitations of the

system.

If water forms binary heterogeneous azeotrope with reactants then the separation

becomes easier provided that the azeotrope is minimum boiling and carries more

amount of water with it. If a minimum boiling ternary azeotrope is formed between

water-reactant-ester then there may/may not be the possibility of ester loss in the

aqueous phase. An ester loss is undesirable and therefore some different strategy has

to be implemented for maintaining the purity in RD. If a pinch is present between the

reactant and water then in such a situations a loss of reactant is sure in aqueous phase.

Under all circumstances it is advantageous to have minimum boiling heterogeneous

azeotrope of water with alcohol or else an entrainer has to be added to ease separation.

The probability of ratio of reactants and products in the column and the presence of

azeotrope depends upon the kinetics of reaction and thermodynamic behavior of the

system. The separation strategy for each system is clearly dependent on the detail

study of system components and the rate of reaction. Still many reactions form
42
complex systems and yet not been attempted in the open literature. Hence, the detail

study from kinetics, thermodynamics to the successful continuous RD runs have to be

attempted to understand the benefits of this technology. Overall conclusion drawn

from the literature suggests that an addition of entrainer surpasses the thermodynamic

limitations of the system and maintains thermal stability of the column besides

increasing the conversion and selectivity of the desired product in comparison with

the conventional RD system.

2.6 Scope of research

Among a vast number of esterification reactions studied till date in RD, there are

certain complex azeotropic reactions which are not attempted in the open literature

and are still under blanket. Certain acetates still follow the traditional method of

synthesis instigating more cost and energy. Methoxy propyl acetate is one such

product which is not studied with this perspective. This fact motivated us to

systematically study this esterification reaction in the RD technology. This ester is a

high boiler and the alcohol forms a homogeneous azeotrope with water. The step wise

procedure is followed in the subsequent chapters, required for the study of reactive

distillation and process intensification. The proposed methodology in this work would

benefit the industry and trigger energy savings and cost savings exceedingly.

43
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