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Award Winning Technology for an

Industrial Solvent

Mike Ashley
Award Winning Technology for an Industrial Solvent
Successful development of vapour phase ester hydrogenation, prompted the concept of using
this equilibrium reaction in reverse to manufacture esters by alcohol dehydrogenation.
Production of ethyl acetate from ethanol was an obvious candidate and the concept was
quickly demonstrated. Improved catalysts indicated an economically feasible route and
fundamental chemical engineering research was conducted to investigate reaction kinetics,
fluid flow and transfer processes. The process was scaled up from the laboratory via “mini-
plants” without recourse to conventional pilot plant operations. Scale factors for unit
operations varied from 80,000 up to 170,000. The first commercial plant was successfully
started-up in May 2001 since when interest has been shown by companies with access to
fermentation ethanol derived from sustainable resources.

The basic flowsheet for this novel process is shown below.


Hydrogen

Ethyl
Acetate
Product
Feed
Ethanol

Recycle Ethanol

Ethanol Dehydrogenation Selective Refining


Dehydration Hydrogenation

The process is in three sections; reaction, product recovery and ethanol dehydration.

Reaction

Dry ethanol is heated and vaporised before entering the dehydrogenation reactor where it is
converted to ethyl acetate. The reaction is endothermic and the vapour is reheated several
times in the reactor to maintain reaction temperature. Crude liquid product is separated from
the cooled reactor outlet stream and the overhead vapour stream, containing mainly
hydrogen, is scrubbed with part of the ethanol feed to recover organics before the major
portion is exported. Liquid product and a small quantity of hydrogen are fed to a trickle bed
reactor, where the carbonyl impurities are hydrogenated to alcohols.

Product Recovery

The stream leaving the hydrogenation reactor contains mainly ethyl acetate, unreacted
ethanol and small quantities of water. This is fed to two columns using a pressure change to
remove the azeotrope composition. Unreacted ethanol is separated for recycle and a crude
ethyl acetate stream is then further distilled to remove trace impurities.

Ethanol Dehydration

In the reaction section, by-product reactions produce a small amount of water. This water
must be removed before unreacted ethanol can be recycled. Water removal can either be
integrated within the ethyl acetate unit or part of a larger external facility depending on
whether feedstock ethanol has a high water content for example; sourced from a
fermentation unit. Molecular sieve processes are generally most economic, although
conventional entrainer distillation systems may be used.

Chemical Engineering Challenges

Most novel chemical processes present chemical engineering challenges. The following
section describes some of the challenges that were addressed during the development and
commercialization of the ethyl acetate process. Resolution of these problems required a
combination of fundamental chemical engineering research and application of state-of-the-art
software tools for steady state and dynamic simulation and computational fluid dynamics.

Dehydrogenation Reactor Design

Ethanol dehydrogenation to ethyl acetate is a


sequential reaction. In the first step, ethanol is
dehydrogenated to acetaldehyde. In the second
step the acetaldehyde reacts with ethanol and is
further dehydrogenated to give ethyl acetate. The
first stage of the reaction is endothermic while the
second stage is exothermic and the overall reaction
is endothermic. Kinetics of the reactions were
measured using a spinning basket reactor.

Langmuir-Hinchelwood expressions were


developed for the major series and parallel
reactions and fitted to the experimental data. The
final kinetic model was then used to develop
tubular and multiple adiabatic bed reactor models
and a four bed adiabatic reactor with inter-bed
reheating was the economic choice for this
application. In parallel a small scale reactor was
used to study catalyst performance and deactivation.

Hydrogenation Reactor Design

Small quantities of methyl ethyl ketone and n-butyraldehyde are made on the
dehydrogenation catalyst. Preliminary studies indicated that these compounds are extremely
difficult to separate from ethyl acetate by fractionation. Selective hydrogenation to their
equivalent alcohols considerably simplified separations and proved to be the economic
option. Laboratory tests identified a platinum group metal/carbon catalyst operating in a
trickle bed regime as having the required selectivity.

It is important to maintain adequate catalyst wetting to maintain catalyst effectiveness and to


avoid hot-spot formation. The system favoured uses low liquid velocities and very low gas
velocities (a flow regime outside the range of published correlations). An experimental
programme was initiated to study pressure drop, liquid hold-up and wetting characteristics of
this catalyst at the chosen flow conditions. These experiments proved that the commercial
reactor can be operated safely and effectively provided liquid distribution and re-distribution
are maintained. This work highlighted the importance of the inert fill on top of the catalyst in
trickle bed reactors, to provide secondary distribution.
Flow/ kmol/m²s
Distance
down bed, h 500

Highest 0.123

Average 0.097

0.1-0.12

0.08-0.1

0.06-0.08

0.04-0.06

0.02-0.04

0-0.02

-0.02-0

This diagram illustrates the predicted liquid flow distribution 0.5m below the top of the catalyst
bed using the commercially installed distributor.

Product recovery

The separation of ethyl acetate product from unreacted ethanol and byproducts is
complicated by low boiling, binary and ternary azeotropes of ethanol, ethyl acetate and water.
It was found that the composition of these azeotropes varies significantly with pressure and
so a pressure swing distillation scheme was adopted to separate the products. An extensive
programme of vapour-liquid-liquid equilibrium data measurement and model regression was
therefore initiated. VLE data for all important binaries in the system were measured and
regressed to liquid activity models. The model predictions were then checked against further
experimental measurements of ternary azeotrope composition and multi-component flashes.

In pressure swing distillation systems, there is an optimum between the column refluxes and
the recycle stream, which gives minimum heat input to the system. In the ethyl acetate
system extensive optimisation studies showed that minimum heat input could be achieved by
limiting the accumulation of water in the column overhead system.

Ethyl Acetate
Ethyl Acetate

Pressure = 9308mmHg
Pressure = 760mmHg

Water Ethanol
Water Ethanol

The diagrams above show distillation lines for the ternary system at two pressures and show
significant change in azeotrope composition with pressure. An interesting feature of the
system is that because of the shape of the distillation curves, by operating with low levels of
water, it is possible to operate the high pressure column overhead composition at lower
concentrations of ethyl acetate than present in the ternary azeotrope.
Environmental Aspects

Consumption of ethyl acetate as an industrial solvent has increased in recent years, due in
the main to it being preferred to Hazardous Atmospheric Pollutants such as MEK and MIBK.
As a growth product, it was a legitimate target for process development. There were a
number of production routes available, all of which ultimately relied upon the use of non-
renewable feedstocks, primarily natural gas or ethylene. In addition these routes require
several steps, each with its own inefficiencies and by-product issues and were not especially
atom efficient. The chart opposite illustrates these various routes

The major benefit of this new process is that it relies only upon the availability of ethanol, the
majority of which is produced by fermentation. As fermentation ethanol is derived from
biomass and this relies on atmospheric carbon dioxide, there is no net carbon dioxide
contribution.
Wacker
Acetaldehyde Ethylene

Tischenko
Ethyl Direct
Wacker Acetate Addition
Davy
Dehydrogenation

Ethanol Acetic
Acid
Esterification
Fermentation

Crop
Starch Natural
Gas

Logically, plants based upon this process would be located close to sources of low cost
ethanol. Additional benefits can be realised by integration of cane sugar, ethanol and ethyl
acetate units in one location. Of particular benefit in this respect is the use of waste bagasse
as a fuel to support the units. For the cane grower, the use of bagasse in-plant often enables
a better rate of return than can be obtained from export of power to a local grid.
For further details please contact:

Davy Process Technology Limited


20 Eastbourne terrace
London W2 6LE
UK

Tel: +44 (0)20 7957 4120


Fax: +44 (0)20 7957 3922
Mail: dpt@davyprotech.com
Web: www.davyprotech.com

Davy Process Technology Limited


Technology Centre
Princeton Drive
Stockton-on-Tees
TS17 8PY
UK

Tel: +44 (0) 1642 853 800


Fax: +44 (0) 1642 853 801
Mail: tc@davyprotech.com
Web: www.davyprotech.com

Davy Process Technology is a Johnson Matthey company

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