sector challenges catalysis

SJ Jenkins and SM Driver

whats going on: we can get a picture of what is happening at an

atomic level but at production scale, catalysis is very different

Catalysing Change
Key challenges in catalysis and a need for cross-discipline collaboration
Carmine DAgostino
DEPARTMENT OF CHEMICAL ENGINEERING AND BIOTECHNOLOGY, UNIVERSITY OF CAMBRIDGE, UK

TS not an overstatement to claim that the modern world

A catalyst is a substance that increases the rate of chemical

would not be the same as we know it without catalysis.

reaction without being used up during the reaction. Catalysts

From fuel to fertilisers, from food to pharmaceuticals,

tend to be divided into two major classes: homogeneous

from plastics to energy production, this technology has

catalysts, which operate in the same phase as where the

revolutionised our daily life in every aspect. Since the 21st

reaction occurs; and heterogeneous catalysts, which operate

century, this technology has played a key role in addressing

in

some of the new challenges in creating alternative processes

catalysts are soluble organo-metallic compounds used for

for producing chemicals and fuels, reducing the impact

organic

of pollution on the environment, and

employed as porous solids containing the active compo-

harmful by-products in manufacturing.

reducing waste and

different

phases.

synthesis.

Typical

examples

Heterogeneous

of

catalysts

homogeneous
are

usually

nent, which catalyses the desired reactions. A representative

SEPTEMBER 2016 | The Chemical Engineer | page 35

sector challenges catalysis

synthesis. Here, gaseous nitrogen and hydrogen at high

pressure (200 bar) are passed over an iron-based catalyst,
for example, iron supported on porous alumina, and produce
ammonia (NH3).
Homogeneous catalysts are usually very active (ie all the
atoms of the active component are active centres) and selective
with a well-defined structure/stoichiometry relation. In most

Heterogeneous catalytic process: Reagent molecules enter

the catalyst pore structure, diffuse across the pores (black
pathway), adsorb onto the surface and then reach the active site
(yellow crystal). The final product desorbs from the surface
and diffuses across the pores back out in the bulk fluid (orange
pathway). Mass transport, adsorption, and kinetics determine
the performance

cases, mass transport limitations can be neglected. However,

this type of catalyst has several drawbacks, especially from
a practical perspective: they are usually expensive and often

CATALYST PORE STRUCTURE

FINAL
PRODUCT OUT

toxic, and their separation from the reactive mixture is

laborious. In addition, they have low thermal stability and can
suffer from irreversible poisoning where a substance that
isnt part of the reaction can partially or totally deactivate the
catalyst. For these reasons, their application is limited to small
production runs of high value molecules, such as specialty
chemicals

and

pharmaceuticals. For

example,

REAGENTS IN

rhodium-

catalysed asymmetric hydrogenation is one of the most

CATALYST ACTIVE SITE

commonly used homogeneous catalysis processes in the

pharmaceutical industry, for the production of various drugs
such as the anti-epileptic drug lacosamide or the anticonvulsive agent pregabalin.

are usually of nanometre dimensions and diffusion of reactants

Heterogeneous catalysts offer several

attractive, advantages over their homogeneous
counterparts, such as easy handling and
separation, high thermal stability and lower
costs. However, there are some major drawbacks

into the catalyst, and products back out, may dissipate a large
part of the available chemical potential. The reaction pathway
for a heterogeneous catalyst is therefore rather complex as,
in addition to the intrinsic chemical reaction, diffusion and
adsorption of reaction species within the catalyst may play a
crucial role. Moreover, the nature of the active sites over the
surface is often not-well defined.

Heterogeneous catalysts offer several attractive, advantages

This complex nature of heterogeneous catalysts makes

over their homogeneous counterparts, such as easy handling

achieving a systematic approach difficult. The main problem

and separation, high thermal stability, and lower costs.

is that very ideal systems such as single crystal, well-de-

However, there are some major drawbacks as well unlike

fined surfaces, under very low pressure and temperatures,

homogeneous catalysts, the structure/stoichiometry relation is

can be understood at lab scale with a good level of fundamen-

complex and often undefined, which makes them less selective

tal details using DFT (density functional theory), scanning

and more challenging to understand; and the active centres are

tunnelling microscopy (STM), and other techniques that work

only the surface atoms, hence the specific activity tends to be

at atomic level. However, at production scale, catalysts are very

low. In addition, heterogeneously-catalysed reactions may be

different they operate at high pressure and temperature, have

severely affected by mass transport limitations and competi-

a very complex surface morphology, and so it becomes much

tive adsorption phenomena. The challenge is therefore to have

more complicated to understand the fundamentals. To find

robust and stable heterogeneous catalysts, which can offer

that understanding we need to bridge the gap between lab and

performances comparable to those of homogeneous catalysts.

production scale. As a starting point, I am currently working

on a project in collaboration with the chemistry depart-

A MOLECULAR JOURNEY INSIDE CATALYST PORES

ment at the University of Cambridge, which is carrying out

preliminary work to address these issues. Well be looking

Our understanding of the way solid surfaces can interact with

at various aspects of catalysis, not only the

molecules and form new products has increased significantly,

parameters but also other physical and chemical properties

main reactive

but heterogeneous catalysts are still predominantly devel-

such as diffusion and adsorption.

oped by an intuitive trial-and-error approach. They are usually

If we are to understand how heterogeneous catalysts work,

used as highly porous solids, in order to provide a very large

we need this multifaceted approach. We need to get out of our

catalytic surface in a small volume. A gramme of porous

comfort zones and work together with chemists and molecular

catalyst may have a surface area of up to 1,000 m2. The pores

scientists to combine our knowledge, techniques and expertise.

SEPTEMBER 2016 | The Chemical Engineer | page 36

N Robinson

example of a heterogeneously-catalysed reaction is ammonia

sector challenges catalysis

FROM THE LAB TO INDUSTRY

catalysts onto an insoluble solid support, a kind of hybrid

Understanding how catalysts work on the atomic scale is perhaps

homo-hetero catalyst which optimises the best of both. This

the first step in designing efficient and effective catalysts. But

can be achieved by what is known as heterogenisation of the

further efforts are needed in scaling up catalytic technol-

homogeneous catalyst onto a solid support. By a careful choice

ogies. Often, novel catalysts that have shown great potential

of solid supports and homogeneous catalyst precursors, a

on a laboratory scale behave rather differently in industrial

range of homogeneous catalysts can be immobilised, including

reactors. There are several reasons for that, often related to

organo-metallic complexes, enzymes, organo-catalysts, acid

reactor design as well as experimental and operating condi-

and base catalysts and very recently, ionic liquids.

tions, which make process scaleup a rather difficult issue. For

In the past decades, immobilisation of homogeneous

example, many catalyst screening tests carried out by chemists

catalysts has developed rapidly but in many cases is still

(who are, naturally, interested in the discovery of a catalyst) use

seen as an art rather than a science. As with heterogenous

materials in the form of a finely-dispersed powder. Yet, in many

catalysts, further developments are needed, such as additional

industrial applications, such as fixed-bed reactors, a catalyst

efforts to understand physical and chemical properties as well

is used in pellet form to guarantee thermal and mechanical

as the engineering of such catalysts on a larger scale, to better

stability of the catalytic bed and make it easier to handle and

understand physicochemical properties and possibly increase

separate the catalyst. That switch from powder to pellets may

the industrial application of such materials.

drastically change the behaviour of the catalyst. Diffusion

limitations may become much larger and this may affect the
reaction rate of diffusion-controlled reactions. This can be the
case of reactions in microporous materials such as zeolites,

it is of paramount importance that both

chemists and chemical engineers come together

where the pore size is such that molecules may struggle to

diffuse across the porous matrix. A detailed knowledge of the

Challenges which need to be addressed include leaching

nature of the pore structure, including pore size distribution

active species, diffusion limitations, unfavourable interac-

and connectivity of the pore network, as well as molecular

tions and surface properties. These may significantly affect

transport properties and reactor hydrodynamics, is crucial for

performances and reusability of catalyst materials. Again,

optimising catalyst design and performances.

chemical engineers have an important role to play here. Most

of these studies are carried out by chemists, so engineering

In the past decades, immobilisation of

homogeneous catalysts has developed
rapidly but in many cases is still seen as
an art rather than a science

principles such as mass transport, adsorption, and stability

are often missing from formulating the solution.
Using heterogenised catalysts in industrial processes has
been achieved, but it is rare; examples include bioprocesses
using immobilised biocatalysts, such as the production of
high fructose corn syrup from corn syrup, or the produc-

Another issue, often associated with industrial catalysts, is the

tion of acrylamide from acrylonitrile. Research efforts in this

need for binding agents to produce suitable catalyst extrudates.

direction could certainly open up new possibilities for the

These additives may affect pore structure as well as surface

design of more efficient catalytic processes. For example,

properties of the catalytic material, which may eventually

this strategy can allow the development of catalytic materials

lead to changes in catalytic behaviour. Indeed, adsorption of

with multiple functionalities to promote different individual

the right species over catalytic surfaces is crucial in order for

reactions within a multiple-step process.

the desired reaction to occur. While there is plenty of evidence

that adsorption properties have a profound impact on catalytic
activity, this aspect has often been overlooked. For example,

Collaboration is key

the effect that solvents have on liquid-phase heterogeneous

In order to address the various challenges in the field, it is of

catalysis has been widely reported but in many instances it is

paramount importance that both chemists and chemical engi-

not yet clear how the solvent modifies the reaction pathway.

neers come together and work closely, sharing knowledge

More

and expertise and avoiding a narrow confinement within

research

into

understanding

the

surface

science

governing such phenomena would certainly be beneficial.

their comfort zones. New, inter-disciplinary research projects

need to be supported by research funding agencies, working

THE BEST OF BOTH CATALYTIC WORLDS

together with the industry and leading experts in the field.

In

this

context,

IChemE

and

the

Royal

Society

of

One of the ultimate goals in catalysis is the design of effi-

Chemistry may have a very important role in knowledge

cient catalytic processes that use solid catalysts and whose

exchange and promotion of such projects and collaborations,

performances are comparable to those of homogeneous cata-

as well as supporting talented researchers with innovative

lysts. One way of achieving this is to immobilise homogeneous

ideas both in industry and academia.

SEPTEMBER 2016 | The Chemical Engineer | page 37