EUROPEAN ROADMAP OF PROCESS INTENSIFICATION

- TECHNOLOGY REPORT -

TECHNOLOGY: PHOTOCHEMICAL REACTORS

TECHNOLOGY CODE: 3.3.4

AUTHOR: Tom Van Gerven, Katholieke Universiteit Leuven

(Belgium)/Delft University of Technology (The Netherlands)

Table of contents

1. Technology
1.1 Description of technology / working principle
1.2 Types and versions
1.3 Potency for Process Intensification: possible benefits
1.4 Stage of development
2. Applications
2.1 Existing technology (currently used)
2.2 Known commercial applications
2.3 Known demonstration projects
2.4 Potential applications discussed in literature
3. What are the development and application issues?
3.1 Technology development issues
3.2 Challenges in developing processes based on the
technology
4. Where can information be found?
4.1 Key publications
4.2 Relevant patents and patent holders
4.3 Institutes/companies working on the technology
5. Stakeholders
5.1 Suppliers/developers
5.2 End-users
6. Experts brief final judgment on the technology

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1. Technology

1.1 Description of technology / working principle

(Feel free to modify/extend the short technology description below)
Photochemical reactors use the energy of light to initiate or catalyze reactions. The
basic principle is that light quanta are absorbed by chemical compounds (reagents,
sensitizers or catalysts) which are electronically excited and become (more) reactive
towards other compounds present. The wavelength of the light is in the range of 200
nm to 400 nm (UV) and 400 nm to 700 nm (visible light). IR induced photochemistry
also exists, but is mainly used in analytical techniques and has not frequently been
investigated for chemical process technology, except for some very specific
applications in the USA. The light can originate either from the sun (4-5% UV) or
from artificial sources (e.g., medium-pressure mercury or xenon lamp, excimer lamp).
In the case of solar-driven photochemical reactors, the energy needs to be
concentrated in order to reach sufficient efficiency.

In non-catalyzed photochemical reactions the light energy is absorbed by the reagent

itself or by a sensitizer. A sensitizer transfers the electronic energy to the reagent or
undergoes a reversible redox reaction with the reagent (which is then
photocatalysis). The reagent becomes then electronically excited by the transfer of
an electron to a higher energy band. Upon returning to its ground state, the molecule
can either transfer its energy to another molecule (thus excitating this molecule) or
produce reactive components such as radicals or ions.

Photocatalysis implies the acceleration of a photoinduced reaction by the presence of

a catalyst. A catalyst can also be considered as a sensitizer. Photoinduced
reactions are activated by absorption of a photon with sufficient energy, i.e. equal or
higher than the band-gap energy (Ebg) of the catalyst. The absorption leads to a
charge separation due to the promotion of an electron (e-) from the valence band of
the semiconductor catalyst to the conduction band thus generating a hole (h+) in the
valence band. In order to have a photocatalyzed reaction, the e--h+ recombination,
subsequent to the initial charge separation, must be inhibited by competition with
other processes involving the produced e- and/or h+. The most widely used
semiconductor catalyst in photoinduced processes is titanium dioxide (TiO2),
because it is chemically and biologically inert, photocatalytically stable, relatively
easy to produce and to use, able to efficiently catalyse reactions, cheap and without
risks to environment or humans. The only disadvantage of TiO2 is that it is not
activated by visible light, but only UV light. In order to overcome this disadvantage,
the catalyst needs to be doped with impurities. Other photocatalysts include Pt,
RuO2 and WO3.

In scientific literature there is a debate on the difference between photocatalysis and

photosynthesis. The first is seen as merely catalyzing a reaction that would be
possible even without the presence of the catalyst (although slower), whereas the
latter implies a reaction that is thermodynamically impossible without the catalyst
(positive sign of the change in Gibbs free energy of the reaction).

1.2 Types and versions

(Describe the most important forms/versions of technology under consideration, including
their characteristic features, differences and similarities)

There is a wide variety of photochemical reactors being developed. However, the

main components of these reactors include (see figure):
a light source, including activator or concentrator if necessary;
a cavitation for the chemical medium;

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 reagents and reaction products;
sensitizers or catalysts (on support) if necessary.

activator

light source

concentrator/facilitator

reactants catalyst reaction

products

support

medium

Figure: Scheme of a reactor set-up for photocatalysis.

Each of these components and the relation/contact between these components can
be configured in several ways. The light source and its position are the major issues
distinguishing photochemical reactors from other reactors.

The different positions of the light source relative to the cavity in which the reagents
and/or catalysts are present can be summarized as follows:
immersion of the lamp in the chemical medium (immersion reactors);
external position of the lamp relative to the reactor (a transparent wall is
required) (annular reactors);
external light production with guided channelling through the reactor (optical
fiber, hollow tube reactor);
alternative set-ups, made possible by intensifying the reactor mass transfer
(e.g. illumination of spinning discs);
use of solar illumination generally requires concentration of the light energy
by focusing with paraboles.

Until recently the light source was dimensioned towards the macro- (solar) or meso-
scale (pressure lamps, excimer lamps). However, recent advances include
microscale illumination (LEDs).

Photocatalytic reactors can use the catalyst in the form of a slurry (thus requiring a
separation step after reaction) or immobilized on the wall or reactor internals (thus
requiring excellent mass transfer).

1.3 Potency for Process Intensification: possible benefits

(In Table 1 describe the most important documented and expected benefits offered by the
technology under consideration, focusing primarily on energy; CO2 emission and costs,
providing quantitative data, wherever possible. Add other benefits, if needed).

Photochemical reactions provide alternatives to a vast range of chemical reactions

and technologies (see 2.4). The advantage of the photochemical alternative is often
that it can be performed at low temperature, thus limiting side reactions. Selectivities

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and conversions of up to 100% can be achieved. However, it can be somewhat
misleading to compare with traditional processes as often another chemical pathway
is followed.

On the other hand, it must also be taken into account that the photochemical
pathway is sometimes the only chemical pathway that is known. In this case no
alternatives exist except the one of no-production. From this point of view, it can be
expected that when the technology would be economically viable, new products will
become commercially available.

Table 1: Documented and expected benefits resulting from technology application

Benefit Magnitude Remarks
Depends on the specific case, for example up to
can go up to
conversion/yield 100% in the case of toluene oxidation to
100%
benzaldehyde.
Depends on the specific case, for example up to
100% in the case of cyclohexane oxidation to
can go up to
selectivity cyclohexanone (whereas in the conventional
100%
process this is about 75% cyclohexanone, 25%
cyclohexanol).
Depends on the specific case. Low temperature
can go down to
low-temperature reactions also generate less by-products
room temperature
(increased selectivity).
At the earths surface solar light contains about 4%
running energy
of UV. This is a downside. However, sunlight can
cost reduced to
solar (free) energy be concentrated (see table 3) and in the case of
zero, large
photocatalysis, the catalyst can be doped in order
investment costs
to be activated by visible light.

1.4 Stage of development

The concept of photochemical reactors is already implemented in industry (see 2.2).

However, applications remain limited due to issues such as costs (lamps, electrical
energy) and energy efficiency (distance lamp reactant, maximum illumination).
Improvements on these issues are needed.

2. Applications

2.1 Existing technology (currently used)

(Describe technology (-ies) that are conventionally used to perform the same or similar
operations as the PI-technology under consideration)

Some photoreactors have been implemented in industry. To date the main

economical viable processes are chain reactions where thermal processes can be
substituted by photochemical processes. Examples include chlorinations,
sulfochlorinations, sulfoxidations, nitrosations (see 2.2.). In these cases the
photoreactions appear to be performed with relatively low capital and electrical costs.
However, the example of Toray (Table 2) shows that while this company uses the
photochemical process, the majority of companies producing caprolactam prefer the
conventional processes (95% of total production).
The only non-chain reactions that are photochemically produced in industry
(vitamins, flavours) are compounds that can only be produced photochemically or
with a high added value.

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Commercial applications mainly use immersion or annular reactors

2.2 Known commercial applications

(Is the technology broadly applied on commercial scale? In which process industry sectors is
the technology most often applied: large volume chemicals specialty chemicals & pharma
consumer products ingredients based on agro feedstocks? What is the estimated number
of existing applications? In Table 2 provide the most prominent examples of realized
applications and provide their short characteristics)

The largest amount of photochemical applications in industry is found in the light

induced polymerization for the production of protective and decorative coatings, inks,
packaging and electronic materials. Commercial applications in bulk chemical,
pharma and agro-sectors are more scarce. Some examples are given in table 2.

Table 2. Industrial-scale applications of the Technology (existing and under

realization)
Product
Company - Short ion Year of
Sector Process/Product characteristic capacity applicat Reported effects
name/type of application /Plant ion
size
conversion
increase from
10% to 80%
cyclohexane to
(cyclohexane
cyclohexanone 1.7*105
to
bulk Toray Ltd. oxime (for ton/y 1963
cyclohexanone
caprolactam (2003)
oxime)
production)
elimination of
intermediate
process steps
higher product
yield
1950s
better selectivity
to
lower specific
1,1,1- 1990s
ca. 3*105 energy
trichloroethane (banned
bulk Dow, Solvay, a.o. ton/y consumption
from 1,1- by
(1984) (decrease of
dichloroethane Montreal
process
Protocol
temperature from
)
350-450C to 80-
100C)
benzylchloride
0.5-
production from
bulk Monsanto 1*105 n.a. 90% yield
toluene
ton/y
chlorination
sulfonic acid
Hoechst (Sanofi- production from 4.5*104
bulk n.a. 12% yield
Aventis) parrafins and ton/y
sulfur dioxide
production of
2500 no other process
specialty BASF trans-vitamin A n.a.
ton/y available
acetate
yield = 60%
Dragoco
no other
(Germany) and rose oxide 60-100
specialty n.a. process
Firmenich (perfume) ton/y
available
(Switzerland)

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2.3 Known demonstration projects
(Are there any demonstration projects known related to the technology under consideration?
In which process industry sectors are those projects carried out: large volume chemicals
specialty chemicals & pharma consumer products ingredients based on agro feedstocks?
In Table 3 provide the short characteristics of those projects.)

Table 3. Demonstration projects related to the technology (existing and under

realization)
Short characteristic
Aimed
of application
Who is carrying year of
Sector investigated, Reported effects
out the project applicati
including product
on
name/type
water
wastewat
Plataforma Solar decontamination, not
er use of solar light
de Almera, Spain disinfection and specified
treatment
desalination
pilot-installation (1
ton/y) for organic
synthesis with solar lower temperature
energy: photo- lower pressure
chemical oxygenation (rose not increased yield
PROPHIS, Kln
synthesis oxide), specified lower energy
heterocyclization, requirements (solar
photo-Friedel-Crafts light)
acylations,
isomerizations

2.4 Potential applications discussed in literature

(Provide a short review, including, wherever possible, the types/examples of products that
can be manufactured with this technology)

Applications of photochemical reactors can be found in bulk chemical industry, fine

chemical industry, pharmaceutical industry, the sectors of wastewater and air
treatment, medicinal applications. The (catalyzed) reactions include:
nitrosylations,
chlorinations, brominations, fluorinations,
sulfochlorinations, sulfoxidations, desulfonations, desulfonylations,
decarboxylations,
oxidations of alkanes to alkenes, oxidations of cyclo-alkanes to ketones,
oxidations of alcohols to carbonyls, oxidations of aromatics to aromatics with
alcohol, ketone or aldehyde groups,
isomerizations,
polymerizations.

3. What are the development and application issues?

3.1 Technology development issues
(In Table 4 list and characterize the essential development issues, both technical and non-
technical, of the technology under consideration. Pay also attention to boundary issues,
such as instrumentation and control equipment, models, etc.) Also, provide your opinion on
how and by whom these issues should be addressed)

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Table 4. Technology development issues

How and by whom

Issue Description
should be addressed?

Interdiciplinary R&D
Light sources remain too often the large, teams at universities
inefficient and short-lasting conventional lamps. (physics, chemistry,
Improved/novel Novel designs of light sources should aim at chemical engineering and
light sources smaller, long-lasting light sources with a high electric/electronic
and catalysts energy conversion. Catalysts need to be engineering) in
developed that suit the features of the light collaboration with light
source (wavelength, energy intensity). equipment manufacturers
and catalyst producers.
The physics of light need to be combined with Interdiciplinary research
chemistry and thermodynamics of chemical teams at universities
Modelling reactions in order to produce more complete (physics, chemistry,
models. These models should be used to chemical engineering and
devise optimal reactor configurations. electronic engineering).
R&D studies at
Scale up and Optimal configuration of light (catalyst) universities (chemical
optimal reactor reactor cavity with minimum energy loss and engineering) in
configuration maximum mass transfer. collaboration with reactor
engineering companies.

3.2 Challenges in developing processes based on the technology

(In Table 5 list and characterize the essential challenges, both technical and non-technical, in
developing commercial processes based on the technology under consideration. Also,
provide your opinion on how and by whom these challenges should be addressed)

Table 5. Challenges in developing processes based on the technology

How and by whom

Challenge Description should the challenge be
addressed?

By improving existing
designs (e.g. LED) or
designing novel light
sources. Within R&D
Reduce energy losses on the path from energy
light efficiency projects including
generation to molecule excitation
electric/electronic
engineering and physics
(both academia and
industry).
Tackle scale up problems, e.g. by Reactor design supported
penetration miniaturization of light and chemical tank by improved models.
depth of light in (microreactors), by improved (micro)mixing, or Academia and industry
view of scale up by introduction of suspended, randomly within chemical
distributed light sources in the bulk solution engineering community.
Developing new
luminescent molecules
with the desired
optimal properties. R&D projects
Provide tailor-made light sources (and catalysts)
wavelength and including
for specific chemical processes.
intensity electric/electronic
engineering and physics
(both academia and
industry).

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exhaustive
List the potential reactions/processes that could
overview of feasibility studies by
occur photochemically, together with the
potential industry
economy requirements to render them viable
applications

4. Where can information be found?

4.1 Key publications
(Provide the list of key publications in Table 6)

Table 6. Key publications on the technology

Publication type
(research
Publication Remarks
paper/review/book/
report)
A.M. Braun, M.T. Maurette, E. Oliveros,
photochemical
Photochemical Technology, Wiley & Sons Ltd., book
technology
London, 1991.
A. Mills, and S. Le Hunte, An overview of
photocatalysis /
semiconductor photocatalysis, J Photochem review
chemistry
Photobiol A: Chem, 108 (1997) 1-35.
O. Carp, C.L. Huisman and A. Reller,
photocatalysis /
Photoinduced reactivity of titanium oxide, Progr. review
chemistry
Solid State Chem., 32 (2004) 33-177.
A. Mills and S.K. Lee, in S. Parsons (ed.),
Advanced oxidation processes for water and photocatalysis /
chapter in book
wastewater treatment, IWA Publishing, London, chemistry
2004, pp. 137-166.
H. de Lasa, B. Serrano and M. Salaices,
photocatalysis /
Photocatalytic reaction engineering, Springer, book
engineering
New York, 2005.

4.2 Relevant patents and patent holders

(Provide the list of relevant patents in Table 7. Under remarks provide, where applicable,
the names/types of products targeted by the given patent.)

Numerous patents exist for the use of light in a photochemical process. A worldwide
patent search on photochemical, photocatalysis and photochemistry resulted in
1764, 186 and 23 patents, respectively. For photochemical reactor and
photocatalytic reactor 89 and 40 patents were found, respectively.

The patents listed here consist of the first ones and the most recent ones, together
with some specific break-throughs (micro-illumination and microreactors). Focus is
on patents not exclusively directed towards air and water treatment.

Table 7. Relevant patents

Remarks, including
names/types of
Patent Patent holder
products targeted by
the patent
WO2006087353 (2006), Photoreactor C Sattler et al. hollow tube reactor
US6827911 (2004), Photoreactor with recovery of suspended
KL Gering (Bechtel BWXT)
self-contained photocatalyst recapture catalyst

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EP1415707, EP1398077 (2004),
PJ Barthe et al. (Corning
Method and microfluidic reactor for microreactor
Inc.)
photocatalysis,.
DE10246626 (2004), Selective
halogenation of alkyl aromatic
compounds, useful as intermediates
K Morgenschweis et al.
for the production of plant protection microreactor
(BASF)
agents, comprises insertion of
halogenating agents in a micro-reactor
under photochemical initiation
US6633042 (2003), Solar
KH Funken et al.
photoreactor
electromagnetic
WO02062465 (2002), Photochemical
D Meissner activation of light
reactor
source
JP9299456 (1997), Photocatalyst K Sakai et al. (Toyoda
LED illumination
apparatus Gosei Co. Ltd.)
US4795617 (1989),
electroluminescent
Electroluminescent chemical L.R. OHare
illumination
activation system
US3458418 (1969), Process for
immersion
carrying out photochemical reactions W. Beckmann (BASF)
photochemical reactor
and apparatus thereof
US3431188 (1969), Process and
I Stoichi et al (Toray)
apparatus for photochemical reaction
US266186 (1953), Two-stage LJ Governale et al. (Ethyl
photochemical reactor Corp.)

4.3 Institutes/companies working on the technology

(Provide the list of most important research centers and companies in Table 8)

Table 8. Institutes and companies working on the technology

Institute/Company Country Remarks

solar-driven wastewater
treatment, thermochemical
Plataforma Solar de Almera Spain
synthesis reactions driven by
photovoltaic cells
Prof. Frei, Laboratory of Chemical
Biodynamics, Lawrence Berkeley
USA photochemical synthesis
Laboratory, University of
California, Berkeley.
Prof. Funken, Deutsche
Forschungsanstalt fr Luft- und Germany solar photochemistry
Raumfahrt, Kln
Prof. A.K. Ray, Dept. of Chemical
Engineering, National University Singapore photocatalytic reactors
of Singapore
Prof. A.M. Braun, Lehrstuhl fur
photochemical synthesis and
Umweltmesstechnik, Universitt Germany
destruction
Karlsruhe
Dr. M.T. Maurette, CNRS photoreactions (synthesis and
France
Toulouse destruction) and photoreactors

In addition several companies are working on photochemical technology. More

details are found in paragraphs 5.1 (suppliers) and 5.2 (end users).

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5. Stakeholders
5.1 Suppliers and developers
(Provide the list of key suppliers/developers in Table 9)

Table 9. Supplier and developers

Institute/Company Country Remarks

Photochemical reactors for chemical industry

The Southern New England
USA ultraviolet reactors
Ultraviolet Company (Rayonet)
photochemical reactors
patent for photochemical
Grantzel Germany reactor, FR2397874 (1979),
GB1461506 (1977),
FR2306734 (1976)
Hans Mangels GmbH Germany DEMA photochemical reactor
Light sources
UV lamps for
photochemistry
Heraeus Instruments GmbH Germany
patent for immersion lamp,
US5334905 (1994)
several types of lamps, not
Philips Electronics Nederland
specifically for photochemistry
several types of lamps, not
Osram Germany
specifically for photochemistry
several types of lamps, not
Canrad-Hanovia USA
specifically for photochemistry
Photochemical reactors for air and water treatment
polluted air treatment
patents for photochemical
reactors, JP2159377
Babcock Hitachi KK Japan
(1990), JP1312077,
JP1312076, JP1312075,
JP1242142, JP1139770
wastewater cleaning
patent for immobilized
Zentox/Photox Corporation USA
photocatalyst, WO9740936
(1997)
wastewater cleaning
Wedeco UK UV photochemical reactors
several patents
wastewater cleaning
Matrix Photocatalytic Inc. Canada
no patents
wastewater cleaning
Clearwater Industries USA
no relevant patents
wastewater cleaning
Photox Bradford Ltd. UK
no patents
wastewater cleaning,
patent for a fixed-bed
photocatalyst reactor,
Lynntech Inc. USA
US6409928 (2002),
US6136186, US6117337,
US5779912

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 air and wastewater cleaning
patent for Photo-Cat water
and air automated
Purifics Environmental
Canada treatment system,
Technologies Inc.
US2005211641 (2005),
US6136203, US5589078,
US5462674

5.2 End users

(Describe the existing and potential end-users, other than those already listed in Table 2)

Various companies could/can be end-users of an economically viable photochemical

process. Several photochemical processes are known and have obvious advantages
over the conventional processes. The main barriers these processes currently face
are the technological problems regarding scale up and illumination efficiency, thus
keeping the process economically uninteresting. However, if these barriers can be
overcome, not only the currently known photochemical reactions can be
implemented, but also new products and new end users are envisaged to become
available.

Industrial patent holders related to photochemical reactors include BASF, Ciba,

DowChemical, DuPont, Ethyl Corp., Philips Petroleum Co., Toray. Corning and
Degussa hold patents related to photocatalysis (see also Table 7).

6. Experts brief final judgment on the technology

(maximum 5 sentences)
Photochemical technology has a certain future as a niche application in chemical
industry. Although new industrial applications of this technology have been scarce in
the last 20 years, recent advances in scientific literature do show that major
improvements in illumination efficiency (LED or even nanoscale illumination) and
scale up (or actually scale down to microreactors) are feasible within the next 10
years. With these improvements the technology should become a competing
technology. If, in a next stage, solar illumination could be incorporated (either as a
substitute for the artificial illumination, or as energy source for photovoltaic cells
generating electricity for the artificial illumination), this technology will have a
comparative advantage over the conventional technology.

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