process intensification using light energy - tu delft ocw · process intensification using light...
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Process Intensification using light energy
Tom Van Gerven
Department of Chemical Engineering
KU Leuven
Belgium
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Content
• Photochemistry, photocatalysis, photosynthesis
• 3 case studies – Optical Fiber (Monolith) Reactor (OFMR)
– Internally Illuminated Microreactor (IIMR)
– Light Efficient Foils for open algae ponds (LEF)
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Light
• Light = the main
form of energy for
plants
Purves et al., 1995
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Light
• Light = an alternative form of energy for industry
Use of sunlight in photocatalytic pilot installation
in Almeria, Spain (PSA, 2004) Use of stripped
optical fibers
(TUD, 2006)
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The Electromagnetic Spectrum
= Solar Energy
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Photochemistry
Photochemistry can lead to more sustainable processes by:
• increased process selectivity to the required products – different chemistry
– low/ambient process temperature
• decreased energy consumption in the process – low/ambient process temperature
– use of solar light
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Photochemistry in industry
Photochemistry is already implemented in industry, although limited
Some examples:
• photo-oximation of cyclohexane to cyclohexanone oxime (Toray, Japan)
photoreactor
• 170,000 ton/y (2003)
• conversion increases from 9-11%
(others) to 80% (Toray)
• selectivity increases from 76-81%
(others) to 86% (Toray)
• elimination of intermediate process
steps
• from 1963 on
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Photochemistry in industry
Photochemistry is already implemented in industry, although limited
Some examples:
• 1,1,1 trichloro-ethane from 1,1 dichloro-ethane
• 300,000 ton/y (1986)
• higher product yield, better
selectivity than other processes
• lower process temperature than other
processes (80-100°C vs. 350-450°C)
• main process route
• 1950’s to 1990’s (production banned) photoreactor
Ullmann’s Encyclopedia, 2006
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Photochemistry in industry
Photochemistry is already implemented in industry, although limited
Some examples:
• photo-oxidation of citronellol to rose oxide (Dragoco, Germany)
60-100 ton/y, main process route
Monnerie & Ortner, 2001
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Photochemistry in industry
Current design in industry:
slurry reactor / immersion reactor with pressure or excimer lamps
tank reactor
stirrer immersed lamp
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Photo(cata)lysis
• Photolysis
– No catalyst
– Deep UV (e.g. 250 nm) required – high energy
• Photocatalysis
– TiO2, ZnO, ... (doping)
– visible light + UV (e.g. 384 nm) – less demanding
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Photocatalysis
Source: Guido Mul
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Air Purification
NO + O2 NO2 NO3-
Source: Guido Mul
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Water Purification
H2O2 + ‘CH’ CO2 + H2O
Andijk Spain
O2 + ‘CH’ CO2 + H2O
No catalyst TiO2
Source: Guido Mul
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Photocatalysis in industry
10-9 10-3 10-6 1 103
Aim = 100 to 1000 times better
Mul & Moulijn, 2006 However, window of reality
Intensification needed!
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Increased interest
0
400
800
1200
1976
1982
1988
1994
2000
2006
Nu
mb
er
of
pu
blic
ati
on
s
Photocatalysis
HDS
Source: Guido Mul
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Photocatalytic reactors
• Basic components
medium
activator
concentrator/facilitator
light source
reaction
products
reactants
support
catalyst
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Photocatalytic reactors
• Basic components
medium
activator
concentrator/facilitator
light source
reaction
products
reactants
support
catalyst
photon transfer
mass transfer
catalyst design
reactor design
desorption catalyst recovery
efficient conversion of input energy into light
adsorption
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Photocatalytic reactors
• Basic components
medium
activator
concentrator/facilitator
light source
reaction
products
reactants
support
catalyst
photon transfer
mass transfer
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Photocatalytic reactors
• Photon transfer
– light intensity decays with distance
– absorption on the way
solution is light source close to catalyst
• Mass transfer = OK in slurry reactors, but
– expensive separation step
– incomplete illumination
solution is immobilized catalyst
with excellent mass and photon transfer
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Photocatalytic reactors
monolithic
reactors
spinning disc reactors
microreactors
optical fibers
LED
Improvement
of mass
transfer
Improvement
of light
transfer
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Comparison of reactor configurations
• Comparison based on catalyst coated surface per reaction liquid volume (m²/m³)
• The catalyst specific surface is not included in the comparison
• No evaluation of illuminated surface, illumination uniformity, minimization of energy loss on the way
• Microreactor and spinning disc reactor reach the values of slurry reactor
• Monolith reactor particularly suited for gas-liquid systems
Photocatalytic reactor catalyst coated surface
per reaction liquid volume
(m²/m³)
slurry reactor
2631
8500-170000
(multi)annular/immersion reactor 27
69
133
170
340
2667
optical fiber/hollow tube reactor 46
53
112
210
1087
1920
2000
monolith reactor 943
1333
spinning disc reactor
50-130
20000-66000
microreactor 7300
12000
14000
250000
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Case 1: OFR
Optical fibers
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Case 1: OFR
Optical fibers
10-fold increase of the illuminated catalyst surface per unit of reactor
volume compared to an annular reactor (Lin et al., 2006)
Drawbacks:
– Decay of light: maximum length is 10cm
– Back-irradiation
– Fiber volume
light in
fiber core
fiber cladding catalyst coating
complete reflection
partial refraction
adsorption and scattering
Wang et al., 2003
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Problem:
Light absorption & rapid diffusion
- Layer thickness
Coating has 2 functions:
- catalyze surface reaction
- reflect light into the fiber
Fiber length limited to < 10 cm
Optical
fiberCatalyst
Reaction
medium
Lig
ht In
ten
sity
Re
act
an
t co
nce
ntr
atio
n
Optical Fiber Reactor
(Carneiro, Mul, Moulijn)
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Optical Fiber Monolith Reactor1
wastewater treatment
monolith merely distributor of optical fibers
Not exploited:
excellent mass transfer characteristics for
gas/liquid systems
Light
source
Fiber bundle
TiO2-coated
optical fiber
Ceramic
monolith
Reservoir
Optical fiber monolith reactor 1.0
1. H. F. Lin, K. T. Valsaraj, J. Appl. Electrochem. 35 (2005) 699-708
(Carneiro, Mul, Moulijn)
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Optical fiber monolith reactor 1.0
1 coating 3 coatings 9 coatings
Choi et al. 2001
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Optical fiber monolith reactor 1.0
Choi et al. 2001
An optimal catalyst
coating satisfies
sufficient light
absorption with rapid
reactant diffusion into
the illuminated layer.
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Wang and Ku, 2003
Optical fiber monolith reactor 1.0
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Advantages:
light propagation process in the fiber
Is NOT DEPENDENT on
physical properties of the catalytic layer
Monolith multiphase advantages considered
Re
act
an
t co
nce
ntr
atio
n
Optical
fiber CatalystReaction
medium
Lig
ht In
ten
sity
Optical fiber monolith reactor 2.0
Monolith: catalyst support
(Carneiro, Mul, Moulijn)
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OFMR 2.0
(Carneiro, Mul, Moulijn)
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Monolith
Optical fiber
Monolith
Gas
Liquid
Liquid inlet
Gas inletGas inlet
Gas outletGas outlet
Liquid outlet
Light ource
Monolith:
Cordierite
25 cpsi
L = 25 cm
Operating conditions:
V = 800 mL
Film flow regime
Fair = 15 dm3/min
FLiq = 0.5 dm3/min
16.7g TiO2
Air presaturated with Chexane
OFMR 2.0
(Carneiro, Mul, Moulijn)
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Side Light Fibers (OFMR 2.1)
(Carneiro, Mul, Moulijn)
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Washer Washer
Detector
Side light
fiber bundle
0
0.5
1
1.5
0 5 10 15 20 25 30 35
Distance from fiber entrance [cm]
Rela
tive
in
ten
sit
y [
I/I0
]
Bare fibers
Tip-coated fibers
Side Light Fibers
Light intensity homogeneous throughout the length
(Carneiro, Mul, Moulijn)
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Top Illumination Reactor (slurry)
Side Light Fiber Reactor (slurry)
Annular Reactor (slurry)
OFMR a) Fiber Optic
b) Liquid
c) Catalyst layer
d) Monolith
Reactor comparison
(Carneiro, Mul, Moulijn)
1g/L catalyst
lamp
Fiber
bundle
lamp
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Reactor Rin
[mol.s-1]
rp
[Einst.s-1]
x
[mol.Einst.-1]
Annular reactor 1.5910-6 1.9610-4 0.008
Side light fiber
reactor 7.6810-10 3.6910-7 0.002
OFMR 2.2810-8 3.6910-7 0.062
Top illumination
reactor 1.2010-7 7.9510-7 0.151
Results
Low exposure of catalyst
to light
Low efficiency of light
utilization
Bad desorption from
catalyst
… but slurry reactor,
requiring post-separation
of catalyst
(Carneiro, Mul, Moulijn)
x = reaction rate (mol/s)
photon flow (Einstein/s) = photonic efficiency
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Further work needs to be done
Top illumination reactorIIMR
Present results
Reactivity (mol / (mR3s))
10-9 10-6 10-3 1
Petroleum
geochemistry
Biochemical
processes
Industrial
catalysis
Reactivity (mol / (mR3s))
10-9 10-6 10-3 1
Petroleum
geochemistry
Biochemical
processes
Industrial
catalysis
OFMR Top Illumination Reactor
(Carneiro, Mul, Moulijn)
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Case 2: IIMR
• Micro- and nanoscale illumination – LED devices
• robust, long-lasting (up to 100000 hrs vs. 1000 hrs for conventional lamps)
• low-energy consuming (100mW vs. 100-1000W for conventional lamps)
• miniaturisation
– Luminescent molecules interspersed with catalyst • physical integration on the nanoscale
• very early research phase
liquid in liquid out
support layer electroluminescent and catalyst
nanocolloids
Fedorov et al., 2002
(Van Gerven, Mul, Moulijn, Stankiewicz)
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LED emission
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LED emission
Advantages of LED compared to conventional (Hg) lamps:
• Higher spectral purity
• Less heat: UV LEDs operate at less than 60°C, Hg bulbs at a factor 10
higher
• Instant on/off: stable, full output within milliseconds
• Compact size: also more robust, long lifetime, less sensitive to break
• Safety and Environment: VOC free radiation (no Hg); no production of
O3 (ozone) because no deep UV radiation
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LED efficiency
Lamp Type Overall Luminous Efficiency (LM/W)
Overall Luminous Efficiency (Percentage)
Incandescent
5 W tungsten 5 0.7
40 W tungsten 12.6 1.9
100 W tungsten 17.5 2.6
Fluorescent
5-24 W compact fluorescent 45-60 6.6-8.8
34 W tube 50 7
Halogen
Glass 16 2.3
Quartz 24 3.5
LED
White 20-70 3.8-10.2
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LED efficiency
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Optimal wavelength?
Wavelength
(nm)
Total power
consumptio
n (W)
Photointens
ity (Einstein
l-1 min-1)
Direct
photolysis
quantum
yield
Photocataly
sis
quantum
yield
Photolysis
rate
constant
(min-1)
Photocataly
sis rate
constant
(min-1)
254 70 1.80 x 10-4 0.095 0.12 0.088 0.112
300 210 6.64 x 10-3 0.051 0.54 0.012 0.128
350 240 3.24 x 10-2 0.008 0.21 0.005 0.129
Alachlor degradation by UV with/without TiO2
C. C. Wang, W. Chu, Chemosphere 50 (2003) 981 – 987
Photolysis: higher quantum yield with shorter wavelength
Photocatalysis: higher quantum yield with medium wavelength
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Optimal wavelength?
Decomposition of NOx
Hsu et al, United States Patent Application
publication, 2009 US2009/0263298 A1
Highest decomposition rate (curve
d) was observed at 385 nm
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Set-up @ KU Leuven
Batch mono-LED reactor
Side
view
Bottom view
Top view
Reactors
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Uniformity of light immission?
Dionysiou et al., 2000
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Use of reflectors
Al foil Silver
0
5
10
15
20
25
30
35
40
Ph
en
ol d
egr
ad
ati
on
(%
)
Reflector type
M. Bass, E. W. Van Stryland, Handbook of
Optics vol. 2 (2nd ed.), McGraw-Hill (1994)
Jamali et al., In submission
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Use of reflectors
Comparison of
Al foil reflector
with no reflector
Irradiance measured in the
centre of the reactor
Jamali et al., In submission
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Optimise LED viewing angle
15 40 120 130
0
25
50
75
Ph
eno
l deg
rad
atio
n (
%)
Viewing angle (degree)
120°
40°
15°
Jamali et al., In submission
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Comparison
UV light
source
irradiance
(W/m2)
Pollutant I.C
(ppm)
Reaction
time
(h)
Reaction
rate
(mol.l-1.s-1)
Degradation
(%)
1 LED
(our results)1
9.055 Phenol 10 4 6.41 x 10-9 87
7 UVA lamps2 70.6 Phenol 20 3.5 1.45 x 10-8 86
The reaction rate in Vezzoli et al. is 2.2 times faster compared to our test.
However, the irradiance used in our experiments was 7.8 times less.
^ ^ ^ ^
^^
1. Vezzoli et al. Applied Catalysis A: General 404 (2011) 155-163 1 Jamali et al., In submission
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Optimal design?
Bucky Ball Batch Reactor
• 20 hexagons and 12 pentagons
• LED on each corner
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From batch to flow
UV light
Quartz
Quartz
Quartz
Quartz
Titanium dioxide
Titanium dioxide
UV light
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Optimal design
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Optimal design
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Improving mass transfer
• Microreactors middle plate
microchannels
lower plate
catalyst coating glass plate
transparent to light
upper plate
Advantages
• excellent temperature control
• excellent flow rate control
Disadvantages
• high pressure drop
• small throughput
(Van Gerven, Mul, Moulijn, Stankiewicz)
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Photo(cata)lytic microreactors
Takei et al., 2005
Fukuyama et al., 2004
Lu et al., 2004
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Research evolution
PAST APPROACH
CURRENT APPROACH
PROPOSED APPROACH
external HID
external LED, OF
internal LED
(Van Gerven, Mul, Moulijn, Stankiewicz)
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Improving energy/catalyst efficiency
MACROPORES
w > 50 nm
MESOPORES
2 < w < 50 nm
MICROPORES w < 2 nm
MACROPORES
w > 50 nm
MESOPORES
2 < w < 50 nm
MICROPORES w < 2 nm
Proof of concept still required!
(Van Gerven, Mul, Moulijn, Stankiewicz)
External light Internal light
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Photosynthesis
Photosynthetic cell culturing (algae biotechnology)
closed photobioreactors (option 1)
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Photosynthesis
Photosynthetic cell culturing (algae biotechnology)
outdoor
open
ponds
(option 2)
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Photosynthesis
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Photosynthesis
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Introduction
The curve is strain dependent
Light-response curve of photosynthesis (P-I curve)
Light compensation point
Light saturation point Light inhibition point Optimum Intensity
Proper intensity range
Photosynthesis
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Photosynthesis
Theoretical
maximum for open
ponds based on
useful solar light
intensity and
photosynthetic
conversion
efficiency
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Photosynthesis
Quest for optimal
combination between
open ponds and closed
photobioreactors
e.g. Proviron, Belgium
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Case 3: LEF
Improved sunlight distribution in algae ponds
(Ranjbar,Van Gerven, Stankiewicz)
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Improving light ingress in pond
(Ranjbar,Van Gerven, Stankiewicz)
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LEF design by modeling
• Ray tracing
technique
• Validation of
model with
literature and
experimental
data
(Ranjbar,Van Gerven, Stankiewicz)
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1-Optimum Degree of Dilution
The maximum intensity of
sunlight is a factor of
geographic latitude. For Gran
Canaries the relation between
degree of dilution and expected
enhancement in productivity is
shown in this graph (for
maximum light intensity at noon
June 21st)
Enlargement Ratio Optimization for Maximum Intensity
(June 21st, Noon)
y = 0,0075x3 - 0,2306x2 + 2,0518x
- 1,2854
R2 = 0,9996
Max=6.5275,for 4.368
1
2
3
4
5
0 2 4 6 8 10 12
Degree of Dilution
En
ha
nc
em
en
t in
Ph
oto
sy
nth
es
is
4.1-6.5 times
Indoor application
(Ranjbar,Van Gerven, Stankiewicz)
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2- Shape and Geometry
Indoor application
‘groove’ ‘parabola’
(Ranjbar,Van Gerven, Stankiewicz)
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2-Effect of Shape on Productivity
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Illu
min
ate
d A
rea (
%)
1 2 3
Irradiance Distribution
Below Compensation Point
Optimal Range
Over Saturation Point
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Illu
min
ate
d A
rea (
%)
1 2 3
Irradiance Distribution
Below Compensation Point
Optimal Range
Over Saturation Point
0
0,5
1
1,5
2
2,5
3
3,5
4
En
han
cem
en
t R
ati
o
Parabola Groove Without LEFs
LEF Performance, Geometry Effect
0
0,5
1
1,5
2
2,5
3
3,5
4
En
han
cem
en
t R
ati
o
Parabola Groove Without LEFs
LEF Performance, Geometry Effect
Indoor application
(Ranjbar,Van Gerven, Stankiewicz)
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The material should have 1-Good optical properties 2-UV durable 3-Not brittle 4-Cheap and easy to form
Since the size of distributor and amount of polymer is a considerable cost, it is preferred to reduce the amount of polymer. A hollow distributor filled with water is easier to implement.
The candidates are 1-PVC (food grade, UV durable) 2-PET 3-Mylar 4-PC
3- Material
1
1,5
2
2,5
3
3,5
4
Solid Mylar Filled with Water Hollow Distributor
0
0,5
1
1,5
2
2,5
3
3,5
4
En
han
cem
en
t R
ati
o
Parabola Groove Without LEFs
LEF Performance, Geometry Effect
Indoor application
(Ranjbar,Van Gerven, Stankiewicz)
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polycarbonate
acrylic
mylar
3- Material
Indoor application
(Ranjbar,Van Gerven, Stankiewicz)
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1- Effect of orientation and daily variation
Outdoor application
Effect of Orientation
1
1,5
2
2,5
3
3,5
4
7 8 9 10 11 12 13 14 15 16 17
Time
Imp
rovem
en
t R
ati
o
E-W
N-S
NW-SE
Summer,
21 JuneAverage daily improvement
•N-S = 1.750
•NW-SE = 2.077
•E-W = 2.766
(Ranjbar,Van Gerven, Stankiewicz)
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2- Effect of annual variation
Outdoor application
1
1,5
2
2,5
3
3,5
21-jun 20-aug 19-okt 18-dec 16-feb 17-apr 16-jun
Date
Imp
rovem
en
t R
ati
o
Average annual improvement
Ordinary LEFs=1.831
E-W orientation
(Ranjbar,Van Gerven, Stankiewicz)
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LEFs in practice
• Concept is proven
• More experimental validation under way
• Current dilution ratio = 1.8, however ideal ratio = 4.1-6.5
• Further optimisation needed
• Pilot scale, cost-benefit calculation still to come
(Ranjbar,Van Gerven, Stankiewicz)
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Conclusion
• Light energy is still under-utilised
• Advances require collaboration between chemical engineers and mechanical engineers/physicists
• Due to the energy crises and the advances in light technology, interest is growing again
• Process intensification required to increase efficiency/productivity