Post on 15-Nov-2020
P. I. in the UK:
PIN, PIG and OBRs
Adam Harvey
Professor of Process Intensification
Process Intensification Group
Chemical Engineering & Advanced Materials
Newcastle University Zeton BV, 7th November 2012
“P.I.” Process Intensification
“The strategy of making dramatic*
reductions in the size of process plant
items by re-examining the fundamentals
of their heat and mass transfer”
*at least an order of magnitude
Before: Current Chemical Process
Large
Smelly
Dirty
Dangerous
After
Smaller
Leaner
More efficient
Reduced Emissions
P. I. in the UK: PIN
“PIN” the Process Intensification Network. Managed by:
Prof David Reay Heriot Watt University
Prof Colin Ramshaw Cranfield University
Prof Adam Harvey Newcastle University
21st Meeting: March 2013
~300 on the mailing list: industry, academia, UK and
overseas
EPIC conference in Manchester 2011 (with the IChemE)
Email dareay@aol.com or adam.harvey@ncl.ac.uk to join
P. I. in the UK: PIN
2nd Edition just
completed
Process Intensification Group [PIG]
5 academic staff:
Adam Harvey (OBRs, biofuels)
Kamelia Boodhoo (SDRs, polymerisation)
Jonathan Lee (RPBs, carbon capture)
David Reay (heat pipes)
Sharon Orta (algae, fuel cells)
5 research associates/visitors
18 PhDs
http://pig.ncl.ac.uk
PIG Activities
Technologies
Oscillatory Baffled Reactors (OBRs)
Spinning Disc Reactors (SDRs)
Rotating Packed Beds (RPBs)
Heat Pipes
Reactive Extraction (RE)
Microreactors: catalytic plate reactors
PIG Activities
Application Areas Technologies
High throughput screening OBR
Heterogeneous Catalysis
i. Catalytic cracking for biofuels
ii. Solid catalysts for biodiesel
ii. OBR
Crystallization SDR, OBR
Biofuels & biorefining OBR, RE
Polymerisation SDR
Thermal management Heat Pipes, Heat pumps, Organic
Rankine Cycles
Bioprocessing SDR
RPB
CO2 Absorption RPB
Biofuel Research Projects
1. Reactive Extraction (Biodiesel) 1. Rapeseed [PhD] Malaysian Govt
2. Jatropha + other inedible [PhD] UKIERI
3. Algae [PhD] Nigerian Govt.
2. Oscillatory Baffled Reactors: 1. Bioethanol production [PhD] Nigerian Govt
2. Biobutanol production [PhD] Malaysian Govt/TSB
3. Biodiesel screening [PhD] EPSRC
3. Catalysis: 1. Heterogeneous, Biodiesel [PhD] EPSRC
2. Vegetable oil cracking [PhD] Indonesian Govt.
3. Catalytic cracking of algae [PhD] Nigerian Govt.
+ various other biofuel/biorefining projects (Intensification of phytoremediation about to start 2013)
Case Study 1: A Saponification reaction
in an Oscillatory Baffled Reactor
Achieves plug flow
by tanks in series
rather than
turbulence
OBR characteristics
Long residence times in a compact
reactor, whilst maintaining plug flow
and good two phase mixing.
Niche:
BATCH CONTINUOUS
For “long” processes
The Reaction
Hydrolysis of a naturally occurring mixture of
alkyl and steryl stearates, using
concentrated sodium hydroxide in an
ethanol and water solvent.
75 m3 Batch Reactor [50 m3 fill]
115 oC
2h "reaction time” in a 24h batch cycle
Molar ratio ~ 0.9
Incentives for Change
1. SAFETY 2. Product quality
3. Energy savings
Experiments Conducted
Temperature fixed at 115 oC
Molar ratios in the range 0.6 - 1.05
Residence times in the range 8 - 25 minutes
TARGET PRODUCT
Desired product, sterol A > 23 %
Undesired product, sterol B < 10 %
Can it be done ?
Effect of Temperature (modelling)
(+ the modelling wasvalidated by experiment!)
Operating Windows
Monitoring: FTIR ATR Cell
SUMMARY: OBR Saponification
The OBR could be used to perform the reaction:
..at lower temperature (safer, reduced energy)
..with improved product quality
..more consistently
..in 1/10th the reaction time (inherent kinetics)
..in a reactor 1/100th the volume
The product can be monitored online
Operation is flexible (wide operating window)
Was the reactor built?
No!
“Champion” made redundant!
No "risk takers“ remaining
Lack of understanding (company dominated
by chemists...)
Recent Directions for OBRS @
Newcastle
1. Mesoscale OBRs (<6mm diameter)
2. Bioreactions
3. Crystallization
“Meso OBRs”: What are they?
(a) Integral baffles
(c) Central baffles
(b) Helical baffles
Meso OBR: Platform
Meso OBRs: What are they for?
Features:
Low flow rate
Can suspend solids
Controllable mixing of L-L systems
Uniform shear
Plug flow
Residence times of the order of hours in
reactor a few metres in length
MesoOBR Application:
Imine synthesis
• Fundamental role in several applications
biological process
polymeric substance synthesis
dynamic combinatorial chemistry
• Reaction can be followed by IR in situ
• Entirely liquid phase
Benzaldehyde N-butylamine
MesoOBRs: “Dynamic Screening”
MesoOBRs: “Dynamic Screening” Validation
MesoOBRs: Multivariate Screening, or
“Dynamic Design of Experiments”
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0
50
100
150
200
250
3000.8
1.01.2
1.41.6
1.82.0
2.2
concentr
ation (
mol dm
-3)
time (s)
ratio
Benzaldehyde reduction profile for different ratio and screening method
dynamic (1 to 2)
steady state (1:1)
steady state (1:1.5)
steady state (1:2)
MesoOBR: Biodiesel
Biodiesel with heterogeneous catalysts
as a familiar example of L-L-S reactions
to trial
Benchmarking with homogeneous
catalysts led to some interesting
results...
Effects of Residence Time, Catalysts and
their Concentrations on the FAME Content
Effects of residence time on FAME content at different catalysts concentrations
for RSO transesterification at 6:1 methanol/RSO molar ratio, Reo = 160, T = 60˚C.
70
80
90
100
0 5 10 15 20 25
% A
vera
ge F
AM
E a
t ste
ad
y s
tate
Residence time (mins)
0.75 wt% NaOH 1.0 wt% NaOH 1.0 wt% KOH
1.0 wt% NaOCH3 1.5 wt% KOH 1.5 wt% NaOCH3
Effects of Reaction Time on the FAME
Content (Numerical Model)
Effects of reaction time on FAME content at different catalysts concentrations for KOH
catalysed transesterification at 6:1 methanol/RSO molar ratio, 60˚C and 1% (w/w) water
based the RSO (** 5 wt% water).
MesoOBR: Biodiesel
1.Reaction times of only 2 minutes required
2. ..but conversion drops thereafter
3. .. so control of conditions has to be tight for this
to be realised/observed
4.Modelling clearly shows that this is due to the
relative rates of the competing transesterification
(biodiesel-forming) and saponification reactions,
and this has been validated by experiment.
OBBs: Oscillatory Baffled Bioreactors
Batch Oscillatory Baffled
Bioreactor: BOBB
Self-contained
Autoclavable
Used for ABE fermentation
O.F. Mixing Enhances Cell Growth
0.02 0.05 0.05 0.06 0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 470 938 1870
Glu
cose
co
nsu
mp
tio
n r
ate
(g
/L.h
)
Spe
cifi
c gr
ow
th r
ate
(1
/h)
Reo
Specific growth rate, μ Glucose consumption rate
ABE productivity in BOBB and STR
0.16
0.21 0.22
0.13
0.16
0.19 0.2
0
0.05
0.1
0.15
0.2
0.25
0.00 0.02 0.10 0.83
Solv
ent
pro
du
ctiv
ity
(g/L
/h)
Power density (W/m3)
BOBB
STR
Objectives PI Bioreactors ABE Findings Conclusion
ABE production per unit energy
Objectives PI Bioreactors ABE Findings Conclusion
13
2.1
0.14
9.9
1.8
0.24 0
2
4
6
8
10
12
14
0.02 0.10 0.83
AB
E p
rod
uct
ivit
y p
er u
nit
p
ow
er (
g A
BE/
kW.h
)
Power density (W/m3)
BOBB
STR
OBRs: Current State of
Commercialisation
1. Various under development with “NiTech”
(Glasgow, UK)
2004 – 2006: Industrial unit, James
Robinsons’, UK
2. Various in operation “behind closed doors”
3. First mesoreactor system sold, 2012
4. Pilot-scale facilities available at Centre for
Process Innovation (CPI), Teesside, UK
(mostly for biological processes)
Acknowledgments
Dr Anh Phan
Nasratun Masngut
Fatimah Mohd Rasdi
Valentine Eze