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