madhav sapre - industrial green chemistryindustrialgreenchem.com/pdf-docs/presentations/lonere...

GREEN ENGINEERING

&

PROCESS OPTIMIZATION

using Process Intensification Platforms

Madhav SapreCTO

Pi – Process IntensificationMumbai

22-04-2014 Copyright Pi-Process Intensification Experts LLP 1

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Sustainable Development

22-04-2014 2Copyright Pi-Process Intensification Experts LLP

“Development that meets the needs of the present without compromising the ability of future

generations to meet their own needs.”World Commission on Environment and Development (1987)

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12 Principles of Green Chemistry

• 1. Prevent waste rather than treat/clean it up later

• 2. Invoke atom economy

• 3. Design safer chemicals

• 4. Use & generate less toxic substances

• 5. Massively reduce quantities of solvents used

• 6. Design syntheses for energy efficiency

• 7. Renewable feedstock for large scale processes

• 8. Minimize steps in synthesis

• 9. Use of highly-selective catalytic reagents

• 10. Design materials that innocuously degrade

• 11. Real-time monitoring for pollution prevention

• 12. Minimise potential for accidents

P.T. Anastas and J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998, p.30

8 out of 12 can be achieved through intensification of processes & flow chemistry.


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12 Design Principles of Green Engineering

• 1. Prevention instead of treatment(of wastes)

• 2. Maximize Efficiency (of mass, energy, space & time)

• 3. Design separation & purification for ↓materials & energy

• 4. Inherent v/s circumstantial use of non-hazardous inputs

• 5. “Output-Pulled “ v/s “Input-Pushed” use of inputs

• 6. Keep-it-Simple ( complexity is an life-long cost attribute!)

• 7. Design GOAL targeted durability (not immortality)

• 8. Target the “need” (not unnecessary capacity/capability)

(“one-size-fits-all” solutions are a design flaw ! )

• 9. Minimize material diversity

(in multicomponent/multiproduct campaigns)

• 10. Integrate material & energy flows

• 11. Design for commercial “after-life”

• 12. Renewable rather than Depleting material & energy inputs

12 out of 12 can be achieved through intensification of processes & flow chemistry.


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Process Intensification


Process Intensification

Reactions

Flow Chemistry

Other Platforms

Unit Operations

Extraction

Distillation

Crystallization

Filtration

Drying

Air Pollution Control - Absorption

Effluent Treatment

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Pi Benefits


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Optimization Innovation


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Optimization - Principles


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Path to Optimization


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An established technique for performing reactions under conditions where :

Mixing

Temperature

Pressure &

Reaction Time

are precisely controlled and safely done.

Variables : ● stoichiometry, ● concentration, ● residence-time,

● temperature and ● pressure are easily adjusted and reactions optimized quickly.

Scale-up : nearly linear and usually done by numbering-up


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Flow Chemistry enables GREEN Engineering


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FLOW Reactors -Fast Track to Optimized ProcessesInspite of continuous processes being widespread in the chemical industry, the development of processes for Fine chemicals & APIs has historically been restricted to the centuries-old technique of iterative-batch-reactions.

Pressure to quickly discover & deliver compounds using scalable processes has compelled the synthetic chemists to harness Flow Chemistry techniques.

Commercial FLOW REACTORS are now an easily available & common enabling technology for performing synthesis in the laboratory & plant scale.

Cost benefits (↓size / ↑safety / ↑ energy efficiency / ↑ yield / ↑ purity) of flow reactors are so compelling, that the cost of the reactor is of subordinate interest.


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FLOW ReactorsTECHNOLOGY PLATFORMS

Selection of apt reactor technology platform is most important for better cost benefit realization :-a) HEAT Transfer Area cost -- for Heat Transfer limited processb) Reactor Volume cost -- for Mass Transfer & slow, kinetically limited process

Key types : Pi offers

Micro-reactors / Microchannel reactors

Falling-film micro-reactors - Tubular & “Dynamic-Tubular” flow reactors Spinning Tube-in-Tube reactors Spinning Disk reactors Spinning Disk FUMI reactors Oscillatory Tube/Baffled flow reactors (OBRs) Microwave assisted flow reactors Sonication-assisted flow reactors Multi-cell flow reactors

Aspirator flow reactors, etc. -


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Industrial Scale “Slurry” FLOW Reactors from Pi


Coflore “ATR” : Dynamic Agitated Tubular Reactor10 L “ATR” replaces a 8000+ L batch reactor with “high solids-slurry”

10 Litre

Ideal for Hydrogenations & Bio-Catalysis, etc.

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Biocatalysis in “Coflore”


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Biocatalysis in “Coflore”


Biocatalytic RESOLUTION of DL-AlanineComparison Batch v/s ATR (continuous)

Gilda Gasparini (AM Technology, UK)

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HYDROGENATION in “Coflore”


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EPOXIDATION in “Coflore”


Drivers: High atom efficiency, Tims & Energy conservation, high selectivity and virtually no degradation products (impurities)

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Industrial Scale Spinning-Disk FLOW Reactors


FUMI Spin Disk Spinning Disk Reactor

SpinPro-300

Volume : 300-1000 ml

Output : 10 T / day +

Forced Uniform Molecular Interdiffusion

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Spinning Disk Reactor - Principle


“FUMI” (Forced Uniform Molecular Interdiffusion)

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Industrial Spinning Disk Reactor


LAB /Small

PLANTREACTOR

1000s Tonnes/YrPLANT

REACTOR


Industrial ApplicationsReactions in Spinning Disk Reactors

GRIGNARD ReactionSafe, Atom Efficient, v-Low Impurities & Work-up

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Reactions in Spinning Disk Reactors

Halogen /Lithium Exchange


21 T/yr on a 2.5” Ø (0.2 ml) Disk // 84 T/yr on a 5” Ø (0.8 ml) Disk

Safe, Atom Efficient, v-High selectivity & No Work-up


14.76 T/yr on a 2.5” Ø (0.2ml) Disk // 60 T/yr on a 5” Ø (0.8ml) Disk

Reactions in Spinning Disk Reactors

Halogen /Lithium Exchange (cascade)Safe, Atom & Time Efficient, v-Low Impurities & Work-up

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Industrial Scale FLOW Reactors from Pi


PlantriX (Micro-Channel Reactors)

Plantrix (SiC) (cGMP) from the Netherlands

300 to 1500 Tonne/Yr50 to 275 Tonne/Yr

High Corrosion-Resistant Grade SiC (EKasiC from ESK) Very few & “secure” connections – safer operations & maintenance “non-leachable” & “diffusion-bonded” SiC (not brazed or bolted !)

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Reactions


GRIGNARD Reaction in PlantriXSiC Micro-Channel Reactor

uses ChemtriX PLANTRIX Micro Reactors

made of EKasic® (SiC) in a pharma API

production plant

Grignard Reactions


NITRATION

Drivers: Control reaction exotherm (runaway, explosive ) for process safetyHigh “mono- nitro” selectivity , high-productivity & GMP production

DSM selected ChemtriX v/s Corning. Reasons: very few and “secure” connections,

“non-leachable” & “diffusion-bonded” SiC (ChemtriX) v/s Glass or “brazed” SiC (Corning)

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• Highly Exothermic– Batch synthesis delayed 2 months for

DSC information

• Batch scale-up problematic– Yield not reproducible– Increased formation of by-product led

to formation of a gum which was difficult to purify

– Batch synthesis required significantly more time than expected STRONG

EXOTHERM onset at 130 ºC (1373 J/g)

Reactions :Nitration (Novartis)

http://dx.doi.org/10.1021/op200055r

Copyright Pi-Process Intensification Experts LLP www.pi-inc.co22-04-2014

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Process

Intensification

of

UNIT

OPERATIONS


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Unit-Ops -- Extraction


SpinPro SDE-300

Volume : 300 ml

Throughput : 10,000 L / day +

Extremely High Extraction Efficiency

Drivers: Complete product extraction, ideal for recovery of solvents/organics from waste water, high-productivity & GMP equipment

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Unit-Ops -- Distillation


Reactor

SplitterExtractive

Distillaton

Solvent

Recovery

Methanol

Recovery

Extractor

Azeo

Column

Decanter

Flash

Column

Color

Column

Flash

Column

Water

Water

Heavies

Methyl

Acetate

Water

Catalyst

Methanol

Acetic Acid

Reactor

Column

Impurity

Removal

Columns

Water

Heavies

Acetic Acid

Methanol

Sulfuric

Acid

Methyl

Acetate

Reactive Distillation

Eastman Chemicals

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Unit-Ops -- Intensified Distillation

22-04-20143

Copyright Pi-Process Intensification Experts LLP 33

HiGee Distillation

30 mt column replaced by a 1.5 mt column for MeOH Distn.

Drivers: v. high vapour-liquid contact surfaces // v. Low reflux ratios //v. Low energy consumption, v. low space requirements

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Unit-Ops -- Absorption


Pulsed-Jet Dynamic

Waveform Absorber

Drivers: v. high gas-liquid contact surfaces // v. high efficiency //v. low space requirements

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SUMMARIZINGProcess Intensified & Optimized Reaction & Operation Platforms

1. small footprint & low CAPEX ( a major advantage for sterile-processing & clean-room projects at a fraction of the CAPEX usually required)

2. v. small (and so low cost) Utility CAPEX -- due to v low peak-loads

3. v. high heat transfer area/volume ratios

4. discernable design-space -- QbD built-in

5. reproducible consistent quality & yields (impurity profile is more precise)

6. genuine feasibility for application of PAT (Process Analytical Tools)

7. highly flexible ( key equipments can be plug-&-produce )

8. v. high turn-down ratios ( 1000 : 1 times production capacities)

9. High intrinsic safety due to extremely low reaction volumes, low residence times and high degree of temp/pressure control.

10. easy Lab to Plant scalability

We now see equipments giving 10,000 MT/yr at 1 Litre reaction volume !


It will be interesting to see how the scene unfolds in INDIA ......

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Major Route Design Factors and Their Interactions


Quality

Safety

Cost

Durability / Robustness

Environmental Impact

Synthesis Process

T.Y.Zhang, Cem.Rev., 2006, 106, 2583.

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WISH YOU A

GREENER TOMORROW

THANK YOU

22-04-2014 37

?

Questions

Copyright Pi-Process Intensification Experts LLP

Madhav [email protected]

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