Citterio PDF

Cortona, September 19-23, 2010 Conference QdB/PAT: Advanced Technological and Regulatory Developments Impacting Pharmaceutical Manufacturing and
Control
Green Processing
Prof. Attilio Citterio Dipartimento CMIC Giulio Natta https://corsi.chem.polimi.it/citterio/
Greener Products (EPP) Selected by Combining Existing Standards

Environmentally Preferable, Well Managed, Sustainable
Recycled content Organic Low emitting Energy efficient Biodegradable

Focus on: Product attributes: Product Content Emission Profile Performance characteristics
EPP
Focus on: Process: Energy Consumption Source Defects Waste Generation Air & Water Emissions
Renewable energy ISO 14000 ISO 9000 LCI/LCA GHG Registry
Green Processing Cortona 2010
Chemical Characteristic Categories & Subcategories

Subcategory Criteria
A. Physical Safety
Fire Reactivity
Special
Flammability Explosivity
Corrosive Oxidant Radioactive
B. Human Health
Acute Chronic Air Water Soil
LD50, CMR
C. Ecological Impact
(includes long-term impacts used in life cycle analyses)
GHG, OD Solubility, ecotoxicity Persistence (PBT, vPvB, vPTor vBT))
Examples of Successful Substitution of Hazardous Chemicals

1. Electronic manufacture with CO2 (2.0 g memory chip needs 1.7 kg of chemicals and fossil fuel as well as 32 kg of water) 2. Boat paint without tin (as alternative to Tributyltin, Rohm and Haas introduced a broad spectrum antifoulant of isothiazolone family) 3. Fire extinguishers without freons (Pyrocool Technologies, Inc. developed non fluorine based fire extinguishing foam (FEF)) 4. Dry cleaning without perc (ScCO2 as viable alternative to 100,000 drycleaners worldwide using percholorethylene as solvent) 5. Car coatings without lead (PPG Industries developed a lead-free cathodic epoxy electrocoat for applications in automotive) 6. Lumber without arsenic (Chemical Specialties, Inc. introduced alkaline copper quaternary (ACQ) wood preservative as alternative to chromated copper arsenate (CCA) (40 million/y pounds of As and 64 of Cr(VI)) 7. Safe metal working fluids without depleting resources (bio-based oil and surfactants in MFW formulation to replace petroleum-based products eliminating several other components (2 billion gallons annually)
JB Manley, PT Anastas, BW Cue Jr. Journal of Cleaner Production 16 (2008) 743-750 Green Processing Cortona 2010
Environmental Chemicals In the News: Nanoparticle Concern

Simultaneous development of products and management of unintentional consequences
Internal dose in biological systems
What physiochemical properties determine the absorption, distribution and elimination of nanomaterials?
Early biological effects and altered structure/
function What physiochemical properties determine biocompatibility?

Adverse effects What are the critical determinants of toxicity for
those that are toxic?
Size of nanomaterials is an essential parameter? What when nanomaterials are chemically bound to matrix?
Reduction of Products/Materials Impact
Chemistry Facilities Process
Supply chain
Energy
After
Packaging
H2O
Before reduction of environmental footprint
Greener Processes: Primary Categories
Material Efficiency & Waste Prevention Energy Water Safety Renewability Product Quality
Other:
Social Responsibility Inventory Storage included in materials efficiency and waste
prevention Process Optimization/Substitution Best Available Technology (BAT)
Process Improvement vs. Innovation

Aim Process optimization Performance improvement of existing concepts Focus Interdisciplinarity
Model, Weak num. method Kinetics/Therm.
Process Systems Multi-scale integration Model, software Modest Engineering of existing/new concepts Process intensification Development of new concepts of process, steps & equipment Experiment, phenomenon, interphase PAT, QdB Strong Chemistry/Catalysis, applied physics materials science, electronics
Process Intensification Strategy
Kinetics Process Heat transfer
Hydrodynamic Mass transfer

R. Bakker in Reengineering the Chemical Processing Plant, Marcel Dekker Ed., 2003
Kinetics Process
Reach the inherent kinetics of phenomena Maximize the transfer rate Fick Law : flow = coefficient x interface x gradient
Novel/Alternative Processes
Routes at increased concentration or even solvent-free Routes at elevated temperature and/or pressure (simple O.C.) Routes mixing the reactants all at once (domino reactions) Routes using unstable intermediates (in case toxic and/or hazardous) Routes in the explosive or thermal runaway regime Process simplification e.g. routes omitting the need of catalysts or (complex) separation UO Gathering
Hessel, V. et al.; Angew. Chem. IE 43 (2004) 406 ER Murphy, et al.; Angew. Chem. 119 (2007) 1764
Process Characteristics of an Intensified Plant
Raw Materials
(Sustainable)
Green Chemistry
Good EA and RMI Low solvents Het. Catalysts Safe reagents
Intensified Process
Product
Low residence times, minimal effluent separation, energetic efficiency, zero wastes, limited supply, improved intrinsic safety, process flexibility, or specification adaptability (QdB), fast answer to market, improved controls (PAT), just in time production on order.
Green Metric related to Chemical Reactions: Non Stoichiometric Conditions

A + MW (g/mol) a Moles x Mass (g) ax Conservation Mass Law: B b z bz Q + q y qy P p y py
ax + bz = qy + py +w, z > x, = z - x Yield, =
p p = Atom economy, AE = a+b q+ p

Reaction mass efficiency, RME =
( )( AE ) py py p = = = ax + bx ax + bz a + b + (b / x) SF
py y = px x
b b = 1+ Stoichiometric factor, SF = 1 + x (a + b) x (q + p) q Environmental impact factor based on MW, E = p qy + w 1 = 1 Environmental impact factor based on actual mass, Em = py ( )( AE )
Reaction Mass Efficiency Master Equation

1 1 1 = RME = ( )( AE ) MRP AE ( ) ( )( ) SF SF ( AE ) [ c + s + ] 1+ ( SF ) ( m p )
Parameters: reaction yield AE atom economy SF stoichiometric factor; MRP
SF =1 implies no excess reagents SF > 1 implies excess reagents used materials recovery parameter
Based on the law of conservation of mass for balanced chemical reaction/equation.

Andraos, J. Org. Proc. Res. Develop. 2005, 9, 149; 404
Key Process Metrics

Process Mass Intensity:
( An + Sn ) PMI = ( P + Q)
An = mass of raw materials input to the process less any amount recovered and recycled as an integral part of the process Sn = mass of ancillary materials less any amount recovered and recycled as an integral part of the process P = mass of recovered product, Q = mass of recovered co-product Key Question: Water to be included or considered as a separate category?
Linear vs. Convergent Syntheses
7 Steps, 80% yield per step

1 2 3 4 5 6 1 2 3 7 4
5 7 6
W = 24 S = 35
W = 16 S = 24
W = total wt of all SM S = sum of steps each SM must pass through

J.S. Hendrickson, Pure App Chern, 1988, 60 (11), 1563.
Linear Synthetic Sequences

S3 S4 Sn+1
S1 + S2
P1 w1
P2 w2
P3 w3
Pn wn
wj =mass of waste in step j; cj = mass of catalyst in step j sj = mass of solvent in step j; pj = MW of target product in step j j = fractional yield in step j; x = moles of reagents in step 1 (scale reaction)
Assumption; stoichiometric conditions in each step

Em ,total =
(w
j =1
+ cj + sj )
n
pn x j j =1
RMEtotal
1 = 1 + En ,total
Overall yield = j
j =1
Theoretical mass of final product = pn x
Product yields is true only if all of collected intermediate product Pj is committed to Succeeding (j + 1)th step.
Algorithm for Convergent Sequences

1. Analyze each linear sequence as above 2. Normalize scales of each sequence by multiplying smaller scale sequence by a factor given by
large scale sequence xlarge overall factor = small scale sequence x small overall
3. Analyze convergent step using larger scale of two sequences. 4. Sequence of steps following convergent step are analyzed as per algorithm for linear sequences using larger scale of two preceding sequences. 5. Overall yield for entire process is given by
total = (overall yield for larger scale path)(yield of convergent step)(overall yield for forward steps)
Unfriendliness Factor Q
In order to take into account the different toxicity of products, the Q factor is introduced. The product of E factor and Q factor (EQ factor) it is an indicator of efficiency/environmental impact of a reaction: EQ Factor = E factor x unfriendliness factor Q Q quantifies the undesirable character of by-products/wastes
Q = 0 for water Q=1 for benign salts as NaCl Q up to 1000 for very toxic products
Waste prevention is always preferred over waste remediation
Energy to Normalise Environmental Impacts

Energy is one of the major constraints on the production process. Because energy is currently produced from depleting resources, there is a natural limit to how much energy can be produced. Therefore, less energy-intensive processes are more sustainable. The analysis must take in consideration the contributions of the energy to transport, the manufacturing process, support to labour, production of energy itself, but also contributions from end-of-life and complete emissions abatement. Energy resources Energy transformation system Fuels Level I. Direct fuel use Level II. Input to process Level III. Raw materials Level IV. Capital
Gross Energy requirements
Green Metrics in Energy (Chemical Processes)

total process energy (MJ) mass of product (kg) total solvent recovery energy (MJ) Ers = mass of product (kg)
En =
Level of energy performance of chemical process.

Level 0 Level 1 Level 2 Base case Benchmark heat integration Optimum heat integration Energy requirement by an unimproved process, energy produced bu a process and recovered is included. Minor improvements including heat exchange networks, improved solvents, incorporation of power generation Optimized heat exchange flowsheet, change in process conditions that enable further heat integration (the basic aspects of the process such as catalysts, feedstock etc are the same as in base case) The same reaction chemistry as in base case but can incorporate changes in feedstock, improved catalyst, different process configuration, alternative separation techniques. Change of enthalpy of reaction at standard conditions assuming 100% yield.
Level 3
Process redesign
Level 4
Theoretical energy requirement
Environmental Performance Metrics in Chemical Manufacturing and for Chemical Products

Manufacturing
Resource Related Material intensity
Product Use
Material intensity
Percent first-pass yield Percent ultimate yield Percent process uptime Percent atomic efficiency Percent post-consumer waste used Material efficiency (unit consumptions, including water/pound of product)

Value per kg Pounds replaced Resources saved

Energy intensity

Energy intensity
BTUs/pound Total energy use Minimum "practical" energy use
Value/BTU used Energy saved by use

Renewable

Packaging Total kgs kgs/kg of product

Percent of product Recyclable
Environmental Performance Metrics in Chemical Manufacturing and for Chemical Products

Manufacturing
Environmental-Burden Related
Product use Packaging Recyclable Biodegradable
Environmental incidents Frequency Severity Practical worst-case scenario Toxic dispersion Airborne toxics Carcinogens Volatile organics Particulates Acid gases "Hazardous" wastes Aquatic toxicity/oxygen demand Listed hazardous air (and water) pollutants TRI chemicals (EPCRA Title III Section 313) 33/50 chemicals
Toxic dispersion Global warming Ozone depletion Persistence Bioaccumulative Hormone mimics
Carbon Dioxide as Green Solvent, Reagent and Raw Material

Solvent Polymer Processing Microelectronics Processing Textile Dyeing
Reactive dyes (Y > 95%)
O O S R O O S O O
Dye Solubility ln(xP/Pref) = A + c(-ref)

10x10-6 10x10-6 333.15 K 333.15 363.15 KK 363.15 393.15 KK 393.15 K data Calculated Calculated data 8x10-6 8x10-6
Mole fraction of DY54 Mole fraction of DY54
6x10-6 6x10-6
Monitored on line by Vis. op.f.

4x10-6 4x10-6 2x10-6 2x10-6 0 0 0.0 0.0 0.2 0.2 0.4 0.4 0.6 0.6 0.8 0.8 1.0 1.0
Density of CO2 (g/cm3)3 Density of CO2 (g/cm )
Reagent
NH2 NaNO2 X ROH/H2O, CO2 (5-65 bar) -NaHCO3
+ N2
HCO3
X
H2O2 -N2, -CO2 X
50-93 %
Raw Material
O O OH
O O O OH
C O
Coates catalyst
a) Alternative Reagents to Prevent Waste

Aromatic polyiodination (Synthesis of Contrast Agents)
3 ICl / mHX - 3 HCl / - mHX
R
R I R1 I I R
3/2 I2 / ox. agent

R
R1
- 3 HY (3/2 H2O) 6/5 I2 / 3/5 HIO3 - 9/5 H2O
Iodinating Atom agent Economy ICl 78% I2 100% 94% I2/HIO3 I2/H2O2 91%
Alternative process based on HIO3 (from natural NaIO3) :

R 5 R1 R + 6 I2 + 3 HIO3
H+
R I 5 R1 I R I + 9 H2O
Monitored on line by redox electrode
Recovery of wasted iodine I- + HIO3 + H+ I2 + H2O

b) Alternative Process Design Reduction of RMI Synthesis of 6-oxo-5H-dibenzo[b,f]azepine
NO2 CH3 RONa
O2N
NO2 H2/Ni
H2N
NH2
H+/
N H
Pd/maleate S 8/ RX
N R
1) NBS, 2) base
N R
N H
1) COCl2, 2) NH3
NaCNO/
RME = 0.06 RMI = 19.3
N
CONH2
4 steps
N
CONH2
6-oxocarbamazepine
carbamazepine
DE Pat.DE-Os 2.011.087; Be Pat.N.597.793; Jp Pat N. 73.066; Eur.pat.EP 0.028.028

E Factor and Energy Balance in the Production of 10-Oxo-5-Carbamoyl5H-dibenzo[b,f]azepine

Step 1 Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 Step 9 Step 10 Step 11 Total "E" factor Energy (x 100Kcal) 7,26 6,60 0,92 1,38 7,48 16,96 1,70 2,37 5,49 15,30 Step 10 1,25 1,50 Step 7 3,08 0,66 4,31 1,57 Step 4 1,65 1,10 Step 1 0,22 0,55 0,00 0,10 0,40 33,46 48,39
20,00
40,00
60,00
80,00
100,00
"E" factor
Energy (x 100Kcal)
Alternative process from key raw material

N CN
O O2 N CONH2
EA = 100%,
Oxidations through Nitroxide Radicals: R2NO Chemistry

+e
Red.
.. N O .. N O .
+R
.+ N O pKa = - 5.5
+ R . (k = 109 M-1s-1)
H-abstraction
.. N O R
BDE = 68-77 kcal/mol (R = H)
-e
Ox.
N O
+ R-
Nitroxide Di t-Bu TEMPO 4-OH-TEMPO
E1/2 0.187 0.203 0.224
E1/2 (V) (H2O) 0.657 0.728 0.813
Nitroxide 4-O-TEMPO Fremy Salt Succinimide-N-oxyl
E1/2 (V) 0.301 0.901 1.112
Keggin Systems for Alkylaromatic Oxidation with Molecular Oxygen

Defective Keggin (insertion of metal cations)
Keggin H4PVMo11O40 Approach: Combinatorial Catalysis

R
OH R' O O
redNPMoV
O2 (1 atm)
O R O O R'
. NO
N OH
oxNPMoV
1/2 O2 H2 O
1/2 O2
H2 O
Oxidation of Benzylic Methylene by O2 Catalyzed by Defective NHPI/Keggin(V)/C

Runa 1 2 3
X
Aromatic
N CN
Cl
Product
X
Yield %b (X) 15(OH) 75(O)

Cl
Time (h) 2 4 6 3 5 2
N CN
X
19(OH) 68(O) 11(OH) 82(O) 12(OH) 64(O)
4 5 6
a
MeO MeO
MeO MeO
16(OH) 12(O)c
X
3(OH) 38(O)
reaction conditions: 50C, 1 atm O2, Cat. [Fe/Cu (2:1)] 2 %, NHPI 2%, CH3CN. bYields are obtained by GC-MS; runs 1 and 2 are on isolated product >95% purity (50 kg scale). C44% of the corresponding acid; 84% at 24 h.
d) Processing of Materials: Carbon Nanotubes Production

MWCNT are produced with FBCCVD technology at Politecnico di Milano (10-15 walls, aggregated in bundles of 200 nm length) from ethylene and H2. When purified they contain < 2% inorganic impurity and < 1% amorphous carbon. Debundled by surfactants and polymers
Catalyst -Al2O3 / Fe
CNT Combined Purification and Derivatization Process

Strong oxidant acid purification
(to eliminate catalyst and amorphous carbon)
COOH
OH
COOH
COOH
OH
OH
Arylation via radical reactions:
Arenediazonium cation /
R*
R*
R*
Water dispersed MWCNT (a) Without derivatisation (b) With covalent functionalisation
Salt Free Arylation of MWCNT by CO2/NaNO2

Classical methods of arenediazonium salts generates as by-products large amounts of salts (RMI = 4-7).
Approach developed to overcome these limits:
CO2 + H2O
NH2
H2CO3
(pKa H CO = 3.3 ~ pKaHNO )

2 3 2
Yield monitored by redox electrode

NaNO2, CO2 (5-65 bar)
COOH
+ N2
HOOC
ROH/H2O, -NaHCO3
HCO3
COOH COOH
HOOC
80-95%
CNT-Polymer composites (dispersion/covalent attachment) - Polyesters, Polyurethanes, Epoxy resins

Recovery of Silica Gel from Rice Hulls
SiO2
HX + 2 NaOH Na2SiO3 NaX + SiO2

140C
Sol/gel on line monitor
HX = CO2 + H2O
Surf. area: 40 m2/g SiO2 content: 86-90% Yield on SiO2: 85-89% Recovery of KCl: 3-4% Recovery of carbon black: 6-10% Recovery of MnO2 = 0.3%
Surf. area = 150-200 m2/g SiO2 purity: 99%
Energy saved based on silica glass fusion: 82%
Organic Sustainable Raw Materials and Bioprocessing
Photosynthetic biomass Starchy crops Sugar crops Oil seeds Lignocellulosics Plants and animals wastes Water Atmospheric gases (e.g. CO2, methane)
Bioprocessing: A more natural and cost-effective means of converting natural feedstocks into platform chemicals
Use Renewable Feedstocks

ENERGY
Wheat Sugar beet Rapeseed Linseed Cramble Potatoes Maize Hemp Barley Flax Nettle Cereal straw Short Rotation Coppice Miscantus
FUEL
Jatropha OSR
OIL
Olive Camelina Echium
STARCH
Calendula Peppermint Borage
FIBRE
Poppy
Heberlea
SPECIALTY
The Biomass Triangle
FOOD
Animal Feed
Energy and Chemicals
Biorefinery of Grain
Grain (Wheat)
Milled Bran
Pentosans: 25% Cellulose: 21% Crude fiber: 10% Protein: 13% Phytate: 4% Starch: 8% Total sugar: 5% Reducing sugars: 4% Lipid: 4% Vitamins: Choline, Inositol, Niacin, Tocopherols, Pantothenic acid, p-Aminobenzoic acid, Thiamine, Riboflavin, Folic acid, Biotin:
Milled Endosperm
Starch: 70% Protein: 10% Phytate: 0.5% Vitamins: Niacin, Biotin, Tocopherols, Pantothenic acid, Pyridoxine, Thiamine, Riboflavin, Folic acid, p-Aminobenzoic acid, Inositol.
Germ
Protein: 25% Total sugar: 17% Raffinose: 7% Lipid: 12% Phytate: 2% Vitamins: Niacin, Biotin Pyridoxine, Pantothenic acid, Thiamine, Riboflavin, p-Aminobenzoic, Folic acid, Inositol.
Aleurone layer
Protein: 18% Vitamins: Niacin, Pantothenic acid, Pyridoxine, Thiamine, Riboflavin, Betaine
-4 -3 Oil -2 -1 Ethylene, Polyethylene Methanol, Ethanol

Natural Gas Methane
Ethane
Glycerol
0 1 2 3 Limestone 4 Ox. N Coal Carbohydrates Lactic acid
Acetone Ethylene Glycol, Ethyl Acetate Polystyrene, Polyvinylchloride Phenol Polyester Acetic Acid
Matching Raw Material and Desired Product Oxidation States
Carbon Monoxide
Carbon Dioxide
The Biorefinery Using the Cn Bio-based Platforms

Chemistry that does not use oil, is recyclable, and biodegradable
C1
C1 platform dominated by the methane business. A basic building block for petrochemicals.
C2
C2 platform dominated by acetic acid and ethanol producers.
C3
C3 platform dominated by lactic acid for use in biodegradable polymers and other compounds (Cargill, Purac, Galactic) C3 platform from Glycerol is a remarkable alternative. C4 bio-based platform based on succinic acid
C4
C5
C5 platform reverts back to sugar compounds such as xylose
Green Raw Materials: Glycerol as C3 Platform Acid-base Reactions

H
Biodiesel
O
OMe
O
-H2O -H2O
OH
O OH
FAME
O O O O O O
HO
OH
RCO2H
OR RO OCOR'
OH O O O
GLYCEROL CARBONATE
GLYCEROL
O OH
HCl -H2O
O
(RO)2CO (CO2)
OH
Fatty Acids
HX, RRC=CH2
XO
(RO)2CO NH3
O O NH
Cl
ROCOOR
OX O
OH
CH3
O O O
O O
O R GLYCEROL
DICARBONATES
R R'
Green Raw Materials: Glycerol as C3 Platform Oxidative Reactions
2,3-dihydroxypropionic acid (Gold nanocluster, O2, Base) 95% COOH

C O
CH2OH CHOH COOH
COOH C O
CH2OH C O
CHO
CHO
CH2OH C O
COOH
O2/Au
HNO3 3-4 days

CH2OH CHOH CH2OH
CH2OH
Acetobacter Sp
Dihydroxyacetone
CH2OH CHOH CHO
H2O2 FeSO4, rt
H2O2 CaCO3 KHSO4 or K2SO4 200C 0,5~1h
COOH CHOH COOH
CHO C O CHO CHOH CHO COOH CHOH CHO
CH2 CH C N
CH2 CH CHO
CHO
(O2/NH3)
Glycerol Reductive Processes

CH3
H2, cat. 150C 50 atm
CH3 CH2 CH3

OH HO O HO H OH OH
CHOH CH3 CHOH CH2OH

C-O bond breaking
3 CH3OH
CH2OH CH2OH
+ MeOH
CH3
C-C bond breaking
CH2OH CHOH
130C
glucose
CH2OH CH2OH
Clostridium CH2 Butyricum (40C)
RT organism
Micro
CH3 CH-I CH3
CH2OH CH2 CH2OH
HI
excess
CH2OH
1,3-propandiol
CH3 CH2 CH2OH
CH3 CH2 CH3
E. Chynoweth, ICIS Chem. Business (Weekly) 39 (1) (2006) 1. E.P. Maris, R.J. Davis Journal of Catalysis 249 (2007) 328337 C. Montassier, D. Giraud, J. Barbier, Polyol Conversion by Liquid Phase Heterogeneous Catalysis over Metals, Elsevier, Amsterdam, 1988, p. 165.
Green Chemistry means that Engineering and Process must Adapt to a more Safety Oriented Chemistry
Politecnico di Milano
Green Chemistry Group Dipartimento CMIC Giulio Natta Via Mancinelli 7, 20131 Milano
Thank you very much for your attention!

Thymine Ribonucleotide Synthesis

O N HO H H OH O H N H OH O
O
O
Br
2,5
N O O O O Br O N O
OCOMe
MeCN/4h 55 %
1 One stage?
O N HO O N O
OCOMe
80 % Zn/MeCN/AcOH 25C/8 h
O N O O O O O N O
R'
.
OCOMe
KOH/MeOH 20C/5 h 93 %
-fragmentation
Overall Yield = 41 % E factor = 18
c) Optimization of One-reactor Multistep Synthesis

Variables: - Solvent (10 + 10 mixtures) - Derivatiz./Reduction Time - Temperature - Metal catalysis (Ti, V, Cu)
O N HO H H OH O H N H OH O
1,1
Br OCOMe
MeCN/H2O(5%)(0.7 h, 10C) Zn/TiCl3/AcOH (1.5 h, 10C)

O N HO O N O
Overall Yield: 89% RMI = 4.2 (from 18)

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Cortona, September 19-23, 2010 Conference QdB/PAT: Advanced Technological and Regulatory Developments Impacting Pharmaceutical Manufacturing and

Greener Products (EPP) Selected by Combining Existing Standards

Recycled content Organic Low emitting Energy efficient Biodegradable

Renewable energy ISO 14000 ISO 9000 LCI/LCA GHG Registry

Green Processing Cortona 2010

Chemical Characteristic Categories & Subcategories

Acute Chronic Air Water Soil

GHG, OD Solubility, ecotoxicity Persistence (PBT, vPvB, vPTor vBT))

Green Processing Cortona 2010

Examples of Successful Substitution of Hazardous Chemicals

Environmental Chemicals In the News: Nanoparticle Concern

function What physiochemical properties determine biocompatibility?

those that are toxic?

Reduction of Products/Materials Impact

Chemistry Facilities Process

Before reduction of environmental footprint

Green Processing Cortona 2010

Greener Processes: Primary Categories

prevention Process Optimization/Substitution Best Available Technology (BAT)

Green Processing Cortona 2010

Process Improvement vs. Innovation

Model, Weak num. method Kinetics/Therm.

Green Processing Cortona 2010

Process Intensification Strategy

Kinetics Process Heat transfer

Hydrodynamic Mass transfer

Green Processing Cortona 2010

Process Characteristics of an Intensified Plant

Green Processing Cortona 2010

Green Metric related to Chemical Reactions: Non Stoichiometric Conditions

ax + bz = qy + py +w, z > x, = z - x Yield, =

p p = Atom economy, AE = a+b q+ p

Reaction Mass Efficiency Master Equation

Based on the law of conservation of mass for balanced chemical reaction/equation.

Green Processing Cortona 2010

Key Process Metrics

Green Processing Cortona 2010

Linear vs. Convergent Syntheses

7 Steps, 80% yield per step

W = total wt of all SM S = sum of steps each SM must pass through

Linear Synthetic Sequences

Assumption; stoichiometric conditions in each step

Theoretical mass of final product = pn x

Green Processing Cortona 2010

Algorithm for Convergent Sequences

Green Processing Cortona 2010

Waste prevention is always preferred over waste remediation

Green Processing Cortona 2010

Energy to Normalise Environmental Impacts

Gross Energy requirements

Green Metrics in Energy (Chemical Processes)

Level of energy performance of chemical process.

Theoretical energy requirement

Green Processing Cortona 2010

Environmental Performance Metrics in Chemical Manufacturing and for Chemical Products

Value per kg Pounds replaced Resources saved

BTUs/pound Total energy use Minimum "practical" energy use

Value/BTU used Energy saved by use

Packaging Total kgs kgs/kg of product

Percent of product Recyclable

Environmental Performance Metrics in Chemical Manufacturing and for Chemical Products

Product use Packaging Recyclable Biodegradable