Real-World Cases in green chemistry.pptx

Center For Green Chemistry
and Green Engineering at Yale
and Green Engineering atYale
Real-World Cases in Green Chemistry
Lecture # 13
Date:
Course #

Outline
• What are the Presidential Green Chemistry Challenge Awards?
• Award Categories
• PGCCA Case Studies:
• 2016: Newlight Technologies, AirCarbon: Greenhouse Gas Transformed into High-
Performance Thermoplastic
• 2012: Buckman International, Inc.: Enzymes Reduce the Energy and Wood Fiber Required to
Manufacture High-Quality Paper and Paperboard
• 2011: Professor Bruce H. Lipshutz, Towards Ending Our Dependence on Organic Solvents
• 2008: SiGNa Chemistry, Inc.: New Stabilized Alkali Metals for Safer, Sustainable Syntheses
• 2005: Archer Daniels Midland and Novozymes, NovaLipidTM: Low Trans Fats and Oils
Produced by Enzymatic Interesterification of Vegetable Oils Using Lipozyme®
• 2002: Pfizer re-design of Sertraline (ZOLOFT®)
• 1996: Dow Chemical Company Designing an Environmentally Safe Marine Antifoulant

Presidential Green Chemistry Challenge Awards,
U.S. EPA 1996-2017
114 winning technologies have resulted in:
• 826 million pounds of hazardous chemicals and solvents eliminated each year—
enough to fill almost 3,800 railroad tank cars or a train nearly 47 miles long.
• 21 billion gallons of water saved each year—the amount used by 820,000 people
annually.
• 7.8 billion pounds of carbon dioxide equivalents released to air eliminated each
year—equal to taking 810,000 automobiles off the road.

Presidential Green Chemistry Challenge: Award
Categories
Focus Area 1: Greener Synthetic Pathways
Focus Area 2: Greener Reaction Conditions
Focus Area 3: The Design of Greener Chemicals
Small Business: for a technology in any of the three focus areas developed by a
small business
Academic: for a technology in any of the three focus areas developed by an
academic researcher
Specific Environmental Benefit (2017): for a technology in any of the three focus
areas that reduces greenhouse gas emissions/Climate Change

Presidential Green Chemistry Challenge: Some
Winning Technologies
• 2016: Newlight Technologies, AirCarbon: Greenhouse Gas Transformed into High-
Performance Thermoplastic
• 2012: Buckman International, Inc.: Enzymes Reduce the Energy and Wood Fiber Required
to Manufacture High-Quality Paper and Paperboard
• 2011: Professor Bruce H. Lipshutz, Towards Ending Our Dependence on Organic Solvents
• 2008: SiGNa Chemistry, Inc.: New Stabilized Alkali Metals for Safer, Sustainable Syntheses
• 2005: Archer Daniels Midland and Novozymes, NovaLipidTM: Low Trans Fats and Oils
Produced by Enzymatic Interesterification of Vegetable Oils Using Lipozyme®
• 2002: Pfizer re-design of Sertraline (ZOLOFT®)
• 1996: Dow Chemical Company Designing an Environmentally Safe Marine Antifoulant

Newlight Technologies, AirCarbon: Greenhouse
Gas Transformed into High-Performance
Thermoplastic
2016 Designing Greener Chemicals and Specific Environmental Benefit:
Climate Change Award

Newlight Technologies: Greenhouse Gas Transformed
into High-Performance Thermoplastic
• 2016 Designing Greener Chemicals and Specific
Environmental Benefit: Climate Change Award
• Developed a low-cost plastic made from methane-
based greenhouse gas that is used to make:
• bags;
• cell phone cases;
• containers;
• furniture; and
• other products.
• The new plastic is:
• net carbon negative; and
• has equal or better performance than
petroleum-based plastic products.
http://bestofwhatsnew.popsci.com/newlight-
technologies-aircarbon

• The Challenge: Greenhouse Gas emissions
• Methane emissions – farms, landfills, energy facilities, etc.
• How to turn carbon emissions (methane) into a useful material?
• Air + GHG  Plastics
• Using biocatalyst
https://www.newlight.com/

Capture: First, concentrated methane or carbon dioxide emissions that would otherwise become part of the
air, from places like farms, landfills, and energy facilities, are directed into Newlight’s bioconversion reactor.
Air – [GHG] – Air
Isolate: Next, those carbon emissions are combined with Newlight’s biocatalyst, which pulls carbon out of
methane or carbon dioxide.
[O] [C] [O]
Polymerize: Finally, carbon, oxygen, and hydrogen are re-assembled to form a long chain thermopolymer,
called AirCarbon, which is by weight approximately 40% oxygen and 60% carbon and hydrogen.
https://www.newlight.com/technology/
PHA’s

PHA’s: Polyhydroxyalkanoates
• R = H or hydrocarbon chains of up to around C13 in length, and x can range from
1 to 3 or more
• Varying x and R effect hydrophobicity, Tg, Tm, and level of crystallinity (can range
from around 70% to very low, giving excellent stiffness or elasticity as needed)
• When R = CH3 and x=1, the polymer is poly-(3-hydroxybutyric acid) (PHB), the
base homopolymer in the PHA natural plastics family.
• PHA natural plastics containing 3-hydroxy acids can also have a chiral center and
are optically active

Buckman International, Inc.
Enzymes Reduce the Energy and Wood Fiber Required
to Manufacture High-Quality Paper and Paperboard
2012 Presidential Green Chemistry Challenge Designing Greener
Chemicals Award

Buckman International, Inc.
Summary:
Traditionally, making strong paper required costly wood pulp, energy-intensive
treatment, or chemical additives. But that may change. Buckman's Maximyze®
enzymes modify the cellulose in wood to increase the number of "fibrils" that bind
the wood fibers to each other, thus making paper with improved strength and
quality—without additional chemicals or energy. Buckman's process also allows
papermaking with less wood fiber and higher percentages of recycled paper,
enabling a single plant to save $1 million per year.

Paper consumption, worldwide
• Paper use increases year after year and
has quadrupled over the past 50 years!
• 2014 – global paper production hit 400
million tons per year (the same year that
atmospheric CO2 levels exceeded 400
parts per million)
• China, USA and Japan: 51%
• China (106 million tons)
• USA (71 million tons)
• Japan (27 million tons),
• Europe: 23% (92 million tons)
• Africa: 2% (8 million tons/year)
• Oceania and Latin America: 8%
Paper consumption per capita by region
Source: State of the Global Paper
Industry, Environmental Paper Network

Paper making
• Cellulose fibers are the basic structural material of paper
• Properties of a sheet of paper like strength and weight depend on bonding between
cellulose fibers
• Existing Technology:
• Papermakers can improve paper strength by:
Adding different wood pulps (costly)
Increasing mechanical treatment (requires significant energy expenditure)
Using various chemical additives (many derived from non-renewable resources)
• Buckman technology: utilizes enzymes (cellulases) to strengthen fibers in paper
making and recycling

Cellulases
• In nature, cellulases are enzymes that catalyze the hydrolysis of
cellulose to degrade and recycle this organic compound (all
together these enzymes completely recycle cellulose)
• Endoclucanases break internal bonds to disrupt the crystalline
structure of cellulose and expose individual chains
• Exocellulases separate pieces of two to four sugar monomers from
the exposed chains
• Cellobiases (b-glucosidases) hydrolyze those fragments into glucose
• Cellulases in nature hydrolyze and recycle cellulose (the most
common organic compound on earth)
• In paper manufacturing, the goal is to modify cellulose fiber,
not destroy it
• Requires the selection and proper application of specific enzymes
from this group to develop the desired results
Cellulose
Image: Wikimedia Commons

Mazimyze® technology for paper production and
recycling
•Approach: Select enzymes within the cellulase group
to modify cellulose fibers in order to improve paper
quality and support greener manufacturing practices.
•Maximyze® technology consists of specific enzymes
that improve inter-fiber bonding in cellulose, resulting
in many benefits:
• A reduction in the amount of wood pulp needed to produce the
paper or paperboard
• An improvement in the quality of the paper or paperboard
• An increase in production rates
• A reduction in energy requirements in manufacture
• An increase in the amount of recycled paper that can be used in
the product
Fibers before and after the
treatment with Maximyze®

Greener Benefits
• Reduces the amount of cellulose fiber required: fewer trees needed, improving the strength of the
paper
• Reduces the resources required for shipping: Lighter weight paper
• Allows for the increased use of recovered paper (recycled paper): Improves strength of paper from
recycled fibers, allowing for increase in use of recycled fibers
• Reduces the energy requirements: Less refining of the paper is required
• Requires less steam to dry the paper: Improves water removal in the drying process
• Increases the proportion of hardwood fiber: Softwood fibers are typically required to maintain the
strength needed in paper; these fibers have higher costs
• Reduces volumes in landfills: Lighter weight paper, less material, improves recycling
• Replaces or reduces the use of current chemical products: Glyoxalated polyacrylamides (g-PAM)
and polyacrylamide copolymers are used to improved paper strength; these are not needed with
Maximyze®

Professor Bruce Lipshutz, University of California,
Santa Barbara
Towards Ending our Dependence on Organic Solvents
2011 Presidential Green Chemistry Challenge Academic Award

Professor Bruce Lipshutz, University of California Santa Barbara
Towards Ending Our Dependence on Organic Solvents
Most chemical manufacturing processes rely
on organic solvents, which tend to be volatile,
toxic, and flammable. Chemical manufacturers
use billions of pounds of organic solvents each
year, much of which becomes waste. Water
itself cannot replace organic solvents as the
medium for chemical reactions because many
chemicals do not dissolve and do not react in
water.
Professor Lipshutz has designed a safe
surfactant that forms tiny droplets in water.
Organic chemicals dissolve in these droplets
and react efficiently, allowing water to replace
organic solvents.
reactions take
place here
Images curtesy of Professor Bruce Lipshutz

Professor Bruce Lipshutz, University of California Santa
Barbara Towards Ending Our Dependence on Organic Solvents
New Nanomicelles as “Nanoreactors” in Water
Benign by design “designer” surfactants
(available from Aldrich)

Professor Bruce Lipshutz, University of California Santa
Barbara Towards Ending Our Dependence on Organic Solvents
Applications of nanomicellar technology
chemistry in water at RT

What is a micelle?
Micelle
Hydrophilic
Hydrophobic

SiGNa Chemistry, Inc.
2008 Presidential Green Chemistry Challenge Small Business Award

SiGNa Chemistry
• Alkali metals and their anhydrides
• Extremely reactive
• Hazardous to use and store
• Uses
• Reducing agents
• Catalysts
• Greener Solution:
• Silica or alumina encapsulated alkali metals (M-SG)
• M-SG reagents are room-temperature stable free-flowing powders that retain
the chemical reactivity of the parent metal, decreasing the danger and
associated cost of using reactive metals.

SiGNa Chemistry:
• Alkali metals are absorbed into silica gel to yield loose black powders (M-SG) that are strong reducing agents.
All react nearly quantitatively with water to form hydrogen.
• Types of M-SG
• Air sensitive powders
• Moisture sensitive but not sensitive to dry air.
• Air and moisture ‘stable’ (can be handled in ambient air with only slow degradation by
atmospheric moisture)
• These materials eliminate many hazards associated with pure alkali metals by providing easily handled
reducing agents and hydrogen sources.
• Applications:
• Reduction of esters to alcohols
• Can be used to desulfurize various compounds,
• Reductive protonation of aromatics,
• Dechlorination of alkyl and aryl halides

Applications of M-SG
• Reduction of carboxylic acids to alcohols
• M-SG mediated deprotection of protected secondary amines
• Reductive protonation of aromatics
Desulfonation Detosylation

Safety demo Na metal vs Na-SG
27
Water Test - Na Metal_500mg Water Test - Stage I Na-SG_1.5g
The catalysts react with water to produce hydrogen in large quantities
The SiGNa chemistry compounds/materials have potential use in fuel cells and
environmental remediation of toxic chemicals.
http://www.signachem.com/resources/

Archer Daniels Midland and Novozymes,
NovaLipidTM:
2005 Presidential Green Chemistry Challenge Greener Synthetic Pathways
Award

ADM and Novozymes
2005 Greener Synthetic Pathways Award
• U.S. FDA requires mandatory labeling of trans fats on nutritional fact panels
(effective January 1, 2006)
• U.S. FDA urging for the reduction of the consumption of trans fats
• Partially hydrogenated vegetable oils is the most common source for trans
fatty acids

Why trans fatty acids?
HO
O
trans
HO
O
cis
The presence of the double bonds is responsible for the liquid
properties of native vegetable oil. Because the cis double
bonds are “kinked”, they disrupt the physical interactions
between fatty acid molecules, preventing them from packing
together tightly to form crystals. This disruption keeps the
fatty acid molecules from associating with each other,
resulting in a liquid structure.
If the double bonds are removed by adding hydrogen
(hydrogenation), the kinks are removed, allowing the fatty acid
molecules to more easily associate with each other. The result
is crystallization (solid fat) at room temperature. Most trans
fatty acids are produced through an industrial process that
added hydrogen to vegetable oils to produce partially
hydrogenated vegetable oil.

Interesterification (IE) to remove trans fatty acids
R = fully or partially hydrogenated fatty acid
chains (with cis and/or trans bonds)
Traditional processes:
• Alkaline chemical catalyst: sodium
methoxide
• Catalyst generates soaps or salts that
are not easily separated (extra waste
stream generated in washing of the oils)
• Side reactions occur, darkening the oil
and requiring bleaching of the oils to
remove color (spent bleaching clay is an
additional waste stream)

Enzymatic Interesterification (IE)
(ADM and Novozyme PGCCA)
R = fully or partially hydrogenated fatty acid
chains (with cis and/or trans bonds)
Enzymatic process:
• Enzyme catalyst (typically not stable
and high cost)
• ADM and Novozyme stabilized the
enzyme to reduce costs and
increase stability
• No use of chemical catalyst and acid
neutralizer
• No generation of by-products (soaps or
salts)
• No generation of waste water
• No generation of solid waste On the market: NovalipidTM - Zero and reduced-trans oils and
shortening products, produced using the enzymatic IE process

Pfizer, Inc.: Re-design of Sertraline
(ZOLOFT®)
2002 Presidential Green Chemistry Challenge Award

Pfizer, Inc.: Re-design of Sertraline (ZOLOFT®)
Product: Sertraline hydrochloride is an inhibitor of synaptosomal serotinin uptake,
used as a pharmaceutical agent for the treatment of depression as well as
dependency and other anxiety related disorders. (ZOLOFT®)
Pfizer won a Presidential Green Chemistry Challenge Award in 2002 for the re-
design of their manufacturing process using the 12 principles of green chemistry.

First Commercial
Route to
Sertraline:
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388

Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic
Process Research & Development, 2004, 8, 385-388

Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process
Research & Development, 2004, 8, 385-388

• Eliminated use of 140 metric tons/year of
titanium tetrachloride
• Avoided generation of 440 metric tons/year of
solid titanium dioxide waste
• Eliminated generation of over 40 metric
tons/year of trans isomer
• Avoided generation of 150 metric tons/year of
35% HCl waste
• Eliminated need for 100 metric tons/year of 50%
NaOH
• Some aqueous washes
• Dramatically reduced the number and volume of
solvents used

Dow Chemical Company:
Designing an Environmentally Safe Marine
Antifoulant
1996 Presidential Green Chemistry Challenge Award

Marine fouling
Fouling, the unwanted growth
of plants and animals on a
ship's surface, costs the
shipping industry
approximately $3 billion a year.
A significant portion of this
cost is the increased fuel
consumption needed to
overcome hydrodynamic drag.
Increased fuel consumption
also contributes to pollution,
global warming, and acid rain.
Image: https://libreshot.com/container-ship-freighter/

Dow Chemical Company: Designing an
Environmentally Safe Marine Antifoulant
Antifoulants are generally dispersed in the paint as it is applied to the
hull. Organotin compounds have traditionally been used, particularly
tributyltin oxide (TBTO). TBTO works by gradually leaching from the
hull killing the fouling organisms in the surrounding area.
TBTO and other organotin antifoulants have long half-lives in the
environment (half-life of TBTO in seawater is > 6 months). They also
bioconcentrate in marine organisms (the concentration of TBTO in
marine organisms to be 104 times greater than in the surrounding
water).
Organotin compounds are chronically toxic to marine life and can
enter food chain. They are bioaccumulative.
Tributyltin oxide (TBTO)

Sea-Nine® 211
http://www.rohmhaas.com/seanine/index.html
Rohm and Haas (now Dow Chemical)
Presidential Green Chemistry Challenge Award,
1996
The active ingredient in Sea-Nine® 211, 4,5-
dichloro-2-n-octyl-4-isothiazolin-3-one
(DCOI), is a member of the isothiazolone family
of antifoulants.
4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI)

International Marine Organization:
What makes a good anti-foulant?
1. Broad spectrum activity
2. Low mammalian toxicity
3. Low water solubility
4. No bioaccumulation in the
food chain
5. Not persistent in the
environment
6. Compatible with paint raw
materials
7. Favorable price/performance
http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf,
Image: https://libreshot.com/container-ship-freighter/

International Marine Organization:
What makes a good anti-foulant?
 Broad spectrum activity
• Low mammalian toxicity – toxic to humans
 Low water solubility
• No bioaccumulation in the food chain -
bioaccumulative
• Not persistent in the environment - (1/2 life
in water > 6 months)
 Compatible with paint raw materials
 Favorable price/performance
http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf
 Broad spectrum activity
 Low mammalian toxicity – low acute toxicity
 Low water solubility
 No bioaccumulation in the food chain – not
bioaccumulative
 Not persistent in the environment – (1/2 life in
water < 1 hour)
 Compatible with paint raw materials
 Favorable price/performance

• TBTO banned worldwide by the International Marine Organization = use was
phased out by 2008
• European Union: Identified TBTO as a severe marine pollutant and SVHC
(Substance of Very High Concern)

Sea-Nine® 211 works by maintaining a hostile growing
environment for marine organisms. When organisms attach
to the hull (treated with DCOI), proteins at the point of
attachment with the hull react with the DCOI. This reaction
with the DCOI prevents the use of these proteins for other
metabolic processes. The organism thus detaches itself and
searches for a more hospitable surface on which to grow.
Only organisms attached to hull of ship are exposed to toxic
levels of DCOI.
Readily biodegrades once leached from ship (half-life is less
than one hour in sea water).
http://msdssearch.dow.com/PublishedLiteratureDO
WCOM/dh_08a4/0901b803808a4d1e.pdf?filepath=
microbial/pdfs/noreg/253-
02760.pdf&fromPage=GetDoc
4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI)

Real-World Cases in Green Chemistry:
A class exercise

Real-World Cases in Green Chemistry
• Students select a Presidential Green Chemistry Challenge Award winner of
interest
• Summarize the “traditional” chemistry, or problem that the award addresses
• Summarize the greener chemistry
• Including the economic and environmental (and human health) benefit
• Create a PowerPoint presentation, report, or poster presentation and present it
back to the class!

Summary
• Presidential Green Chemistry Challenge Awards: Case studies for understanding
real-world examples of Green Chemistry technologies
• PGCCA case studies are examples of greener technologies that also have
economic benefits, and work just as good (or better) than traditional
counterparts
• Environmental and human health benefits, economic benefits, and performance benefits are
3 main aspects of green chemistry technologies
• Use the PGCCA’s as examples to learn more about applied Green Chemistry!

Real-World Cases in green chemistry.pptx

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