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PGCCA example paper and paper board making.pptx
1. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
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
2. Center For Green Chemistry
and Green Engineering at Yale
Buckman International, Inc.
Summary:
Traditionally, making strong paper required costly wood pulp, energy-intensive
treatment, or chemical additives. But that may change. Buckman's Maximyzeยฎ
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
qualityโwithout 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.
3. Center For Green Chemistry
and Green Engineering at Yale
Paper consumption, worldwide
โข Paper use increases year after year and
has quadrupled over the past 50 years!
โข 2014 โ global paper production hit 400
million tons per year (the same year that
atmospheric CO2 levels exceeded 400
parts per million)
โข China, USA and Japan: 51%
โข China (106 million tons)
โข USA (71 million tons)
โข Japan (27 million tons),
โข Europe: 23% (92 million tons)
โข Africa: 2% (8 million tons/year)
โข Oceania and Latin America: 8%
Paper consumption per capita by region
Source: State of the Global Paper
Industry, Environmental Paper Network
4. Center For Green Chemistry
and Green Engineering at Yale
Paper making
โข Cellulose fibers are the basic structural material of paper
โข Properties of a sheet of paper like strength and weight depend on bonding between
cellulose fibers
โข Existing Technology:
โข 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)
โข Buckman technology: utilizes enzymes (cellulases) to strengthen fibers in paper
making and recycling
5. Center For Green Chemistry
and Green Engineering at Yale
Cellulases
โข 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)
โข Endoclucanases break internal bonds to disrupt the crystalline
structure of cellulose and expose individual chains
โข Exocellulases separate pieces of two to four sugar monomers from
the exposed chains
โข Cellobiases (b-glucosidases) hydrolyze those fragments into glucose
โข Cellulases in nature hydrolyze and recycle cellulose (the most
common organic compound on earth)
โข In paper manufacturing, the goal is to modify cellulose fiber,
not destroy it
โข Requires the selection and proper application of specific enzymes
from this group to develop the desired results
Cellulose
Image: Wikimedia Commons
6. Center For Green Chemistry
and Green Engineering at Yale
Mazimyzeยฎ technology for paper production and
recycling
โขApproach: Select enzymes within the cellulase group
to modify cellulose fibers in order to improve paper
quality and support greener manufacturing practices.
โขMaximyzeยฎ technology consists of specific enzymes
that improve inter-fiber bonding in cellulose, resulting
in many benefits:
โข A reduction in the amount of wood pulp needed to produce the
paper or paperboard
โข An improvement in the quality of the paper or paperboard
โข An increase in production rates
โข A reduction in energy requirements in manufacture
โข An increase in the amount of recycled paper that can be used in
the product
Fibers before and after the
treatment with Maximyzeยฎ
7. Center For Green Chemistry
and Green Engineering at Yale
Greener Benefits
โข Reduces the amount of cellulose fiber required: fewer trees needed, improving the strength of the
paper
โข Reduces the resources required for shipping: Lighter weight paper
โข 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
โข Reduces the energy requirements: Less refining of the paper is required
โข Requires less steam to dry the paper: Improves water removal in the drying process
โข Increases the proportion of hardwood fiber: Softwood fibers are typically required to maintain the
strength needed in paper; these fibers have higher costs
โข Reduces volumes in landfills: Lighter weight paper, less material, improves recycling
โข 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
Maximyzeยฎ
8. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
Professor Bruce Lipshutz, University of California,
Santa Barbara
Towards Ending our Dependence on Organic Solvents
2011 Presidential Green Chemistry Challenge Academic Award
9. Center For Green Chemistry
and Green Engineering at Yale
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
10. Center For Green Chemistry
and Green Engineering at Yale
Professor Bruce Lipshutz, University of California Santa
Barbara Towards Ending Our Dependence on Organic Solvents
New Nanomicelles as โNanoreactorsโ in Water
Benign by design โdesignerโ surfactants
(available from Aldrich)
Images curtesy of Professor Bruce Lipshutz
11. Center For Green Chemistry
and Green Engineering at Yale
Professor Bruce Lipshutz, University of California Santa
Barbara Towards Ending Our Dependence on Organic Solvents
Applications of nanomicellar technology
chemistry in water at RT
Images curtesy of Professor Bruce Lipshutz
12. Center For Green Chemistry
and Green Engineering at Yale
What is a micelle?
Micelle
Hydrophilic
Hydrophobic
13. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
SiGNa Chemistry, Inc.
2008 Presidential Green Chemistry Challenge Small Business Award
14. Center For Green Chemistry
and Green Engineering at Yale
SiGNa Chemistry
โข Alkali metals and their anhydrides
โข Extremely reactive
โข Hazardous to use and store
โข Uses
โข Reducing agents
โข Catalysts
โข Greener Solution:
โข Silica or alumina encapsulated alkali metals (M-SG)
โข 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.
15. Center For Green Chemistry
and Green Engineering at Yale
SiGNa Chemistry:
โข 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.
โข Types of M-SG
โข Air sensitive powders
โข Moisture sensitive but not sensitive to dry air.
โข Air and moisture โstableโ (can be handled in ambient air with only slow degradation by
atmospheric moisture)
โข These materials eliminate many hazards associated with pure alkali metals by providing easily handled
reducing agents and hydrogen sources.
โข Applications:
โข Reduction of esters to alcohols
โข Can be used to desulfurize various compounds,
โข Reductive protonation of aromatics,
โข Dechlorination of alkyl and aryl halides
16. Center For Green Chemistry
and Green Engineering at Yale
Applications of M-SG
โข Reduction of carboxylic acids to alcohols
โข M-SG mediated deprotection of protected secondary amines
โข Reductive protonation of aromatics
Desulfonation Detosylation
17. Center For Green Chemistry
and Green Engineering at Yale
Safety demo Na metal vs Na-SG
17
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/
18. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
Archer Daniels Midland and Novozymes,
NovaLipidTM:
2005 Presidential Green Chemistry Challenge Greener Synthetic Pathways
Award
19. Center For Green Chemistry
and Green Engineering at Yale
ADM and Novozymes
2005 Greener Synthetic Pathways Award
โข U.S. FDA requires mandatory labeling of trans fats on nutritional fact panels
(effective January 1, 2006)
โข U.S. FDA urging for the reduction of the consumption of trans fats
โข Partially hydrogenated vegetable oils is the most common source for trans
fatty acids
20. Center For Green Chemistry
and Green Engineering at Yale
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 โkinkedโ, 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.
21. Center For Green Chemistry
and Green Engineering at Yale
Interesterification (IE) to remove trans fatty acids
R = fully or partially hydrogenated fatty acid
chains (with cis and/or trans bonds)
Traditional processes:
โข Alkaline chemical catalyst: sodium
methoxide
โข Catalyst generates soaps or salts that
are not easily separated (extra waste
stream generated in washing of the oils)
โข Side reactions occur, darkening the oil
and requiring bleaching of the oils to
remove color (spent bleaching clay is an
additional waste stream)
22. Center For Green Chemistry
and Green Engineering at Yale
Enzymatic Interesterification (IE)
(ADM and Novozyme PGCCA)
R = fully or partially hydrogenated fatty acid
chains (with cis and/or trans bonds)
Enzymatic process:
โข Enzyme catalyst (typically not stable
and high cost)
โข ADM and Novozyme stabilized the
enzyme to reduce costs and
increase stability
โข No use of chemical catalyst and acid
neutralizer
โข No generation of by-products (soaps or
salts)
โข No generation of waste water
โข No generation of solid waste On the market: NovalipidTM - Zero and reduced-trans oils and
shortening products, produced using the enzymatic IE process
23. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
Pfizer, Inc.: Re-design of Sertraline
(ZOLOFTยฎ)
2002 Presidential Green Chemistry Challenge Award
24. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
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. (ZOLOFTยฎ)
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.
25. Center For Green Chemistry
and Green Engineering at Yale
First Commercial
Route to
Sertraline:
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
26. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic
Process Research & Development, 2004, 8, 385-388
27. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process
Research & Development, 2004, 8, 385-388
28. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process
Research & Development, 2004, 8, 385-388
29. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
30. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
31. Center For Green Chemistry
and Green Engineering at Yale
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
32. Center For Green Chemistry
and Green Engineering at Yale
โข Eliminated use of 140 metric tons/year of
titanium tetrachloride
โข Avoided generation of 440 metric tons/year of
solid titanium dioxide waste
โข Eliminated generation of over 40 metric
tons/year of trans isomer
โข Avoided generation of 150 metric tons/year of
35% HCl waste
โข Eliminated need for 100 metric tons/year of 50%
NaOH
โข Some aqueous washes
โข Dramatically reduced the number and volume of
solvents used
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Pfizer, Inc.: Re-design of Sertraline (ZOLOFTยฎ)
33. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
Dow Chemical Company:
Designing an Environmentally Safe Marine
Antifoulant
1996 Presidential Green Chemistry Challenge Award
34. Center For Green Chemistry
and Green Engineering at Yale
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/
35. Center For Green Chemistry
and Green Engineering at Yale
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)
36. Center For Green Chemistry
and Green Engineering at Yale
Dow Chemical Company: Designing an
Environmentally Safe Marine Antifoulant
Sea-Nineยฎ 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-Nineยฎ 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)
37. Center For Green Chemistry
and Green Engineering at Yale
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/
38. Center For Green Chemistry
and Green Engineering at Yale
International Marine Organization:
What makes a good anti-foulant?
๏ผ Broad spectrum activity
โข Low mammalian toxicity โ toxic to humans
๏ผ Low water solubility
โข No bioaccumulation in the food chain -
bioaccumulative
โข Not persistent in the environment - (1/2 life
in water > 6 months)
๏ผ Compatible with paint raw materials
๏ผ Favorable price/performance
http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf
๏ผ Broad spectrum activity
๏ผ Low mammalian toxicity โ low acute toxicity
๏ผ Low water solubility
๏ผ No bioaccumulation in the food chain โ not
bioaccumulative
๏ผ Not persistent in the environment โ (1/2 life in
water < 1 hour)
๏ผ Compatible with paint raw materials
๏ผ Favorable price/performance
39. Center For Green Chemistry
and Green Engineering at Yale
Dow Chemical Company: Designing an
Environmentally Safe Marine Antifoulant
โข TBTO banned worldwide by the International Marine Organization = use was
phased out by 2008
โข European Union: Identified TBTO as a severe marine pollutant and SVHC
(Substance of Very High Concern)
40. Center For Green Chemistry
and Green Engineering at Yale
Dow Chemical Company: Designing an
Environmentally Safe Marine Antifoulant
Sea-Nineยฎ 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)
41. Center For Green Chemistry
and Green Engineering at Yale
Center For Green Chemistry
and Green Engineering atYale
Real-World Cases in Green Chemistry:
A class exercise
42. Center For Green Chemistry
and Green Engineering at Yale
Real-World Cases in Green Chemistry
โข Students select a Presidential Green Chemistry Challenge Award winner of
interest
โข Summarize the โtraditionalโ chemistry, or problem that the award addresses
โข Summarize the greener chemistry
โข Including the economic and environmental (and human health) benefit
โข Create a PowerPoint presentation, report, or poster presentation and present it
back to the class!
43. Center For Green Chemistry
and Green Engineering at Yale
Summary
โข Presidential Green Chemistry Challenge Awards: Case studies for understanding
real-world examples of Green Chemistry technologies
โข PGCCA case studies are examples of greener technologies that also have
economic benefits, and work just as good (or better) than traditional
counterparts
โข Environmental and human health benefits, economic benefits, and performance benefits are
3 main aspects of green chemistry technologies
โข Use the PGCCAโs as examples to learn more about applied Green Chemistry!
Editor's Notes
Readings: Pulp & Paper International, November 2012: https://www.buckman.com/wp-content/uploads/2018/04/PPI-2012-Greener-Pckg.pdf
Buckman Maximyze enzyme video: https://www.youtube.com/watch?v=42H7SsCX7zI
June 18, 2012: Buckman Wins Presidential Green Chemistry Challenge Award article: https://www.buckman.com/news/buckman-wins-presidential-green-chemistry-challenge-award/
Full summary and description of award winning technology can be found here: https://www.epa.gov/greenchemistry/presidential-green-chemistry-challenge-2012-designing-greener-chemicals-award
Source: State of the Global Paper Industry, Environmental Paper Network, http://environmentalpaper.org/wp-content/uploads/2018/04/StateOfTheGlobalPaperIndustry2018_FullReport-Final-1.pdf
If you look at a per capita basis on these numbers: Exploration of per capita consumption figures reveals a more
nuanced story. The global average is 55 kg per person per year. North American consumption is four times that (215 kg)
while the African average is just 7 kg. Chinaโs average per capita consumption is just higher than the global average at
76 kg. Eastern European levels are similar to Chinaโs (77 kg) with the Western European average being almost double that (147 kg). Seven of the ten countries with the largest per capita consumption are in Europe.
Paper consumption is at unsustainable levels and globally it is steadily increasing, particularly in Asia, while remaining at unequal levels of access in some parts of the world, particularly Africa.
Increasing production in response to new market demand is driving development of new virgin-fibre pulp mills, especially in Asia, Africa and South America.
Expansion is resulting in numerous social conflicts in many nations including Brazil, Indonesia, Canada, India, Chile and Mozambique.
The industry has substantial climate change impacts and critical opportunities for reducing greenhouse gas emissions through better land management and fibre choices need to be seized, urgently.
Corporate social responsibility commitments and purchasing policies have continued to proliferate and have helped to drive some specific social and environmental improvements โon-the-ground,โ but execution, transparency and progress on many voluntary commitments is lagging.
Image from: https://www.buckman.com/innovation/maximyze-for-packaging/
And, from the Presidential Green Chemistry Challenge Award Nomination package.
YouTube video of technology: https://www.youtube.com/watch?time_continue=2&v=42H7SsCX7zI
From: Presidential Green Chemistry Challenge Award Application
Benefits - Here is a summary of benefits of this technology in real-world applications (details follow in specific case studies given later in this document).ย
- First, improving the strength of a paper product allows reducing the amount of cellulose fiber required to attain the required specifications. The basis weight of the paper can be reduced, so less fiber (i.e. fewer trees) is required to create the same product. In addition to the environmental benefit, the primary cost for manufacture of a paper product is the fiber raw material; so this provides a significant economic benefit to the manufacturer.ย
- Another economic and environmental benefit relates to transport of the end paper product: a lighter weight paper or board translates into reduced resources required for shipping.ย
- One problem with recycled paper is that there is a loss of strength when paper is made from recycled fiber. The enzymatic action of Maximyze products improves the strength of paper made from recycled fibers, and allows a papermaker to use more recovered paper.ย
- Next, less refining is required. Refining is a mechanical treatment unique to paper making. This is an energy-intensive process that collapses the fiber and modifies its surface to improve inter-fiber bonding. In Maximyze applications, modifying fibers by enzymatic treatment allows significant reduction in energy requirements for refining, up to complete elimination.ย
- The combination of enzyme action and reduced refining results in fewer fiber fragments and fines, which improves water removal in the papermaking process so less steam is required to dry the paper on the paper machine.ย
Often addition of softwood fiber is required to maintain the strength needed in paper. Maximyze allows an increase in the proportion of hardwood fiber. To the papermaker this reduces cost (softwood fibers have a higher cost). We can regard the use of hardwoods for pulp to have fewer deleterious environmental effects. For example, Eucalyptus plantations supply cellulose fiber much more quickly, requiring less forest land compared to softwoods.ย
- Most paper is recycled, but the use of lighter-weight paper might have an effect of reducing volumes in landfills.ย
- This focus area involves designing and implementing chemical products that are less hazardous than the products or technologies they replace. Maximyze can replace or reduce the use of current chemical products used for improving paper strength. These include synthetic chemicals like glyoxalated polyacrylamides (g-PAM) and polyacrylamide copolymers which require the use of more toxic materials sourced at least in part from petroleum-based raw materials. Related to this is the incredible efficiency of enzymes. One enzyme can catalyze as many as 40 million conversions in a second, so a very small amount of Maximyze is required. Table 1 compares the enzymatic technology with conventional g-PAM chemistry, showing that the amount of additive required with the enzyme is a small fraction of the g-PAM required.ย
For additional information and readings:
Lipshutz, B., Current Opinion in Green and Sustainable Chemistry, 2018, 11: 1-8
Lipshutz, B., J. Org. Chem., 2017, 82, 2806-2816
Lipshutz, B., ACS Sustainable Chem. Eng., 2016, 4, 5838 - 5849
More resources and readings, along with videos on SiGNa technologies can be found here: http://www.signachem.com/resources/?fwp_languages=english&fwp_categories=videos
Watch the video demonstrations of sodium metal versus the SiGNa chemistry โ each of the pictures are hyperlinked to the videos above, available through the SiGNa Chemistry website.
Most of the carbon-carbon bonds in fats are single bonds, which allow the carbons to freely rotate, making the attached groups chemically identical. However, the number of unsaturated bonds (double bonds) may vary from one to many in the hydrocarbon part of the fatty acid. Since double bonds do not allow free rotation between the attached carbons, any attached chemical groups are fixed in their respective positions.
There are two possible orientations for groups attached to the carbons in a double bond. If they are on the same side of the double bond (close together), they are in the cis conformation. The opposite of the cis conformation is the trans conformation, where the residues at ends of the double bond are farther apart. Double bonds in natural vegetable oils and in animal fats are mostly in the cis conformation; however, a few exceptions are known where the trans conformation is present.
The presence of the double bonds is responsible for the liquid properties of native vegetable oil. Because the cis double bonds are โkinkedโ, 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.
The presence of the double bonds is responsible for the liquid properties of native vegetable oil. Because the cis double bonds are โkinkedโ, 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.
https://www.mayoclinic.org/diseases-conditions/high-blood-cholesterol/in-depth/trans-fat/art-20046114 - for info about trans fats and health effects
Additional information โ see the full nomination package from ADM and Novozyme
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Sertraline (Pfizer) is the active ingredient in Zoloft, the most widely prescribed antidepressant drug. The development and manufacture of Zoloft began with the โdiscoveryโ of how the Sertraline structure could be made in the laboratory. The first commercial manufacturing route for making Sertraline involved the use of hazardous chemicals such as toluene, hexane and tetrahydrofuran. This route involved the use of 140 metric tons of titanium tetrachloride, which resulted in the formation of 440 metric tons of solid titanium dioxide waste per year. 150 metric tons/year of 35% hydrochloric acid waste was generated and there was a need for 100 metric tons/year of 50% sodium hydroxide.
ย
Scientists at Pfizer, Inc. re-designed the production process of Sertraline using the twelve principles of green chemistry and were able to completely eliminate the requirement for titanium tetrachloride, resulting in the elimination of the aqueous titanium dioxide waste stream. The re-design of the process also allowed for the elimination of the use of hexane, toluene and tetrahydrofuran. The new process produces 26 Liters of solvent waste per kilogram of product (Sertraline), compared to the first commercial route of 98 Liters per kilogram. It should be noted that the product, Zoloft, remains the same high purity and activity. Therefore, despite the change in process, the product is just as good.
This is the first commercial route to Sertraline โ for this example we will focus on the last 4 steps and compare to the Current Commercial Route to Sertraline.
The first commercial synthesis of sertraline hydrochlorde involves a condensation reaction of the tetralone (2) with excess of monomethylamine, which is catalyzed by titanium tetrachloride to form the imine (3). The reduction of 3 produces the racemic syn- and anti-diastereomers of the amine. The desired syn-amine is then selectively crystallized and resolved to produce 4 as the D-(-)-mandelic acid salt.
ย
Drawbacks: Uses undesirable reagents and/or produces hazardous byproducts. Control and safe handling of these reagents, including the removal of their byproducts, result in time-consuming operations that affect the efficiency of the commercial process.
Titanium tetrachloride: safety concerns (extreme reactivity with water)
By-products produced: titanium dioxide and monomethylamine hydrochloride)
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
Talking points:
Use of TiCl4 in step 2 produces lots of TiO2 waste
Step 2: toluene, hexanes, THF โฆ the best solvents?
TiCl4 is used to take out water, what other ways can you remove the water?
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Talking points:
Step 3, catalyst not too selective
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Talking points:
How many molecules are isolated? Each time a molecule is isolated, what needs to happen (crystallization, purification, exposure to workers, etc.)
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
New Commercial Route to Sertraline
Talking points:
Step 2 eliminated use of TiCl4 (nasty stuff & get rid of TiO2 waste)
Step 2 & 3, better solvent used
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Talking points:
Step 3, more selective catalyst, better ratio of cis/trans
Step 2 & 3, better solvent used
Taber, G.P., Pfisterer, D.M., and Colberg, J., Organic Process Research & Development, 2004, 8, 385-388
Talking points:
How many molecules are isolated? 3 vs. 5 in scheme 2
The New Commercial Synthesis:
Improvements: Improved safety (eliminate use of TiCl4), improved productivity (eliminating need to filter byproducts โ which can be time consuming due to small particle size obtained from two byproducts)
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Process: Ethanol used for solvent for telescoping of two steps (not isolating) to increase conversion (99%) significantly and also reduce formation of byproducts. Switch to ethanol for solvent, relying on the low-solubility of 3 in alkanol solvents to drive the reaction to equilibrium to the final product. Conversion from 3 to 6 improved significantly by finding a more selective catalyst (through a design of experiments approach) (Pd/CaCO3, 1% w/w to 2) for the cis isomer. The catalyst not only improved the cis/trans ratio, but also resulted in lower levels of contaminating mono and deschloro impurities.
Additional resources:
Michael Cannโs educational modules: http://www.scranton.edu/faculty/cannm/green-chemistry/english/environmental.shtml
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.
The main compounds used worldwide to control fouling are the organotin antifoulants, such as tributyltin oxide (TBTO). They are effective at preventing fouling, but have widespread environmental problems due to their persistence in the environment and the toxic effects they cause, including acute toxicity, bioaccumulation, decreased reproductive viability, and increased shell thickness in shellfish. These harmful effects led to an EPA special review of organotin antifoulants and to the Organotin Antifoulant Paint Control Act of 1988. This act mandated restrictions on the use of tin in the United States and charged the EPA and the U.S. Navy with conducting research on alternatives to organotins.
Based on the need for new antifoulants, Rohm and Haas Company began to search for an environmentally safe alternative to organotin compounds. The ideal antifoulant would prevent fouling from a wide variety of marine organisms without causing harm to non-target organisms. Compounds from the 3-isothiazolone class were chosen as likely candidates and over 140 were screened for antifouling activity in laboratory and field tests. The 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nineโข antifoulant) was chosen as the candidate for commercial development.
Extensive environmental testing was done comparing Sea-Nineโข antifoulant to TBTO, the current industry standard. Sea-Nineโข antifoulant degraded extremely rapidly with a half life of one day in seawater and one hour in sediment. TBTO, on the other hand, degraded much more slowly, with a half life in seawater of nine days and six to nine months in sediment. Tin bioaccumulated, with bioaccumulation factors as high as 10,000 X, while Sea-Nineโข antifoulant's bioaccumulation was essentially zero. Both TBTO and Sea-Nineโข were acutely toxic to marine organisms, but TBTO had widespread chronic toxicity, while Sea-Nineโข antifoulant showed no chronic toxicity. Thus the maximum allowable environmental concentration (MAEC) for Sea-Nineโข antifoulant was 0.63 parts per billion (ppb) while the MAEC for TBTO was 0.002 ppb. Sea-Nineโข antifoulant has been sold world-wide and hundreds of ships have been painted with coatings containing it. Rohm and Haas Company obtained EPA registration for the use of Sea-Nineโข antifoulant, the first new antifoulant registration in over a decade
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.
The main compounds used worldwide to control fouling are the organotin antifoulants, such as tributyltin oxide (TBTO). They are effective at preventing fouling, but have widespread environmental problems due to their persistence in the environment and the toxic effects they cause, including acute toxicity, bioaccumulation, decreased reproductive viability, and increased shell thickness in shellfish. These harmful effects led to an EPA special review of organotin antifoulants and to the Organotin Antifoulant Paint Control Act of 1988. This act mandated restrictions on the use of tin in the United States and charged the EPA and the U.S. Navy with conducting research on alternatives to organotins.
Based on the need for new antifoulants, Rohm and Haas Company began to search for an environmentally safe alternative to organotin compounds. The ideal antifoulant would prevent fouling from a wide variety of marine organisms without causing harm to non-target organisms. Compounds from the 3-isothiazolone class were chosen as likely candidates and over 140 were screened for antifouling activity in laboratory and field tests. The 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nineโข antifoulant) was chosen as the candidate for commercial development.
Extensive environmental testing was done comparing Sea-Nineโข antifoulant to TBTO, the current industry standard. Sea-Nineโข antifoulant degraded extremely rapidly with a half life of one day in seawater and one hour in sediment. TBTO, on the other hand, degraded much more slowly, with a half life in seawater of nine days and six to nine months in sediment. Tin bioaccumulated, with bioaccumulation factors as high as 10,000 X, while Sea-Nineโข antifoulant's bioaccumulation was essentially zero. Both TBTO and Sea-Nineโข were acutely toxic to marine organisms, but TBTO had widespread chronic toxicity, while Sea-Nineโข antifoulant showed no chronic toxicity. Thus the maximum allowable environmental concentration (MAEC) for Sea-Nineโข antifoulant was 0.63 parts per billion (ppb) while the MAEC for TBTO was 0.002 ppb. Sea-Nineโข antifoulant has been sold world-wide and hundreds of ships have been painted with coatings containing it. Rohm and Haas Company obtained EPA registration for the use of Sea-Nineโข antifoulant, the first new antifoulant registration in over a decade
SVHC = substance of very high concern
Links for more info: International Marine Organization: http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf
Photo from: https://libreshot.com/container-ship-freighter/ - free download
SVHC = substance of very high concern
Links for more info: International Marine Organiztaion: http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf
SVHC = substance of very high concern
Links for more info: International Marine Organiztaion: http://www.imo.org/en/OurWork/Environment/Anti-foulingSystems/Documents/FOULING2003.pdf
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.
The main compounds used worldwide to control fouling are the organotin antifoulants, such as tributyltin oxide (TBTO). They are effective at preventing fouling, but have widespread environmental problems due to their persistence in the environment and the toxic effects they cause, including acute toxicity, bioaccumulation, decreased reproductive viability, and increased shell thickness in shellfish. These harmful effects led to an EPA special review of organotin antifoulants and to the Organotin Antifoulant Paint Control Act of 1988. This act mandated restrictions on the use of tin in the United States and charged the EPA and the U.S. Navy with conducting research on alternatives to organotins.
Based on the need for new antifoulants, Rohm and Haas Company began to search for an environmentally safe alternative to organotin compounds. The ideal antifoulant would prevent fouling from a wide variety of marine organisms without causing harm to non-target organisms. Compounds from the 3-isothiazolone class were chosen as likely candidates and over 140 were screened for antifouling activity in laboratory and field tests. The 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nineโข antifoulant) was chosen as the candidate for commercial development.
Extensive environmental testing was done comparing Sea-Nineโข antifoulant to TBTO, the current industry standard. Sea-Nineโข antifoulant degraded extremely rapidly with a half life of one day in seawater and one hour in sediment. TBTO, on the other hand, degraded much more slowly, with a half life in seawater of nine days and six to nine months in sediment. Tin bioaccumulated, with bioaccumulation factors as high as 10,000 X, while Sea-Nineโข antifoulant's bioaccumulation was essentially zero. Both TBTO and Sea-Nineโข were acutely toxic to marine organisms, but TBTO had widespread chronic toxicity, while Sea-Nineโข antifoulant showed no chronic toxicity. Thus the maximum allowable environmental concentration (MAEC) for Sea-Nineโข antifoulant was 0.63 parts per billion (ppb) while the MAEC for TBTO was 0.002 ppb. Sea-Nineโข antifoulant has been sold world-wide and hundreds of ships have been painted with coatings containing it. Rohm and Haas Company obtained EPA registration for the use of Sea-Nineโข antifoulant, the first new antifoulant registration in over a decade
See the MS Word exercise named โRWCGC Exerciseโ
And, use the 8 PGCCA nomination packages that are supplied