This document provides an overview of green chemistry techniques to improve sustainability in chemical processes and products. It begins with examples of green chemistry and green engineering approaches. It then outlines the 12 principles of green chemistry and 12 principles of green engineering which guide the application of these techniques. The principles are organized into three categories: designing systems holistically, eliminating hazards and pollution, and maximizing resource efficiency. The document concludes with an introduction to green chemistry metrics for measuring sustainability and sections on material selection and reaction conditions.
Helping to solve the problems of the depletion of many elements and the growing volumes of hazardous waste together by building closed loop design into chemicals and materials.
By James Clark, Green Chemistry Group, University of York
Helping to solve the problems of the depletion of many elements and the growing volumes of hazardous waste together by building closed loop design into chemicals and materials.
By James Clark, Green Chemistry Group, University of York
what green chemistry is, which principles guide it and what are it's benefits this slide provide a brief description on economical, health and environmental benefits of green chem.
These approaches encompass new synthesis and processes as well as new tools for instructing aspiring chemists how to do the chemistry in a more environmentally benign manner. The pros to industry as well as the environment are all a part of the positive impact that Green Chemistry is having in the chemistry community and in the society in general. It is important that chemists develop novel Green Chemistry options even on an incremental basis. While all the elements of the lifecycle of a new chemical or process may not be environmentally benign, it is nonetheless pivotal to improve those stages where improvements can be made. The next phase of assessment can then focus on the elements of the lifecycle that are still in need of the improvement. Even though a new Green Chemistry methodology does not solve at once every problem allied with the lifecycle of a particular chemical or process, the advances that it does make are nonetheless very key. Green Chemistry that mainly possesses the spirit of sustainable development was booming in the 1990s
This slide show. gives the total knowledge of green chemistry and its applications in various fields. It also describes the essentiality of green chemistry and its role in decreasing pollution
Green chemistry: Production of electricity from AmmoniaArosek Padhi
This slide shows a new method to produce electricity from ammonia. This technique use replenish-able methods and resources to produce electricity thus giving better outputs of energy
Application and scope of atom economy green chemistryAhmadUmair14
these are slides are made to explain the scope and applications about green chemistry and atom economy and where they both can be utilized. hope you love it
what green chemistry is, which principles guide it and what are it's benefits this slide provide a brief description on economical, health and environmental benefits of green chem.
These approaches encompass new synthesis and processes as well as new tools for instructing aspiring chemists how to do the chemistry in a more environmentally benign manner. The pros to industry as well as the environment are all a part of the positive impact that Green Chemistry is having in the chemistry community and in the society in general. It is important that chemists develop novel Green Chemistry options even on an incremental basis. While all the elements of the lifecycle of a new chemical or process may not be environmentally benign, it is nonetheless pivotal to improve those stages where improvements can be made. The next phase of assessment can then focus on the elements of the lifecycle that are still in need of the improvement. Even though a new Green Chemistry methodology does not solve at once every problem allied with the lifecycle of a particular chemical or process, the advances that it does make are nonetheless very key. Green Chemistry that mainly possesses the spirit of sustainable development was booming in the 1990s
This slide show. gives the total knowledge of green chemistry and its applications in various fields. It also describes the essentiality of green chemistry and its role in decreasing pollution
Green chemistry: Production of electricity from AmmoniaArosek Padhi
This slide shows a new method to produce electricity from ammonia. This technique use replenish-able methods and resources to produce electricity thus giving better outputs of energy
Application and scope of atom economy green chemistryAhmadUmair14
these are slides are made to explain the scope and applications about green chemistry and atom economy and where they both can be utilized. hope you love it
Green Chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products .
Presentation.pptx. Green Chemistry and principal of green ChemistryHajira Mahmood
A complete and comprehensive approach towards green chemistry & its applications. it plays significance role to sustain user friendly environment by reducing waste and enhance energy efficiency & atom economy. It leads less hazardous chemicals that are easy to discard.
It's a power packed presentation which can be used to win prizes and rewards for benefits of nature .It deals about the use of green chemistry,what is the use of green chemistry.The green chemistry is the base of future which enables us to switch from the harmful,toxic bases such as plastic to other nature enhancement promoting substance use.
Green Chemistry is about:
1. Waste minimization of source
2. Use of catalysts in place of reagents
3. Using non-toxic reagents
4. Use of renewable resources
5. Improved atom efficiency
CFD Simulation of By-pass Flow in a HRSG module by R&R Consult.pptxR&R Consult
CFD analysis is incredibly effective at solving mysteries and improving the performance of complex systems!
Here's a great example: At a large natural gas-fired power plant, where they use waste heat to generate steam and energy, they were puzzled that their boiler wasn't producing as much steam as expected.
R&R and Tetra Engineering Group Inc. were asked to solve the issue with reduced steam production.
An inspection had shown that a significant amount of hot flue gas was bypassing the boiler tubes, where the heat was supposed to be transferred.
R&R Consult conducted a CFD analysis, which revealed that 6.3% of the flue gas was bypassing the boiler tubes without transferring heat. The analysis also showed that the flue gas was instead being directed along the sides of the boiler and between the modules that were supposed to capture the heat. This was the cause of the reduced performance.
Based on our results, Tetra Engineering installed covering plates to reduce the bypass flow. This improved the boiler's performance and increased electricity production.
It is always satisfying when we can help solve complex challenges like this. Do your systems also need a check-up or optimization? Give us a call!
Work done in cooperation with James Malloy and David Moelling from Tetra Engineering.
More examples of our work https://www.r-r-consult.dk/en/cases-en/
Welcome to WIPAC Monthly the magazine brought to you by the LinkedIn Group Water Industry Process Automation & Control.
In this month's edition, along with this month's industry news to celebrate the 13 years since the group was created we have articles including
A case study of the used of Advanced Process Control at the Wastewater Treatment works at Lleida in Spain
A look back on an article on smart wastewater networks in order to see how the industry has measured up in the interim around the adoption of Digital Transformation in the Water Industry.
Explore the innovative world of trenchless pipe repair with our comprehensive guide, "The Benefits and Techniques of Trenchless Pipe Repair." This document delves into the modern methods of repairing underground pipes without the need for extensive excavation, highlighting the numerous advantages and the latest techniques used in the industry.
Learn about the cost savings, reduced environmental impact, and minimal disruption associated with trenchless technology. Discover detailed explanations of popular techniques such as pipe bursting, cured-in-place pipe (CIPP) lining, and directional drilling. Understand how these methods can be applied to various types of infrastructure, from residential plumbing to large-scale municipal systems.
Ideal for homeowners, contractors, engineers, and anyone interested in modern plumbing solutions, this guide provides valuable insights into why trenchless pipe repair is becoming the preferred choice for pipe rehabilitation. Stay informed about the latest advancements and best practices in the field.
TECHNICAL TRAINING MANUAL GENERAL FAMILIARIZATION COURSEDuvanRamosGarzon1
AIRCRAFT GENERAL
The Single Aisle is the most advanced family aircraft in service today, with fly-by-wire flight controls.
The A318, A319, A320 and A321 are twin-engine subsonic medium range aircraft.
The family offers a choice of engines
Event Management System Vb Net Project Report.pdfKamal Acharya
In present era, the scopes of information technology growing with a very fast .We do not see any are untouched from this industry. The scope of information technology has become wider includes: Business and industry. Household Business, Communication, Education, Entertainment, Science, Medicine, Engineering, Distance Learning, Weather Forecasting. Carrier Searching and so on.
My project named “Event Management System” is software that store and maintained all events coordinated in college. It also helpful to print related reports. My project will help to record the events coordinated by faculties with their Name, Event subject, date & details in an efficient & effective ways.
In my system we have to make a system by which a user can record all events coordinated by a particular faculty. In our proposed system some more featured are added which differs it from the existing system such as security.
Water scarcity is the lack of fresh water resources to meet the standard water demand. There are two type of water scarcity. One is physical. The other is economic water scarcity.
Democratizing Fuzzing at Scale by Abhishek Aryaabh.arya
Presented at NUS: Fuzzing and Software Security Summer School 2024
This keynote talks about the democratization of fuzzing at scale, highlighting the collaboration between open source communities, academia, and industry to advance the field of fuzzing. It delves into the history of fuzzing, the development of scalable fuzzing platforms, and the empowerment of community-driven research. The talk will further discuss recent advancements leveraging AI/ML and offer insights into the future evolution of the fuzzing landscape.
About
Indigenized remote control interface card suitable for MAFI system CCR equipment. Compatible for IDM8000 CCR. Backplane mounted serial and TCP/Ethernet communication module for CCR remote access. IDM 8000 CCR remote control on serial and TCP protocol.
• Remote control: Parallel or serial interface.
• Compatible with MAFI CCR system.
• Compatible with IDM8000 CCR.
• Compatible with Backplane mount serial communication.
• Compatible with commercial and Defence aviation CCR system.
• Remote control system for accessing CCR and allied system over serial or TCP.
• Indigenized local Support/presence in India.
• Easy in configuration using DIP switches.
Technical Specifications
Indigenized remote control interface card suitable for MAFI system CCR equipment. Compatible for IDM8000 CCR. Backplane mounted serial and TCP/Ethernet communication module for CCR remote access. IDM 8000 CCR remote control on serial and TCP protocol.
Key Features
Indigenized remote control interface card suitable for MAFI system CCR equipment. Compatible for IDM8000 CCR. Backplane mounted serial and TCP/Ethernet communication module for CCR remote access. IDM 8000 CCR remote control on serial and TCP protocol.
• Remote control: Parallel or serial interface
• Compatible with MAFI CCR system
• Copatiable with IDM8000 CCR
• Compatible with Backplane mount serial communication.
• Compatible with commercial and Defence aviation CCR system.
• Remote control system for accessing CCR and allied system over serial or TCP.
• Indigenized local Support/presence in India.
Application
• Remote control: Parallel or serial interface.
• Compatible with MAFI CCR system.
• Compatible with IDM8000 CCR.
• Compatible with Backplane mount serial communication.
• Compatible with commercial and Defence aviation CCR system.
• Remote control system for accessing CCR and allied system over serial or TCP.
• Indigenized local Support/presence in India.
• Easy in configuration using DIP switches.
Sachpazis:Terzaghi Bearing Capacity Estimation in simple terms with Calculati...Dr.Costas Sachpazis
Terzaghi's soil bearing capacity theory, developed by Karl Terzaghi, is a fundamental principle in geotechnical engineering used to determine the bearing capacity of shallow foundations. This theory provides a method to calculate the ultimate bearing capacity of soil, which is the maximum load per unit area that the soil can support without undergoing shear failure. The Calculation HTML Code included.
Sachpazis:Terzaghi Bearing Capacity Estimation in simple terms with Calculati...
C11 1 intro to gc techniques_final
1. TRP 1
Introduction to Green
Chemistry Techniques
IAMC Toolkit
Innovative Approaches for the Sound Management of
Chemicals and Chemical Waste
2. Introduction to Green Chemistry Techniques
The design of chemical products poses numerous challenges in
chemistry such as non-ideal conversion, competing reactions,
hazardous chemicals, raw material impurities, etc.
This presentation provides an overview of Green Chemistry
techniques to improve material efficiency, reduce pollution
intensity, and also produce safer products and processes.
The presentation provides an overview of Green Chemistry &
Green Engineering design principles as well as guidelines for
Green Chemistry metrics, material selection and reaction
conditions.
Since Green Chemistry & Green Engineering are often applied
together, common design principles are also shown.
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 2
3. 1. Examples of Green Chemistry & Green Engineering
2. Green Chemistry & Green Engineering design principles
3. Overview of Green Chemistry techniques:
Green chemistry metrics
Material selection
Reaction conditions
4. Key messages
Contents
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 3
4. Green Chemistry & Green
Engineering Examples
Green Chemistry & Green Engineering examples
Green Chemistry & Green Engineering design principles
Overview of Green Chemistry techniques
Green Chemistry metrics
Material selection
Reaction conditions
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 4
5. Green Chemistry Example: Biocatalytic
Process to Manufacture Simvastatin*
The traditional multistep synthesis of simvastatin, a leading drug for treating high cholesterol, is
wasteful (yield <70%) and uses hazardous and toxic reagents, requiring significant amounts of
solvents.
Codexis and UCLA developed a cost-effective synthesis process to manufacture simvastatin using
an engineered biocatalyst to improve the reaction yield and reduce hazards and wastes.
Environmental, health and safety benefits:
Catalyst manufactured from renewable feedstocks
Simvastatin yields of 97% possible (compared to <70% for traditional routes)
Reduced use of toxic and hazardous substances like tert-butyl dimethyl silane chloride,
methyliodide, n-butyl lithium
Reduced energy intensity since the reaction is operated at ambient temperature and near
atmospheric pressure
Aqueous reaction conditions reduce quantity of solvents used
Bi-product (methyl 3-mercaptopropionic acid) is recycled in the process
Primary waste streams are handled in standard wastewater treatment facilities
Economic benefits:
Biocatalytically manufactured, simvastatin meets customer requirements
Operating costs decreased since amounts of feedstock materials and solvents as well as
energy and water were reduced
* Source: ACS Green Chemistry Case Study, 2012
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 5
6. Green Engineering Example: Production of
Methyl Acetate with Reactive Distillation
Synthesis and purification of some chemicals can
involve reactors and multiple distillation columns to
increase the overall product yield, separate by-
products and meet product purity requirements.
Reactive distillation is a chemical processing
Improvement technology that combines chemical
reaction and distillation in one equipment, in which the
conversion is increased by continuously removing
reaction products from the reaction zone by
distillation.
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 6
Reactive distillation is especially useful for preventing
equilibrium-limited reactions like esterification.
Benefits:
Increase conversion, raw material productivity
and selectivity
Avoid/reduce separating reactants and solvents,
reduce by-products and pollution intensity
Reduce number of separation columns (capital
investment)
Decrease energy intensity
Reactive distillation for methyl acetate production
Acetic acid
Methanol
Catalyst
Return
from
impurity
removal
columns
Impurities
Methyl
acetate
Water
Acetic acid
Methanol
Catalyst
Methyl
acetate
Solvent
Azeo
HeaviesWater
Reactor
Water
Liquid
extraction Decanter
Traditional production of methyl acetate
Distillation
Extractive
distillation
Solvent
recovery
Methanol
recovery
Azeotrope
distillation
Entrainer
recovery
Colour
column
Flash column
distillation
Source: based on
Huss et al., 2009
Source: based on US EPA
7. Green Chemistry & Green
Chemistry Design Principles
Green Chemistry & Green Engineering examples
Green Chemistry & Green Engineering design principles
Overview of Green Chemistry techniques
Green Chemistry metrics
Material selection
Reaction conditions
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 7
8. Definitions
Green Chemistry1 is the design of chemical products and processes that reduce or
eliminate the use or generation of hazardous substances. Green Chemistry applies
across the life cycle of a chemical product, including its design, manufacture, use and
ultimate disposal. Green Chemistry is also known as sustainable chemistry.
Green Engineering1 is the design, commercialization and use of processes and
products in a way that minimizes pollution, promotes sustainability and protects human
health without sacrificing economic viability and efficiency.
Chemical process improvement is a component of green engineering focusing on
improving process resource efficiency and reducing waste.
Green Chemistry and Green Engineering2 are tools and principles applied across the
life cycle so that chemical products and their production are resource-efficient with
minimum pollution and safe for human health and the environment.
The 12 principles of Green Chemistry and 12 principles of Green Engineering can be
used to guide their application in the design and commercialization of chemical
products and processes (see following slides).
Sources: 1 United States Environmental Protection Agency; Anastas and Warner, 1998 2 based on Jimenez-Gonzalez and Constable, 2011
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 8
9. 12 Principles of Green Chemistry
1. Prevention: It is better to prevent waste than to treat
or clean up waste after it has been created.
2. Atom economy: Synthetic methods should be
designed to maximize the incorporation of all materials
used in the process into the final product.
3. Less hazardous chemical syntheses: Wherever
practicable, synthetic methods should be designed to
use and generate substances that possess little or no
toxicity to human health and the environment.
4. Designing safer chemicals: Chemical products
should be designed to effect their desired function
while minimizing their toxicity.
5. Safer solvents and auxiliaries: The use of auxiliary
substances (e.g., solvents, separation agents, etc.)
should be made unnecessary wherever possible and
innocuous when used
6. Design for energy efficiency: Energy requirements
of chemical processes should be recognized for their
environmental and economic impacts and should be
minimized. If possible, synthetic methods should be
conducted at ambient temperature and pressure.
7. Use of renewable feedstocks: A raw material or
feedstock should be renewable rather than depleting
whenever technically and economically practicable
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 9
8. Reduce derivatives: Unnecessary derivatization
(use of blocking groups, protection/deprotection,
temporary modification of physical/chemical
processes) should be minimized or avoided if
possible, because such steps require additional
reagents and can generate waste.
9. Catalysis: Catalytic reagents (as selective as
possible are superior to stoichiometric reagents.
10. Design for degradation: Chemical products should
be designed so that at the end of their function the
break down into innocuous degradation products and
do not persist in the environment.
11. Real-time analysis for pollution prevention:
Analytical methodologies need to be further
developed to allow for real-time, in-process
monitoring and control prior to the formation of
hazardous substances.
12. Inherently safer chemistry for accident
prevention: Substances and the form of a
substance used in a chemical process should be
chosen to minimize the potential for chemical
accidents, including releases, explosions, and fires.
Source: Anastas and Warner, 1998
10. 12 Principles of Green Engineering
1. Inherent rather than circumstantial:
Designers need to strive to ensure that all
materials and energy inputs and outputs are
as inherently non hazardous as possible.
2. Prevention instead of treatment: It is better
to prevent waste than to treat or clean up
waste after it is formed.
3. Design for separation: Separation and
purification operations should be designed to
minimize energy consumption and materials
use.
4. Maximize efficiency: Products, processes,
and systems should be designed to
maximize mass, energy, space, and time
efficiency.
5. Output-pulled versus input-pushed:
Products, processes and systems should be
“output pulled” rather than “input pushed”
through the use of energy and materials.
6. Conserve complexity: Embedded entropy
and complexity must be viewed as an
investment when making design choices on
recycle, reuse, or beneficial disposition.
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 10
7. Durability rather than immortality:
Targeted durability, not immortality, should
be a design goal.
8. Meet need, minimize excess: Design for
unnecessary capacity or capability (e.g.,
„one size fits all“) solutions should be
considered a design flaw.
9. Minimize material diversity: Material
diversity in multicomponent products should
be minimized to promote disassembly and
value retention.
10. Integrate material and energy flows:
Design of products, processes, and
systems must include integration and
interconnectivity with available energy and
materials flows.
11. Design for commercial „afterlife“:
Product, processes, and systems should be
designed for performance in a commercial
„afterlife“
12. Renewable rather than depleting:
Material and energy inputs should be
renewable rather than depleting.
Source: Anastas and Warner, 1998
11. Green Chemistry and Green Engineering
Design Principles
In practice, it is helpful to treat Green Chemistry and Green Engineering
as a common approach to improve the sustainability of products and
processes.
The many principles of Green Chemistry and Green Engineering can be
organized into three guiding design principles*:
Design systems holistically and use life cycle thinking through design (e.g.
consider impacts of chemical products over its life cycle including
consumer use and end of life) and being sustainable (e.g. use renewable
feedstocks)
Eliminate and minimize hazards and pollution through design (e.g. avoid
persistence of products, safer production), measurement (e.g. real-time
analysis, waste) and being sustainable (conserve ecosystems and protect
human health and well-being)
Maximize resource efficiency through design (e.g. use catalysis, reduce
derivatives), measurement (e.g. mass balances, quantify by-products),
efficiency (e.g. minimize energy requirements, optimize efficiency) and
being sustainable (e.g. minimize depletion of natural resources)
*Adapted from the American Chemical Society
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12. Design Systems Holistically and Use Life
Cycle Thinking
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 12
Design Being sustainable
Minimize chemistry impacts
Consider the effect of the overall process and life cycle on the choice of
chemistry.
Holistic approach
Engineer processes and products holistically, use systems analysis and
integrate environmental impact assessment tools.
Use life cycle thinking
Use life cycle thinking in all engineering and chemistry activities.
End of use
Products, processes and systems should be designed for performance in a
commercial “afterlife”.
Durability
Targeted durability, not immortality, should be a design goal.
Conserve complexity
Embedded entropy and complexity must be viewed as an investment when
making design choices on recycling, reuse or beneficial disposition.
Collaborate with engineers
Consult a chemical or process engineer.
Consider incompatibilities
Recognize where safety and waste minimization are incompatible.
Minimize material diversity
Material diversity in multicomponent products should be minimized to promote
disassembly and value retention.
Use renewables
A raw material feedstock should be renewable rather than depleting whenever
technically and economically practical.
Material and energy inputs should be renewable rather than depleting.
Innovate to achieve
Create engineering solutions beyond current or dominant technologies.
Improve, innovate and invent (technologies) to achieve sustainability.
Think locally
Develop and apply engineering solutions while being aware of local geography,
aspirations and cultures.
Engage
Actively engage communities and stakeholders in the development of
engineering solutions.
Apply measures
Help develop and apply sustainability measures.
Green Chemistry Green Engineering Source: based on the American Chemical Society
13. Eliminate and Minimize Hazards and Pollution
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 13
Design Measure Being sustainable
Avoid persistence
Chemical products should be designed so that at
the end of their function they do not persist in the
environment and break down into innocuous
degradation products.
Inherently non-hazardous
Designers need to strive to ensure that all material
and energy inputs and outputs are as inherently
non-hazardous as possible.
Synthetic methods
Wherever practical, synthetic methodologies
should be designed to use and generate
substances that possess little or no toxicity to
human health and the environment.
Safer processes
Substances and the form of a substance used in a
chemical process should be chosen so as to
minimize the potential for chemical accidents,
including releases, explosions and fires.
Prevention
It is better to prevent waste than to treat or clean
up waste after it has been formed.
Real-time analysis
Analytical methodologies need to be developed
further to allow for real-time in-process monitoring
and control prior to the formation of hazardous
substances.
Losses
Measure catalyst and solvent losses in aqueous
effluent.
Thermochemistry
Investigate basic thermochemistry.
Incompatibilities
Recognize where safety and waste minimization are
incompatible.
Waste
Monitor, report and minimize laboratory waste
emitted.
Conserve and improve
Conserve and improve natural ecosystems while
protecting human health and well-being.
Source: based on the American Chemical Society Green Chemistry Green Engineering
14. Maximize Resource Efficiency
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 14
Design Measure Being efficient Being sustainable
Output-pulled vs. input-pushed
Products, processes and systems should
be “output pulled” rather than “input
pushed” through the use of energy and
materials.
Atom economy
Synthetic methods should be designed to
maximize the incorporation of all materials
used in the process into the final product.
Find alternatives
The use of auxiliary substances (e.g.,
solvents, separation agents) should be
made unnecessary whenever possible and
innocuous when used.
Reduce derivatives
Unnecessary derivatization (blocking
group, protection-deprotection and
temporary modification of physical /
chemical processes) should be avoided
whenever possible.
Use catalysis
Catalytic reagents (as selective as
possible) are superior to stoichiometric
reagents.
Mass balances
Establish full mass balances for a
process.
Heat and mass transfer
Anticipate heat and mass transfer
limitations.
Conversion
Report conversions, selectivities
and productivities.
By-product formation
Identify and quantify by-products.
Utilities
Quantify and minimize the use of
utilities.
Reduce
Separation and purification
operations should be designed to
minimize energy consumption and
materials use.
Minimize
Energy requirements should be
recognized for their environmental
and economic impacts and should
be minimized. Synthetic methods
should be conducted at ambient
temperature and pressure.
Optimize
Products, processes and systems
should be designed to maximize
mass, energy, space and time
efficiency.
Integrate
Design of products, processes and
systems must include integration
and interconnectivity with available
energy and material flows.
Prevent
Strive to prevent waste.
Minimize
Minimize depletion of natural
resources.
Conserve and improve
Conserve and improve natural
ecosystems while protecting human
health and well-being.
Source: based on the American Chemical Society Green Chemistry Green Engineering
15. Overview of Green Chemistry
Techniques
Green Chemistry & Green Engineering examples
Green Chemistry & Green Engineering design principles
Overview of Green Chemistry techniques
Green Chemistry metrics
Material selection
Reaction conditions
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 15
16. Introduction to Green Chemistry Metrics
Metrics can be used to measure the greenness of a
chemistry, process or product.
Consider the following when using metrics to measure the
greenness:
Where to draw the boundary to best capture the impact of
the process or product
Metrics should be easily understood and promote
continuous improvement
A system of metrics help provide a fuller picture
All metrics should contribute to achieving Green Chemistry
goals
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 16
17. Examples of Green Chemistry Metrics (I)
In addition to traditional chemistry metrics such as yield,
selectivity; one can use the following metrics to measure the
greenness of the chemistry:
Atom economy
Reaction mass efficiency
Optimum efficiency
(Process) Mass intensity
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 17
AE =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
× 100
RME =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
× 100
OE =
𝑅𝑀𝐸
𝐴𝐸
× 100
PMI =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑖𝑛 𝑎 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑜𝑟 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑠𝑡𝑒𝑝
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
18. Examples of Green Chemistry Metrics (II)
In addition to traditional chemistry metrics such as yield,
selectivity; one can use the following metrics to measure the
greenness of the chemistry:
UNIDO│IAMC Toolkit│Images may not be copied, transmitted or manipulated 18
Renewables intensity = 𝑅𝐼 =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑛𝑒𝑤𝑎𝑏𝑙𝑦 𝑑𝑒𝑟𝑖𝑣𝑎𝑏𝑙𝑒 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙𝑠 𝑢𝑠𝑒𝑑
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
Renewables percentage =
𝑅𝐼
𝑃𝑀𝐼
× 100
Waste intensity = 𝑊𝐼 =
𝑡𝑜𝑡𝑎𝑙 𝑤𝑎𝑠𝑡𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑖𝑛𝑝𝑢𝑡
Waste percentage =
𝑊𝐼
𝑃𝑀𝐼
× 100
19. Green Chemistry Metrics: Example
Benzyl alcohol (C6H5CH2OH) (10.81g, 0.10mol, 108.1g/mol) reacts
with p-toluene sulfonylchloride (CH3C6H4SO2Cl) (21.9g, 0.115mol,
190.65g/mol) in toluene (500g) and triethylamine (15g) to give the
sulfonate ester (CH3C6H4SO2OC6H5CH2) (262.29g/mol) isolated in
90% yield (0.09mol, 23.6 g). Calculate the following parameters:
atom economy
reaction mass efficiency
mass intensity
mass productivity
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=
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
× 100
=
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
× 100
=
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑖𝑛 𝑎 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑠𝑡𝑒𝑝
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
=
1
𝑚𝑎𝑠𝑠 𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦
× 100
Source: Gonzalez and Constable
20. Green Chemistry Metrics: Example
Benzyl alcohol (C6H5CH2OH) (10.81g, 0.10mol, 108.1g/mol) reacts
with p-toluene sulfonylchloride (CH3C6H4SO2Cl) (21.9g, 0.115mol,
190.65g/mol) in toluene (500g) and triethylamine (15g) to give the
sulfonate ester (CH3C6H4SO2OC6H5CH2) (262.29g/mol) isolated in
90% yield (0.09mol, 23.6 g). Calculate the following parameters:
atom economy
reaction mass efficiency
mass intensity
mass productivity
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=
262.29
108.1 + 190.65
× 100 = 87.8%
=
23.6
10.81 + 21. 9
× 100 = 70.9%
=
10.81 + 21.9 + 500 + 15
23.6
= 23.2
𝑔
𝑔
= 23.2
𝑘𝑔
𝑘𝑔
=
1
𝑚𝑎𝑠𝑠 𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦
× 100 = 4.3%
Source: Gonzalez and Constable
21. Comparison of Metrics for Different
Chemistries (I)
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Stoichiometry
of B mole
(%)
Yield (22%) Atom
economy
(%)
Reaction mass
efficiency (%)
Mass intensity
excluding
water (kg/kg)
Mass
productivity
(%)
Acid salt 135 83 100 83 16.0 6.3
Base salt 273 90 100 80 20.4 4.9
Hydrogenation 192 89 84 74 18.6 5.4
Sulfonation 142 89 89 69 16.3 6.1
Decarboxylation 131 85 77 68 19.9 5.0
Esterification 247 90 91 67 11.4 8.8
Knoevenagel 179 91 89 66 6.1 16.4
Cyanation 122 88 77 65 13.1 7.6
Bromination 214 90 84 63 13.9 7.2
N-acylation 257 86 86 62 18.8 5.3
S-alkylation 231 85 84 61 10.0 10.0
C-alkylation 151 79 88 61 14.0 7.1
N-alkylation 120 87 73 60 19.5 5.1
O-arylation 223 84 85 58 11.5 8.7
Source: Gonzalez and Constable
22. Comparison of Metrics for Different
Chemistries (II)
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Stoichiometry
of B mole
(%)
Yield (22%) Atom
economy
(%)
Reaction mass
efficiency (%)
Mass intensity
excluding
water (kg/kg)
Mass
productivity
(%)
Epoxidation 142 78 83 58 17.0 5.9
Borohydride 211 88 75 58 17.8 5.6
Iodination 223 96 89 56 6.5 15.4
Cyclization 157 79 77 56 21.0 4.8
Amination 430 82 87 54 11.2 8.9
Lithal 231 79 76 52 21.5 4.7
Base hydrolysis 878a 88 81 52 26.3 3.8
C-acylation 375 86 81 51 15.1 6.6
Acid hydrolysis 478 92 76 50 10.7 9.3
Chlorination 314 86 74 46 10.5 9.5
Elimination 279 81 72 45 33.8 3.0
Grignard 180 71 76 42 30.0 3.3
Resolution 139 36 99 31 40.1 2.5
N-dealkylation 2650a 92 64 27 10.1 9.9
aInflated by use of solvent as reactant Source: Gonzalez and Constable
23. Chem21 Metrics Toolkit
The CHEM21 project (Chemical Manufacturing Methods for the 21st
Century Pharmaceutical Industries) developed a Green Chemistry toolkit
for the pharmaceutical industries which can be applied to all chemical
processing industries.
The bench-scale toolkit involves a ‘zero pass’ and ‘first pass’ screening
process.
Zero pass: use at the discovery phase where large numbers of
screening reactions are carried out on a small scale with the most
promising reactions selected fro the ‘first pass’. This stage looks at
metrics yield, conversion, selectivity, AE, RME, restricted solvents and
health & safety
First pass: more in-depth investigation of a reaction’s greenness
including comparing different routes to the same target compound.
Additional metrics include MI, critical elements, energy, chemicals of
concern, and more detailed analysis
An excel tool can be downloaded here:
http://pubs.rsc.org/en/Content/ArticleLanding/2015/GC/c5gc00340g#!divA
bstract
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24. Overview of Green Chemistry
Techniques
Green Chemistry & Green Engineering examples
Green Chemistry & Green Engineering design principles
Overview of Green Chemistry techniques
Green Chemistry metrics
Material selection
Reaction conditions
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25. Improving Reaction Conditions: Material
Selection – Solvents
Solvents are used in many industries for processing (e.g.
distillation, equipment cleaning), synthesis (reactant) and
formulation of products (carrier).
Solvents typically have serious health and environmental
hazards including waste management issues, so:
Avoid materials not integrated in the product (e.g.
solvents) where possible
If solvents are necessary, use ones with less health and
environmental impacts, and minimize their use while
optimize effectiveness
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26. Improving Reaction Conditions: Material
Selection – Solvent Properties & Selection (I)
Solvent properties are an essential criteria when selecting solvents
for a process. Select solvents according to Green Chemistry
principles (satisfy solubility requirements while minimizing health,
safety and environmental impacts).
The ‘CHEM21 solvent selection guide’ can be used to evaluate
existing and new solvents according to health, safety and
environmental factors and classify them as:
Recommended
Problematic
Hazardous
The background paper and an excel tool can be found here:
http://pubs.rsc.org/en/content/articlelanding/gc/2016/c5gc01008j#!
divAbstract
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27. Improving Reaction Conditions: Material
Selection – Solvent Properties & Selection (II)
Once the solvents have been evaluated for health, safety and
environmental impacts, the final selection as made based on
functional performance and costs.
The following can be used to select solvents based on their
properties:
Property databases: e.g. search for water-miscible solvents with
a boiling point between 70-95°C (e.g. CRC handbook)
Principal components analysis: can be used to identify a system
of EHS-friendly solvents to replace a single component
hazardous solvent according to desired properties such as
boiling point, melting point, dipole moment, solubility
parameters. An practical way to address solubility challenges is
to use the Hansen solubility parameters of mixtures to replace
the functionality of a single component. For more information:
http://hansen-solubility.com/
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28. Improving Reaction Conditions: Material
Selection - Catalysts
Catalysts lower the reaction’s activation energy and speeds up the
rate of reaction and can result in increased reaction efficiency.
Example: BASF developed a new process to manufacture
ibuprofen, replacing a technology with six stoichiometric steps and
less than 40% atom utilization with a technology with three steps
and 80% atom utilization, and large amounts of aqueous waste
was eliminated.
Possible benefits of catalysis:
Productivity: increased yield, selectivity, and reactor volume
efficiency; reduced cycle time and variability
Environmental: increased resource efficiency; reduction of
undesired by-products; elimination or reduction of solvents;
Safety: can reduce the use of hazardous chemicals
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29. Overview of Green Chemistry
Techniques
Green Chemistry & Green Engineering examples
Green Chemistry & Green Engineering design principles
Overview of Green Chemistry techniques
Green Chemistry metrics
Material selection
Reaction conditions
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30. Reaction Conditions
Reactions conditions are an important way to improve
the greenness of the chemistry and process.
The most common reaction conditions which can be modified
by the manufacturer include:
Stoichiometry
Temperature
Order and rate of reagent addition
Mixing
Design of experiments can be used to optimize reaction
conditions using a minimum number of experiments. See
more in ‘Introduction to Operational Excellence’.
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E11_1_Intro to OE
31. Common Activities in Batch Processing and Impacts
on Green Chemistry
Acid and base washes
pH adjustment
Salt washes
Use of desiccants
Chromatographic clean-
ups
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Carbon cleanup
Use of filter aids
Put and take distillations
Distillations
Isolation steps /
crystallization
Many activities in the batch chemical processing impacts
Green Chemistry. Common activities, the problems they
cause and possible options to solve the problem are found in
the reference document ‘Green Chemistry impacts in batch
chemical processing’.
The batch chemical processing activities include:
C11_2_Chem processing GC impacts
32. Improving Reaction Conditions: Stoichiometry
Basic chemistry places importance on balancing equations
for reactions. There is a balance between mass efficiency
(reducing waste) and having excess reagent to drive
reactions to completion. General principles for improving
stoichiometry impacts include aiming:
For reactions which need equimolar (or close to) quantities
of reactants to reduce excess waste
To minimize stoichiometric excesses of catalysts (e.g.
reduce excess strong Lewis acids used as a catalyst in the
nitrification of aromatics)
To use bound catalysts which can be regenerated (e.g.
Lewis solid acid (zeolite-based) which can be regenerated
and avoid large quantities of waste)
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33. Improving Reaction Conditions: Temperature
General Green Chemistry on selecting chemistries and temperature:
Use reactions which can be run as close to ambient temperature (and
to a lesser degree, pressure) as possible and avoid running reactions
at very cold temperatures (< -20°C) since this is energetically very
unfavourable.
Balance temperature with reactions rates to optimize reaction kinetics
while avoiding conditions which could cause an accident
Estimate heat of reaction (endothermic or exothermic) before
validating with experiments
Be careful with exothermic reactions:
It is important to characterize impacts of reaction temperature, reaction
rate, order of addition, mixing, pressure and heat evolution/removal.
Avoid run-away reaction conditions (heat evolution increases
exponentially while heat removal is linear). Note: using the Arrhenius
relationship, a 10°C increase in temperature can result in a 2-3 times
increase of reaction rate and likewise heat release.
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34. Improving Reaction Conditions: Mixing
Mixing is an important Green Chemistry issue in chemical processing and up-
scaling. Mixing helps to overcome heat transfer and mass transfer limitations in
chemical processing. Proper mixing:
Avoids temperature and reagent concentration gradients (in reactors of all shapes
and sizes) so that reactants are consumed and form product in equimolar amounts
at the desired temperature thereby maximizing yield and reducing waste
Prevents localized temperature hotspots and localized runaway reactions which
could cause accidents (for exothermic reactions)
Can control the rate of reaction if the kinetic rate is very high and the reaction is
mass-transfer limited (e.g. simple acid or base neutralization reaction in which
kinetic rate ~ 108 m3/mol-s)
General tips:
Solid-liquid: ensure solids or uniformly distributed in liquid
Gas-liquid or liquid-liquid: ensure phases are uniformly mixed and interfacial area
is optimized for desired reaction. Improper mixing in 2-phase systems can lead to
problems with filtration, decrease product yield, increase processing time and lead
to increased costs
Improve mass transfer, increase product yield and decrease waste by considering
alternative solvents (e.g. ionic liquids, supercritical fluids), phase transfer catalysts,
or alternative reactors (e.g. vortex mixers, microreactors)
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35. Improving Reaction Conditions: Order and
Rate of Reagent Addition
The order and rate of reagent addition can have significant impacts on
the process and final product, in particular:
Optimization can lead to significant reductions in reaction time, energy
consumption and waste
Make reactions more controllable and safe. E.g. for exothermic or
endothermic reactions, by adding reagents in a certain order, excessive
temperatures (exothermic) or uncontrolled precipitation (endothermic) can
be avoided
Order and rate of addition can be used:
In micro or minireactors to achieve optimal reaction rate and temperature
To control kinetic rate and possibly reduce undesired by-products,
impurities and maximize yield
To control temperature by heating or cooling reagents before addition
In multiphase systems to prevent emulsion, control rate and timing of
phase formation
Note: order and rate of addition should always be optimized together with
mixing
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37. Key Messages (1)
The design of chemical products pose numerous challenges
in chemistry such as non-ideal conversion, competing
reactions, hazardous chemicals, raw material impurities, etc.
and Green Chemistry techniques can improve material
efficiency, reduce pollution intensity, and also produce safer
products and processes.
Green Chemistry and green engineering should be integrated
to make green products using green processes. All design
principles can be grouped in three guiding design principles:
Design systems holistically and use life cycle thinking
Eliminate and minimize hazards and pollution
Maximize resource efficiency
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38. Key Messages (2)
Green Chemistry can be applied in a practical way using the following
parameters:
Green Chemistry metrics: Quantifiable and verifiable metrics can be used
to measure the greenness of reactions, processes or products. Often a
system of metrics (with different boundaries) are required to understand
the full impacts.
Material selection:
Solvents are often the source of EHS impacts. Alternative, safer
solvents can typically be found by comparing properties or using a
solvent system mixture with similar single component prosperities (e.g.
using Hansen solubility parameters)
Reactions conditions are an important way to improve the greenness of
the chemistry and process. The most common reaction conditions which
can be modified by the manufacturer include:
Stoichiometry
Temperature
Order and rate of reagent addition
Mixing
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40. Fusce posuere, magna sed pulvinar ultricies,
purus lectus malesuada libero, sit amet magna
eros quis (ARIAL 32).
Sources
CSD Engineers, Switzerland/ISSPPRO, Germany, 2015
Anastas, P. T. and Warner, J. C. Green Chemistry: Theory and Practice. Oxford
University Press: New York, 1998
Chem21 Chemical Manufacturing Methods for the 21st Century Pharmaceutical
Industries: http://www.chem21.eu/
EPA Presidential Green Chemistry Challenge Awards 1997.
https://www.epa.gov/greenchemistry/presidential-green-chemistry-challenge-1997-
greener-synthetic-pathways-award
Jimenez Gonzalez, C. and Constable, D.J.C. Green Chemistry and Engineering: A
Practical Design Approach. Wiley, 2011
Prat, D. Wells, A., Hayler, J. Sneddon, H. McElroy, C.R. Abou-Shehada, S. et
al., Green Chem., 2016, 18, 288
USEPA. http://www2.epa.gov/greenchemistry/definition. Accessed June 2015.
USEPA. http://www2.epa.gov/green-engineering/about-green-engineering#definition.
Accessed June 2015.
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41. Images
ISSPPRO GmbH, Germany, 2015
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42. Disclaimer
This presentation was prepared with the requested diligence
and with the generally accepted principles of the relevant
field.
If a third party uses the contents of the presentation in order
to take decisions, the authors disclaim any liability for any
kind of direct or indirect (consequential) damage.
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