Green Chemistry

Dr. Nguyễn Đăng Khoaa, Dr. Lê Vũ Hàa, Dr. Hồ Hoàng Phướcb

a Faculty of Chemical Engineering, Ho Chi Minh City University of Technology,
Vietnam
b Chemical Engineering, Competence Centre for Catalysis, Chalmers University of
Technology, Sweden
Contact: khoand1989@hcmut.edu.vn, lvha@hcmut.edu.vn, phuoc@chalmers.se
Off-line appointments (applied to the whole course): 9:00 – 10:00 Wednesday, 11:00 – 12:00 Thursday at 211B2
 Time Planned Content

Week 1 Introduction to Green Chemistry

Week 2
Week 3 The 12 principles of green chemistry
Week 4
Week 5
Week 6 Green improvements of chemical production: Catalysis
Week 7
Week 8
Week 9 Green improvements of chemical production: Solvents
Week 10
Week 11
Green improvments of chemical production: Renewable materials
Week 12

Week 13 Emerging Greener Technologies and Alternative Energy Sources

Week 14 Green improvement of industrial processes: Some examples
Week 15 Summarization
Texbook
1) P.C. Anastas and J.C. Warner ‘Green Chemistry Theory and Practice’, Oxford University Press, New York, 1998
2) M. Lancaster, GREEN CHEMISTRY: An Introductory Text, University of York, RSC, 2002

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 Outline
• Review some important contents of Green Chemistry
• Exercises
• Final exam information

Source: Center for Green Chemistry and Green Engineering at Yale

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 Importance of chemical industry

Fossil-based
Renewable

Natural sources

Bulk chemicals/ Fine Customers of

Speciality
Commodity chemcials
Basic chemicals chemicals chemicals chemical industry
• Olefins • Plastics & Engineering Resins
• Active pharmaceutical • Automotive/Transportation
ingredient • Paints & Coatings
• Chlor-Alkali • Packing
(Chlorine, caustic soda) • Biocides • Cleaning products • Building & construction
• Acid sulfuric, ammonia
• Solvents, etc.

✓ Starting material other chemicals ✓ High purity ✓ Blends of two or

more fine
✓ High demand ✓ Low volume production chemicals
✓ High volume production (<1000 tons/year)
✓ Continous process ✓ Batched process
✓ Low price ✓ High cost (>10$/kg)

What are some common bulk chemicals (organic inorganics)? What are their uses for?
https://www.spglobal.com/commodityinsights/en/ci/research-analysis/q23-formula-for-success-in-the-chemical-industry-analyzing-energy-at-the-extremes.html
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 A presentative scheme of a chemical plant

Energy Energy

Materials Product Product

Reactor
Purification
(feedstocks) T, P Byproduct
Waste
Catalyst Solvent

• Industry/chemical industry → important role → our daily-used products

• Materials (reagents, solvents) → toxicity? Renewable?
• Energy consumption → efficiency? Sources (Fossil? Renewable?)
• Processes (steps? yield?)
• Purification (solvent, energy?)
• Safe operation (accidents)
• Waste (kinds of wastes? Impact?)
• Products → safety? Environmental impact?

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Pollutions: Air, Water → What are possible sources?

Vietnam:

• Main energy source?

• What are the issues?

• Acid rain? Impact?

• Greenhouse gas? Impact?

• Kinds of fuels in Vietnam?

• Standard for sulfur limitation?

• Regulation for fuel standard around the world?

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 Green chemistry: History? When? Who?

the Pollution Prevention Act of 1990

Paul Anastas and John C. Warner co-

authored the groundbreaking book, Green
Chemistry: Theory and Practice in 1998.

The design of chemical products & processes that reduce or eliminate

the use or generation of hazardous substances

“Green Chemistry is a revolutionary approach to the way that products are made; it
is a science that aims to reduce or eliminate the use and/or generation of
hazardous substances in the design phase of materials development.”

– John Warner, Co-Founder of Green Chemistry

Aims? Benefits (business/economic and environmental)?

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 The 12 Principles of Green Chemistry: Summary

Imperial College London

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 Measures of Reaction Efficiency

Reaction: A + B → P (main product) + U (unwantted materials)

In which A is a limiting reagent (get consumed first in a chemical reaction)

Transformed quantity of substrate A

Conversion (%) = x 100
Total amount of substrate A

Actual quantity of the target product achieved

% Selectivity = x 100
Transformed quantity of substrate A

Actual quantity of the target product achieved

% Yield = x 100
Theoretical quantity of products achievable

Yield (%) = Conversion (%) x Selectivity (%)/100

~ 100%: quantitative, > 90%: excellent, > 80%: very good, > 70%: good, > 50%: fair, and < 40%:
poor

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 E-factor = total waste (g) / product (g) The lower your E-Factor, the better performing your product is
E-factor of some industry sectors

Relative molecular mass of the desired product

% Atom Economy = x 100
Relative molecular mass of all reactants

Benign: pleasant and kind;

not harmful or severe

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 CATALYSIS?

Chemical plant More than 85% of chemical production

→ use catalysts

Feedstock Products
Separation/
Catalysts Purification
Energy Waste

▪ Catalyst is a compound that accelerates chemical reactions but remains itself unchanged.

Catalysis is the increase in the rate of a chemical reaction due to the participation of a catalyst.

▪ Scientifically, a catalyst (material that enables catalysis) allows for the lowering of the activation

energy for a reaction to occur.

▪ Decreased activation energy results in faster and less energy intensive reactions and

processes.

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 CATALYSIS?

▪ Types of catalysis?
▪ Common Materials for catalysts?
▪ Heterogeneous catalysis application: chemical synthesis, energy
production, environmental protection
▪ Companies for catalyst suppliers?
▪ Some typical catalytic processes in industry?
▪ Three-way catalytic converter: Function? Catalysts?

ACS Catal. 2021, 11, 20, 12446–12468

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 SOLVENTS

Definition
Classification Classify the solvents in the Figure into 3 groups of solvents?
Properties Nonpolar:
VOCs Polar aprotic:
Impacts of solvent uses Polar protic:
Interaction with microwave?

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 SOLVENTS

✓ Washing
Industry: ✓ Degreasing
✓ Dry Cleaning

Solvents → Cost
Unit operations
✓ Extraction
✓ Recrystallization
Chemical Manufacture
✓ Disolution of solids for easy handling
✓ Heat exchange reagents

Reactions

✓ If need solvents: minimum use, less toxic solvents, and renewable solvents
✓ Chemistry without organic solvents

1) Solvent-free processes 3) Supercritical fluids

2) Water-based processes 4) Ionic liquids
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 Renewable feedstocks

• What is a Feedstock?
• Renewable vs. Depleting
• Current feedstock consumption Made from CO2
P2X or PtX
• Types of Renewable Feedstocks
Cellulose
• CO2 Hemicellulose
• Biomass Lignin
Starch
• Agricutural wastes
• Industrial Applications

Rememeber to review some typical processes in the videos?

• Bioethanol
• Bioethylene
Pathways
• Fuels
• Plastics (e.g. PE, PET)
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 Renewable feedstocks

• What is a Feedstock?
• Renewable vs. Depleting
• Current feedstock consumption Made from CO2
P2X or PtX
• Types of Renewable Feedstocks
Cellulose
• CO2 Hemicellulose
• Biomass Lignin
Starch
• Agricutural wastes
• Industrial Applications

Rememeber to review some typical processes in the videos?

• Bioethanol
• Bioethylene
Pathways
• Fuels
• Plastics (e.g. PE, PET)
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 Advantages of microreactor systems

• Scale-out: process is optimized & reactor is designed only once in Lab

• Increasing production volume can be easily obtained by assembly more
number of reactors
• Microreactors + other technologies (e.g. microwave) to improve energy
efficiency
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 Renewable feedstocks

▪ Open book (no mobile phone, no internet, no communication)

▪ Bring with you a minicalculator
▪ Duration: 90 min

Part I: Multiple choices a, b, c, d → select (circle) the best option (only one)
30 questions x 0.2 points = 6 points

Part II: Writing (4 points)

Note: You must write your answers directly on the exam paper and give the exam
paper to the examiner before you leave the room

You need to review all the homeworks given to you

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 Evaluate a process based on Green chemistry perspectives

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 SYNTHESIS COMPARISON EXERCISE
Dihydropyrimidone is a pharmaceutical compound that displays medicinal properties as vasodilatory calcium-
channel blockers and anti-viral, anti-bacterial, and anti-inflammatory agents. More than one synthetic schemes
have been proposed for its synthesis since the late 1800s. Compare the two synthetic routes and analyze which
pathway is greener. In your argument, be sure to consider and compare all aspects of the reaction.

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 Gasoline (or petrol) is a mixture of hydrocarbons containing about 87% C by weight. The
graph shows the gasoline consumption (thousand barrels) per day in Vietnam.

(Source: https://www.theglobaleconomy.com/Vietnam/gasoline_consumption/)
It is given that one barrel is equal to 159 L, and the density of gasoline is approximately
0.755 kg/L. We assume that the gasoline in Vietnam contains 500 ppmw (part per million in
weight) of sulfur (or 500 mg S/kg gasoline) according to level 2 (ASTM D2622) or Euro II.
Look at the year 2021, assuming that carbon and sulfur are converted into CO2 and SO2,
respectively, during the consumption of gasoline (as a fuel in transportation).
1. Calculate amount of S (in kg) contains in total gasoline consumed per day in 2021.
2. Calculate amount of SO2 (in kg) released to the atmosphere every day in 2021.
(S = 32 and SO2 = 64 g/mol).
3. Calculate amount of CO2 (in kg) emitted into the atmosphere every day in 2021?
(C = 12 and CO2 = 44 g/mol).
4. What are the impacts of SO2 on the environment and human health?

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 (thousand barrels per day)
Gasoline consumption

1 barrel = 159 L 500 mg S/kg gasoline Gasoline density: 0.755 kg / L

To know amount of S → need to know total amount of gasoline consumed in kg?

From data → know amount of gasoline consumed in volume (barrel)

How to convert volume from barrel to L?

How to determine the mass (kg) from volume (L)? → density definition?

→ Know S → how to calculate from S to SO2?

→ Do the same for C

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 Gasoline consumption
(thousand barrels per day)

1 barrel = 159 L 500 mg S/kg gasoline Gasoline density: 0.755 kg / L

500 mg/kg = 500 mg/ 1000 000 mg = 5 mg/ 10000 mg = 0.0005 mg/mg → 0.05 wt%
Year 2021
Barrel (thousand) 132.5
1 barrel --> L 159
C + O2 → CO2 Gasoline Volume (thousand L) 21067.5
Density kg/L 0.755
12 44 Mass (thousand kg) 15905.963
Percentage (wt%) 87
C
Mass (thousand kg) 13838.187
S + O2 → CO2
CO2 Mass (thousand kg) 50740.02
32 64 S
Percentage (wt%) 0.05
Mass (thousand kg) 7.9529813
SO2 Mass (thousand kg) 15.905963

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