Imperial College

Revised end of Lecture 2: Effective Mass Yield - EMY London

mass of desired product

EMY = x 100 %
mass of non-benign reagents

Whereas atom economies and E-factors are unlikely to measure the true
sustainability of a chemical reaction, EMY values do discriminate between
environmentally benign and non-benign reagents.

4.I6 2 - A1
 Imperial College
Green Metrics - the corrected slide from lecture 2 London

e.g. esterification of n-butanol with acetic acid

Typical procedure: 37g butanol, 60 g glacial acetic acid and 3 drops of H2SO4 are
mixed together. The reaction mixture is then poured into 250 cm3 water. The
organic layer is separated and washed again with water (100 cm3), saturated
NaHCO3 (25 cm3) and more water (25 cm3). The crude ester is then dried over
anhydrous Na2SO4 (5 g), and then distilled. Yield = 40 g (69 %).

Metric Value Greenness

yield 69 % Moderate
atom economy 85 % Good (byproduct is water)
E-factor 462 / 40 = 12.2 Poor
EMY 40/37 x 100 = 108 % Very good

EMY indicates that the

reaction is very 'green'
4.I6 2 - A2
 Imperial College
Recap of the conclusions from lecture 2 London

Atom efficiencies and E-factors are often useful, simple guides to the 'greenness'
of reactions, but may be overly focussed on waste.

EMY values take into account the toxicity of reagents and are therefore more
likely to reflect the true 'greenness' of a process.

However, EMY values require us to decide what and what is not benign!

The only true way of judging 'greenness' is by a life cycle analysis, but this is far
too time consuming to be practical. We therefore use atom economies, E-factors
and EMY data as simple (but imperfect) guides.

Remember Lecture 1 - "Green Chemistry is not easy!"

The difficulties measuring greenness are a major reason.

4.I6 2 - A3
 Imperial College
Exam style question - answer next time London

Maleic anhydride may be prepared using two routes:

Oxidation of benzene:

Oxidation of but-1-ene:

The benzene oxidation route typically occurs in 65 % yield, while the but-1-ene
route only gives yields of 55 %.

(a) Assuming that each reaction is performed in the gas phase only, and that no
additional chemicals are required, calculate (i) the atom economy and (ii) the
effective mass yield of both reactions. You should assume that O2, CO2 and H2O
are not toxic.

(b) Which route would you recommend to industry? Outline the factors which might
influence your decision.

4.I6 2 - A4
 Imperial College
4.I6 Green Chemistry London

Lecture 3: Renewable versus Depleting Resources

or Biomass versus Petrochemicals

"Many of the raw materials of industry…can be

obtained from annual crops grown on the farms"

Henry Ford, 1932

4.I6 Green Chemistry Lecture 3 Slide 1

 Imperial College
Lecture 3 - Learning Outcomes London

By the end of this lecture you should be able to

• describe the concept of carbon neutrality

• describe the use of biomass as a source of renewable fuels
• explain how biomass may be used as a source of chemicals

4.I6 3 - 2
 Imperial College
Major petrochemical building blocks London

Seven major raw materials from petroleum: C2-C4 and BTX

ethylene propylene butenes butadienes
benzene (B) toluene (T) xylenes (X)

Each also has extensive derivative chemistry, e.g. ethylene

CH2=CH2
Cl2 H2, CO
O2 , H2O,
C6H6
CH2ClCH2Cl PdCl2 CH3CH2CHO
O2, Ag
-HCl CH3CHO PhCH2CH3
O2, O2

O2 AcOH,
CH2=CHCl -H2
PdCl2 CH3CH2CO2H H2
O2 H2O
H2O
CH3CO2H CH2=CHOAc CH2=CHPh

HOCH2CH2OH CH3CH2CH2OH
(CH3CO)2O

CH3CH2OH
4.I6 3 - 3
 Imperial College
The problem with petroleum? Its use as a fuel… London

• non-sustainable
Definition of sustainable development:
"meeting the needs of the present without compromising the ability of future
generations to meet their own needs" UN Bruntland Commission 1987

• adverse direct and indirect environmental effects

• limited supplies (economic pressure and potential security risk)
• political entanglement
But the vast majority of contemporary industrial chemistry is
based on petrochemicals - in the US > 98 % of all commercial
chemicals are derived from petroleum (in Europe it is > 90 %)

4.I6 3 - 4
 Imperial College
Energy consumption London

Projected Global Energy Consumption to 2030

15
109 tonnes of
oil equivalent
oil
10

gas biomass +
5 other renewables
coal
nuclear
0
1971 1980 1990 2000 2010 2020 2030 hydro

• energy demands will increase and so will CO 2 production

• biomass-based fuels attracting increasing attention

Source: World Energy Outlook 2005 (International Energy Authority)
4.I6 3 - 5
 Imperial College
What is biomass? London

Biomass is all organic (living and dead) material on the planet. More realistically,
the biomass that we shall consider in this lecture is made up of:

• agricultural residues
Chemical composition
• food processing wastes
Cellulose - Sugars / Starches

• livestock production wastes Hemicellulose

• municipal solid waste Lignin

• wood waste

4.I6 3 - 6
 Imperial College
But doesn't burning biomass still produce CO2? London

(CH2O)n + n O2 n CO2 + n H2O

Biomass is said to be carbon neutral, i.e. the CO2 absorbed from the atmosphere
during plant growth is returned to it upon burning.

biomass oil natural gas

Energy release on 15 45 55
combustion (GJ tonne-1 )

As burning biomass is less calorific than burning fossil fuels, alternative ways to
produce energy from it have attracted attention.

What is the difference between carbon

neutrality and carbon offsetting?

4.I6 3 - 7
 Imperial College
Energy from biomass London

Method employed depends on the source of biomass (and on its water content)
15 %
combustion heat, CO2, H2O

thermolysis charcoal,
(450 - 800 °C) fuel, gases
So will using biomass for
energy increase the supply
pyrolysis of renewable feedstocks?
C2H2, charcoal
(1500 °C)
water content

gasification CO, H2, CH4, CO2

(650 - 1200 °C)

hydrothermolysis charcoal, biorenewable

(250 - 600 °C) fuel, CO2 raw materials?

fermentation ethanol, CO2

> 85 % anaerobic CH4, H2O

digestion
4.I6 3 - 8
 Imperial College
Biofuels - 1. Biodiesel London

Production of Biodiesel

triglyceride, main fatty acid ester,

component of biodiesel
vegetable oil

e.g. palm oil based triglycerides contain:

42.8 % palmitic acid (1-hexadecanoic acid; CH3(CH2)14 CO2H)

40.5 % oleic acid (cis-9-octadecenoic acid; CH3(CH2)7CH=CH(CH2)7CO2H)
10.1 % linoleic acid (cis,cis-9,12-octadecadienoic acid; CH3(CH2)3(CH2CH=CH)2(CH2)7CO2H)
4.5 % stearic acid (1-octadecanoic acid; CH3(CH2)14 CO2H)
0.2 % linolenic acid (cis,cis,cis-9,12,15-octadecatrienoic acid; CH3(CH2CH=CH)3(CH2)7CO2H)

Other sources include soybean, rapeseed and sunflower seed.

4.I6 3 - 10
 Imperial College
Biodiesel: pros and cons London

Advantages:
• GM can increase oil yield (some sunflower seeds contain 92% oleic acid)
• Bacteria could be even more productive
• Wide range of oils tolerated (even waste chip-shop oil can be recycled in
this way)

• Carbon neutral fuel source (in theory) and biodegradable

• Glycerin by-product
Disadvantages:
• Land use (maximum biodiesel fraction of car fuel market in the UK ≈ 5 %)
• Higher viscosity than normal diesel (unreliable in cold weather)
• To keep costs low the transesterification step must be fast - catalyst is often
4.I6 3 - 11
 Imperial College
But fatty acids may also be used as chemical raw materials London

1. Modification of the acid function

Wax esters (lipids)

Metal triglyceride Fatty amides

ROH
carboxylates
NR3 -H2O

Na, Al, Zn, Mg Fatty acid

hydroxides Nitriles

H2 H2

1-alkenes -H2O
Fatty alcohol Amine

ethylene RX
oxide
Sulfosuccinates
(surfactants) R4N+ salts
Na2SO3
Alcohol ethoxylate
maleic anhydride (pesticides)

4.I6 3 - 12
 Imperial College
Fatty acids chemistry continued London

2. Modification of the alkene function

medium chain acids short chain acids

and alkenes and diacids

olefin metathesis
(C2H4) ozonolysis

conjugated fatty base H+ or NOx

Fatty acid cis-trans isomers
acids (lipids)

(i) H+, H2O

[O]
(ii) H2

diols (precursors epoxides

for polyurethanes)

4.I6 3 - 13
 Imperial College
Example: erucic acid (C22 ) London

brassylic acid erucamide

(nylon 13,13 precursor (slip agent)
and musks)

HO2C(CH2)11 CO2H

erucic acid (rapeseed)

CH3(CH2)20 CO2H CH3(CH2)20 CH2OH

behenic acid behenyl alcohol

(PVC antiblocking agent) (cosmetics)

4.I6 3 - 14
 Imperial College
Biofuels - 2. Bioethanol London

yeast
C6H12 O6 2 C2H5OH + 2 CO2

Advantages
• Cheap hydrated bioethanol can be used neat as a car fuel, but requires
specially adapted engines. Anhydrous bioethanol must be mixed with petrol
(up to 22 %) but can then be used in conventional engines.

Disadvantages
• Of all the saccharides present in biomass, only glucose is readily
fermented, lowering competitiveness and increasing waste (genetic
engineering may solve this problem).

• Enzymes do not operate if the EtOH concentration is too high (typically

needs to be < 15 %). Energy intensive and expensive distillation is therefore
required.
Large amount of research now looking at the
conversion of ligninocellulosic feedstocks into sugars

4.I6 3 - 15
 Imperial College
12 major sugar derived chemicals London

1,4-diacids, 2,5-furandicarboxylic acid 3-hydroxypropionic acid

e.g succinic acid

aspartic acid glucaric acid glutamic acid

itaconic acid levulinic acid 3-hydroxybutyrolactone

glycerol sorbitol xylitol

4.I6 3 - 16
 Imperial College
Each has extensive derivative chemistry, e.g. levulinic acid London

χ -valerolactone cellulose 2-methyl THF solvent, fuel

solvent oxygenate
H2SO4 > 200°C

acrylic acid
1,4-pentanediol glucose
monomer
200°C

polyester
precursor 5-amino
levulinic acid
levulinate -HCO2H
esters
herbicide
biodiesel
additive

diphenolic monomer acetyl

levulinic acid
acid acrylic acid
bisphenol A
substitute
4.I6 3 - 17
 Imperial College
The difference between petrochemicals and biomass chemicals? London

Slide 3 Slide 17

Hydrocarbon-based chemistry Carbohydrate-based chemistry

The major difference is oxygen content

4.I6 3 - 18
 Imperial College
An alternative source of biomass chemicals - Syn-gas London

Three classical routes:

1. Steam reforming of methane

1:3

2. Shell Gasification process

1:1

3. Coal gasification
1:1

1:0

In theory any hydrocarbon can be used, e.g.

toluene steam
dealkylation
4.I6 3 - 19
 Imperial College
Existing Syn-gas technology London

polyethylene

aldehydes
CO, H2 -H2O esters
acids oligomers C2H4 EtOH ethers
alcohols
O2 + Ag

ethylene Biomass H2O + Rh catalyst

oxide

N2 Fischer Tropsch
NH3 CO + H2 Gasoline
CO2
CO + Ir / Rh cat. CH3CO2H
HCHO
urea
MeOH zeolite H-ZSM-5

ROH CO, H2 alkanes

HCl Al2O3 / Pt
urea-formaldehyde
(Bakelite) resins acrylic aromatics
polymers acid MeCl
4.I6 3 - 20
 Imperial College
Renewable chemical feedstocks - summary London

Four approaches:

• use naturally-occurring chemicals extracted directly from plants

e.g. natural rubber, sucrose, vegetable oils, fatty acids, starch

• use chemicals extracted by a one-step modification of biomass

e.g. fermentation to give lactic acid (lecture 2), bioethanol,
furans, levulinic acid, adipic acid, poly(hydroxyalkanoates)

• synthesise chemicals by multi-step conversion of biomass chemicals

e.g. polylactide

• use biomass as a source of basic building blocks (H , CO, CH

2 4 etc)
e.g. Syn-gas economy, polyethylene

The four approaches will now be exemplified using examples from polymer
chemistry.
4.I6 3 - 9
 Imperial College
Renewable polymers - approach 1 London

The four approaches to using biomass-derived feedstocks are all found in

polymer chemistry.

Approach 1: use naturally-occurring chemicals extracted directly from plants

e.g. starch amylopectin

amylose

Advantages of polysaccharides
e.g. cellulose • Cheap and biodegradable
Disadvantages
• Crystalline (not plastic)
• Properties difficult to modify
4.I6 3 - 21
 Imperial College
Approach 2: one-step modification of biomass London

e.g. Polyhydroxyalkanoates - PHAs

R = Me: poly(hydroxybutyrate) - PHB

R = Et: poly(hydroxyvalerate) - PHV

In the absence of N2 bacteria

form PHAs as energy storage
(just as plants produce starch).

Accumulation of PHA in
rhodobacter sphaeroides

Advantages of PHAs:
Desirable physical properties (PHB is similar to polypropylene) and biodegradable

Disadvantages:
High cost of production and processing ($15 per kg - polyethylene costs $1 per kg)
4.I6 3 - 22
 Imperial College
Approach 3: multi-step conversion of biomass chemicals London

e.g. Poly(lactic acid) - PLA

enzymatic Me
degradation CH2OH fermentation
O O OH
HO HO
HO O O
n
corn starch lactic acid

step-growth (-H2O)
condensation
O
Me O ring-opening Me
polymerisation O heat Me
O
O O
n (chain growth) Me O
O Me n
O O

polylactic acid, PLA lactide oligomers

4.I6 3 - 23
 Imperial College
Polylactide London

The synthesis of PLA is now being carried out on an industrial scale by Cargill
in a distinctly green manner…

O
Me Me O
O 160 °C O
O O
Me n
O Me
O

No solvent - reaction is a melt phase polymerisation

The industrial process is 'catalysed' by tin (II) bis(2-ethylhexanoate).

The development of other catalysts for this process is dealt with in 4I-11:
3pm Friday 2nd and Friday 9th March

4.I6 3 - 24
 Imperial College
Approach 4: The Syn-gas economy London

polyethylene

aldehydes
CO, H2 -H2O esters
acids oligomers C2H4 EtOH ethers
alcohols
O2 + Ag

monomers ethylene Biomass H2O + Rh catalyst

polymers
oxide

N2 Fischer Tropsch
NH3 CO + H2 Gasoline
CO2
CO + Ir / Rh cat. CH3CO2H
HCHO
urea
MeOH zeolite H-ZSM-5

ROH CO, H2 alkanes

HCl Al2O3 / Pt

urea-formaldehyde acrylic aromatics

(Bakelite) resins polymers acid MeCl
4.I6 3 - 25
 Imperial College
Conclusions London

Although entirely different, global warming and green chemistry share a

common potential solution - biomass.

Biomass can be converted into fuel and into raw materials for the chemical
industry in the same way that oil is currently used to produce fuel
(petroleum) and petrochemicals (particularly C2 - C4 alkenes, and BTX
aromatics).

Four ways biomass can be used to provide raw materials:

• (i) direct use of naturally occurring compounds
• (ii) one step modification of biomass
• (iii) multi-step conversion of biomass
• (iv) gasification of biomass to syn-gas
The use of biomass as a source of fuel fits well into existing petrochemical
infrastructure.

The use of biomass as a source of raw materials requires the development

of new reduction chemistry (petrochemicals use oxidation chemistry).
4.I6 3 - 26
 Imperial College
Learning outcomes revisited London

By the end of this lecture you should be able to

• explain the concept of carbon neutrality

Burning biomass returns CO2 to the atmosphere.
Burning fossil fuels increases atmospheric CO2.

• describe the use of biomass as a source of renewable fuels

Low temperature: biotechnology / fermentation to produce bioethanol.
High temperature: charcoal, gases, heat etc.
Fatty acids: production of biodiesel.

Potentially most important: gasification to syn-gas

•describeand
thesubsequent Fischer-Tropsch
use of biomass like chemistry
as a source of chemicals

4.I6 3 - 27