UEMK4613 Green Chemical Process

Tutorial 1
1. How are green chemistry and green engineering different from ‘chemistry and engineering’?

Solution:

The main difference is that Green Chemistry and Green Engineering methodically and deliberately
apply a series of principles that help us to:
• Maximize the use of resources (energy and mass)
• Minimize EHS hazards and pollution
• Account for the holistic implications of the processes
One can perform chemistry and engineering that are not green, but the best chemistry and
engineering will be most often the greener and more cost effective one.

2. Why is chemical persistence a problem? Give three examples of chemicals with persistence
problem.

Solution:

Chemicals that are persistent in the environment have the unfortunate tendency to accumulate in
unwanted places and generally have a number of unintended consequences, especially if said
chemical has negative environment, health and safety effects. Some examples from recent history
illustrate the point.
For example,
1. chlorofluorocarbons were designed to be persistent and generally unreactive and led to the
ozone hole in the polar regions given the unique atmospheric chemistry.
2. Polychlorinated biphenyl (PCB)’s was added to transformers to reduce the risk of fires and
ended up causing a variety of long-term environmental impacts in a variety of species.
3. Many plastics are persistent and ubiquitous; they are also responsible for filling up landfills,
vinyl chloride monomer (PVC) is a potent carcinogen and PVC is only very slowly
degraded, and the list goes on.
3. Using the 12 Principles of Green Chemistry, comment if the bioethanol production from corn is a
green process.

Solution:

Green Chemistry Critique

Principle
1 Prevention Agricultural impacts from farming corn are enormous, from
energy embedded in fertilizer production (ammonium nitrate,
calcium phosphate and potassium sulfate for example), fuels for
cultivation and harvest, transportation impacts, impacts from
pesticides, erosion, etc.
Impacts from the actual production of ethanol at a corn miller are
generally low as these production facilities are becoming more
efficient all the time.
However, there are a variety of enzymes that are used and the
production of these is generally waste intensive.
2 Atom economy Essentially, you are taking simple starches, enzymatically
converting them to glucose, and fermenting the glucose. If you
restrict your boundary to this, it is a reasonably atom economical
reaction.
3 Less Hazardous There are a host of potential human and eco-toxic effects from
Chemical agriculture related to energy use, pesticide and herbicide use,
Synthesis transportation, etc.
4 Designing Safer Not Applicable.
Chemicals
5 Safer Solvents and The enzymes are auxiliary substances, but these are catalytic,
Auxiliaries although not recycled, and they are derived from renewable
sources.
6 Design for Energy The energy required to produce ethanol from corn, depending on
Efficiency who you want to believe, is either more or less than the energy you
derive from it for fuel. Whether for fuel or as a solvent, corn-based
ethanol does not make a lot of sense.
7 Use of Renewable Yes
Feedstocks
8 Reduce Not Applicable.
Derivatives
9 Catalysis Enzymes are used as noted above, and these are catalytic.
10 Design for Ethanol, the rest of the corn-related waste and the enzymes are
Degradation very biodegradable
11 Real-time This is used throughout processing.
Analysis for
Pollution
Prevention
12 Inherently Safer Ethanol is flammable and has a reasonably low flash point. It is
Chemistry for hazardous, but well understood and we generally know how to
Accident prevent explosions and fires.
Prevention
4. Dimethyl carbonate can be produced by the following reaction:

2CH3OH + COCl2 + 2NaOH → CH3OCOOCH3 + 2NaCl + H2O

Describe which of the Principles of Green Chemistry you could apply to this reaction to improve
its greenness given the information provided.

Solution:

Principle 1. Prevention
It is better to prevent waste than to treat it or clean up after it is formed. In the reaction above,
looking at the stoichiometry, there will be an aqueous waste stream with sodium hydroxide and
sodium chloride in significant concentrations. The sodium hydroxide being formed is corrosive
and will need to be neutralized and treated. Is there a way to produce the desired carbonate while
avoiding the generation of this waste stream? How about separating and purifying the final product
and the related waste? Is there a way to obtain a final product that is close to being pure?

Principle 2. Atom Economy

Synthetic methods should be designed to maximize the incorporation into the final product of all
materials used in the process. This is the concept of atom economy. In reactions with 100% atom
economy, all the materials added to the chemistry are incorporated into the final product. Can we
design an addition reaction that can produce the carbonate with no by-products?

Principle 3. Less Hazardous Chemical Synthesis.

Wherever practicable, synthetic methodologies should be designed to use and generate substances
that possess little or no toxicity to human health and the environment. This reaction requires
phosgene, a highly acute toxicant. Can we devise a different synthetic pathway that avoids the use
of phosgene and doesn’t replace it with another toxic material?

Principle 9. Catalysis.
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. This reaction
is stoichiometric. Is there a way that this chemical can be produced by catalytic means?

Principle 12. Inherently Safer Chemistry for Accident Prevention

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.

5. Dimethyl carbonate can be produced by the catalytic oxidative carbonylation of methanol as shown
below:

2CH3OH + CO + 0.5O2 → CH3OCOOCH3 + H2O

According to the green chemistry principles, this reaction or the reaction of Q4 is a better option?

Solution:

This catalytic carbonylation reaction is likely to be superior to the reaction shown in Q4. CO and
phosgene are both acutely toxic, although the mode of action for each is different, and the target
organs are different.

- The Threshold Limit value (TLV) for CO is 30 ppm (UK OEL), while the TLV for phosgene
is 0.06 ppm (UK OEL).
 - The fact that the above reaction is more atom economical, and the only waste produced is water,
are both good things and superior to the reaction shown in Q4 where a brine is produced.
- While brines (Brine is a high-concentration solution of salt (usually NaCl) in water) are
comparatively less innocuous than many waste streams, it is still a waste that needs to be
disposed of.
- Finally, the use of a catalyst is potentially a good thing, although one would have to assess the
LCI/A of the catalyst. Certain metal catalysts may have an extremely large number of impacts
even though only small amounts of catalyst are used. If the catalyst is recyclable, this is
obviously an additional advantage.

* Threshold Limit value (TLV): Time weighted (average) concentration of an airborne substance to
which workers could be safely exposed over an eight hour working day throughout a life time.

6. Five grams of methanol (CH3OH, FW = 32 g) reacts with excess ethanoic acid (CH3COOH)
to produce 9.6 g of methyl ethanoate (CH3OOCCH3, FW = 74 g). Calculate the percentage
yield.

𝐶𝐻3 𝑂𝐻 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 ↔ 𝐶𝐻3 𝑂𝑂𝐶𝐶𝐻3 + 𝐻2 𝑂

Solution:

The balanced equation for the reaction shows that one mole of methanol can produce one
mole of methyl ethanoate:

𝐶𝐻3 𝑂𝐻 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 ↔ 𝐶𝐻3 𝑂𝑂𝐶𝐶𝐻3 + 𝐻2 𝑂

1 mole → 1 mole
Replacing the numbers of moles with their equivalent formula masses shows that:
32 g 𝐶𝐻3 𝑂𝐻 = 74 g 𝐶𝐻3 𝑂𝑂𝐶𝐶𝐻3
5
5 g 𝐶𝐻3 𝑂𝐻 = 32 × 74 = 11.56𝑔 𝐶𝐻3 𝑂𝑂𝐶𝐶𝐻3
 Theoretical yield = 11.56g

Given actual yield = 9.6g

actual mass of product

Percentage yield = × 100%
theoretical mass of product
actual yield
yield = × 100%
theoretical yield
9.6
= × 100 = 83%
11.56
7. What is the atom economy for making hydrogen by reacting coal with steam? Is an effective way
to produce hydrogen?
C(s) + 2H2O(g) → CO2(g) + 2H2(g)

Solution:

C(s) + 2H2O(g) → CO2(g) + 2H2(g)

12 2 × 18 44 2×2

formula mass of desired product

Atom economy = × 100%
formula mass of all reactants
4
% Atom economy = × 100% = 8.3%
48
This process has a low atom economy and is therefore an inefficient way to produce hydrogen. It
also uses a non-renewable resource: coal.

8. Ethanol can be produced by fermentation of sugars:

C6H12O6  2C2H5OH+ 2CO2
The raw material sugar (from sugar cane or sugar beet) is mixed with water and yeast at just above
room temperature in a reactor vessel. The yeast contains an enzyme called zymase which acts as
the biological catalyst to convert sugar to ethanol in fermentation, it works best at an optimum of
pH ~4. Under anaerobic conditions at an optimum temperature of 30 to 40C, the sugars react via
the enzymes in the yeast cells to form ethanol and carbon dioxide gas

Ethanol can also be produced by the reaction of steam and ethene in the presence of a strong acid
catalyst (phosphoric acid, H3PO4). The reversible reaction is carried out at a moderately high
temperature (e.g., 300C) and a high pressure (e.g., 60–70 times atmospheric pressure). The higher
temperature and catalyst speed up the reaction and increasing pressure moves the equilibrium to
the right (side least gaseous molecules at 300C)
CH2=CH2 + H2O  CH3CH2OH (or C2H5OH)
The ethene is obtained from catalytic or steam cracking reactions at high temperatures of 450 to
900C of alkane hydrocarbons from the fractional distillation of crude oil:
Butane  Ethane + Ethene
The ethane can be further cracked to make more ethane:
Ethane  Ethene + Hydrogen
Overall, a synthetic route for ethanol is generated as follows:
Crude oil  Ethane  Ethene  Ethanol

Are the two methods (fermentation and cracking & ethane hydration) of ethanol production 'green'
and 'sustainable' processes? Answer the following questions:
i. What is the source of raw material? Will it run out?
ii. What are the energy costs? and catalyst costs?
iii. Are there any implications for climate change? Are there any environmental issues?
iv. What is the atom economy? Is there much waste.
v. Is it a profitable process? Does it make a profitable product?
 vi. Does the fermentation process have any issues with society? e.g. are there particular
benefits or risks?
vii. Is there any issue with waste products?

Solution:

i. What is the source of raw material? Will it run out?

Fermentation: Sugar beet and sugar cane grow quickly, particularly in warm climates and
labour may be very cheap in third world countries. So we have a sustainable renewable
resource thanks to photosynthesis.
Cracking & ethene hydration: Crude oil, from which ethene is obtained by cracking, will
eventually run out, and oil is a non-renewable resource, so not sustainable in the distant
future.

ii. What are the energy costs? and catalyst costs?

Fermentation: Some energy is required to keep the fermenting mixture at the optimum
temperature of 30-40C. Yeast is relatively cheap to produce, since it reproduces and grows
quite naturally.
Cracking & ethene hydration: Both processes need energy to sustain high pressure and high
temperature reaction conditions. There is also an extra cost for catalysts which would cost a
lot more than yeast.

iii. Are there any implications for climate change? Are there any environmental issues?
Fermentation: Carbon dioxide is produced in the process, contributing to global warming,
but, isn't it recycled via photosynthesis when more sugar beet or sugar cane is grown?
Cracking & ethene hydration: Neither processes directly harm the environment, though there
are dangers from oil spillages in transporting oil in tankers.

iv. What is the atom economy? Is there much waste.

Fermentation: C6H12O6  2C2H5OH+ 2CO2
180 2(46)
2 × 46
Atom economy = × 100% = 51%
180
The atom economy is only 51% because 49% by mass of the sugar is lost as carbon dioxide.
Not only that, as the yeast cells are killed off by the high concentration of ethanol, not all of
the sugar is actually fermented further decreasing the efficiency of the process.

Cracking & ethene hydration:

Cracking: Ethane  Ethene + Hydrogen
30 28
28
Atom economy for cracking = × 100% = 93%
30
Atom economy is theoretically 100% for the ethene hydration route.
Cracking ethane and other hydrocarbons is quite high (93%) with only hydrogen gas as the
waste product (but this can be used in hydrogenation processes and making ammonia).

Ethene hydration: CH2=CH2 + H2O  CH3CH2OH (or C2H5OH)

28 18 46
46
Atom economy for ethene hydration = × 100% = 100%
46
The atom economy is very high for the hydration of ethene (theoretically 100% with just
one product).

v. Is it a profitable process? Does it make a profitable product?

 Fermentation: It would seem so from the point of view of the food and drinks industry,
breweries and vineyards make good profits, though a vineyard's economy-profits can be
dependent on the weather. BUT, is it profitable to use the alcohol as a biofuel? e.g. blended
with petrol from oil.
Cracking & ethene hydration: Both processes are fast and efficient and can be run on a
continuous basis and at the moment the raw materials, from oil, are relatively cheap, but the
price will increase as oil reserves become depleted in the future.

vi. Does the fermentation process have any issues with society? e.g. are there particular benefits
or risks?
Fermentation: There are no particular health and safety issues or great risks for the
surrounding local communities, unlike the potential hazards of running an oil refinery. The
risks come later with alcohol abuse! Benefits may include jobs for the local economy and
revenue for local farmers growing the sugar cane or sugar beet.
Cracking & ethene hydration: There are important health and safety issues to deal with in
the petrochemical industry. You are dealing with highly flammable and explosive gases
being processed at high temperatures and pressures. This poses dangers at all the time and
so all the processes must be carefully monitored and controlled, this is also increases the
costs of the processes because it requires very standards of engineering and safety measures.

vii. Is there any issue with waste products?

Fermentation: The waste carbon dioxide can be safely released into the atmosphere, but it
could be used in fizzy carbonated drinks or even pumped into greenhouses to increase the
rate of photosynthesis - case of good recycling?
Cracking & ethene hydration: The only waste product from cracking is hydrogen gas, but
this can be used to hydrogenate vegetable oils to make margarine or reacted with nitrogen
to make ammonia.

9. You are in the solvent selection stage of designing a chemical reaction. Dimethyl formamide,
dichloromethane (DCM), methyl ethyl ketone and toluene seem to work well. You have looked at
the properties of the solvents as summarized in Table Q9:

Table Q9 TLVs, vapor pressure and flash point of three solvents.

Vapour
CAS TLV Flash Point
Solvent Pressure
Number ppm C
mm Hg
Dichloromethane 75-09-2 50 436.5 None, but can form flammable vapour-air mixtures above ~100 °C
Dimethyl formamide 68-12-2 10 3.7 58
Methyl ethyl ketone 78-93-3 200 94.5 -9

a. Using the OEL of the solvent as a surrogate of health hazard, and the vapor pressure as a
surrogate for exposure potential, which solvent would you recommend from the health
viewpoint?
b. Using the flash point as a surrogate of flammability hazard, which solvent would you
recommend from the safety viewpoint.
c. Are there additional factors that would need to be considered when selecting amongst these
solvents?

Solution:

a. Methyl ethyl ketone, based primarily on the highest TLV of the three options. It is volatile,
but not extremely high. DCM is very volatile and has a low TLV, and DMF has a very low
TLV, although it is not too volatile.
b. Dimethyl formamide or Dichloromethane – On the basis of the flash point alone, they both
are less flammable.
c. Many other factors such as waste disposal, ease of recycling, ease of biotreatability, VOC
emissions, environmental impacts to water and air, reactivity and compatibility, life cycle
assessment consideration, amongst others.