Sustainable Development and

Environmental Treatment Technology

Chapter 7. A Greener Future with
Green Chemistry and Pollution
Prevention Methodologies
 Reference textbooks

[1] David T. Allen & David R. Shonnard, Green Engineering_

Environmentally Conscious Design of Chemical Processes,
chapter 9, Prentice Hall, 2001
[2] Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and
Practice; Oxford University Press: New York, 1998
Part 1: Green Chemistry
Green Chemistry ?
• Why?
– History
• What?
– Definitions
• How?
– Principles
• Examples
 WHY?
• In 1970’s – need to improve environmental
quality
– Environmental Control, required by Laws
– Contaminants produced and THEN treated before
releasing them to the environment
– Excellent idea IF there is good control and
handling of environmental laws
• It is continuous, slow and expensive
 WHY?
• 1991 – Green Chemistry is promoted by
EPA (Environmental Protection Agency) –
(by Paul Anastas)
 What is Green Chemistry?
“The design of chemical processes,
products and technologies that reduces
or eliminates the use and generation of
hazardous substances”

Sources:
http://center.acs.org/applications/greenchem/
http://www.ec.gc.ca/p2progress/2000-2001/en/sec2_3_2.cfm
 Green chemistry is looking to:
Waste generation
Material consumption

Reduce / Minimize Hazard

Risk
Energy consumption
Environmental Impact

COST! ($$$$)

of a chemical production process

 Green Chemistry – focal points
• The focus area of the EPA’s Green Chemistry
Program considers :
- The use of alternative synthetic pathways
- The use of alternative reaction conditions
- The design of safer chemicals that are, for
example, less toxic than current alternatives or
inherently safer with regard to accident potential.
An Ideal Chemical Reaction
• Is Simple.
• Is Safe.
• Has a High Yield and Selectivity.
• Is Energy Efficient.
• Uses Renewable and Recyclable Reagents and
Raw Materials.

Source : Green Engineering, Allen and Shonnard, p. 177

Brief Overview of Green Chemistry Methodologies

- Alternative Feedstocks (desired properties: non-

toxic, renewable,…)
- Green Solvents.
- New synthesis Pathways.
- Inherently Safer Chemistry.
Green Chemistry Benefits:
• Reduced waste, eliminating costly end-
of-the-pipe treatments
• Safer products
• Reduced use of energy and resources
• Improved competitiveness of chemical
manufacturers and their customers
www.epa.gov/greenchemistry/
 What has happened since its introduction?
• 1996 Presidential Green Chemistry Challenge
Awards (PGCCA) - promote non contaminant
technologies.
• 1997 Green Chemistry and Engineering Conference
• 1999 Journal “Green Chemistry”

• Until 2006 all the technologies nominated to the

PGCCA had eliminated the use or production of:
– 1.2 billion pounds of chemicals and solvents per year
– 57 million pounds of CO2 has been reduced
– 16 billion gallons of water per year have been saved
www.epa.gov/greenchemistry/
There are twelve principles of Green Chemistry as

described in Paul Anastas and John Warner in Green

Chemistry: Theory and Practice (Oxford University Press:

New York, 1998). They are described / explained next

 1. Prevent waste
• It is better to prevent waste than to treat or clean up
waste after it is formed.

Possible sources of waste reduction:

Inputs
“eco-friendly” solvents, high purity reagents, solvent
recycling.
Production
Optimization of reaction time, temperature and pressure.
New synthesis pathways.
Discharges
Reduce water usage, improve filtering procedures and
reuse waste products.
• In 1992, the E-Factor, or Environmental Impact Factor, was
introduced by Roger Sheldon. This metric helps to quantify
the amount of waste generated per kilogram of product.

Industry Products Kg waste / Kg

(tons) products

Petroleum Refinery 106 – 108 <0.1

Chemical 104 – 106 1-5

Production
Specialized 102 - 104 5 – 50
Chemical
Compounds
Pharmaceutical 10 - 103 25 – 100+
New Industries:
Large gain margins $$$
More complex chemistry
R A Sheldon J Chem Tech Biotechnol 1997 68 381
More waste production
 1. Prevent waste – Example
New synthesis route (based on molecular oxygen) of ethylene
oxide significantly improves the E-factor (from 5 to 0.3)
 1. Prevent waste – Example
When byproducts cannot be avoided, other innovative
solutions should be considered and a productive one is to seek
an industrial ecology approach where waste can become a new
raw material with significant value for another process as it re-
enters the life-cycle, for example, the utilization of biofuel
byproducts
2. Design safer chemicals and products:

• Design chemical products to be fully effective, yet

have little or no toxicity.
• …chemicals that are less hazardous to human health
and the environment are:
– Less toxic to organisms and ecosystems
– Not persistent or bioaccumulative in organisms or
the environment
– Inherently safer with respect to handling and use
3. Design less hazardous chemical syntheses:

• Use and generate substances with little or no

toxicity to humans and the environment.
• Avoid reactions that give dangerous by-
products
 4. Use renewable feedstocks:

• Use raw materials and feedstocks that are renewable

rather than depleting.
• Agricultural products
• Wastes of other processes;
• Reduce dependency from fossil fuels (petroleum,
natural gas, or coal).
 5. Use catalysts:

• Catalysts: should be as selective as possible; catalysts

are usually easier to recover and reuse than excess
reagents
• Catalysts are usually used in small amounts
• Catalysts improve production and reduce energy
consumption
 6. Maximize atom economy:

Atom economy: How many of the atoms of the reactants

are incorporated into the final product and how many are
wasted?

Atom economy criteria: synthesis methods should be

designed to maximize all materials used to produce the final
product (has high AE number)
 Atom Economy
H3C-CH2-CH2-CH2-OH + Na-Br + H2SO4  H3C-CH2-CH2-CH2-Br + NaHSO4 + H2O
1 2 3 4 5 6

Weight Weight of
Reagents Formula Reagents Utilized of Unutilized Unutilized
MW Atoms Utilized Atoms Atoms
Atoms
H3C-CH2-CH2-CH2-OH 74 4C, 9H 57 OH 17

Na-Br 103 Br 80 Na 23

H2SO4 98 ------ 0 2H, 4O, S 98

Total 275 4C, 9H, 137 3H, 5O, 138

4C, 12H, 5O, Br, Na, S Br Na, S

% Atom Economy = (MW of atoms utilized/MW of all reactants) X 100 =

(137/275) X 100 = 50%
 - Acetylene (addition) : CH  CH + HCl  CH2 = CHCl

carbon hydrogen Chlorine oxygen

Product 2 3 1
Reagents 2 3 1
Atom efficiency 100% 100% 100%
Example: Mass efficiency (2·MC +3·MH +1·MCl )/(2·MC +3·MH +3·MCl) = 1

Consider these - Ethylene (substitution) : CH2 = CH2 + Cl2  CH2 = CHCl + HCl
CH2 = CH2 + HCl + ½ O2  CH2 = CHCl + H2O
different routes Balanced process: 2 CH2 = CH2 + Cl2 + ½ O2  2 CH2 = CHCl + H2O
for synthesis of carbon hydrogen chlorine oxygen
Product 2 3 1
vinyl chloride Reagents 2 4 2
Atom efficiency 100% 75% 50%
Mass efficiency (2·MC +3·MH +1·MCl )/(2·MC +4·MH +2·MCl) = 0,634
Addition reaction route Product 2 3 1 0
Reagents 2 5 1 1
has highest atom Atom efficiency 100% 60% 100% 0%
Mass efficiency (2·MC +3·MH +1·MCl )/(2·MC +5·MH +1·MCl +1·MO) = 0,776
economy (AE)
Product 2 3 1 0
Reagents 2 4 1 ½
Note: in the table, Mass Atom efficiency 100% 75% 100% 0%
Mass efficiency (2·MC +3·MH +1·MCl )/(2·MC +4·MH +1·MCl +½·MO) = 0,874
efficiency = Atom
- Ethane (subst.-elimination) : CH3 - CH3 + ½ Cl2 + ¾ O2  CH2 = CHCl + 1½ H2O
economy
carbon hydrogen chlorine oxygen
Product 2 3 1 0
Reagents 2 6 1 1½
Atom efficiency 100% 50% 100% 0%
Mass efficiency (2·MC +3·MH +1·MCl )/(2·MC +6·MH +1·MCl +1½·MO) = 0,698
 Chemical Reactions and Atomic Economy
• Addition > Substitutions > Eliminations
• Re-arrangements: 100 % efficient
– Ex: Diels-Alder
• Addition ( A + B  AB)
No waste needs to be treated because the reaction is direct.
• Substitution (AB + C  AC + B)
Necessarily generates stoichiometric quantities of substances as
byproducts and waste that are not part of the target molecule.
• Elimination (AB  A + B)
Does not require other substances, but does generate
stoichiometric quantities of waste that are not part of the
final target molecule.
 7. Safer solvents and auxiliaries

• The use of auxiliary substances (solvents, separation

agents, etc…) should be avoided wherever possible and
safe / harmless when their use is unavoidable

Solvents:
• Organic solvents = high VOC’s

• Alternatives
– Synthesis without solvents
– Water
– Supercritical fluids (CO2)
– Ionic Liquids
 8. Analyze in real time to prevent pollution:

• Include in-process real-time monitoring and control

to minimize or eliminate the formation of byproducts.

PAT: Process Analytical Technologies

• Measure quality and execution properties DURING

manufacturing
• Information is gather continuously to improve process
 Other principles
 Processes are designed to be inherently safe
 Processes are designed to be energy efficient
 Design for degradation: products should be designed so
that they break down into harmless degradation products
at the end of their function
 Unnecessary derivatization of product should be avoided
whenever possible because such steps require
additional reagents and can generate waste.
In conclusion, what is green chemistry looking for?

• Waste minimization, inherently safer and energy

efficient process design
• Use of catalysts
• Use of non-toxic reagents
• Use of renewable sources
• Improvement of atomic economy
• Use of non-solvent or environmental benign solvents
Examples of Green Chemistry
Disinfection of water:
• Disinfection of water by chlorination.
Chlorine oxidizes the pathogens there by
killing them, but at the same time forms
harmful chlorinated compounds.
• A remedy is to use another oxidant, such as

O3 or
supercritical
water
oxidation
 Production of allyl alcohol
• Traditional route: Alkaline hydrolysis of allyl chloride,
which generates the product and hydrochloric acid as a by-
product
CH2=CHCH2Cl + H2O CH2=CHCH2OH + HCl

problem product

• Greener route, to avoid chlorine: Two-step using propylene

(CH2=CHCH3), acetic acid (CH3COOH) and oxygen (O2)

CH2=CHCH3 + CH3COOH + 1/2 O2 CH2=CHCH2OCOCH3 + H2O

CH2=CHCH2OCOCH3 + H2O CH2=CHCH2OH + CH3COOH

• Added benefit: The acetic acid produced in the 2nd reaction can be
recovered and used again for the 1st reaction, leaving no unwanted by-
product.
 Production of styrene
• Traditional route: Two-step method starting with benzene,
(which is carcinogenic) and ethylene to form ethylbenzene,
followed by dehydrogenation to obtain styrene
CH2CH3
catayst
+ H2C=CH2

ethylbenzene

CH2-CH3 CH=CH2
catayst

styrene
ethylbenzene

Greener route: To avoid benzene, start with xylene

(cheapest source of aromatics and environmentally safer than
benzene).
Poly lactic acid (PLA) for plastics production
(The merits of this example: use renewable raw materials, use
ambient temperature and pressure in processing steps)
 Polyhydroxyalkanoates (PHA’s)
(The merits of this example: use renewable raw materials,
biodegradable products)
 Part 2: POLLUTION
PREVENTION AND UNIT
OPERATIONS
 Overall View of Chemical Production
Natural
resources and +
Raw Materials Energy+Water use
other feed-
pretreatment
techniques
Waste heat, energy
and emissions PROCESS
from all processes

Pollution from
waste streams as +
well as product Product Waste Streams
and by product
disposal
* It is also important to consider all possible sources of pollution, from
the initial natural ressources required to the final disposal of the product.
Raw Materials Energy +
Water use
+

Waste
Stream
Environment
Dermal
Inhalation

Ingestion
Products
 What is Pollution Prevention?

Any action (or actions) that prevents the release of

hazardous and/or toxic substances into the
environment – source reduction.
Pollution Prevention means “source reduction,” as
defined under the Pollution Prevention Act, and other
practices that reduce or eliminate the creation of
pollutants through : increased efficiency in the use of
raw materials, energy, water, or other ressources, or
protection of natural resources by conservation.

Source : EPA
http://www.epa.gov/opptintr/p2_97/append-c.pdf
 Benefits of Pollution Prevention

– Improved environmental protection in all aspects (air,

water, soil, ecology, human health)

– Reduced costs of raw material, energy, water, waste

handling, waste treatment and disposal

– Improved worker health and safety, public image and

product quality.
 Waste Management Hierarchy

Source Reduction
Pollution
Prevention In-Process Recycle
Encompasses
the first 4 On-Site Recycle

Off-Site Recycle

Waste Treatment

Secure Disposal

Direct Release into the Environment

 Pollution Prevention (P2) vs.
Pollution Control (PC)

Traditional Process
Products
Raw Materials,
Energy Chemical
Process Pollution
Control
Wastes

Greener Process Higher income,

Products
Raw Materials, Higher operating costs
Energy
Modified
Chemical Pollution
Control Lower PC costs
Process
Wastes
Recycle
 Important Considerations

• Material selection
• Waste generation mechanisms
• Operation conditions
• Material storage and transfer
• Energy consumption
• Process safety
 Raw Material Selection
• Raw materials are used as feedstocks, solvents, reactants,
mass separating agents, diluents and fuels.
• Critical questions:
– What are the environmental, toxicological, and safety
properties of the material?
– How do these properties compare to alternative choices?
– To what extent does the material contribute to waste
generation or emission release in the process?
– Are there alternative choices that generate less waste or
emit less while maintaining or enhancing the overall yield
of the desired product?
 Solution
• No. 6 FO:
– volume needed = (1000000 BTU/148000 BTU/gal) =
6.76 gal;
– mass needed = (6.76 gal)(1 ft^3/7.48 gal)(61.23 lb/ft^3)
= 55.18 lb;
– SO2 generated = (55.18 lb)(0.0084 lb S/lb)(64.06 lb
SO2/32.06 lb S) = 0.928 lb SO2

• No. 2 FO: 0.243 lb SO2

• Natural Gas: 0.0 lb SO2
 Waste Reduction Opportunities in Raw-
Material Selection

1. The elimination of feedstock impurities.

2. The use of less hazardous raw materials.

3. A reduction in the number of raw materials used.

4. The utilization of waste materials from other processes.

 Upgrading Raw Materials to Prevent
Pollution – A Case Study
• Figure 9.2-1 shows the major uses of process water at a
midsize refinery.
• When the concentrated calcium salts in the blowdown water
from cooling tower met with the alkaline boiler blowdown,
salts precipitated in the past.
• This precipitate plugged sewer lines, degraded wastewater
treatment equipment, and resulted in greater sludge generation
rates from wastewater treatment processes. It has been shown
that every pound of solid precipitate in oily wastewater creates
about 10 pounds of oily sludge.
Hazardous Waste
 Upgrading Raw Materials to Prevent
Pollution – A case study of the process water
in a refinery

• At a US petroleum refinery, the solution to this waste disposal

problem involved the pretreatment of all process water using

reverse osmosis to separate dissolved solids from the feed water,

thereby eliminating the source of solids for the oily sludge.

 Upgrading Raw Materials to Prevent
Pollution – A case study of the process
water in a refinery
• The greatest savings are due to the reduction in hazardous
wastewater sludge generation. Savings in sludge disposal
costs alone are greater than the cost of pretreatment.
• Consumption of chemicals for treating the boiler and
cooling water have been reduced by more than 90%. The
resultant savings amounts to 1/3 of the cost of reverse
osmosis.
• Maintenance costs are reduced.
 UNIT OPERATIONS AND
POLLUTION PREVENTION (P2)

- Chemical Reactors

- Separation Devices

- Separative Reactors

- Heat Exchangers
Chemical reactors

Constitute the most important operations under technical or
environmental perspectives: both conversion and selectivity
affect downstream steps of separation, recycle, treatments,
energy consumption and discharges


There are `three relevant aspects´ in reaction design for P2 :
 Materials (reagents, catalysts and solvents); changes include
new process chemistry, cleaner feedstock, enriched oxidants,
use of inert, higher reactivity, aqueous or supercritical fluids
 Type of reaction and reactors (multiplicity, kinetic, flow model);
including process intensification by catalysis, reactor designs
and integration of process functions (separation, energy transfer)
 Operating conditions (concentration, temperature and mixing)
 Strategies for Reducing Waste in Chemical Reactors

• Select reactor type

(PFR, CSTR, etc) to maximize selectivity
rather than throughput
• Alter process conditions (P, T, C)
• Improve physical mixing in reactor
• Improve process control
• Improve feed distribution
• Provide separate reactor for recycle
• Change process chemistry!
Strategies of Green Chemistry applied to Reactor design

• Emphasis of green chemistry tends to be on synthesis routes

and solvent selection (Change process chemistry !), rather
than equipment engineering:
– biologically-catalyzed reactions
– low-toxicity reactants and solvents
– aqueous and solvent-less reaction processes
– use catalysts
 Selection of Reaction Type
The mechanisms of chemical reactions, that include multiplicity and
kinetics, affect the strategies for P2:
• both yield and selectivity are dependent on rate constants and
order for parallel, series or reversible reactions, which determine
the optimal residence times, concentrations, temperature or
mixing
• the selectivity in equilibrium reactions can be improved by
“recycle to extinction”: e.g. methane reforming and shift, where
CO2 is separated and recirculated without net formation on a
global process basis
• using separative reactors to add reagents or remove products in-
situ, permit to control byproducts and equilibria in multiple
reactions
Recycle the by-product (waste) if this by-product is a product of
an reversible reaction = “Recycle to extinction”
 Selection of Reactor Type
 Plug flow reactors permit a better control of operations because they
are differential devices (tubular), and reduce processing inventories.
Plug flow reactors can be staged and each stage can be operated at
different conditions to minimize waste formation
 Fixed-bed catalytic reactor: can be used when hot spots are a problem
for highly exothermic reactions (it will likely avoid the unwanted
temperature excursions)
 Fluidized reactors can avoid hot spots in highly exothermic processes
where heat control is critic to limit temperature sensitive side-reactions.
A very short residence time can be achieved in a fluidized catalytic
reactor, which will minimize unwanted side reactions
 Selection of Reactor Type

Heat transfer to and from traditional CSTR: not suitable for reactions
with large heat effects
 Selection of Reactor Type

Heat transfer arrangements for fixed-bed catalytic reactors:

configurations (b) and (c) can achieve very good temperature control
 Selection of Reactor Type

A very short residence time can be achieved in a fluidized catalytic

reactor, which will minimize unwanted side reactions
 Selection of Operating conditions
Concentration.- Selectivity in multiple reactions could be
sensitive to initial reagent composition, as product rates depend
on concentration; e.g. for parallel reactions, increasing R0 will

minimize wastes if nP nw and vice versa: R  kP P

(desired reaction); R  kW W (unwanted side reaction); the

ratio of two reaction rates is vP/vw= kP/kw·[R]np-nw

Temperature.- The ratio of rate constants for desired and
unwanted side reactions affects selectivities, so that byproducts
can be prevented by changing reactor temperatures:  (kP/kw)
= e(Ep-Ew)(1/To-1/T)/
 Pollution Prevention for Separation Units

Separations:

Separation unit operations generate waste because

• the separation steps themselves are not 100% efficient, and
• require
– additional energy input or
– waste treatment

to deal with off-spec products.

 Choice of Mass Separating Agent

Selecting a mass seperation agent (chemical compound like solvent)

is an important issue for pollution prevention in order to avoid:
- Exposure to toxic substances for facility workers and consumers
who use the final product.
- Excessive energy consuption in the recovery of the solvent or
other raw materials
- Associated health impacts of the emitted criteria pollutants (CO,

CO2, NOx, and SOx, particulate matter)

 Pollution Prevention Approaches for
Separation Equipment

1. Minimize the wastes and emissions that are

routinely generated;
2. Control excursions in operating conditions;
3. Improve the design efficiency.
Process Wastes Generated from Distillation

• By allowing impurities to remain in a

product,
• By forming waste within the column itself
(in reboiler),
• By inadequate condensing of overhead
product (through the condenser vent), and
• By excessive energy use.
 Pollution Prevention Methods for
Distillation Columns
1. Increase the reflux ratio, add a section to the column,
retray/repack the column, or improve feed distribution to
increase column efficiency.
2. Changing the feed location may increase product purity.
3. Insulate or preheat feed to reduce the load on the
reboiler.
4. Reduce the pressure drop in column, which reduce the
load on reboiler.
5. Vacuum distillation may reduce reboiler requirements.
 Separative Reactors
The separative reactor has a very high potential for reducing waste
generation:
- Hybrid systems that combine chemical reactions and product
separation in a single process unit.
- When chemical reaction and separation ocurr in concert, the
requirements for downstream processing units are reduced,
leading to lower capitals costs.
- Unwanted byproduct generation can be minimized in series
reactions by the removal of the desired product
- Separation units that have been integrated with reaction include
distillation, membrane separation, and adsoption.
 Pollution Prevention Applications for Membrane
Separative Reactiors
Reaction coupled with membrane separation also is used to
increase the efficiency of chemical reactions:
- Can be used to selectively remove either products or
byproducts from the reaction zone
- Overcoming low conversions in equilibrium-limited reactions
and reduce waste generation in series reactions.
- Can also be used to selectively permeate reactants into the
reaction zone in order to control excessive byproduct
formation (e.g. Permeation of O2 in partial oxidation or
oxidative coupling reactions).
 Heat Exchanger – Potential Wastes

• Thermal degradation in process streams

• Leaks in exchanger tubes, leading to contamination of

process streams

• Liquid waste from blowdown

• Cleaning chemicals from maintenance

 Strategies for Reducing Wastes in
Heat Exchangers
• Reduce tube-wall temperature

– Use lower pressure steam

• Use in-line cleaning techniques

• Monitor exchanger fouling

• Use corrosion-resistant tubes