Green

And the Design of Chemical Processes and Products

Follow these principles
and guidelines to design
your process plant
to be 'greener'

David T. Allen
University of Texas, Austin

C
hemical products and processes
make modern life possible. The
systems that provide housing,
transportation, health care,
and food fbr billions of people rely on
chemical products, but as demand for
these essential materials grows, the
environmental impacts of the prod-
ucts and the processes that create
them are becoming a greater concern.
As this concern about the magnitude
of the associated environmental foot-
prints increases, engineers, and par-
ticularly chemical engineers, will face
new challenges.
To grasp the nature and mag-
nitude of the challenges that will
be faced by engineers, it is useful
to invoke a simple equation that
emerged from the environmental
movement in the U.S. in the early
1970s. At that time, there was sub-
stantial debate concerning whether chel Carson and Barry Commoner population, [P, number of people);
the environmental challenges faced argued that it was the nature of affluence (A, expressed in units such
by the U.S. were largely driven by technology that was the source of as gross domestic product |GDP|
population growth, or by the nature environmental problems [2, 3\. Of per capita), and technology, (T, ex-
of technology. Books like "The Popu- course, neither population nor the pressed as impact per unit of GDP):
lation Bomb" [il, argued that rapid nature of technology is exclusively
increases in population could not be I = P (number of people) * A ($ GDP
tho cause of the environmental chal-
supported by available resources. lenges we face. It is a combination per capita) * T (impact per $ GDP)
These ideas had been expressed at of factors that drive environmental This relatively simple equation has
least since the time of Thomas Mal- impacts. In the early 1970s, Ehrlich changed the way many environmen-
thus, in the 18th century, but rap- and Holdren 14, 5] expressed this talists view the role of technology. The
idly increasing and unprecedented idea simply with what has come to IPAT equation makes clear that in-
world populations, gave these argu- be called the IPAT equation. Envi- stead of being a cause of the problem,
ments new life. In contrast, promi- ronmental impacts (/), Ehrlich and better technologies, providing lower
nent environmentalists such as Ra- Holdren argued, are the product of impacts per dollar of GDP, are viewed
36 CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007
 ;is the enabler of improved
world-wide affluence.
The engineering
challenge
flow much better will our
technologies need to be?
World populations are cur-
rently growing at rates of
l-2''>^/yr. Worldwide eco-
nomic output is increasing
hy 3-5%/yr, with larger
increases in some rapidly
developing countries. As-
suming that the product of
population and affluence
r)('r capita is increasing
aL .5'?'i/yi; using the simple
logic of the IPAT equa-
tion, the product of popu-
lation and affluence (P*A)
will increase by 60% in 10
years, hy 250% in 25 years,
.md by more than a fac-
tor of 10 in 50 years. Just
to keep impacts the same,
our technologies will need
to improve by a factor of
2-3 in 25 years and 10 in
50 years.
Can engineers, particu-
larly cheniical engineers,
reduce the environmental
impacts of their designs by
a factor of 10? Engineering
directed at the problem of
reducing the environmen-
tal footprints of processes
and products is referred to
by a variety of terms, in-
cluding green engineering,
cleaner production, and
eco-efficiency. While all of
these terms are in com-
mon use, and can have subtly difTer-
ent meanings, in this article the term
"green engineering", as deiined by the
U.S. Environmental Protection Agency
(EPA; Washington, D.C), will he used.
"Green engineering is the design,
commercialization, and use of pro-
cesses and products, which are feasi-
ble and economical while minimizing
1) generation of pollution at the source
and 2) risk to human health and the
environment. Green engineering em-
braces the concept that decisions to
protect human health and the envi-
ronment can have the greatest impact
and cost effectiveness when applied
early to the design and development
phase of a process or product" [6].
Green-engineering principles
The general approach that has been
used in green engineering, and com-
plementary efforts in green chemistry,
is to defme a broad set of principles
that can guide designs, then to de-
velop metrics and design tools that
support these objectives. Anastas and
Warner [7] proposed guiding prin-
ciples for green chemistry that have
been widely accepted, and a parallel
set of 12 green engineering principles
have been defined by McDonough and
others [8]:
Principle 1. Designers need to strive
to ensure that all material and energy
inputs and outputs are as inherently
nonhazardous as possible.
Principle 2. It is better to prevent
waste than to treat or clean up waste
after it is formed.
Principle 3. Separation and purifi-
cation operations should be designed
to minimize energy consumption and
materials use.
Principle 4. Products, processes,
and systems should be designed to
maximize mass, energy, space, and
time efficiency.
Principle 5. Products, processes, and
systems should be "output pulled"
rather than "input pushed" through
the use of energy and materials.
Principle 6. Embedded entropy
and complexity must be viewed as
an investment when making design
choices on recycle, reuse, or benefi-
cial disposition.
Principle 7. Targeted durability, not
immortality, should be a design goal.
Principle 8. Design for unnecessary
capacity or capability (for example,
"one size fits all") solutions should be
considered a design flaw.
Principle 9. Material diversity in
multicomponent products should he
minimized to promote disassembly
and value retention.
Principle 10. Design of products,
processes, and systems must include
integration and interconnectivity with
available energy and materials flows.
Principle 11. Products, processes, and
systems should be designed for perfor-
mance in a commercial "afterlife".
CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007
Principle 12. Material and energy
inputs should be renewable rather
than depleting.
An alternative set of nine guid-
ing principles has been defined by
65 scientists and engineers partici-
pating in a green-engineering work-
shop. These principles are posted on
EPA's website [61:
1. Engineer processes and products ho-
listically, use systems analysis, and
integrate environmental impact as-
sessment tools.
2.Conserve and improve natural eco-
systems while protecting human
health and well-being.
3.Use life-cycle thinking in all engi-
neering activities.
4. Ensure that all material and energy
inputs and outputs are as inherently
safe and benign as possible.
5.Minimize depletion of natural re-
sources.
6.Strive to prevent waste.
7.Develop and apply engineering so-
lutions, while being cognizant of
local geography, aspirations, and
cultures.
8. Create engineering solutions beyond
current or dominant technologies;
improve, innovate, and invent (tech-
nologies) to achieve sustain ability.
9.Actively engage communities and
stakeholders in development of en-
gineering solutions.
These two separate Hsts of guiding
principles show that while there is
not universal agreement about the
precise objectives of green engineer-
ing, guiding principles generally sug-
gest reducing energy use, reducing
material use, reducing emissions, and
thinking about entire supply chains
(life cycles).
Green-engineering metrics
Developing guiding principles is the
first st«p in the process of green en-
gineering, but, the principles provide
only general guidance, not specific
goals. To be put into practice, spe-
cific, measurahle objectives (metrics)
must be established. For the design
of chemical processes and products,
among the most widely recognized
set of sustainability metrics are those
developed by the Canadian National
Roundtable on the Environment and
the Economy \9\ and the American
37
 Feature Report

TABLE 1. REPRESENTATIVE ENVIRONMENTAL PERFORMANCE METRICS

FOR CHEMICAL MANUFACTURING PROCESSES (BRIDGESTO SUSTAINABILITY,2000)
Compound Process Material Energy Water Toxics Pollutants Poilutants
intensity/lb /Ib prod. /Ib prod, /Ib prod. /Ib prod. + COj
prod. (103 BTU/ (gal./lb) (Ib/lb) (Ib/lb) /Ib prod.
(Ib/ib) Ib) (Ib/lb)
Acetic acid from methanol by iow 0,062 1.82 1.24 0.000 0 0.133
pressure carbonylation
Acrylonitriie by ammoxidation of 0.493 5,21 3.37 0.015 0.008 0.966
pfopyiene
Maelic anhy- from n-butane by par- 0.565 0.77 1.66 0 0 2.77
dride tial oxidation
Sulfurto acid from pyrometailurgical 0.002 0.073 0.57 -0.65 -0.63 -0.04
sulfur dioxide
Sulfuric acid from suifur 0.001 -0.87 0,7 0,002 0.002 0.002
Nute: iif.'gative va DO,'; I'iir niat.i^nal list; indicat): tiiat wai^lc niatt'riiils IVuni ulhi'r ptn • C H r - l ' ' ^ ,1 r"l- l l - I ' l l il raw mutt'niiLs; liir jind water use aw raw mattri-
als are not inclut: f'd in the material itwe: negative values for eiiergj' use Lndicutp ih 1 ni't energy gonorat.or

Institute fnr Chemical Engineers general guidelines identified in the icals, manufactured through partial
(AIChE), through their Center for gi'een-engineering principles: use oxidation processes, were considered
Waste Reduction Technologies [70, i i , less energy, use less raw materials, (Figure 1). For each product, a base-
see also Chapter 8 of Reference 121. generate less waste. What makes the case process Ilowsheet was identified.
The team of engineers and scientists AiChE measures particularly valu- Tben, heat-integration opportunities,
assembled by the AIChE identified able for chemical manufacturing, at moderate and aggressive levels of
five core sustainability metrics for however, is that benchmarks have integration, were evaluated. Finally,
chemical processes fas summarized been developed. For many commodity process redesign was considered, in-
in Allen and Shonnard I72|: chemicals, the values of indices have cluding new catalysts, new separa-
• Energy consumed from all sources been calculated for industry standard tion processes, and other new unit
within the manufacturing or deliv- flowsheets. A few examples are shown operations. The changes in energy
ery process per unit of manufactured in Table 1(73,141. efficiency for each process, for these
output (with electricity consump- These data provide benchmarks design stages, are shown in Figure 1.
tion converted to equivalent fuel against wbich engineers can compare Improvements in energy efficiency arc
use, based on an average efficiency tbeir designs. With a set of measur- clearly possible. Some of the efficiency
of converting energy to electricity in able performance indicators, the third improvements halved energy use, rel-
power piants) step in the process of green engineer- ative to tbe base case.
• Total mass of materials used directly ing, evaluating alternative designs, In some ways, this case study is
in the product, minus the mass of can be performed. typical. A study sponsored by tbe U.S.
the product, per unit of manufac- Dept. of Energy (DOE; Washington,
tured output Green-engineering practices D.C.) \18\ considered tbe processes
• Water consumption (including The tools that can he used in develop- used to produce commodity chemi-
water present in waste streams, ing alternative designs are too broad in cals and compared tbe actual energ>'
contact cooling water, water vented scope to be fully summarized here. In- used to the theoretical minimum en-
to the atmosphere and the fraction terested readers can refer to the text- ergy, where the theoretical minimum
of non-contact cooling water lost to book on green engineering \12], soft- is defined as the difference in Gibbs
evaporation) per unit of manufac- ware tools on the U.S. EPA's website free energy between products and re-
tured output [61, and other sources, such as special actants. Not surprisingly, there were
• Emissions of targeted pollutants issues of the journals. Environmen- substantial differences between theo-
(those listed in the Toxic Release tal Science and Technology [15] and retical minimums and actual energy
Inventory) per unit of manufac- Industrial and Engineering Chernis- usage. The data for ethylene, as an
tured output try Research []6]. While not all of the example, were striking, but not sur-
• Total pollutants (including acidify- tools can be discussed in detail here, a prising. Ethylene is manufactured
ing emissions, eutrophying emis- case study of the design of a group of by thermal cracking of ethane and
sions, salinity, and ozone depleting partial oxidation processes, using en- propane or napthas, a process that
substances) per unit of manufac- ergy consumption as the green engi- requires very high reactor tempera-
tured output neering metric, is illustrative. In this tures. After the ethylene is produced,
These metrics match well with the evaluation \17],fivecommodity chem- separating ethylene and propylene

38 CHEMICAL ENGINEERiNG WWW,CHE.COM DECEMBER 2007


120
Acetic Acetic
acid anhydride
100
^ 1 Base case ^ 9 Benchmarked heal integration
n^ Optimum heat integration ^M Process redesign
FIGURE 1. Energy efficiencies of five partiai oxidation processes in a base case
flow sheet and after multipie tiers of green engineering [77]
products typically requires cryogenic
operations. This combination of high
antl low temperature processing re-
quirements makes the actual energy
consumption much greater than the
net internal energy differences be-
tween feedstocks and products. The
theoretical minimum energy analy-
sis is a great simplification of actual
process requirements, hut it raises
the question of whether alternative
reaction or separation technologies
might lead to much more energy ef-
ficient processes. Could a catalytic
route for ethylene or propylene man-
ufacturing be employed? Could non-
cryogenic separations in ethylene
manufacture be used?
The DOE report [18] identifies a
variety of processes where improve-
ments in catalysis, for example, could
lead to improvements in energy effi-
ciency. More than 800 trillion Btu of
annual energy savings associated with
improvements in catalysts were iden-
tified in the analy-sis. With oil valued
at $90/bbl (roughly $0.40-0,50/lh, with
20,000 Btu/lb), these potential energy
savings have a value of tens of billions
of dollars per year.
These simple case studies suggest
that once quantifiable sustainability
metrics are identified, engineering
tools can he used to identify substan-
tial improvements in chemical process
designs. Changes within processes
Maieic Terephthalic Caproiactam
anhydride acid
can he identified that reduce energy
use, material use, and emissions,
however, the design changes should
not stop there. All of the guiding prin-
ciples for green engineering stress the
importance of life cycles and supply
chains. So. in addition to looking for
improvements in single processes and
facilities, systems and supply chains
of chemical processes should be exam-
ined. Practitioners of green engineer-
ing should examine whether chemi-
cal manufacturing systems can be
designed that use waste energy and
waste materials from other processes.
This is not a new idea in chemical en-
gineering. For decades, chemical engi-
neers have practiced the art of using
waste materials and waste heat from
one process in other processes. Con-
sider a classic example — the manu-
facture of vinyl chloride.
Billions of pounds of vinyl chlo-
ride are produced annually. Approxi-
mately half of this production occurs
through the direct chlorination of
ethylene. Ethylene reacts with mo-
lecular chlorine to produce ethylene
dichloride (EDO. The EDC is then
pyrolyzed, producing vinyl chloride
and hydrochloric acid.
CI2 CIH2C-CH2CI
CIH2C-CH2CI -> H2C=CHC1 -t- HCI
In this synthesis route, one mole
CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007
of hydrochloric acid is produced for
every mole of vinyl chloride. Consid-
ered in isolation, this process might
be considered wasteful. Half of the
original chlorine winds up, not in the
desired product, but in a waste acid.
But the process is not operated in iso-
lation. The waste hydrochloric acid
from the direct chlorination of eth-
ylene can be used as a raw material
in the oxychlorination of ethylene. In
this process, hydrochloric acid, ethyl-
ene and oxygen are used to manufac-
ture vinyl chloride.
rik.^i + ri'>\j='_'riij -p TTJWO —?
By operating both the oxychlorina-
tion pathway and the direct chiorina-
tion pathway, the waste hydrochloric
acid can he used as a raw material
and essentially all of the molecular
chlorine originally reacted with ethyl-
ene is incorporated into vinyl chloride.
The two processes operate synergisti-
cally and an efficient design for the
manufacture of vinyl chloride involves
both processes.
Additional efficiencies in the use of
chlorine can be obtained by expanding
the number of processes included in
the network. In the case involving di-
rect chlorination and oxychlorination
processes, both processes incorporate
chlorine into the final product. More
extensive chlorine networks have
emerged, linking isocyanate producers
into vinyl chloride manufacturing net-
works. In isocyanate manufacturing,
molecular chlorine is reacted with car-
bon monoxide to produce phosgene:
CO + CI2 -^ COCI2
The phosgene is then reacted with an
amine to produce an isocyanate and
byproduct hydrochloric acid:
RNH2 + COCI2 ^ RNCO + 2HC1
The isocyanate is subsequently used
in urethane production, and the hy-
drochloric acid is recycled. The key
feature of the isocyanate-process
chemistry is that chlorine does not
appear in the final product. Thus,
chlorine can be processed through the
system without being consumed. It
may be transformed from molecular
chlorine to hydrochloric acid, but the
chlorine is still available for incor-
39
 Feature Report
pnration into final products, such as
vinyl chloride, that contain chlorine.
A chlorine-hydrogen chloride net-
work incorporating both isocyanate
and vinyl chloride has developed in
the Guff Coast of the US. \19]. The
molecular chlorine is sent to hoth
direct chlorination processes and to
isocyanate manufacturing. The by-
product hydrochloric acid is sent to
oxychlorination processes or calcium
chloride manufacturing. The network
has redundancy in chlorine flows.
such that most processes could rely
on either molecular chlorine or hy-
drogen chloride.
Chlorine is not the only material
for which such material cycles could
be identified. A far more ubiquitous
material, water, can also be effec-
tively cycled through multiple pro-
cesses. Water is used in virtually all
industrial processes and major oppor-
tunities exist for reuse since, in gen-
eral, only a small amount of water is
consumed; most water in industrial
applications is used for cooling, heat-
ing or processing of materials, not as
a reactant. Further, different indus-
trial processes and industrial sectors
have widely varying demands for
water quality. Water exchanges and
reuse provide a significant opportu-
nity. An example of such opportuni-
ties is described by Keckler and Allen
References
1. Ebrlich. P.R./The IVpulati.m Bomh." BalIan-
tine, New York, N.Y., 1968.
2. Carson, R., "Silent Sping," Houghton-Miffiin.
Boston, Ma.'is., 1962.
3. Commoner. IJ.. The Environmental Cost of
Economic Growth, in "Population. Resources
and the Envinmment,' edited by R. G. Rid-
ker, U.S. (iovernment Printing OITic(\ Wash-
ington. D C . pp. 339-363,1972.
4. Ehrlich, P. and Huldren, J., Impact of Popula-
tion Growth, Science 171,1212-1217.1971.
ft. Ebrlicb, P. find Holdren. .1., Impact, of Popula-
tion (jrowlh, in "Population. Resources and
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ton, D.C., pp. 365-;i77,1972.
6. Weh site of the US. Environmental Protec-
tion Agency, Washington, D.C. (www.epa.gov/
oi)pt/greenengineering). accessed November
2007.
7. Anastas. P.T. and Warner,.I.e.."Green Chemis-
try: Theory and Practice," Oxford University
Preas. New York. N.Y. 1998.
40 CHEMICAL ENGINEERING WWW.CHE COM
[301, (For more on water reuse, see
CE, October 2006, pp. 50-54).
Identifying which processes could
be most efficiently integrated is not
simple and the design of tbe ideal
network depends on available mar-
kets, what supphers and markets for
materials are nearby, and other fac-
tors. What is clear, however, is that
the chemical process designers must
understand not only their process,
but also processes that could supply
materials, and processes that could
use their byproducts. And, tbe analy-
sis should not be limited to chemical
manufacturing. Continuing with our
example of waste hydrochloric acid
and the manufacture of vinyl chloride,
hyproduct hydrochloric acid could be
used in steel making, or byproduct
hydrochloric acid from semiconduc-
tor manufacturing might be used in
manufacturing chemicals.
Final remarks
This papej- has outlined the general
steps in promoting green engineering
— defining guiding principles, estab-
lishing metrics and using engineer-
ing tools to meet design objectives.
The metrics and design tools that are
part of green engineering should be
employed not only within chemical
processes but also between processes.
If these methods become a part of all
8. McDonough. W.. Braungart, M., Anastas, P.T,
and Zimmerman, J.B., Applying the Prin-
ciples of Orpon Engineering to Cradlo-to-
cradle Design. Eni'. Sci. and 7lTft., 37 (231.
pp. 434A-S41A,a003,
9. National Roundtable on the Enviriinment and
the Economy iNRTEE), "Mea.suring Eco-efR-
ciency in Busint'.'^.s: Keasibility of a Core Set
of Indicators". Renouf" Publishing, Ottowa.
Canada, 1999 (ISBN 1-895643-98-8).
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(AIChE). Center for Waste Reduction Tech-
nologies (CWRT), "Sustainability Metrics In-
terim Report # r , AIChE CWRT, New York.
N.Y,1998.
U. AIChE CWRT, "Sustainahility Metrics In-
terim Report #2", AIChE CWRT New York,
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neering: Environmentally Conscious Design
of Chemicai Processes," Prentice Hall, Engle-
wood Cliffs, N.J., 2001.
13. Bridges to Sustainabiiity, "^ustainahility
Metrics: Making Decisions fur Major Chemi-
cal Products and FaciliLie.s", Houston, Tex.,
2000.
DECEMBER 2007
engineering designs, then the overall
challenge that confronts us — improv-
ing the ^.Ticiencies of our technologies
by an order of magnitude over a gen-
eration — can be achieved. •
Edited by Gerald Ondrey
Note: This article waB baited on materials in
"Green Engineering: Envimnmpntnlly Con-
sciitus Design <if Chemical PnicesHi'si" [12\.
More details on the types of quantitative de-
sign tools that arp beniminK avnilahlc for
chfmical unginetrs can bu found there.
Author
David T. Allen is the Melviii H. Gertz ResKnts
Chair in Chemical Enginel^^i^g and the nirec-
tor of th(! Center fur Energy and Environmental
Re.iources at the UniverHJly of Texas at Austin
(1 University Station C0400. Austin. TX 7H712.
Phone: 512-471-0049; Fax: 512-471-1720; Kmail:
8llen@che.iitexas.edu). His research interests
lie in air quality and pollulion prevention. He is
the author of four iKKiks and over 180 papers in
these areas. The qiiahtv cf his rctficarth luia ln"<"n
recognized by the National Science foundation
Ithrough the Presidential Young Investigator
Award), the AT&T Foundation (through an In-
dustrial Ecology P'ellowship), thf American In-
stitute of Chemical F^ngineers (through tht? I'ecil
Award for contributions to environmental en-
gineering), and lhe State of Texas ahrough the
Governor'H Environmental Excellence' AwarcH.
In addition. Dr. Allen i.-* actively involved in de-
veloping green engineering educational materi-
als for the chemical engineering curriculum.
His most recent effort iw a textV>ook nn design of
chemical proi-eswes and prcKhicts, jointly devel-
oped wilh the U.S. RPA. Dr. Allen received his
B.S. ChE, with diwtinctiun. from Cornell Uni-
versity in 197y. Hi.s M.S. and Ph.D. degrees in
ChE were awarded by tbe Ciilifcirnia In.-ttitute
of Technology in 1981 and 19H;i. He has beld
reftylar faculty appointments at UCLA and the
University of Texas, and visiting UHpointinenta
at the California ln.stitute of TeclinolDgy and
the University of California, Santa Barbara; he
joined the University of Texas in 1995.
14. Schwarz, J.,Beloff,B..and Beaver. E.. Use Sus-
tainability Metrics to Guide Decision-making",
Chcm.Enf'.Prri)i.,9fini, pp. 5S-fi'J. 2002.
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Engineering,37 (23) pp. 5,269-5470. 2003.
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Green Chemistry and Engineering 41 (18),
pp. 4,43&-4,688, 2002.
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Energy Performance Levels for the II.S.
('h<'mical Industry," reptirt prepared for U.S.
I>ept. of Enei^, Washington, D.C, June,
2001.
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file of the U.S. Chemical Industry," report
prepartid for DOE. May 2000, available at:
ntt p://w wwl.oere.energy.gov/industry/cheni-
i c H Is/tool s_profile.html
19. McCoy, M., Chlorine Link.s Gulf Coast Firm.s,
Chem. and Rn/i. Newa, Sept. 7. pp. 17-20,
1998,
20. Keckler, S.E. and Allen, D.T. Material Reuse
Modeling; A Network Flow Programming
Approacb, J.of lnd.Ecol., 2(4) 79-92 (19981.