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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 and cost effectiveness when applied Principle 12. Material and energy
world-wide affluence. early to the design and development inputs should be renewable rather
phase of a process or product" [6]. than depleting.
The engineering An alternative set of nine guid-
challenge Green-engineering principles ing principles has been defined by
flow much better will our The general approach that has been 65 scientists and engineers partici-
technologies need to be? used in green engineering, and com- pating in a green-engineering work-
World populations are cur- plementary efforts in green chemistry, shop. These principles are posted on
rently growing at rates of is to defme a broad set of principles EPA's website [61:
l-2''>^/yr. Worldwide eco- that can guide designs, then to de- 1. Engineer processes and products ho-
nomic output is increasing velop metrics and design tools that listically, use systems analysis, and
hy 3-5%/yr, with larger support these objectives. Anastas and integrate environmental impact as-
increases in some rapidly Warner [7] proposed guiding prin- sessment tools.
developing countries. As- ciples for green chemistry that have 2.Conserve and improve natural eco-
suming that the product of been widely accepted, and a parallel systems while protecting human
population and affluence set of 12 green engineering principles health and well-being.
r)('r capita is increasing have been defined by McDonough and 3.Use life-cycle thinking in all engi-
aL .5'?'i/yi; using the simple others [8]: neering activities.
logic of the IPAT equa- Principle 1. Designers need to strive 4. Ensure that all material and energy
tion, the product of popu- to ensure that all material and energy inputs and outputs are as inherently
lation and affluence (P*A) inputs and outputs are as inherently safe and benign as possible.
will increase by 60% in 10 nonhazardous as possible. 5.Minimize depletion of natural re-
years, hy 250% in 25 years, Principle 2. It is better to prevent sources.
.md by more than a fac- waste than to treat or clean up waste 6.Strive to prevent waste.
tor of 10 in 50 years. Just after it is formed. 7.Develop and apply engineering so-
to keep impacts the same,
Principle 3. Separation and purifi- lutions, while being cognizant of
our technologies will need
cation operations should be designed local geography, aspirations, and
to improve by a factor of
to minimize energy consumption and cultures.
2-3 in 25 years and 10 in
materials use. 8. Create engineering solutions beyond
50 years.
Principle 4. Products, processes, current or dominant technologies;
Can engineers, particu- and systems should be designed to improve, innovate, and invent (tech-
larly cheniical engineers, maximize mass, energy, space, and nologies) to achieve sustain ability.
reduce the environmental time efficiency. 9.Actively engage communities and
impacts of their designs by Principle 5. Products, processes, and stakeholders in development of en-
a factor of 10? Engineering systems should be "output pulled" gineering solutions.
directed at the problem of rather than "input pushed" through These two separate Hsts of guiding
reducing the environmen- the use of energy and materials. principles show that while there is
tal footprints of processes Principle 6. Embedded entropy not universal agreement about the
and products is referred to and complexity must be viewed as precise objectives of green engineer-
by a variety of terms, in- an investment when making design ing, guiding principles generally sug-
cluding green engineering, choices on recycle, reuse, or benefi- gest reducing energy use, reducing
cleaner production, and cial disposition. material use, reducing emissions, and
eco-efficiency. While all of Principle 7. Targeted durability, not thinking about entire supply chains
these terms are in com- immortality, should be a design goal. (life cycles).
mon use, and can have subtly difTer- Principle 8. Design for unnecessary
ent meanings, in this article the term capacity or capability (for example, Green-engineering metrics
"green engineering", as deiined by the "one size fits all") solutions should be Developing guiding principles is the
U.S. Environmental Protection Agency considered a design flaw. first st«p in the process of green en-
(EPA; Washington, D.C), will he used. Principle 9. Material diversity in gineering, but, the principles provide
"Green engineering is the design, multicomponent products should he only general guidance, not specific
commercialization, and use of pro- minimized to promote disassembly goals. To be put into practice, spe-
cesses and products, which are feasi- and value retention. cific, measurahle objectives (metrics)
ble and economical while minimizing Principle 10. Design of products, must be established. For the design
1) generation of pollution at the source processes, and systems must include of chemical processes and products,
and 2) risk to human health and the integration and interconnectivity with among the most widely recognized
environment. Green engineering em- available energy and materials flows. set of sustainability metrics are those
braces the concept that decisions to Principle 11. Products, processes, and developed by the Canadian National
protect human health and the envi- systems should be designed for perfor- Roundtable on the Environment and
ronment can have the greatest impact mance in a commercial "afterlife". the Economy \9\ and the American

CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007 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


of hydrochloric acid is produced for
120 every mole of vinyl chloride. Consid-
Acetic Acetic Maieic Terephthalic Caproiactam ered in isolation, this process might
acid anhydride anhydride acid
100 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 —?

^ 1 Base case ^ 9 Benchmarked heal integration


n^ Optimum heat integration ^M Process redesign
By operating both the oxychlorina-
tion pathway and the direct chiorina-
tion pathway, the waste hydrochloric
FIGURE 1. Energy efficiencies of five partiai oxidation processes in a base case acid can he used as a raw material
flow sheet and after multipie tiers of green engineering [77] and essentially all of the molecular
chlorine originally reacted with ethyl-
products typically requires cryogenic can he identified that reduce energy ene is incorporated into vinyl chloride.
operations. This combination of high use, material use, and emissions, The two processes operate synergisti-
antl low temperature processing re- however, the design changes should cally and an efficient design for the
quirements makes the actual energy not stop there. All of the guiding prin- manufacture of vinyl chloride involves
consumption much greater than the ciples for green engineering stress the both processes.
net internal energy differences be- importance of life cycles and supply Additional efficiencies in the use of
tween feedstocks and products. The chains. So. in addition to looking for chlorine can be obtained by expanding
theoretical minimum energy analy- improvements in single processes and the number of processes included in
sis is a great simplification of actual facilities, systems and supply chains the network. In the case involving di-
process requirements, hut it raises of chemical processes should be exam- rect chlorination and oxychlorination
the question of whether alternative ined. Practitioners of green engineer- processes, both processes incorporate
reaction or separation technologies ing should examine whether chemi- chlorine into the final product. More
might lead to much more energy ef- cal manufacturing systems can be extensive chlorine networks have
ficient processes. Could a catalytic designed that use waste energy and emerged, linking isocyanate producers
route for ethylene or propylene man- waste materials from other processes. into vinyl chloride manufacturing net-
ufacturing be employed? Could non- This is not a new idea in chemical en- works. In isocyanate manufacturing,
cryogenic separations in ethylene gineering. For decades, chemical engi- molecular chlorine is reacted with car-
manufacture be used? neers have practiced the art of using bon monoxide to produce phosgene:
The DOE report [18] identifies a waste materials and waste heat from
variety of processes where improve- one process in other processes. Con- CO + CI2 -^ COCI2
ments in catalysis, for example, could sider a classic example — the manu-
The phosgene is then reacted with an
lead to improvements in energy effi- facture of vinyl chloride.
amine to produce an isocyanate and
ciency. More than 800 trillion Btu of Billions of pounds of vinyl chlo- byproduct hydrochloric acid:
annual energy savings associated with ride are produced annually. Approxi-
improvements in catalysts were iden- mately half of this production occurs RNH2 + COCI2 ^ RNCO + 2HC1
tified in the analy-sis. With oil valued through the direct chlorination of The isocyanate is subsequently used
at $90/bbl (roughly $0.40-0,50/lh, with ethylene. Ethylene reacts with mo- in urethane production, and the hy-
20,000 Btu/lb), these potential energy lecular chlorine to produce ethylene drochloric acid is recycled. The key
savings have a value of tens of billions dichloride (EDO. The EDC is then feature of the isocyanate-process
of dollars per year. pyrolyzed, producing vinyl chloride chemistry is that chlorine does not
These simple case studies suggest and hydrochloric acid. appear in the final product. Thus,
that once quantifiable sustainability chlorine can be processed through the
CI2 CIH2C-CH2CI
metrics are identified, engineering system without being consumed. It
tools can he used to identify substan- may be transformed from molecular
tial improvements in chemical process CIH2C-CH2CI -> H2C=CHC1 -t- HCI chlorine to hydrochloric acid, but the
designs. Changes within processes In this synthesis route, one mole chlorine is still available for incor-
CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007 39
Feature Report

pnration into final products, such as [301, (For more on water reuse, see engineering designs, then the overall
vinyl chloride, that contain chlorine. CE, October 2006, pp. 50-54). challenge that confronts us — improv-
A chlorine-hydrogen chloride net- Identifying which processes could ing the ^.Ticiencies of our technologies
work incorporating both isocyanate be most efficiently integrated is not by an order of magnitude over a gen-
and vinyl chloride has developed in simple and the design of tbe ideal eration — can be achieved. •
the Guff Coast of the US. \19]. The network depends on available mar- Edited by Gerald Ondrey
molecular chlorine is sent to hoth kets, what supphers and markets for
direct chlorination processes and to materials are nearby, and other fac- Note: This article waB baited on materials in
"Green Engineering: Envimnmpntnlly Con-
isocyanate manufacturing. The by- tors. What is clear, however, is that sciitus Design <if Chemical PnicesHi'si" [12\.
product hydrochloric acid is sent to the chemical process designers must More details on the types of quantitative de-
sign tools that arp beniminK avnilahlc for
oxychlorination processes or calcium understand not only their process, chfmical unginetrs can bu found there.
chloride manufacturing. The network but also processes that could supply
has redundancy in chlorine flows. materials, and processes that could
such that most processes could rely use their byproducts. And, tbe analy- Author
on either molecular chlorine or hy- sis should not be limited to chemical David T. Allen is the Melviii H. Gertz ResKnts
Chair in Chemical Enginel^^i^g and the nirec-
drogen chloride. manufacturing. Continuing with our tor of th(! Center fur Energy and Environmental
Chlorine is not the only material example of waste hydrochloric acid Re.iources at the UniverHJly of Texas at Austin
(1 University Station C0400. Austin. TX 7H712.
for which such material cycles could and the manufacture of vinyl chloride, Phone: 512-471-0049; Fax: 512-471-1720; Kmail:
8llen@che.iitexas.edu). His research interests
be identified. A far more ubiquitous hyproduct hydrochloric acid could be lie in air quality and pollulion prevention. He is
material, water, can also be effec- used in steel making, or byproduct the author of four iKKiks and over 180 papers in
these areas. The qiiahtv cf his rctficarth luia ln"<"n
tively cycled through multiple pro- hydrochloric acid from semiconduc- recognized by the National Science foundation
Ithrough the Presidential Young Investigator
cesses. Water is used in virtually all tor manufacturing might be used in Award), the AT&T Foundation (through an In-
industrial processes and major oppor- manufacturing chemicals. dustrial Ecology P'ellowship), thf American In-
stitute of Chemical F^ngineers (through tht? I'ecil
tunities exist for reuse since, in gen- Award for contributions to environmental en-
gineering), and lhe State of Texas ahrough the
eral, only a small amount of water is Final remarks Governor'H Environmental Excellence' AwarcH.
consumed; most water in industrial This papej- has outlined the general In addition. Dr. Allen i.-* actively involved in de-
veloping green engineering educational materi-
applications is used for cooling, heat- steps in promoting green engineering als for the chemical engineering curriculum.
ing or processing of materials, not as His most recent effort iw a textV>ook nn design of
— defining guiding principles, estab- chemical proi-eswes and prcKhicts, jointly devel-
a reactant. Further, different indus- lishing metrics and using engineer- oped wilh the U.S. RPA. Dr. Allen received his
B.S. ChE, with diwtinctiun. from Cornell Uni-
trial processes and industrial sectors ing tools to meet design objectives. versity in 197y. Hi.s M.S. and Ph.D. degrees in
have widely varying demands for The metrics and design tools that are ChE were awarded by tbe Ciilifcirnia In.-ttitute
of Technology in 1981 and 19H;i. He has beld
water quality. Water exchanges and part of green engineering should be reftylar faculty appointments at UCLA and the
University of Texas, and visiting UHpointinenta
reuse provide a significant opportu- employed not only within chemical at the California ln.stitute of TeclinolDgy and
nity. An example of such opportuni- processes but also between processes. the University of California, Santa Barbara; he
joined the University of Texas in 1995.
ties is described by Keckler and Allen If these methods become a part of all

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40 CHEMICAL ENGINEERING WWW.CHE COM DECEMBER 2007