Green

Follow these principles and guidelines to design your process plant to be 'greener'
David T. Allen University of Texas, Austin 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 products and the processes that create them are becoming a greater concern. As this concern about the magnitude of the associated environmental footprints increases, engineers, and particularly chemical engineers, will face new challenges. To grasp the nature and magnitude 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 substantial debate concerning whether the environmental challenges faced by the U.S. were largely driven by population growth, or by the nature of technology. Books like "The Population Bomb" [il, argued that rapid increases in population could not be supported by available resources. These ideas had been expressed at least since the time of Thomas Malthus, in the 18th century, but rapidly increasing and unprecedented world populations, gave these arguments new life. In contrast, prominent environmentalists such as Ra36

And the Design of Chemical Processes and Products

chel Carson and Barry Commoner argued that it was the nature of technology that was the source of environmental problems [2, 3\. Of course, neither population nor the nature of technology is exclusively tho cause of the environmental challenges we face. It is a combination of factors that drive environmental impacts. In the early 1970s, Ehrlich and Holdren 14, 5] expressed this idea simply with what has come to be called the IPAT equation. Environmental impacts (/), Ehrlich and Holdren argued, are the product of

population, [P, number of people); affluence (A, expressed in units such as gross domestic product |GDP| per capita), and technology, (T, expressed as impact per unit of GDP): I = P (number of people) * A ($ GDP per capita) * T (impact per $ GDP) This relatively simple equation has changed the way many environmentalists view the role of technology. The IPAT equation makes clear that instead of being a cause of the problem, better technologies, providing lower impacts per dollar of GDP, are viewed

CHEMICAL ENGINEERING WWW.CHE.COM DECEMBER 2007

;is the enabler of improved world-wide affluence.

and cost effectiveness when applied early to the design and development phase of a process or product" [6].

The engineering challenge

flow much better will our technologies need to be? World populations are currently growing at rates of l-2''>^/yr. Worldwide economic output is increasing hy 3-5%/yr, with larger increases in some rapidly developing countries. Assuming that the product of population and affluence r)('r capita is increasing aL .5'?'i/yi; using the simple logic of the IPAT equation, the product of population and affluence (P*A) will increase by 60% in 10 years, hy 250% in 25 years, .md by more than a factor 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, particularly cheniical engineers, reduce the environmental impacts of their designs by a factor of 10? Engineering directed at the problem of reducing the environmental footprints of processes and products is referred to by a variety of terms, including green engineering, cleaner production, and eco-efficiency. While all of these terms are in common use, and can have subtly difTerent 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 processes and products, which are feasible and economical while minimizing 1) generation of pollution at the source and 2) risk to human health and the environment. Green engineering embraces the concept that decisions to protect human health and the environment can have the greatest impact

Green-engineering principles
The general approach that has been used in green engineering, and complementary efforts in green chemistry, is to defme a broad set of principles that can guide designs, then to develop metrics and design tools that support these objectives. Anastas and Warner [7] proposed guiding principles 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 purification 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 beneficial 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 performance in a commercial "afterlife".

Principle 12. Material and energy inputs should be renewable rather than depleting. An alternative set of nine guiding principles has been defined by 65 scientists and engineers participating in a green-engineering workshop. These principles are posted on EPA's website [61: 1. Engineer processes and products holistically, use systems analysis, and integrate environmental impact assessment tools. 2.Conserve and improve natural ecosystems while protecting human health and well-being. 3.Use life-cycle thinking in all engineering activities. 4. Ensure that all material and energy inputs and outputs are as inherently safe and benign as possible. 5.Minimize depletion of natural resources. 6.Strive to prevent waste. 7.Develop and apply engineering solutions, while being cognizant of local geography, aspirations, and cultures. 8. Create engineering solutions beyond current or dominant technologies; improve, innovate, and invent (technologies) to achieve sustain ability. 9.Actively engage communities and stakeholders in development of engineering solutions. These two separate Hsts of guiding principles show that while there is not universal agreement about the precise objectives of green engineering, guiding principles generally suggest 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 stp in the process of green engineering, but, the principles provide only general guidance, not specific goals. To be put into practice, specific, 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
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TABLE 1. REPRESENTATIVE ENVIRONMENTAL PERFORMANCE METRICS FOR CHEMICAL MANUFACTURING PROCESSES (BRIDGESTO SUSTAINABILITY,2000) Compound Process Material intensity/lb prod. (Ib/ib) Energy /Ib prod. (103 BTU/ Ib) 1.82 5,21 0.77 0.073 -0.87 Water /Ib prod, (gal./lb) 1.24 3.37 1.66 0.57
0,7
,1 r"l- l l - I ' l l il

Toxics /Ib prod. (Ib/lb) 0.000 0.015 0 -0.65 0,002

Pollutants /Ib prod. (Ib/lb)

0

Poilutants
+ COj

/Ib prod. (Ib/lb) 0.133 0.966 2.77 -0.04 0.002

Acetic acid Acrylonitriie

from methanol by iow 0,062 pressure carbonylation by ammoxidation of pfopyiene 0.493 0.565 0.002 0.001

0.008 0 -0.63 0.002

Maelic anhy- from n-butane by pardride tial oxidation Sulfurto acid Sulfuric acid from pyrometailurgical sulfur dioxide from suifur

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 ' ' ^ als are not inclut: f'd in the material itwe: negative values for eiiergj' use Lndicutp ih

raw mutt'niiLs; liir jind water use aw raw mattri1 ni't energy gonorat.or

Institute fnr Chemical Engineers (AIChE), through their Center for Waste Reduction Technologies [70, i i , see also Chapter 8 of Reference 121. The team of engineers and scientists assembled by the AIChE identified five core sustainability metrics for chemical processes fas summarized in Allen and Shonnard I72|: Energy consumed from all sources within the manufacturing or delivery process per unit of manufactured output (with electricity consumption converted to equivalent fuel use, based on an average efficiency of converting energy to electricity in power piants) Total mass of materials used directly in the product, minus the mass of the product, per unit of manufactured output Water consumption (including water present in waste streams, contact cooling water, water vented to the atmosphere and the fraction of non-contact cooling water lost to evaporation) per unit of manufactured output Emissions of targeted pollutants (those listed in the Toxic Release Inventory) per unit of manufactured output Total pollutants (including acidifying emissions, eutrophying emissions, salinity, and ozone depleting substances) per unit of manufactured output These metrics match well with the
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general guidelines identified in the gi'een-engineering principles: use less energy, use less raw materials, generate less waste. What makes the AiChE measures particularly valuable for chemical manufacturing, however, is that benchmarks have been developed. For many commodity chemicals, the values of indices have been calculated for industry standard flowsheets. A few examples are shown in Table 1(73,141. These data provide benchmarks against wbich engineers can compare tbeir designs. With a set of measurable performance indicators, the third step in the process of green engineering, evaluating alternative designs, can be performed.

icals, manufactured through partial oxidation processes, were considered (Figure 1). For each product, a basecase process Ilowsheet was identified. Tben, heat-integration opportunities, at moderate and aggressive levels of integration, were evaluated. Finally, process redesign was considered, including new catalysts, new separation processes, and other new unit operations. The changes in energy efficiency for each process, for these design stages, are shown in Figure 1. Improvements in energy efficiency arc clearly possible. Some of the efficiency improvements halved energy use, relative to tbe base case.

In some ways, this case study is typical. A study sponsored by tbe U.S. Dept. of Energy (DOE; Washington, D.C.) \18\ considered tbe processes Green-engineering practices The tools that can he used in develop- used to produce commodity chemiing alternative designs are too broad in cals and compared tbe actual energ>' scope to be fully summarized here. In- used to the theoretical minimum enterested readers can refer to the text- ergy, where the theoretical minimum book on green engineering \12], soft- is defined as the difference in Gibbs ware tools on the U.S. EPA's website free energy between products and re[61, and other sources, such as special actants. Not surprisingly, there were issues of the journals. Environmen- substantial differences between theotal Science and Technology [15] and retical minimums and actual energy Industrial and Engineering Chernis- usage. The data for ethylene, as an try Research []6]. While not all of the example, were striking, but not surtools can be discussed in detail here, a prising. Ethylene is manufactured case study of the design of a group of by thermal cracking of ethane and partial oxidation processes, using en- propane or napthas, a process that ergy consumption as the green engi- requires very high reactor temperaneering metric, is illustrative. In this tures. After the ethylene is produced, evaluation \17],fivecommodity chem- separating ethylene and propylene

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120

Acetic acid
100

Acetic anhydride

Maieic anhydride

Terephthalic acid

Caproiactam

of hydrochloric acid is produced for every mole of vinyl chloride. Considered 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 isolation. The waste hydrochloric acid from the direct chlorination of ethylene can be used as a raw material in the oxychlorination of ethylene. In this process, hydrochloric acid, ethylene and oxygen are used to manufacture vinyl chloride.
rik.^i + ri'>\j='_'riij -p TTJWO ?

^ 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 requirements makes the actual energy consumption much greater than the net internal energy differences between feedstocks and products. The theoretical minimum energy analysis 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 efficient processes. Could a catalytic route for ethylene or propylene manufacturing be employed? Could noncryogenic separations in ethylene manufacture be used? The DOE report [18] identifies a variety of processes where improvements in catalysis, for example, could lead to improvements in energy efficiency. More than 800 trillion Btu of annual energy savings associated with improvements in catalysts were identified 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 substantial improvements in chemical process designs. Changes within processes

can he identified that reduce energy use, material use, and emissions, however, the design changes should not stop there. All of the guiding principles 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 examined. Practitioners of green engineering should examine whether chemical manufacturing systems can be designed that use waste energy and waste materials from other processes. This is not a new idea in chemical engineering. For decades, chemical engineers have practiced the art of using waste materials and waste heat from one process in other processes. Consider a classic example the manufacture of vinyl chloride. Billions of pounds of vinyl chloride are produced annually. Approximately half of this production occurs through the direct chlorination of ethylene. Ethylene reacts with molecular chlorine to produce ethylene dichloride (EDO. The EDC is then pyrolyzed, producing vinyl chloride and hydrochloric acid. CI2 CIH2C-CH2CI

By operating both the oxychlorination pathway and the direct chiorination pathway, the waste hydrochloric acid can he used as a raw material and essentially all of the molecular chlorine originally reacted with ethylene is incorporated into vinyl chloride. The two processes operate synergistically 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 direct 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 networks. In isocyanate manufacturing, molecular chlorine is reacted with carbon 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 hydrochloric 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 incor39

CIH2C-CH2CI -> H2C=CHC1 -t- HCI In this synthesis route, one mole

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Feature Report
pnration into final products, such as vinyl chloride, that contain chlorine. A chlorine-hydrogen chloride network 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 byproduct 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 hydrogen chloride. Chlorine is not the only material for which such material cycles could be identified. A far more ubiquitous material, water, can also be effectively cycled through multiple processes. Water is used in virtually all industrial processes and major opportunities exist for reuse since, in general, only a small amount of water is consumed; most water in industrial applications is used for cooling, heating or processing of materials, not as a reactant. Further, different industrial processes and industrial sectors have widely varying demands for water quality. Water exchanges and reuse provide a significant opportunity. An example of such opportunities is described by Keckler and Allen [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 markets, what supphers and markets for materials are nearby, and other factors. 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 analysis 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 semiconductor manufacturing might be used in manufacturing chemicals. engineering designs, then the overall challenge that confronts us improving the ^.Ticiencies of our technologies by an order of magnitude over a generation can be achieved. Edited by Gerald Ondrey
Note: This article waB baited on materials in "Green Engineering: Envimnmpntnlly Consciitus Design <if Chemical PnicesHi'si" [12\. More details on the types of quantitative design 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 nirector 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: [email protected]). 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 Industrial Ecology P'ellowship), thf American Institute of Chemical F^ngineers (through tht? I'ecil Award for contributions to environmental engineering), and lhe State of Texas ahrough the Governor'H Environmental Excellence' AwarcH. In addition. Dr. Allen i.-* actively involved in developing green engineering educational materials for the chemical engineering curriculum. His most recent effort i a textV>ook nn design of w chemical proi-eswes and prcKhicts, jointly developed wilh the U.S. RPA. Dr. Allen received his B.S. ChE, with diwtinctiun. from Cornell University 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.

Final remarks
This papej- has outlined the general steps in promoting green engineering defining guiding principles, establishing metrics and using engineering 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

References
1. Ebrlich. P.R./The IVpulati.m Bomh." BalIantine, 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. Ridker, U.S. (iovernment Printing OITic(\ Washington. D C . pp. 339-363,1972. 4. Ehrlich, P. and Huldren, J., Impact of Population Growth, Science 171,1212-1217.1971. ft. Ebrlicb, P. find Holdren. .1., Impact, of Population (jrowlh, in "Population. Resources and the Environment," edited by R. G. Ridker. U.S. Government Printing Ofiice. WaHhington, D.C., pp. 365-;i77,1972. 6. Weh site of the US. Environmental Protection Agency, Washington, D.C. (www.epa.gov/ oi)pt/greenengineering). accessed November 2007. 7. Anastas. P.T. and Warner,.I.e.."Green Chemistry: Theory and Practice," Oxford University Preas. New York. N.Y. 1998. 8. McDonough. W.. Braungart, M., Anastas, P.T, and Zimmerman, J.B., Applying the Principles of Orpon Engineering to Cradlo-tocradle Design. Eni'. Sci. and 7lTft., 37 (231. pp. 434A-S41A,a003, 9. National Roundtable on the Enviriinment and the Economy iNRTEE), "Mea.suring Eco-efRciency in Busint'.'^.s: Keasibility of a Core Set of Indicators". Renouf" Publishing, Ottowa. Canada, 1999 (ISBN 1-895643-98-8). 10. American Institute of Chemical Engineers (AIChE). Center for Waste Reduction Technologies (CWRT), "Sustainability Metrics Interim Report # r , AIChE CWRT, New York. N.Y,1998. U. AIChE CWRT, "Sustainahility Metrics Interim Report #2", AIChE CWRT New York, N.Y,1999. 12. Allen, DT and Shonnard. D.R.. -Green Engineering: Environmentally Conscious Design of Chemicai Processes," Prentice Hall, Englewood Cliffs, N.J., 2001. 13. Bridges to Sustainabiiity, "^ustainahility Metrics: Making Decisions fur Major Chemical Products and FaciliLie.s", Houston, Tex., 2000.
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14. Schwarz, J.,Beloff,B..and Beaver. E.. Use Sustainability Metrics to Guide Decision-making", Chcm.Enf'.Prri)i.,9fini, pp. 5S-fi'J. 2002. 15. Euv. Sci.and Tech., Special Issue on Green Engineering,37 (23) pp. 5,269-5470. 2003. 16. Ind.and Eng.Ckem. Hes., Special Istsue on Green Chemistry and Engineering 41 (18), pp. 4,43&-4,688, 2002. 17. Bridges to Su.iitainahility. "A Pilot Study of Energy Performance Levels for the II.S. ('h<'mical Industry," reptirt prepared for U.S. I>ept. of Enei^, Washington, D.C, June, 2001. 18. "Energetics, Energy and Environmental I'rnfile of the U.S. Chemical Industry," report prepartid for DOE. May 2000, available at: ntt p://w wwl.oere.energy.gov/industry/chenii 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.

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