Perspective

Green Engineering: Environmentally Conscious Design of Chemical Processes and Products

David T. Allen
Dept. of Chemical Engineering, University of Texas, Austin, TX 78712

David R. Shonnard
Dept. of Chemical Engineering, Michigan Technological University, Houghton, MI 49931

Introduction

t is impossible to imagine modern life without the products provided by the chemical industry. Chemical processes provide a vast array of products and materials used in health care, consumer products, transportation, food processing, electronic materials, and construction. Yet, these same chemical processes that provide products essential for modern economies also generate substantial quantities of wastes and emissions. Recent national scale inventories of wastes and emissions indicate that advanced industrialized economies utilize 4080 ton of material per year, per capita (Adriaanse et al., 1997); the majority of these materials are used once and then discarded. Since most material use and material displacement are associated with the extraction, production and use of commodity materials, these material flows provide both challenges and opportunities for chemical engineers. The challenge is to keep the costs of chemical products (particularly commodity products) affordable, while continuing to reduce environmental impacts. The opportunities will come from rethinking the approach to meeting environmental goals. Rather than using traditional, end-of-pipe approaches to environmental management, approaches that avoid the generation of wastes or pollutants, variously known as green engineering, environmentally conscious manufacturing, ecoefficient production, or pollution prevention, can provide alternatives that are costeffective and result in significant environmental improvements. These general ideas have been receiving increasing attention in the chemical engineering research community for more than a decade, and a number of educational institutions are offering chemical engineering courses and even specializations in pollution prevention or green engineering. But, there remain challenging questions. What constitutes green engineering? What are the tools that a chemical engineer must master to design chemical processes and products that will meet the environmental constraints and goals of the 21st century? It can be argued that green engineering is simply good chemical engineering. Previous Perspectives published in the Journal have noted the role of green engineering in process engineering (Grossmann and Westerberg, 2000; Harold and Ogunnaike, 2000), and chemical engineers have worked for decades to design processes that are energy- and mass-efficient. The viewpoint September 2001

advanced here, however, is that chemical engineers will require a new group of tools to address the challenges of green engineering and that these tools can fall into three categories: assessment, improvement, and integration.

Assessing the Environmental Performance of Chemical Processes and Products

What constitutes a green process or a green product? Early attempts to identify green products focused on the development of ecolabels, such as those shown in Figure 1. Generally administered by governments, these labels attempted to condense complex, multiattribute environmental footprints of products into a single logo (U.S. EPA, 1993; Allen et al., 1998). Either a product was green and could display an eco-label, or it was not. Unfortunately, true environmental performance is rarely so simple. Products and the processes used to manufacture them consume energy, utilize nonrenewable and renewable materials, and generate emissions. In creating designs, product and process engineers are continually forced to make decisions that involve trade-offs between multiple environmental impacts. Consider, for example, the chemical process designer trying to determine whether to use indirect or direct contact heating in a process application. The direct contact heating (e.g., steam injection) may be more energy-efficient than the use of a heat exchanger, but generates a wastewater stream. Alternatively, consider the dilemma of a product designer trying to select a material for an automotive bumper. Should the designer select a steel bumper that is easily recycled or a lightweight polymer composite that leads to better fuel economy? Such trade-offs are unavoidable. Every product and process will generate an environmental footprint, and only rarely will one design alternative be unambiguously environmentally preferable. Designers will continually face trade-offs between different environmental impacts, yet must ultimately make decisions. Further, designers must reconcile environmental performance with cost and other criteria. Informing these decisions will require a new set of tools that chemical engineers will need to master. In addition, the tools must be robust enough to be used at a variety of decision points in process and product design. The chemical engineer, evaluating hundreds of design alternatives for a process in its initial development stages will need more streamlined tools than the Vol. 47, No. 9 AIChE Journal

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uations, but will face another level of design decisions that will engineer performing a process modification on an existing facility. influence environmental performance. Figure 2 provides an For chemical engineers, key groups of environmental assessexample of the type of decision that a process designer would face. ment tools are beginning to emerge. The tools deal with two disIn this simple example, absorption with a regenerable solvent is tinct issues: 1. how to assess potential environmental impacts at a used to capture (and recycle or sell) toluene and ethyl acetate, variety of stages during process design; 2. how to reconcile enviwhich might otherwise be emitted into the atmosphere. To increase ronmental impacts with other decision criteria. the fraction of the hydrocarbons absorbed, the circulation rate of Assessing Environmental Impacts. While detailed environmenthe solvent can be increased, but this will increase the duties of the tal impact assessments have been performed for decades, their reboiler, condenser and pumps in the system, increasing energy use implementation has generally been restricted to evaluations of and atmospheric emissionsprimarily of criteria pollutants (sulfur completed designs. This severely restricts the range of options that and nitrogen oxides, particulates, and carbon monoxide), and of the can be considered to improve environmental performance. A betgreenhouse gas CO2. The ter approach would be to evaluate environmental perprocess engineer will need formance at each step in the emission estimation tools to design process. Consider evaluate such trade-offs, and how this might be implementwill need to evaluate the ed in a typical process design. potential environmental and At the earliest stages of a economic costs associated process design, only the most with different types of emiselementary data on raw matesionsin this example the rials, products and by-prodrelative costs of hydrocarbon ucts of a chemical process emissions as opposed to emismay be available, and large sions of criteria pollutants and numbers of design alternaCO2. tives may need to be considAssessing Environmental ered. Yet, despite the availCosts. A second type of enviability of only limited inforronmental assessment tool mation, there is a need to will allow the chemical identify potentially hazardous process designer to reconcile process materials, consider environmental impacts with alternative reaction pathways, other decision criteria. Since and identify key emission evaluation of costs is the pripoints in the process. mary mechanism for business Chemical engineers need decision-making, significant tools that will allow them to efforts have been made to quickly assess the potential quantify environmental costs Figure 1. Eco-labels from around the world. environmental persistence, and benefits. The most releGenerally administered by governments, these labels bioaccumulation potential, vant work for the design of attempt to condense complex, multi-attribute environand toxicity of new chemical chemical processes has been mental footprints of products into a single logo. products and intermediates. done by the American InstThey also need tools that will itute of Chemical Engineers' allow key compounds of concern or emission points in chemical Center for Waste Reduction Technologies (AIChECWRT, 2000). processes to be identified. Table 1 provides a simple example of the The CWRT Total Cost Assessment (TCA) methods identify five type of assessment that chemical engineers will need to perform tiers of environmental costs. with limited information. Table 1 shows two alternative synthesis routes for the producTier I: costs normally captured by engineering economic evalution of methyl methacrylate and demonstrates how they can be ations quickly evaluated to assess potential environmental concerns. The Tier II: administrative and regulatory environmental costs not data in Table 1 can be estimated using group contribution methods normally assigned to individual projects when measurements are not available; the estimates of persistence, Tier III: liability costs bioaccumulation, toxicity and stoichiometry can then be combined Tier IV: costs and benefits, internal to a company, associated to provide preliminary guidance (Allen and Shonnard, 2001). In with improved environmental performance this case, the concerns are dominated by the health and safety Tier V: costs and benefits, external to a company, associated issues associated with sulfuric acid, and the isobutlyene route with improved environmental performance appears preferable because it requires less acid. Although more detailed data are available for these two processes, this level of Tier I costs are the types of costs quantified in traditional ecodata is typical of what might be available for new process nomic analyses. Traditional accounting systems that focus on Tier chemistries. I costs often charge some types of environmental costs to overOnce the basic structure of a process has been designed, the head, and these costs may therefore be hidden during project cost engineer will be able to perform more detailed environmental evalevaluations. These are referred to as Tier II or hidden costs. A less

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tangible set of costs are those designated as Tier IIIliability Improving Environmental Performance of costs. Liability costs could include compliance obligations, remeChemical Processes and Products diation obligations, fines and penalties, obligations to compensate for private parties, punitive damages, and natural resource damOnce a set of tools is available for assessing environmental ages. A final set of costs are designated as Tier IV or V, which can impacts and costs, chemical engineers can apply traditional analysis be referred to as image or relationship costs (AIChECWRT, and design methods to improve mass efficiency, energy efficiency, 2000). These costs arise in relationships with customers, investors, and environmental performance. Advances in catalysis, reaction insurers, suppliers, lenders, employees, regulators, and communiengineering, separations, process synthesis, process control, and ties. They are perhaps the most difficult to quantify. other areas can all make contributions. But, are there tools and skills Thus, a basic framework for estimating costs and benefits assothat will need to be developed specifically to im-prove environmenciated with environmental activities consists of five tiers, begintal performance? Our perspective is that a few such tools will ning with the most tangible costs and extending to the least quanemerge. They might include better methods for modeling very dilute tifiable costs. Tier I costs, by definition, are captured effectively by solutions (since pollutants are generally present at very low concenconventional accounting methods. Tier II costs are certain, yet are trations) at process conditions and the ability to predict the yields of often difficult to separate from general overhead expenditures. trace byproducts under process reaction conditions. On balance, Estimating Tier III-V costs poses different challenges. These costs however, the tools for improving environmental performance will be are, in many cases, the same as the due to unplanned tools that chemical events, such as Table 1. Stoichiometric, Persistence, Toxicity and Bioaccumulation Data for Two engineers have Synthesis Routes for Methyl Methacrylate incidents that worked for decades lb(kg) Produced Atmospheric Bioconc. Factor result in civil fines, to master. or Required per Half-Life/Aquatic (Conc. in remediation costs lb(kg) of Methyl Half-Life** 1/TLV Lipids/Conc. or other charges. Compound Methacrylate* (ppm)1 in Water) Moving While these events Acetone-cyanohydrin route Beyond Plant are not planned, Acetone 0.68 (0.31) 52 d/wk 1/750 3.2 Hydrogen cyanide 0.32 (0.15) 1 yr/wk 1/10 3.2 they do occur. Boundary: Methanol 0.37 (0.168) 17 d/d 1/200 3.2 Therefore, it is Integrating Sulfuric acid*** 1.63 (0.74) 1/2 (est.) prudent to estimate Methyl methacrylate 1.00 (0.45) 7 h/wk 1/100 2.3 Process the expected value of these costs. Isobutylene route Design with Isobutylene 1.12 (0.51) 2.5 h/wk 1/200 (est.) 12.6 Arriving at an Methanol 0.38 (0.172) 17 d/d 1/200 3.2 Supply Chain expected value for Pentane 0.03 (0.014) 2.6 d/d 1/600 81 Management Sulfuric acid*** 0.01 (0.005) 1/2 (est.) Tier III-V costs Methyl methacrylate 1.00 (0.45) 7 h/wk 1/100 2.3 involves estimatand Product *A negative stoichiometric index indicates that a material is consumed; a positive index indicates that it is produced ing the probability Stewardship in the reaction. that an event will **The atmospheric half-life is based on the reaction with the hydroxyl radical; aquatic half-life via biodegradation is While it is approbased on expert estimates. occur, the costs lifetime of sulfuric acid in the atmosphere is short due to reactions with ammonia. priate for chemical associated with the ***The TLV is the threshold limit value, and the inverse is a measure of inhalation toxicity potential for a chemical. engineers to focus event, and when Bioconcentration factor is an indicator of a chemicals potential to accumulate through the food chain. on evaluating and the event will improving the envioccur. For examronmental performance of chemical processes, it is also important to ple, if the goal is to estimate the expected value of a civil fine or recognize that chemical manufacturing processes are linked to both penalty (a Tier III cost), the likelihood that a fine will be assessed suppliers and customers. Customers will be concerned about the and the likely magnitude of that fine must be calculated. If the environmental performance of chemical products that they use, and probability of a fine being assessed is 0.1 (1 chance in 10) per year so process design engineers must increasingly become stewards for and the likely magnitude of the fine is $10,000, the expected annutheir products. In addition, chemical processes are linked to their supal cost due to fines would be $1,000. For events that will occur in pliers, so engineers must be aware of the linkages between their future years, such as costs of complying with anticipated future processes and other chemical processes and other industrial sectors. regulations, knowledge of when the event will occur is critical to Product and Process Stewardship. Life cycle assessment (LCA) determining the present value of the expected costs. has become an important part of environmental product and Summary of Environmental Assessment Tools. A robust set of process stewardship. The tools of life cycle assessment recognize environmental impact and cost assessment tools, designed specifithat products, services, and processes all have a life cycle. For cally for chemical processes are beginning to emerge. These tools products, the life cycle begins when raw materials are extracted or are currently in their initial development stages and much work harvested. Raw materials then go through a number of manufacremains to be done in taking them from directional indicators of turing steps until the product is delivered to a customer. The prodperformance to quantitative environmental impact and cost evaluuct is used, then disposed of or recycled. Figure 3 shows these ation tools. Nevertheless, the evaluation frameworks are beginning product life cycle stages along the horizontal axis, as well as enerto take shape and the next generation of chemical engineers can gy consumption and wastes and emissions generated in all of these expect to integrate the evaluation of environmental objectives into life cycle stages. every phase of the design process.

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process might be considered wasteful. Half of the original chlorine Processes also have a life cycle. The life cycle begins with planwinds up, not in the desired product, but in a waste acid. The ning, research and development. The products and processes are process, however, is not operated in isolation. The waste then designed and constructed. A process will have an active lifehydrochloric acid from the direct chlorination of ethylene can be time, then will be decommissioned, and, if necessary, remediation used as a raw material in the oxychlorination of ethylene. In this and restoration may occur. Figure 3, along its vertical axis, illusprocess, hydrochloric acid, ethylene, and oxygen are used to mantrates the main elements of this process life cycle. Again, energy ufacture vinyl chloride: consumption, wastes, and emissions are associated with each step in the life cycle. HCl + H2C=CH2 + 0.5 O2 H2C=CHCl + H2O Traditionally, product designers have been concerned primarily with product life cycles up to and including the manufacturing step. Chemical process designers have been concerned primarily with By operating both the oxychlorination pathway and the direct process life cycles up to and including the manufacturing step. That chlorination pathway, the waste hydrochloric acid can be used as a focus is changing. raw material and Increasingly, chemical essentially all of the product designers molecular chlorine must consider how originally reacted their products will be with ethylene is incorrecycled. They must porated into vinyl consider how their chloride. The two customers will use processes operate syntheir products and ergistically and an what environmental efficient design for the hazards might arise. manufacture of vinyl Process designers chloride involves both must avoid contamiprocesses. nation of the sites at Additional efficienwhich their processes cies in the use of chloare located. Simply rine can be obtained stated, engineers must by expanding the become stewards for number of processes their products and included in the netprocesses throughout work. In the network Figure 2. Absorption with a regenerable solvent is used to capture toluene and their life cycles. An involving direct chloethyl acetate, which might otherwise be emitted into the atmosphere. introduction to this rination and oxychloTo increase the fraction of the hydrocarbons absorbed, the circulation emerging area is prorination processes, rate of the solvent can be increased, but it will increase energy use and vided by Allen and both processes incoratmospheric emissions of criteria pollutants. The process engineer will Shonnard (2001). porate chlorine into need emission estimation tools to evaluate the potential environmenIntegrating Materthe final product. tal and economic costs associated with different types of emissions. ial and Energy Flows Recently, more exten(Adapted from Allen and Shonnard, 2001) along Supply Chains: sive chlorine networks Industrial Ecology. have emerged linking Chemical processes do not operate in isolation. The products and several isocyanate producers into vinyl chloride manufacturing byproducts of one process serve as raw materials for other cheminetworks (McCoy, 1998). In isocyanate manufacturing, molecucal processes. To understand how the environmental performance lar chlorine is reacted with carbon monoxide to produce phosgene: of a chemical process is governed not only by the design of the process, but also by how the process integrates with other processCO + Cl2 COCl2 es and material flows, consider a classic examplethe manufacture of vinyl chloride. The phosgene is then reacted with an amine to produce an isoBillions of pounds of vinyl chloride are produced annually. cyanate and byproduct hydrochloric acid: Approximately half of this production occurs through the direct chlorination of ethylene. Ethylene reacts with molecular chlorine RNH2 + COCl2 RNCO + 2 HCl to produce ethylene dichloride (EDC). The EDC is then pyrolyzed, producing vinyl chloride and hydrochloric acid: The isocyanate is subsequently used in urethane production, and the hydrochloric acid is recycled. The key feature of the isoCl2 + H2C=CH2 Cl H2C-CH2 Cl cyanate 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 Cl H2C-CH2 Cl H2C=CH Cl + HCl chlorine to hydrochloric acid, but the chlorine is still available for incorporation into final products, such as vinyl chloride, that conIn this synthesis route, 1 mol of hydrochloric acid is produced tain chlorine. A chlorine-hydrogen chloride network incorporating for every mol of vinyl chloride. Considered in isolation, this

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processes and products are beginning to emerge. Chemical engiboth isocyanate and vinyl chloride has been developed in the U.S. neers can and should play a key role in the development of this Gulf Coast. next generation of design tools, which will help to create more Identifying which processes could be most efficiently integrated energy-efficient, mass-efficient, and intricately networked indusis not simple. The design of the ideal network depends on availtrial processesan industrial ecology. able markets, what suppliers 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 Acknowledgment processes that could supply materials, and processes that could use their byproducts. The analysis also should not be limited to chemThe authors gratefully acknowledge the support and insights proical manufacturing. vided by Sharon Austin Continuing with our and Nhan Nguyen of the example of waste U.S. Environmental hydrochloric acid and the Protection Agency. manufacture of vinyl chloride, byproduct Literature cited hydrochloric acid could be used in steel making, or Adriaanse, A., S. byproduct hydrochloric Bringezu, A. Hamacid from semiconductor mond, Y. Moriguchi, E. manufacturing might be Rodenburg, D. Rogich, used in manufacturing and H. Schtz, chemicals. Resource Flows: The Finding productive uses Material Basis of for byproducts is a princiIndustrial Economies, ple that has been used for World Resources decades in chemical manInstitute, Washington, ufacturing. What is relaD.C. (1997). tively new, however, is the Allen, D. T., F. J. Consoli, search for chemical G. A. Davis, J. A. Fava, byproduct uses in indusand J. L. Warren, PubFigure 3 Product life cycles including raw material extraction, materitries that extend far lic Policy Applications al processing, use and disposal steps, as shown along the beyond chemical manuof Life Cycle Assesshorizontal axis. facturing. Chemical engiment, SETAC Press, Process life cycles include planning, research, design, operaneers should take on Pensacola, FL (1998). tion, and decommissioning steps as shown along the vertical design tasks such as manAllen, D. T. and D. R. axis. In both product and process life cycles, energy and aging the heat integration Shonnard, eds., Green materials are used at each stage of the life cycle, and emisbetween a power plant and Engineering: Environsions and wastes are created. an oil refinery, or integratmentally Conscious ing water use between Design of Chemical semiconductor and commodity chemical manufacturing. Such Processes, Prentice Hall, Englewood Cliffs, NJ (2001). design tasks are currently at the brink of our design abilities. To American Institute of Chemical EngineersCenter for Waste make these design tasks as common in the next decades as heat Reduction Technologies (AIChECWRT), Total Cost integration within a process, we will need to broaden our perspecAssessment Methodology, AIChE, New York (2000). tives. We must begin to integrate process design tools from fields Grossmann, I. E. and A. W. Westerberg, Research Challenges in ranging from chemical manufacturing to semiconductor manufacProcess Systems Engineering, AIChE J., 46, 1700 (2000). turing, as well as from pulp and paper processing to polymer recyHarold, M. P. and B. A. Ogunnaike, Process Engineering in the cling. Evolving Chemical Industry, AIChE J., 46, 2123 (2000). McCoy, M., Chlorine Links Gulf Coast Firms, Chem. and Eng. News, 17 (Sept. 7, 1998). Summary U.S. Environmental Protection Agency, The Use of Life Cycle Assessment in Labeling Programs, Office of Pollution Preliminary engineering design tools for assessing, improving, Prevention and Toxics, EPA/742-R-93-003 (1993). and integrating the environmental performance of chemical

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