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Chemical Engineering Chemical Engineering PROFESSIONAL SCIENCE SAMPLER INCLUDING Chapter 4: Green Engineering From Green Techniques for Organic Synthesis and Medicinal Chemistry, Second Edition by Wei Zhang. Chapter 5: Process Intensification in the Chemical Industry: A Review From Sustainable Development in Chemical Engineering Innovative Technologies, First Edition. Edited by Vincenzo Piemonte, et al. Chapter 1: Chemistry for Development From The Chemical Element: Chemistry’s Contribution to Our Global Future. Edited by Javier Garcia-Martinez and Elena Serrano-Torregrosa Green Engineering Christopher L. Kitchens1 and Lindsay Soh2 1 Clemson University, Clemson, South Carolina, USA 2 Chemical and Biomolecular Engineering Department, Lafayette College, Easton, Pennsylvania, USA . Introduction: Green Engineering Misconceptions and Realizations During your career you have likely come across a colleague or co-worker who held the opinion that any greener alternative to a current process, chemical, or product is 1) more expensive, 2) doesn’t work as well, or 3) is only motivated by external regulation [1]. This misconception is a primary argument of those opposing green innovation, but highlights that any greener alternative will not be adopted unless it is economically jus- tified and does not sacrifice function [2]. Examples of such innovation are broad reaching across manyaspects of the chemical industry as evidenced by the Presidential Green Chemistry Challenge Award winners [3]. It must also be realized that 1) the economics must be evaluated over the entire life cycle and 2) it is always better to incorporate greener alternatives in the design stage, rather than having to retrofit existing processes. Often different design stages of chemical processes are conducted independently thus hindering their systemic evaluation and possibly squandering opportunities for improvement. For example, the choice of raw materi- als, solvents, or reaction pathway is done based on operating costs that maximize the economic differential between product and consumables, including energy. If this is done before a rigorous evaluation of the capital and operating costs associated with separations, waste generation and treatment, fugitive emissions, safety measures, and risk assessment, then it is quite possible that a greener and more economical alternative is overlooked. In order to avoid this opportunity loss and not handicap a process design with initial design choices, it is imperative to incorporate both guiding green engineering design principles as well as quantifiable green chem- istry metrics with conventional design tools in the initial design stages [4]. While the economic advantage of a greener alternative may not be evident in preliminary design, advantages may emerge later during risk assess- ment analysis. Risk assessment is a systematic process of evaluating the probability of any event with adverse implications and the potential loss associated with each event, including economic loss. A comprehensive risk assessment by itself requires significant effort, time and expense, thus it is prohibitive to conduct duringthe early stages of a process design. Understanding the potential implications of design choices on risk assessment is reasonable and if done correctly, can streamline the overall design process by avoiding scenarios that require significant risk assessment. This is the concept of inherently safer design; Green Engineering Principle #1 [5]. Green engineering is defined by the U.S. Environmental Protection Agency as “the design, commercializa- tion, and use of processes and products in a way that reduces pollution, promotes sustainability, and minimizes risk to human health and the environment without sacrificing economic viability and efficiency [6].” This is a working definition that has evolved to focus on a risk aversion viewpoint that weighs both human health Green Techniques for Organic Synthesis and Medicinal Chemistry, Second Edition. Edited by Wei Zhang and Berkeley W. Cue. © 2018 John Wiley & Sons Ltd. Published 2018 by John Wiley & Sons Ltd. Green Techniques for Organic Synthesis and Medicinal Chemistry and the environment [7]. The definition also places emphasis on sustainability from an economic standpoint, which reinforces the concept that any green engineering alternative must also be economical. Principles of Green Engineering Complementing the seminal publication by Anastas and Warner that defined the 12 Principles of Green Chemistry [8]. Anastas and Zimmerman later published the 12 Principles of Green Engineering, which are presented in abbreviated form [5]. Each of these benchmark principles focuses on different life-cycle stages of the engineering design or improvement process spanning from raw material and energy sources to end of life; systems design to process intensification. In all, the 12 Principles can be categorized into reducing hazard, increasing efficiency, minimizing excess, and increasing sustainability. Many of the Principles are more straight forward to understand, others are less obvious, such as (3) design for separations, (5) output pulled, (6) reduce complexity, (9) minimize material diversity, and (8) avoid excess capacity. Typically, 70% of the materials and energy in a process are dedicated to separations, and generally theseparationisdesignedbasedontheupstreamprocess.Adesign for separations approach seeks to enhance efficiency by crafting the upstream such that the downstream separation requires less energy and materials. The end result may require increased upstream cost (e.g., in a reactor system), but the reduced separations cost will result in a decreased net cost. The concept of “output pulled” is derived from Le Chatelier’s Principle, where a process should be developed in the direction which exploits equilibrium. In other words, a process will proceed more efficiently along a minimization of the Gibbs free energy, or it is easier to paddle down a river with the current versus against the current. Reducing complexity, minimizing material diversity, and reducing capacity can each be viewed as steps toward risk reduction. In such cases, increased complexity leads to higher probability that an unforeseen adverse event can occur; increased material diversity leads to potential chemical incompatibilities or reduced ability for material reuse; and excess capacity leads to greater potential for accidental spills or releases. The Principles of Green Engineering 1) Strive for inherently nonhazardous materials and energy inputs. 2) Prevent waste rather than treat. 3) Design separations and purifications to minimize energy and materials consumption. 4) Maximize mass, energy, space, and time efficiency. 5) “Output Pulled”rather than “Input Pushed”. 6) Reduce complexity. 7) Design for durability, not immortality. 8) Avoid unnecessary capacity or capability. 9) Minimize material diversity. 10) Integration of energy and material flows. 11) Design for commercial afterlife. 12) Renewable rather than depleting. The 12 Principles of Green Engineering serve as guidelines by which to develop a mindset conducive toward inherently greener products and processes. While these Principles inherently address several conventional design goals – maximizing profits, increasing energy efficiency, and use of safeguards to manage hazards– adherence to these Principles can provide additional guidance toward greener, safer, and more sustainable products or processes. 4 Green Engineering . Green Chemistry Metrics Applied to Engineering A practicing chemical engineer may say: “In my plant we strive to maximize efficiency, recover and recycle solvents and reactants, recover waste heat, use catalysts, and minimize toxic releases to the environment. Are we not Green Engineers?” Reply: YES. These are aspects of Green Engineering that are driven by economics. Now ask yourself: What happens at the product’s end of life? Where are the raw materials sourced from? What happens when an accidental exposure or release does occur? Can we do better? YES. How can we do better? In order to answer this question, we need metrics to be able to perform quantitative evaluation of existing processes or products and new alternatives. A metric is a quantifiable standard of measure that can be used for comparison. Green chemistry metrics can be used to determine if one product or process is “greener” than another (Comparative) or identify aspects of a product or process that can be improved (Improvement). Many green chemistry metrics exist, as discussed in previous chapters; the challenge is to choose the most appropriate. The types of metrics that can be implemented span from very simplistic to extremely complex. Simple met- rics are useful for rapid, transparent, and direct comparisons of similar scenarios, which can be used to easily display advantages of one reaction, process, or product over another. These green chemistry metrics include atom economy, E-factor, effective mass yield, reaction mass efficiency, environmental index, and soon.Con- ventional metrics that are on the same level of complexity include reaction yield, which is a product of reaction conversion and selectivity or cost∑ index. Cost index (CI) is a baseline economic analysis that compares the cost of products to reactants: CI = − v ∗ Cost per pound or mole;wherev isthemassormolestoichiometric factor. Similar to the Green Chemistry metrics, the cost index can be very useful in an initial cursory compar- ison of two very similar scenarios but neglect significant details as
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