COMPUTER MODELING FOR ENVIRONMENTAL MANAGEMENT SERIES COMPUTER SIMULATED PLANT DESIGN for WASTE MINIMIZATION/POLLUTION PREVENTION © 2000 by CRC Press LLC PUBLISHED TITLES Computer Generated Physical Properties Stan Bumble COMPUTER MODELING FOR ENVIRONMENTAL MANAGEMENT SERIES Computer Simulated Plant Design for Waste Minimization/Pollution Prevention Stan Bumble FORTHCOMING TITLES Computer Modeling and Environmental Management William C. Miller © 2000 by CRC Press LLC LEWIS PUBLISHERS Boca Raton London New York Washington, D.C. COMPUTER MODELING FOR ENVIRONMENTAL MANAGEMENT SERIES Stan Bumble, Ph.D. COMPUTER SIMULATED PLANT DESIGN for WASTE MINIMIZATION/POLLUTION PREVENTION This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe. © 2000 by CRC Press LLC Lewis Publishers is an imprint of CRC Press LLC No claim to original U.S. Government works International Standard Book Number 1-56670-352-2 Library of Congress Card Number 99-057318 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Library of Congress Cataloging-in-Publication Data Bumble, Stan. Computer simulated plant design for waste minimization/pollution prevention / Stan Bumble. p. cm. (Computer modeling for environmental management series) Includes bibliographical references and index. ISBN 1-56670-352-2 (alk. paper) 1. Chemical plants Design and construction Computer simulation. 2. Chemical plants Environmental aspects Computer simulation. 3. Waste minimization Computer simulation. 4. Pollution Computer simulation. I. Title. II. Series. TP155.5.B823 2000 660 ′ .28 ′ 286 —dc21 99-057318 Preface When I asked an EPA repository of information for any references on the subject of this book, I was given a very swift and professional reply: “There isn’t any.” This was, of course, counter to my experience of years working on this subject and collecting huge numbers of papers and referrals that detailed progress and enthusiasm for my attempts. A sum- mary of these findings is in this book. I think it true that the kind of person who will be successful in finding results or creating results in Computer Simulated Plant Design for Waste Minimi- zation/Pollution Prevention is not the average kind of scientist or engineer one finds today. Indeed, the proper person for this work is a multidisciplined computer scientist, chemical engineer, chemist, mathematician, etc. There are not many people like that today, particularly creative ones. However, you will meet some in this book. The book is divided into five parts and each part has a number of sections. The title of the parts describes the main theme of the part but not all of the included matter. The first part is entitled Pollution Prevention and Waste Minimization. It begins with descriptions of process flowsheets and block flow diagrams. It then describes pollution prevention, cost, and energy. It describes control of exhausts from processes or, in other words, reduction of emissions. There is then a very brief description of the design or simulation of a plant so the reader can get the flavor of it before pollution prevention is discussed more thoroughly. Reaction systems and separation systems appropri- ate for waste minimization are then introduced. Con- tinuing in this manner, computer simulation as it pertains to pollution prevention is introduced. The Inorganic Chemical Industry Notebook Section from EPA is then shown as an example. The important introduction to models is introduced next and this is systematized with process models and simulation. Process information and waste minimization are tied together. The very important cost factors are dis- cussed with waste minimization and Department of Energy (DOE) processes. A number of sections on pollution prevention then occur and a discussion proceeds on tools for P2. A discussion of the redesign of products and pro- cesses follows. A very proper set of results for the environment, health, and safety in the early design phases of a process is presented. An interesting article is summarized that correlates the size of plants and the exposure to pollution. The work on the motivation for pollution prevention among top executives in the company is very educational. This is also true of the article on why the reason for pollution prevention has not been more favorably received publicly. A description of a graduate student’s work on a plantwide controllability and flowsheet structure for complex continuous plants is shown. A 3D Design, 3D chemical plant program is described. A computer-aided flowsheet design and analysis for nuclear fuel reprocessing is also de- scribed. Conceptual designs of “clean processes” are shown as well as the development of tools to facilitate the design of plants that generate as little pollution as possible. Computer Simulated Plant Design for Waste Minimization/Pollution Prevention and flowsheet tools for spreadsheets are shown. Integrated synthe- sis and analysis of chemical process designs using heuristics in the context of pollution prevention are studied. Also presented are model-based environ- mental sensitivity analysis for designing a clean process plant. Ways to reduce gas emissions in util- ity plants and elsewhere are shown. Upsizing or inputting the waste of one plant into another is strongly urged. This is further discussed for zero emissions where plants are clustered together. Permix is a reactor design, from SRI, which helps pollution prevention. Batch chromatography is a technique that can help develop optimum processes. There are P2 opportunities that can be identified from the various sectors mentioned before. Excerpts on waste minimization are included from the latest Federal Register. The definitions of bioaccumulation, persistence, and toxicity are discussed as they will be used to spotlight the worst chemical compounds. © 2000 by CRC Press LLC © 2000 by CRC Press LLC The ATSDR section concentrates on health. There is a chapter on OSHA software. The idea of having communities monitor toxic compounds is discussed (EMPACT). The very fine work of the EDF (Environ- mental Defense Fund) in matters of health and Scorecard is reviewed. Screening for endocrine disruptors is discussed. A paper on reducing risk for man and animals is included. Risk is then discussed as a “human science.” The IPPS (industrial pollution projection system) is a way to compare pollution country by country. Part II begins with a sequential set of chapters that prepares the reader for chapters on mathematical methods considered or used in computer programs for pollution prevention and waste minimization. They are in order: Linear Programming, The Simplex Model, Quadratic Programming, Dynamic Program- ming, Combinatorial Optimization, Elements of Graph Theory, Organisms and Graphs, Trees and Search- ing, Network Algorithms, Extremal Programs, Trav- eling Salesman Problem, Optimization Subject to Diophantine Constraints, Integer Programming, MINLP (Mixed Integer Nonlinear Programming), Clus- tering Methods, Simulated Annealing, Tree Anneal- ing, Global Optimization Methods, Genetic Program- ming, Molecular Phylogenetic Studies, and Adaptive Search Techniques. It is to be noted that Organisms and Graphs is included in Part II, Mathematical Methods, although it is a little different than the other methods cited. It refers to processes in living organisms that are to be compared to processes or flowsheets in chemical plants. Advanced mathematical techniques are used in RISC-Lenz work and also the work of Drs. Friedler and Fan. Scheduling of processes for waste minimi- zation is for batch and semicontinuous processes. Multisimplex can optimize 15 controls and responses at once. Extremal optimization provides high quality solutions to hard optimization problems,. Petri nets and Synprops compare two processes and show the graph model and concurrent processing together. Petri net-digraph models are for automating HAZOP analyses of batch process plants. DuPont CRADA is a description of neural network controllers for chemi- cal process plants. KBDS is about design history to support chemical plant design, and dependency- directed backtracking helps when objects, assump- tions, or external factors have changed previously in a design. Interactive collaborative environments al- low different people at far removed places to work on the same drawings. The control kit for O-matrix is a control system without the need for programming, the clean process advisory system (CPAS) is a sys- tem of software tools for design information on clean techniques for pollution prevention to conceptual process and product designers when needed. Fi- nally, nuclear applications are discussed. Also, it is important to have a process for viewing of the envi- ronmental impact at the beginning of the design process. There are tools to accomplish this such as OPPEE (Optimization for Pollution Prevention, and Energy and Environment) as well as CPASTM. Fol- lowing is a discussion of computers, as they are very important in this work. The future will lead to better computers for doing the work needed for pollution prevention and waste minimization. Part III is entitled Computer Programs for Pollu- tion Prevention and/or Waste Minimization. It first discusses such programs as HYSYS, ICPET, and HYSIS. Then a discussion of Green Design describes environmentally benign products. There is then a study of chemicals and materials from renewable resources. One of the software companies into simu- lation software by the name of Simulation Sciences is then discussed. Two federal agencies, NFS and EPA, are interested in providing funds for deserving applied research for environmentally benign meth- ods in industrial processes, design, synthetic pro- cesses, and products used in manufacturing pro- cesses. BDK is then discussed, and is an integrated batch development. An ingenious and very useful program called Process Synthesis is then introduced. It optimizes the structure of a process system, while minimizing cost and maximizing profit and will be discussed further later. Synphony is the commercial name for the process synthesis program that is now available. It determines all possible flowsheets from all possible operating units and raw materials for a given product and ranks these. The following pro- grams are then discussed: Aspen, CAPD (Computer- Aided Process Design), work at CMU, Silicon Graph- ics/Cray Research, work by Floudas, etc. Work on robust self-assembly using highly designable struc- ture and self-organizing systems are then described. The work of El-Hawagi and Spriggs on Mass Integra- tion is then given prominence. The synthesis of mass energy integration for waste minimization via in-plant modification then follows naturally. A very clever scheme for the whole picture of environmen- tally acceptable reactions follows. Work concerning pollution prevention by reactor network synthesis is outlined. LSENS is the NASA program for chemical kinetics. It was the first of its kind and DOE’s pro- gram followed. Chemkin was developed at Sandia and is used by many people. It was instrumental in the application to NOx chemistry and has a huge library of thermodynamic and kinetic data, but uses the NASA format. There follows a discussion of what Chemkin can do. Multiobjective Optimization is a continuous optimizer and performs waste minimiza- tion. Risk Reduction through Waste Minimizing Pro- © 2000 by CRC Press LLC cess Synthesis follows. It combines process design integration, risk reduction, waste minimization and Chemkin. Kineticus is a program written by a gradu- ate student at Drexel University. It can perform similar operations to Chemkin. SWAMI (Strategic Waste Minimization) from EPA enhances process analysis techniques and identifies waste minimiza- tion techniques. Super Pro is a program that designs manufacturing processes with environmental con- straints. P2-Edge software helps engineers and de- signers incorporate pollution prevention into the design stage. CWRT is a program for aqueous efflu- ent stream pollution prevention design options. The OLI program ESP (Environmental Simulation Pro- gram) enhances the productivity of engineers and scientists (it is a steady state program). Process Flowsheeting and Control has multiple recycles and control loops. Environmental Hazard Assessment for Computer-Generated Alternative Syntheses is the general Syngen program for generation of short- est and least costly synthesis paths. The computer generated wastewater minimum program in a dairy plant is described. A LCA (Life Cycle Analysis) Pro- gram is described. Minimization of free energy (for chemical equilibrium) and free radicals are discussed. A pollution prevention process modification using on-line optimization is described. Genetic algorithms for generation of molecules is outlined. Finally, cod- ing theory, cellular optimization, Envirochemkin, and the chemical equilibrium program are used together as the best among alternatives. Part IV is entitled Computer Programs for the Best Raw Materials and Products of Clean Processes. The first section describes how regression is used with much data to predict physical properties. Later this is extended to Risk Based Concentrations. The prop- erties are predicted from chemical groups. This method is used in a spreadsheet and is tied in with an optimization scheme, and the whole program is called SYNPROPS and used to replace toxic solvents with benign solvents with the same physical proper- ties. There is toxic ignorance for almost 75% of the top-volume chemicals in use. However, SYNPROPS (from groups) can yield MCL, tap water, ambient air, and commercial/industrial/residential soil risk based concentrations. There is then a study of drug design followed by a discussion of a source of pollution: aerosols. A program called Computer-Aided Molecu- lar Design (CAMD) is discussed. An applied case is described; Texaco Chemical Company plans to re- duce HAP emissions through an early pressure re- duction program by vent recovery system. The work of Drs. Fan and Friedler is introduced with a de- scription of the design of molecules with desired properties by combinatorial analysis. Some of the extensive mathematical background needed for this follows. There then follows another method which is called Automatic Molecular Design Using Evolution- ary Techniques. This uses genetic software tech- niques to automatically design molecules under con- trol of a fitness function within the realm of nanotechnology. Algorithmic generation of feasible partitions returns us to the method of Fan and Friedler. Testsmart promotes faster, cheaper, and more humane lab tests without cruelty to animals and also uses SAR techniques to obtain toxicity data. European Cleaner Technology Research, Cleaner Manufacturing in the European Union in- volving substitution, minimization, etc. is described and Cleaner Synthesis is discussed. This finds an alternate, cleaner synthesis rather than dealing with after-effects. THERM is introduced. This is a very useful program that derives thermodynamic func- tions from groups, puts them in NASA format for use in Chemkin and LSENS, and also obtains thermody- namic functions for reactions. Design trade-offs for pollution prevention are then discussed, as is the shift of responsibility to industry with pollution prod- uct defects. Programming waste minimization within a process simulation program aims at eliminating pollution at the source. The discussion leads to product and process design tradeoffs for pollution prevention. This entails integrating multiobjective design optimization with statistical quality control and lifecycle analysis. Incorporating pollution pre- vention in the U.S. Department of Energy Design Projects is next. This raises awareness and provides specific examples of pollution prevention design opportunities. A description of PMN (Pre Manufac- turing Notice) within TSCA follows. There is then a short article on why pollution prevention founders. ICPET (Institute for Chemical Process and Environ- mental Technology) is described as supplying inno- vative computer modeling and numerical techniques. The programs HYSYS, IVPET, and HYSIS are then discussed. Cost effective optimization is highlighted. Pinch technology as part of process integration and the effective use of heat is described. The Geographic Information System is shown as important to many parts of environmental work. Chronic environmen- tal effects are included in the Health chapter. The EDF Scorecard, which tracks pollution and its causes in many geographies has had large impact. Also, HAZOP and process safety identifies hazards in a plant and what causes it. Safer by Design is a study about making plants safer by design. Design theory and methodology includes three parts: product and process design tradeoffs for pollution prevention, pollution prevention and control, and integration of environmental impacts into product design. Part V is entitled Pathways to Prevention. It opens with a similarity between the Grand Partition Func- © 2000 by CRC Press LLC tion of Statistical Mechanics and the mass and en- ergy balance of chemical engineering. Then part of the data for mechanisms from the Department of Chemistry from the University of Leeds is shown. Blurock’s extensive Reaction program is then de- scribed. R & D concerning catalytic reaction tech- nology controlling the efficiency of energy and mate- rial conversion processes under friendly and environmental measures is shown. An article for building the shortest synthesis route is included. A description of how DuPont controls greenhouse emissions is given (for at least one plant). Another article describes how software simulations lead to better assembly lines. A theoretical connection be- tween equations of state and connected irreducible integrals as well as the mathematics of generating functions is shown. An article on ORDKIN, a model of order and kinetics for the chemical potential of cancer cells is reproduced. Another article shows what chemical engineers can learn from nature as to isolation versus interaction in research. There is also a description of design synthesis using adaptive search techniques and multicriteria decision analy- sis. The Path Probability method is shown with ap- plication to environmental problems. The method of steepest descents is shown. The Risk Reduction Laboratory/ Pollution Prevention Branch Research (RREL/PPRB) is discussed. The PPRB is a project that develops and demonstrates cleaner production technologies, cleaner products and innovative ap- proaches to reducing the generation of pollutants in all media. © 2000 by CRC Press LLC The Author Stan Bumble, Ph.D., has guided research, develop- ment, and engineering at DuPont and Dow Corning with computer programs that optimized the best products and properties. He has used computer programs for assisting the U.S. government with the development of their missile program and with the recovery of disaster victims. He has helped (with the assistance of computers) the U.S. Department of Justice and the Environmental Protection Agency at many hazardous sites such as Love Canal. © 2000 by CRC Press LLC Table of Contents Part I. Pollution Prevention and Waste Minimization 1.1Chemical Process Structures and Information Flow 1.2Analysis Synthesis & Design of Chemical Processes 1.3Strategy and Control of Exhausts 1.4Chemical Process Simulation Guide 1.5Integrated Design of Reaction and Separation Systems for Waste Minimization 1.6A Review of Computer Process Simulation in Industrial Pollution Prevention 1.7EPA Inorganic Chemical Industry Notebook Section V 1.8 Models 1.9Process Simulation Seen as Pivotal in Corporate Information Flow 1.10Model-Based Environmental Sensitivity Analysis for Designing a Clean Process Plant 1.11Pollution Prevention in Design: Site Level Implementation Strategy For DOE 1.12Pollution Prevention in Process Development and Design 1.13Pollution Prevention 1.14Pollution Prevention Research Strategy 1.15Pollution Prevention Through Innovative Technologies and Process Design at UCLA’s Center for Clean Technology 1.16Assessment of Chemical Processes with Regard to Environmental, Health, and Safety Aspects in Early Design Phases 1.17Small Plants, Pollution and Poverty: New Evidence from Brazil and Mexico 1.18When Pollution Meets the Bottom Line 1.19Pollution Prevention as Corporate Entrepreneurship 1.20Plantwide Controllability and Flowsheet Structure of Complex Continuous Process Plants 1.21Development of COMPAS 1.22Computer-Aided Design of Clean Processes 1.23Computer-Aided Chemical Process Design for P2 1.24LIMN-The Flowsheet Processor 1.25Integrated Synthesis and Analysis of Chemical Process Designs Using Heuristics in the Context of Pollution Prevention 1.26Model-Based Environmental Sensitivity Analysis for Designing a Clean Process Plant 1.27Achievement of Emission Limits Using Physical Insights and Mathematical Modeling 1.28Fritjof Capra’s Foreword to Upsizing 1.29ZERI Theory 1.30SRI’s Novel Chemical Reactor - PERMIX 1.31Process Simulation Widens the Appeal of Batch Chromatography 1.32About Pollution Prevention 1.33Federal Register/Vol. 62, No. 120/Monday, June 23, 1997/Notices/33868 1.34EPA Environmental Fact Sheet, EPA Releases RCRA Waste Minimization PBT Chemical List 1.35ATSDR 1.36OSHA Software/Advisors 1.37Environmental Monitoring for Public Access and Community Tracking 1.38Health: The Scorecard That Hit a Home Run 1.39Screening and Testing for Endocrine Disruptors 1.40Reducing Risk 1.41Risk: A Human Science 1.42IPPS [...].. .Part II Mathematical Methods 2 .1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2 .10 2 .11 2 .12 2 .13 2 .14 2 .15 2 .16 2 .17 2 .18 2 .19 2.20 2. 21 2.22 2.23 2.24 2.25 2.26 2.27 2.28 2.29 2.30 2. 31 2.32 2.33 2.34 2.35 2.36 Linear Programming The Simplex Model Quadratic Programming Dynamic Programming Combinatorial... HAZOP and Process Safety Safer by Design Design Theory and Methodology Part V Pathways to Prevention 5 .1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5 .10 5 .11 5 .12 5 .13 5 .14 5 .15 5 .16 The Grand Partition Function A Small Part of the Mechanisms from the Department of Chemistry of Leeds University REACTION: Modeling Complex Reaction Mechanisms Environmentally Friendly Catalytic Reaction Technology Enabling Science... Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Figure Figure Figure Figure 16 17 18 19 Toxicity vs Log (Reference Concentration) Parallel Control Series Control Feedback Control A Simple Series Circuit The Feeding Mechanism Organisms and Graphs P-graph of Canaan Geneology Made by Papek Program Example and Matrix Representation... Simulator Reckoning on Chemical Computers Part III Computer Programs for Pollution Prevention and/or Waste Minimization 3 .1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3 .10 3 .11 3 .12 3 .13 Pollution Prevention Using Chemical Process Simulation Introduction to the Green Design Chemicals and Materials from Renewable Resources Simulation Sciences EPA/NSF Partnership for Environmental Research BDK-Integrated Batch Development... Process Design and Simulations Robust Self-Assembly Using Highly Designable Structures and Self-Organizing Systems Self-Organizing Systems Mass Integration Synthesis of Mass Energy Integration Networks for Waste Minimization via In-Plant Modification © 2000 by CRC Press LLC 3 .14 3 .15 3 .16 3 .17 3 .18 3 .19 3.20 3. 21 3.22 3.23 3.24 3.25 3.26 3.27 3.28 3.29 3.30 3. 31 3.32 3.33 3.34 Process Desig Pollution... Design for Environmentally and Economically Sustainable Dairy Plant Life Cycle Analysis (LCA) Computer Programs Pollution Prevention by Process Modification Using On-Line Optimization A Genetic Algorithm for the Automated Generation of Molecules Within Constraints WMCAPS Part IV Computer Programs for the Best Raw Materials and Products of Clean Processes 4 .1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4 .10 4 .11 4 .12 ... 4 .1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4 .10 4 .11 4 .12 4 .13 4 .14 4 .15 4 .16 4 .17 4 .18 4 .19 4.20 4. 21 4.22 4.23 4.24 4.25 4.26 4.27 4.28 Cramer’s Data and the Birth of Synprops Physical Properties form Groups Examples of SYNPROPS Optimization and Substitution Toxic Ignorance Toxic Properties from Groups Rapid Responses Aerosols Exposed The Optimizer Program Computer Aided Molecular Design (CAMD): Designing... Chemkin Computer Simulation, Modeling and Control of Environmental Quality Multiobjective Optimization Risk Reduction Through Waste Minimizing Process Synthesis Kintecus SWAMI SuperPro Designer P2-EDGE Software CWRT Aqueous Stream Pollution Prevention Design Options Tool OLI Environmental Simulation Program (ESP) Process Flowsheeting and Control Environmental Hazard Assessment for Computer- Generated... c=2.5 Order-Disorder, c=3 p/p0 for Rhombus u/kT vs Occupancy Activity vs Theta F/kT: Bond Figure Probability vs Theta, c = 2.77 Probability vs Theta, c = 3 d vs Theta d for Rhombus Metastasis/Rhombus A Fault Tree Network Selected Nonlinear Programming Methods Trade-off Between Capital and Operating Cost for a Distillation Column Structure of Process Simulators Acetone-Formamide and Chloroform-Methanol... and are therefore usually not included in conceptual process designs Difficulties in evaluating environmental performance, needed for summarizing flow-sheet information, include (1) relevant properties of chemicals (toxicity, environmental degradation constants) are not readily available to chemical engineers in process simulators, chemical process design handbooks, etc.; (2) location-specific knowledge . Bumble COMPUTER MODELING FOR ENVIRONMENTAL MANAGEMENT SERIES Computer Simulated Plant Design for Waste Minimization/Pollution Prevention Stan Bumble FORTHCOMING TITLES Computer Modeling and Environmental. Corporate Information Flow 1. 10Model-Based Environmental Sensitivity Analysis for Designing a Clean Process Plant 1. 11Pollution Prevention in Design: Site Level Implementation Strategy For DOE 1. 12Pollution. Number 1- 5 667 0-3 5 2-2 Library of Congress Card Number 9 9-0 57 318 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Library of Congress Cataloging-in-Publication