OF WES 2 or further information should be addressed to the Permissions Department, John Wiley & Sonjf # s R 77 y Library of Congress Cataloging in 2ublication Data: Reklaitis, G. V., 1942- Introduction to mat ial and energy balances. Includes index. 1. Chemical en, yeering—Mathematies. 2. Mathemat cal optimization, 3. Nonlinear programming. I. Schnei der, Daniel R, IL. ‘ile TPH49.R44 19836200042 ISBN 0-471-04131-9 3400 Printed in the United States of America wo 8 7 6Introduction to Material and Energy Balances G. V. Reklaitis School of Chemical Engineering Purdue University West Lafayette, Indiana 47907 With contributions by Daniel R. Schneider Monsanto Company St, Louis, Missouri ESTE WRd ES BE RESERUA John Wiley & Sons New York Chichester Brisbane ‘Toronto { Singapore 1TO JANINEPREFACE | Steady-state material and energy balance computations are the most frequent type of calculations carried out by all chemical engineers. Yet, in spite of their univer- sality, this class of computations is quite neglected in the chemical engineering curriculum. Unlike the transport, thermodynamics, and reactor design computa- tions, which are taught in a rigorous and systematic fashion, balance calculations are generally presented at a purely intuitive level, usually in the first chemical engineering course, and then only briefly revisited in the senior design course. In the senior course, it is usually assumed that balance calculations are well known to the students; hence, having little systematic knowledge to fall back ‘on, the students bludgeon through the flowsheet calculations required in design projects by sheer persistence. Given the inadequate academic training, it is not surprising therefore that balance calculations continue to be one of the vague arts of the profession. The comprehensive treatment of this subject presented here is an at- tempt to fill this obvious gap in chemical engineering education. The book has three specific goals: \ 1. To provide a thorough exposition of balance equation concepts. 2. To develop a framework for the analysis of flowsheet information and speci- fications. 3. To present systematic approaches for manual and computer-aided solution of balance problems. | The first goal is met with a detailed development of the structure, properties, and interrelationships of species and element balances as well as a comprehensive discussion of both the general energy balance equation and the thermochemical calculations required to evaluate the terms arising in that equation. For instance the homogeneity of the material and energy bal ions is used to exp! the concept of basis and to clarify which v. igned values as bz ‘The species and element balances are developed using the algebraic view of reaction stoichiometry and the rate-of-reaction concept. The latter device considerably sim- plifies the formulation of the balance equations for multiple reactions. The former approach leads directly to the valuable notion of independent reactions, to con- structions for generating such reactions, and to a simple rule for testing the equiv- alence of species and element balances. ‘The energy conservation equation development includes discussion of tradi- nal concepts such as state variables, state functions, and units of measure. In addition, the difficult but central issue of interconversion between the enthalpy, phase distribution, wmperature, pressure, and composition of a system is also: introduced. For simplicity, this discussion is confined either to single species or to vilvill Preface ideal vapor-liquid systems. Moreover, the interconversion computations are re- stricted to the use of the elementary dew point, bubble point, and isothermal flash calculations. Evaluation of the enthalpy function using thermodynamic tables, heat capacity correlations, and heats of transition are also covered in detail. The heat- of-reaction calculations are fully developed using generalized stoichiometry con- structions, and the steady-state energy balance equation is formulated both in the heat-of-reaction and the total enthalpy form. Special attention is directed at the selection of problem reference state and at the use of enthalpy data with different reference values. In short, the sclection of topics addresses all essential consider- ations that arise in the selection, formulation, and evaluation of balance equations. ‘The second goal, of providing a framework for the analysis of process infor- mation, is achieved by extensive use of a “degree-of-freedom” analysis. ‘Th essentially an orderly way of analyzing the information and counting the variables and balance equations associated. with each unit in the process as well as with the entire process as a whole. It provides a systematic way for determining whether the problem is underspecified, overspecified, or correctly specified. Such a system- atic analysis is extremely important in design applications, in which, by definition, the problem is underspecified, as well as in process analysis applications, in which overspecified problems often must be dealt with—usually by deleting inaccurate or superfluous data, The degree-of-freedom analysis also provides criteria for se- lecting the location of the basis for the calculations, for determining the order in which manual unit calculations should be executed, for identifying whether the material balances can be solved independently of the energy balances, and for determining whether or not carrying unknown variables from unit to unit will be required. Together with the equation-solving and root-finding techniques included in the text, the degree-of-freedom analysis thus serves to fulfill the third goal, that of providing a logical procedure for solving balance equations by manual means. In addition to manual calculation methods, computer-oriented procedures for solving balance problems are also analyzed. The widely used sequential modular strategy is discussed and is contrasted to the simultaneous or equation-oriented approach. The discussion of computer-oriented strategies using flowsheets modeled in terms of elementary material balance :nodules allows the key issues of process flowsheeting to be introduced in a straightforward manner. Thus, the selection of tear streams, treatment of nonstandard specifications (or control blocks), an in- troduction to elementary multivariable equation-solving and sequencing methods, as well as a comparative examination of the sequential and simultaneous strategies can all be given purely in terms of material balance problems. After the basic energy balance chapters, computer-oriented strategies are reconsidered, and it is shown how the elementary material balance modules can be extended to accom- modate energy balances. Thus, the way is pointed to the more complex unit op- eration modules used in practical flowsheeting systems. The discussion of modules involving energy balances also suggests the need for computerized storage and use of thermochemical and other physical properties data. An introduction is therefore given to computerized physical properties estimation systems. However, the scope of the exposition is confined to the properties, data, and methods discussed inPreface Ix considering manual calculations. The text thus meets the third goal by giving an elementary but thorough presentation of the various approaches for solving full- scale flowsheet problems via the computer. | Finally, in order to illustrate the problem-solving methodology and {o expose the student to realistic chemical engineering applications, the text includes a range of multiunit process examples. These examples encompass not only conventional chemical processes such as the ethylene oxide/glycol plant, the ammonia process, the acetic anhydride process, and the Claus. process, but also novel processes currently under development, for instance, those for the conversion of coal to gases and liquids, These problems are described in adequate detail to be understandable within the limited engineering vocabulary of the sophomore engineering student, ‘The level of the presentation is aimed at the sophomore chemical engineering student and uses mathematical concepts familiar to him or her: derivatives of nonlinear functions and manipulations involving linear equations. All additional mathematical methodology required in the exposition, for example, root-finding methods and algebraic properties of linear equations, is presented as needed so that its utility and applicabitity are immediately demonstrated in the context of the discussion. The computer-oriented portions of the exposition contain no program- ming details so that emphasis can be placed on the underlying methodoldgy rather than on code implementation. A FORTRAN program listing and a description of a rudimentary modular balance program are given in the solution manual for use at the instructor's option, i Although this book is intended for the first course in chemical engineering, its scope is sufficiently broad that the entire contents might not be covered in one course. Cuts can be instituted as follows. First, Section 1.3 can be assigned to the student as review. Chapters 2 and 3 should be discussed in their entirety. Section 4.3 can be covered selectively, and Section 5.2.2 can be omitted withoitt loss of continuity. Chapter 6, 7, and 8 should be covered in detail. However, in Chapter 9, Section 9.2.2 can be omitted without loss of continuity. The book includes nearly 200 worked examples many of which involve multiunit flowshcets of some com- plexity. It is normally possible to discuss only about one third of these examples in class. Moreover, while it is desirable to explain the details of the simpler ex- amples, for the larger problems it is more important to focus on the strategy of solution and to leave the details for reading outside of the lecture room: Finally, the more advanced material in Chapters 3 and 4 as well as the discussion and implementation of the computer-oriented approaches treated in Chapters 5 and 9 are suitable topics for the process design course cither as review or as supplement, ‘Thus, the text can both serve as a primary reference for the introductory chemical engineering course and as a supplementary reference for the design course. This work is really the result of the confluence of many sources and influences the complete acknowledgment of which is quite impossible. The linear algebraic treatment of stoichiometry clearly is extracted from the classical work of Aris and Denbigh. Elements of the degree-of-freedom analysis have been used sporadically by many chemical engineers: whoever the originator, to him goes the credit. The comprehensive book Material and Energy Balance Computations by Ernest Henleyx Preface and Edward Rosen, which assuredly was ahead of its time, has been an important factor influencing the choice of topics. The very idea of writing this book must be credited to Daniel R, Schneider, who, while a colleague at Purdue, was a partner in evolving the basic approach, in developing the overall outline of the book, and even in formulating some of the examples. The text itself has benefited materially from the critical comments offered by Dan Schneider and by Profs. Lowell B. Koppel, Robert G. Squires, and Roger E, Eckert, Important clarifications and suggestions were also contributed directly by Profs. Alden Emery and Ferhan Kayihan and indirectly by the numerous teaching assistants and even more nu- merous students whose questions and skepticism helped to reshape the manuscript over the past seven years. Finally, 1 am thankful for the supportive atmosphere created by my colleagues in the School of Chemical Engineering and for the patient, conscientious efforts of the clerical staff of the School in typing and processing a succession of drafts. G. V. Reklaitis.CONTENTS CHAPTER 1 INTRODUCTION 4.1. THE ROLE OF THE CHEMICAL ENGINEER 1.2 THE ROLE OF BALANCE CALCULATIONS 7 1.3 REVIEW OF BASIC CONCEPTS 1 1.3.1. The Conservation Principles 12 1. 2 Chemical Stoichiometry [44 | 1.3.3 Equation-Solving Concepts 18 1.3.4 Dimensional Quantities and Their Manipulation 24 1.4. PREVIEW OF SUBSEQUENT CHAPTERS at | CHAPTER 2 MATERIAL BALANCES IN NONREACTING | ‘STEMS 33 sy ADQ ZBL 2.1. FORMULATING THE MATERIAL BALANCE PROBLEM | 33 2.1.1 Material Balance Variables . 34 Balance Equations and Their Properties | 37 Balance Information 1 42 2.2 ANALYSIS OF THE MATERIAL BALANCE PROBLEM | 49 2.2.1 The Degree of Freedom + 50 2.2.2 Solution Strategy 56 2.3 SYSTEMS INVOLVING MULTIPLE UNITS. | 60 2.3.1 Independent Sets of Balance Equations | 60 2.3.2. Degree-of-Freedom Analysis / 65 2.3.3. Special Multiunit Configurations | 69 2.3.4 Strategy of Solution | o7 2.4 SUMMARY , 85 CHAPTER 3 SPECIES BALANCES IN REACTING SYSTEMS 106 3.1 SPECIES BALANCES WITH A SINGLE CHEMICAL REACTION 107 3.1.1. The Rate of Reaction Concept | 109 3.1.2. The Limiting Reactant and Conversion | 112 3.1.3 Degree-of-Freedom Analysis 114 xlxil Contents 3.2 SPECIES BALANCES WITH MULTIPLE CHEMICAL REACTIONS 3.2.1 Generalized Stoichiometry 3.2.2. The Fractional Yield 3.2.3 Degree-of-Freedom Analysis 3.3. THE ALGEBRA OF MULTIPLE CHEMICAL REACTIONS. 3.3.4 Linear Independence of Rea 3.3.2. Determination o 3.3.3 Independent Spe 3.4. SUMMARY CHAPTER 4 ELEMENT BALANCES 4.1. THE ELEMENT BALANCE EQUATIONS 4.1.1 The Atom Matrix and General Balance Equations 4.1.2. The Algebra of Element Balances 4,13 Degree-of-Freedom Analysis 4.2 THE RELATIONSHIP BETWEEN ELEMENT AND SPECIES BALANCES 4.2.1 Nonreacting Systems 4.2.2 Reacting Systems 4.2.3. The Maximum Number of Independent Reactions 4.3, APPLICATIONS INVOLVING CHEMICAL PROCESSING OF FOSSIL FUELS 4.3.1 Fossil Fuels and Their Constituents 4.3.2. Characterization of Fossil Fuels 4.3.3. Major Types of Chemical Processing Operations for Fossil Fuels 4.4 CONVERSION OF ELEMENT BALANCES TO SPECIES BALANCES 4.4.1 The Relation between Atom Matrix and Reaction Stoichiometry 4.4.2. Construction of a Set of Independent Reactions 4.4.3. Application to Systems with Incomplete Stoichiometry 4.5 SUMMARY CHAPTER 5 MATERIAL BALANCES IN PROCESS FLOWSHEETS 5.1. STRATEGY FOR MANUAL COMPUTATIONS 5.1.1 Sequencing with Complete Solution 5.1.2 Sequencing with Partial Solution 5.1.3 Root-Finding Methods 124 126 133 137 149 150 154 161 164 187 188. 190 196 200 209 210 218 220 220 222 224 236 237 240 245, 251 264 264 265 267 2775.2 STRATEGY FOR MACHINE COMPUTATIONS 5.2.1 The Sequential Solution Si Contents Strategy 5.2.2. The Simultaneous Solution Strategy 5.3. SUMMARY CHAPTER 6 INTRODUCTION TO ENERGY BALANCES 6.1 DEFINITION OF TERMS 6.2 FORMS OF ENERGY ASSOCIATED WITH MASS. 6.3 FORMS OF ENERGY IN TRANSITION 6.4 SYSTEMS OF UNITS 6.5 THE LAW OF CONSERVATION OF ENERGY 6.5.1. The Basic Closed-System 6.5.2. Superimp Balance Equation 6.5.3 The General Conservation Equation 6.5.4 ‘The Enthalpy Function 6.6 SUMMARY CHAPTER 7 ENERGY BALANCES FOR NONREACTING SYSTEMS 7.1 CHARACTERIZATION OF THE STATE OF A SYSTEM 7.1.1 The Phase Rule 7.1.2. Single-Component Systems 7.1.3 Multicomponent, Multiph: 7.2 ENERGY BALANCES USING TABULAR THERMODYNAMIC. DATA 7.2.1 The Steam Tables 7.2.2. Energy Balance Appl 7.2.3. Energy Balance Applica 7.3. ENERGY BALANCES WITHOUT COMPLETE ase Systems ions: Closed Systems ions: Open Systems THERMODYNAMIC TABLES 73.1, Heat Capacities 7.3.2 Heats of Phase Transition 7.3.3. Enthalpy of Mixtures 7.4 ANALYSIS OF NONREACTING SYSTEMS 7.4.1 The Energy Balance Variables 7.4.2. Properties of the Energy Balance Equations 7.4.3. Degree-of-Freedom Analysis 7.5 SUMMARY xii 286 1286 4332 1344 ‘370 (371 |375 (377 1380 | 385 1385 ||390 |} 393 | 395 | 399 | 400 (400 1401 404 | 413 1415 419 424 | 434xiv Contents. CHAPTER 8 ENERGY BALANCES FOR REACTING SYSTEMS 8.1 THE HEAT-OF-REACTION CONCEPT 8.2 HEAT-OF-REACTION CALCULATIONS. 8.2.1 Correction of AH, for T, P, and Phase 8.2.2 Heats of Formation and Their Use 8.2.3. Heats of Combustion and Their Use 8.3 ENERGY BALANCES WITH SINGLE CHEMICAL REACTION 8.3.1. The Single-Input/Single-Output Case 8.3.2 Alternate Forms of the Balance Equation 8.4 ENERGY BALANCES WITH MULTIPLE CHEMICAL. REACTIONS 8.5 ENERGY BALANCES WITH UNKNOWN STOICHIOMETRY 8.6 DEGREE-OF-FREEDOM ANALYSIS 8.6.1 Single-Unit Systems 8.6.2 Multiunit Systems 8.7 SUMMARY CHAPTER 9 MATERIAL AND ENERGY BALANCES IN PROCESS FLOWSHEETS 9.1 STRATEGY FOR MANUAL CALCULATIONS 9.1.1 The Single-Unit Case 9.1.2 The Multiunit Case 9.2 STRATEGY FOR MACHINE COMPUTATIONS 9.2.1 The Sequential Solution Strategy 9.2.2. The Simultaneous Solution Strategy 9.3 SUMMARY APPENDIX PHYSICAL PROPERTIES DATA INDEX 478 478 480 481 486 489 489 492 496 500 510 510 Sit 523 537 539 540 552 573 574 592 613 635 673Introduction to Material and “Energy BalancesCHAPTER 1 ! Introduction The objective of this book is to develop the concepts and solution methods that are required to determine the distribution of material and energy flows in a chemical process. These so-called material and energy balance calculations are both the most elementary and the most frequently performed computations carried out by chem- ical engineers. They are as basic a tool of the chemical engineer as are ledger-book balancing methods to an accountant. This book will help the reader to develop a mastery of this basic tool both for use in manual calculations as well as for imple- mentation on computers. The consideration of solution strategies appropriate for computer implementation is given special attention because the use of computers to perform “bread-and-butter” balance calculations is growing in the field and is clearly the way of the future. However, our study of computer-oriented strategies is at the conceptual level, stopping short of delving into coding details. Hénce, prior mastery of any specific programming language is not a prerequisite. | In this first chapter, we begin with a discussion of the role of chemical engineers in general and of the place of balance calculations both in the work of the profes- sional engincer as well as in the curriculum required of B.S. Chemical Engineering graduates. In the following section, we review some of the basic concepts derived from chemistry, physics, and mathematics that are employed in balance calcula tions. The chapter concludes with a preview of the organization of the contents of the remainder of the text. | | 1.1 THE ROLE OF THE CHEMICAL ENGINEER | ‘The two primary functions of the chemical engineer are to develop and design processes that convert raw materials and basic energy sources into desired chemical products or higher energy forms and to improve and operate existing processes so that they become as safe, reliable, efficient, and economical as possible. The design function involves the synthesis of appropriate sequences of chemical and physical transformation steps and the selection of the conditions under which these trans- formations are to take place given basic information about the chemical reactions 1 {