Chemical Process Principles

1159 Pages·2016·30.41 MB·English

by  Hougen O.A.

CHEMICAL PROCESS PRINCIPLES
ADVISORY BOARD
For Books in Chemical Engineering
T. H. CHILTON, Chem. E.
Engineering Department, Experimental Station,
E. I. du Pont de Nemours and Company
T. B. DREW, SM.
Professor of Chemical Engineering, Columbia
University
O. A. HouGEN, Ph.D.
Professor of Chemical Engineering, University of
Wisconsin
D. B. :g^YEs; A.D.
Vice President, Heyden Chemical Corporatioti
i
K. M. WATSON, Ph.D.
Professor of Chemical Engineering, University of
Wisconsin
HAROLD C. WEBER, D.SC.
Professor of Chemical Engineering, Massachusetts
Institute of Technology
CHEMICAL PROCESS
PRINCIPLES
A COMBINED VOLUME CONSISTING OF
Part One • MATERIAL AND ENERGY BALANCES
Part Two • THERMODYNAMICS
Part Three • KINETICS AND CATALYSIS
OLAF A. HOUGEN
AND
KENNETH M. WATSON
PROFESSORS OP CHEMICAL ENGINEERINC
UNIVERSITY OF WISCONSIN
NEV YORK
JOHN WILEY & SONS, INC.
CHAPMAN AND HALL, LIMITED
LONDON
e M
}o&i'^
PART I
COPYRIGHT, 1943
BY
OLAF A. HODGEN
AND
KENNETH M. WATSON
PART II
COPYBIGHT, 1947
BY
OLAF A. HOTJGEN
AND
KENNETH M. WATSON
PART III
COPTBIGHT, 1947
BY
OLAF A. HonoEN
AND
KENNETH M. WATSON
All Rights Reserved
Thin hook or any 'part thereof must not
he reproduced in any form without
the written permission- of the publisher.
PRINTED If* THE UNITED STATES OF AMERICA
PREFACE
" In the following pages certain industrially important principles of chem
istry and physics have been selected for detailed study. The significance
of each principle is intensively developed and its applicability and limitations
scrutinized." Thus reads the preface to the first edition of Industrial Chemical
Calculations, the precursor of this book. The present book continues to give
intensive quantitative training in the practical applications of the principles
of physical chemistry to the solution of complicated industrial problems and
in methods of predicting missing physicochemical data from generalized
principles. In addition, through recent developments in thermodynamics
and kinetics, these principles have been integrated into procedures for process
design and analysis with the objective of arriving at optimum economic
results from a minimum of pilot-plant or test data. The title Chemical Process
Principles has been selected to emphasize the importance of this approach to
process design and operation.
The design of a chemical process involves three types of problems, which
although closely interrelated depend on quite different technical principles.
The first group of problems is encountered in the preparation of the material
and energy balances of the process and the establishment of the duties to be
performed by the various items of equipment. The second type of problem
is the determination of the process specifications of the equipment necessary
to perform these duties. Under the third classification are the problems of
equipment and materials selection, mechanical design, and the integration
of the various units into a coordinated plot plan.
These three types may be designated as process, unit-operation, and plant-
. design problems, respectively. In the design of a plant these problems cannot
be segregated and each treated individually without consideration of the
others. However, in spite of this interdependence in application the three
types may advantageously be segregated for study and development because
of the different principles involved. Process problems are primarily chemical
and physicochemical in nature; unit-operation problems are for the most
part physical; the plant-design problems are to a large extent mechanical.
In this book only process problems of a chemical and physicochemical
nature are treated, and it has been attempted to avoid overlapping into the
fields of unit operations and plant design. The first part deals primarily
with the applications of general physical chemistry, thermophysics, thermo
chemistry, and the first law of thermodynamics. Generalized procedures
for estimating vapor pressures, critical constants, and heats of vaporization
have been elaborated. New methods are presented for dealing with equilib
rium problems in extraction, adsorption, dissolution, and crystallization.
The construction and use of enthalpy-concentration charts have been extended
to complex systems. The treatment of material balances has been elaborated
to include the effects of recycling, by-passing, changes of inventory, and
accumulation of inerts.
vi PREFACE
In the second part the fundamental principles of thermodynamics are pre
sented with particular attention to generalized methods. The applications
of these principles to problems in the compression and expansion of fluids,
power generation, and refrigeration are discussed. However, it is not at
tempted to treat the mechanical or equipment problems of such operations.
Considerable attention is devoted to the thermodynamics of solutions
with particular emphasis on generalized methods for dealing with deviations
from ideal behavior. These principles are applied to the calculation of equilib
rium compositions in both physical and chemical processes.
Because of the general absence of complete data for the solution of process
problems a chapter is devoted to the new methods of estimating thermody
namic properties by statistical calculations. This treatment is restricted to
simple methods of practical value.
All these principles are combined in the solution of the ultimate problem
of the kinetics of industrial reactions. Quantitative treatment of these
problems is difficult, and designs generally have been based on extensive
pilot-plant operations carried out by a trial-and-error procedure on succes
sively larger scales. However, recent developments of the theory of absolute
reaction rates have led to a thermodynamic approach to kinetic problems
which is of considerable value in clarifying the subject and reducing it to the
point of practical applicability. These principles are developed and their
apphcation discussed for homogeneous, heterogeneous, and catalytic systems.
Particular attention is given to the interpretation of pilot-plant data. Eco
nomic considerations are emphasized and problems are included in estabhshing
optimum conditions of operation.
In covering so broad a range of subjects, widely varying comprehensibility
is encountered. It has been attempted to arrange the material in the order
of progressive difficulty. Where the book is used for college instruction in
chemical engineering the material of the first part is suitable for second- and
third-year undergraduate work. A portion of the second part is suitable
for third- or fourth-year undergraduate work; the remainder is of graduate
level. To assist in using the book for undergraduate courses in thermody
namics and kinetics those sections of Part II which are recommended for such
survey courses are marked. This material has been selected and arranged
to give continuity in a preliminary treatment which can serve as a foundation
for advanced studies, either by the individual or in courses of graduate level.
The authors wish to acknowledge gratefully the assistance of Professor
R. A. Ragatz in the revision of Chapters I and VI, and the suggestions of Pro
fessors Joseph Hirschfelder, R. J. Altpeter, K. A. Kobe, and Dr. Paul Bender.
OLAF A. HOUQEN
KENNETH M. WATSON
MADISON, WISCONSIN
August, 194s
CONTENTS
Page
PREFACE . v
TABLE OF SYMBOLS ix
PART I
MATERIAL AND ENERGY BALANCES
Chapter
I STOICHIOMETRIC PRINCIPLES 1
II BEHAVIOR OF IDEAL GASES 27
III VAPOR PRESSURES 53
IV/ HUMIDITY AND SATURATION 89
V SOLUBILITY AND SORPTION Ill
Vr/ MATERIAL BALANCES 167
YJy THERMOPHYSICS 201
viy/ THERMOCHEMISTRY 249
IXy FUELS AND COMBUSTION 323
• X CHEMICAL, METALLURGICAL, AND PETROLEUM PROC
ESSES 383
PART II
THERMODYNAMICS
XI THERMODYNAMIC PRINCIPLES . . . . . . . . ' 437
XII THERMODYNAMIC PROPERTIES OF FLUIDS . . .. 479
XIII EXPANSION AND COMPRESSION OF FLUIDS . . .. 538
XIV THERMODYNAMICS OF SOLUTIONS 595
XV PHYSICAL EQUILIBRIUM 644
XVI CHEMICAL EQUILIBRIUM 691
XVII THERMODYNAMIC PROPERTIES FROM MOLECULAR STRUC
TURE 756
vii
viii CONTENTS
PART III
KINETICS AND CATALYSIS
Chapter Page
XVIII HOMOGENEOUS REACTIONS 805
XIX CATALYTIC REACTIONS 902
XX MASS AND HEAT TRANSFER IN CATALYTIC BEDS . . 973
XXI CATALYTIC REACTOR DESIGN . 1007
XII UNCATALYZED HETEROGENEOUS REACTIONS . . . 1049
APPENDIX jcvii
AUTHOR INDEX xxiii
SUBJECT INDEX xxvii
TABLE OF SYMBOLS
A area
A atomic weight
A component A
A total work function
a activity
external surface per unit mass
Om
ttp external surface per particle
ttv external surface per unit volume
B component B
B constant of Calingaert-Davis equation
B thickness of effective^ film
C component C
C concentration per unit volume
c degrees centigrade
c number of components
c over-all rate constant
c. heat capacity at constant pressure
c. heat capacity at constant volume
c. Sutherland constant
c concentration of adsorbed molecules per unit mass of
catalyst
c specific heat
c velocity of light
molal heat capacity at constant pressure
Cp
molal heat capacity at constant volume
Cv
d surface concentration of adsorbed molecules per unit
catalyst area
D diameter
diffusivity of A and B
DAB
Dp effective particle diameter equal to diameter of sphere
having the same external surface area as particle
D', effective diameter equal to diameter of sphere having
, same area per unit volume as particle
d differential operator
E energy in general
E energy of activation, Arrhenius equation
E^ effectiveness factor of catalysis