INduSTRiAl

CRYSTAllizATiON
INduSTRiAl
CRYSTAllizATiON
EdiTEd by
J. W. MulliN
University of London

PlENUM PRESS. NEW YORk ANd LONdoN

 Library of Congress Cataloging in Publication Data

Symposium on Industrial Crystallization, 6th, Ust( nad Labem, Czechoslovak

Republic, 1975.
Industrial crystallization.

Symposium held Sept. 1-3, 1975.

Includes index.
1. Crystallization-Congresses. I. Mullin, John William. II. Title.
PT156.C67S961975 660.2'84298 76-10859
ISBN-13: 978-1-4615-7260-2 e-ISBN-13: 978-1-4615-7258-9
001: 10.1007/978-1-4615-7258-9

Proceedings of the Sixth Symposium on Industrial Crystallization held

at list. nad Labem, Czechoslovakia, September 1-3, 1975

©1976 Plenum Press, New York

Softcover reprint of the hardcover 15t edition 1976
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted,

in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
 Preface

Industrial Crystallization Symposia have been organized by

the Crystallization Research Group at the Czechoslovak Research
Institute for Inorganic Chemistry, Usti nad Labem, since 1960.
Over the years, the increasing popularity of the unit operation
of crystallization has been clearly demonstrated by the steady
increase in numbers of both the papers presented and the
attendances at the meetings.

The 6th Symposium (1-3 September 1975) was organized jointly

with the European Federation of Chemical Engineering Working Party
on Crystallization, and the 44 papers presented were arranged into
four sessions - A: Secondary Nucleation, B: Crystal Growth Kinetics,
C: Crystal Habit Modification, D: Crystallizer Design, E: Indus-
trial Crystallizer Operation and Case Studies. The same groupings
are preserved in this edited version of the proceedings.

This is the first time that the Industrial Crystallization

Symposium papers have appeared in one volume. After the 5th
(1972) Symposium, authors we.re encouraged to submit their papers
to an international journal specializing in crystallization.
However, the results were not altogether satisfactory in that
less than one third of the papers presented at the meeting were
offered for consideration. This time, therefore, the organizing
committee decided to attempt to keep the papers together by
making arrangements for their pUblication by Plenum Press.

A distinctive feature of the Industrial Crystallization

Symposia is the intimate blend of fundamental and applied research
work on a truly world-wide basis. At the 1975 meeting papers
were presented by authors from Bulgaria, Czechoslovakia, DDR,
France, Holland, Japan, Poland, Spain, Switzerland, UK, USA,
USSR, West Germany and Yugoslavia. The work reported indicates
the tremendous diversity of interest in a subject whose inter-
dependent parts range from solid-state physics to phase equilibria,
from diffusional mass transfer to fluid mechanics, from strength
of materials to solution structure.

v
 PREFACE

In editing this version of the proceedings of the 6th

Symposium I have received invaluable help from many sources. I
should like first to thank rnw colleagues on the symposium
organizing committee, Dr. J. Nyvlt and Dr. R. Rychly (Czechoslo-
vakia), Prof. E.J. de Jong (Holland), Prof. U. Fasoli (Italy),
Dr. R.F. Strickland-Constable (UK) and Dr. B. Messing (West
Germany), for their help with the preliminary refereeing
procedures. I am also indebted to the symposium session chairmen,
and to others who participated in the meeting, for help and
advice in collating and clarifying many of the papers. And last,
but by no means least, I want to thank Miss Valerie H. Potter
and her colleagues at University College London for undertaking
the daunting task of retyping a substantial proportion of the
manuscripts.

London, 1976 J.W. MULLIN

 Contents

Session A
SECONDARY NUCLEATION

Secondary Nucleation - A Review 3

G.D. Botsaris

Attrition and Secondary Nucleation in

Agitated Crystal Slurries 23
P.D.B. Bujac

Collision Breeding from Solution or Melt 33

R.F. Strickland-Constable

Secondary Nucleation of Potash Alum . . . . . 41

K. Toyokura, K. Yamazoe, J. Mogi, N. Yago,
and Y. Aoyama

Control of Particle Size in Industrial NaCl-

Crystallization 51
C.M. van 't Land and B.G. Wienk

Secondary Nucleation and Crystal Growth as

Coupled Phenomena • . . . . . . . • 61
J. Estrin and G.R. Youngquist
The Grinding Mechanism in Fluid Energy Mill and
Its Similarity to Secondary Nucleation . . 67
S. Okuda

Secondary Nucleation in Agitated Crystallizers 77

U. Fasoli and R. Conti

vii
viii CONTENTS

Session B
CRYSTAL GROWTH KINETICS

Theory and Experiment for Crystal Growth from Solution:

Implications for Industrial Crystallization 91
P. Bennema

Computer Simulation of Crystal Growth from Solution . . . . . 113

T.A. Cherepanova, A.V. Shirin, and V.T. Borisov

Surface Perfection as a Factor Influencing the

Behaviour of Growth Layers on the {lOO} Faces
on Ammonium Dihydrogen Phosphate (ADP) Crystals
in Pure Solution . . . . . . . . . . . . . . . . . . . . 123
V.R. Phillips and J.W. Mullin

Growth Rate of Citric Acid Monohydrate Crystals in

a Liquid Fluidized Bed . . . . . . . . . . . . . . . . . 135
C. Laguerie and H. Angelino

The Occurrence of Growth Dispersion and Its

Consequences . . . . . . . . . . . . . . . . . . . 145
A.H. Janse and E.J. de Jong

Kinetics of Ti02 Precipitation . . . . . . . . . . . . . . . 155

o. Sohnel and J. Marecek
Investigations on the Ostwald Ripening of Well
Soluble Salts by Means of Radioactive Isotopes . . . 163
A. Winzer and H.-H. Emons

Recrystallization in~Suspensions . . . . . . . . . . . . . 173

J. Skrivanek, S. Zacek, J. Hostomsky, and V. Vacek

Crystal Growth Kinetics of Sodium Chloride

from Solution . . . . . . . . . . . . . . . . . . 187
R. Rodriguez-Clemente

Session C
CRYSTAL HABIT MODIFICATION

Survey of Crystal Habit Modification in Solution . . . . . . . 203

R. Boistelle

Some Problems of Crystal Habit Modification . . . . . . . . . 215

E.V. Khamskii
CONTENTS ix

Solvent Effects in the Growth of Hexamethylene

Tetramine Crystals . . . . . . . . . . . . . . . . . . 223
J.R. Bourne and R.J. Davey

Effect of Isodimorphously Included Co(II), Fe(II)

and Cu(II) Ions on the Crystal Structures of
ZnS04.7H 20 and MgS04.7H20 . . . . . . . . . . . . . . . 239
C. Balarew and V. Karaivanova

The Effect of Ionic Impurities on the Growth of

Ammonium Dihydrogen Phosphate Crystals . . . . . . . 245
R.J. Davey and J.W. Mullin

Influence of Mn(II), Cu(II) and Al(III) Ions on

Size and Habit of the Ammonium Sulphate Crystals . . . . 253
M. Broul

The Influence of Surface-Active Agents on Gypsum

Crystallization in Phosphoric Acid Solutions . . . . . . 263
J. Schroeder, W. Skudlarska, A. Szczepanik,
E. Sikorska, and S. Zielinski

Isomorphous Series in Crystals of MeS04.nH20 Type . . . . . . 269

S. Aslanian and C. Balarew

The Transformation of Amorphous Calcium Phosphate

into Crystalline Hydroxyapatite . . . . . . . . . . . . 277
LG. Brecevic and H. Furedi-Milhofer

The Effect of Fe(III) Ions Upon the Growth of

Potassium Dihydrogen Phosphate Monocrystals . . . 285
J. Karniewicz, P. Posmykiewicz, and B. Wojciechowski

Session D
CRYSTALLIZER DESIGN

Crystallizer Design and Operation . . . . . . . . . . 291

J.W. Mullin

The Design of a Crystallizer . . . . . . . . . . . . . . 303

K. Toyokura, F. Matsuda, Y. Uike, H. Sonoda,
and Y. Wakabayashi

Design Criteria for DTB-Vacuum Crystallizers . . . . . . . . . 311

A.G. Toussaint and J.M.H. Fortuin

Integral Design of Crystallizers as Illustrated by the

Design of a Continuous Stirred-Tank Cooling
Crystallizer .... . . . . . .. . . . . 319
C.J. Asselbergs and E.J. de Jong
x CONTENTS

Design of Batch Crystallizers • • • • • • • • • • • • • • 335

J. NYvlt
Population Balance Models for Batch Crystallization • • • •• 343
H.M. Hulburt

The Crystallization of Some Chloro-Organic Compounds

in a Batch Crystallizer with Programmed Cooling 353
I.V. Melikhov, E.V. Mikhin, and A.M. Peckler

A New Technique for Accurate Crystal Size Distribution

Analysis in an MSMPR Crystallizer • • • • . • • •
S. Jancic and J. Garside

Session E
CRYSTALLIZER OPERATION AND CASE STUDIES

Transient Behavior in Crystallization - Design Models

Related to Plant Experiences.. ••••.•• 375
J.P. Shields

Stability and Dynamic Behaviour of Crystallizers 391

B.G.M. de Leer, A. Koning, and E.J. de Jong

The Importance of Classification in Well-Mixed

Crystallizers • • . • • • • . • • . 403
A.H. Janse and E.J. de Jong

Purification of H3P04.!H20 by Crystallization 413

Y. Aoyama and K. Toyokura

The Operation of a NaOH.3!H 20 Crystallizer by Direct

Contact Cooling. • • • •.• • • • 421
T. Akiya, M. Owa, S. Kawasaki, T. Goto, and K. Toyokura

Progress in Continuous Fractional Crystallization 431

G.J. Arkenbout, A. van Kuijk, and W.M. Smit

The Prevention of Deposition on Crystallizer Cooling

Surfaces Using Ultrasound • • • • • . • . • . • 437
M.J. Ashley

Case Study of Incrustation in an Industrial

Salt Crystallizer 449
C.M. van It Land and K.J .A. de Waal

Operation of a Large-Scale KCl Crystallization Plant 461

W. WOhlk and G. Hofmann

Index 471