213

Design of Crystallizers
Auslegung von Kristallisatoren

ALFONS MERSMANN
Lehrstuhl B fir Verfahrenstechnik, TU Munchen, Arcisstr. 21, 8000 Munich 2 (F.R.G.)
(Received December 7, 1987; in final form February 2, 1988)

Abstract

It is shown how to design a crystallizer starting with data which must be determined in laboratory crystallizers
and other measuring equipment. A survey on kinetic data of a large number of systems is given in order to show
the range of parameters involved in crystallization.
The paper deals with the scale-up problems of crystallizers which are important when laboratory data are
transferred to large-scale crystallizers.

Kurzfassung

Ausgehend von Daten aus Laborkristallisatoren oder einfachen MeDapparaturen wird die Auslegung von
Kristallisatoren beschrieben. Ein ijberblick iiber die kinetischen Gr6Ben zahlreicher Systeme (Keimbildungsrate
und Kristallisationsgeschwindigkeit) sol1 die Bandbreite der Parameter zeigen, welche fur die Auslegung solcher
Apparate benotigt werden.
Ferner beschaftigt sich der Aufsatz mit der MaBstabsvergrdBerung von Kristallisatoren und zeigt, wie
sich experimentelle Daten aus Riihrwerkskristallisatoren zur Auslegung anderer und vor allem such gragerer
Kristallisationsapparate nutzen lassen.

Synopse Keimbildung kann diese Gr$e aus der Beziehung

Die Auslegung von Apparaten zur Kristallisation 3 x 10-‘ms-‘iG,a=28AC,,,,seo

von Sto#en aus Liisungen ist eine sehr komplexe Auf- PS
gabe. Die Striimung in solchen Kristallisatoren soll eine < 15 x lo-’ m s-*
ausreichende Makro- und Mikrovermischung der Lo-
sung bewirken sowie die Kristalle gleichmaJig in a’er abgeschiitzt werden, wiihrend bei homogener primiirer
Suspension verteilen und in Schwebe halten. Bei der Keimbildung (AC/C* > 1) die tjbersiittigung AC,,,, ,,,,m
ungefiihr zwischen
Kiihlungskristallisation wird der L6sung Wiirme entzo-
sen, wahrend bei der Verdampfungskristallisation 0,1 Mol I-’ < Acmet,hom t2 Mol I-’
Wtirme zuzufiihren ist. In beiden Fallen sind die
WiirmeCibertragungsfl&chen so zu dimensionieren, da$ lie@ [l]. Die Kristallwachtstumsgeschwindigkeit ist bei
Verkrustungen miiglichst vermieden werden. Dtjiisionslimitierung der Ubersiittigung AC (‘G, w AC)
Weiterhin kommt es entscheidend darauf an, im und bei Einbaulimitierung h&&g dem Quadrat der rela-
Kristallisator eine optimale obersdttigung durch die tiven ijbersiittigung (G,i N (AC/C *)‘) proportional und
geeignete Wahl verschiedener BetriebsgroBen (Kiihl- mu8 experimentell bestimmt werden. Dies gilt such fur
bzw. Verdampfingsrate bei diskontinuierlich betriebe- die Rate B, der Keimbildung, welche zweckmajig auf
nen Kristallisatoren, Ltisungs- und Suspensionsstrome den Volumenanteil cp der Kristalle bezogen wird.
und damit die mittlere Verweilzeit bei kontinuierlichem Zm Falle sekundiirer Keimbildung trdgt man diese
Betrieb) aufrecht zu erhalten, urn zuliissige Keimbil- Keiml#dungsrate zweckm@ig entweder iiber der rela-
dungsraten und Kristallwachstumsgeschwindigkeiten tiven Ubersiittigung AC/C* oder iiber der Kristallwachs-
nicht zu iiberschreiten. Tabelle 5 gibt eine iibersicht tumsgeschwindigkeit G fur verschiedene speziJische
iiber die im einzelnen durchzuftihrenden Messungen und Leistungen E des Laborkristallisators auf. Manche
Rechnungen. Kristaliisate sind relativ abriebsfreudig und miissen
Zuniichst ist die Weite des metastabilen Bereiches deshalb in der Suspension schonend aufgewirbelt und
AC,,, experimentell zu bestimmen. Bei sekundiirer umgew6Izt werden. Es empfiehlt sich, die Abriebs-

0255-2701/88/$3.50 Chem. Eng. Process., 23 (1988) 213-228 0 Elsevier Sequoia/Printed in The Netherlands
 214

geschwindigkeit G, experimentell zu ermitteln, welche Kristallisatoren (FlieJbetten, FC-Kristallisatoren)glei-

der kinetischen Wachstumsgeschwindigkeit G entge- then o&r such groperen Volumens umrechnen lassen.
gengesetzt gerichtet ist, so daJ die Kristalle nur mit der
eflektiven Geschwindigkeit G,@= G - G, in ihrer
Griipe zunehmen [23]. 1.Introduction
Die minimale Riihrerdrehzahl eines Riihrwerks-
kristallisators zum Suspendieren der Kristalle ergibt The design of crystallizers depends on the funda-
sich aus Abb. 4, wiihrend Abb. 5 Auskunfi iiber die mental questions whether the crystallization process is
kleinste Drehzahl gibt, welche im Hinblick auf eine continuous or batchwise and whether supersaturation
volumetrische Produktionsrate und den dafiir erforder- is generated by cooling of the solution or evaporation
lichen umgewalzten Liisungsstrom in einem Leitrohr- of the solvent, by drowning out or by reaction crystal-
oder Umwtilzkristallisator erforderlich ist. lization. Owing to the limited length of this article,
Bei kontinuierlich betriebenen, ~011 durchmischten reaction and precipitation crystallization will be dis-
Kristallisatoren mit nicht klassierender Produktent- cussed in a further paper [ 11. Emphasis is placed upon
nahme kann die efektive mittlere KorngroJe & aus Gl. the design of continuously operated crystallizers.
(9) berechnet werden. Zur Auswertung dieser Gleichung At first, balances have to be formulated for mass,
sind die eflektiven Raten der mittleren Wachstums- energy and population density. The last of these three
geschwindigkeit G,, und der Keimbildung &, eff er- balances presupposes the consideration of mixing,
forderlich. Richtwerte dieser kinetischen Gr@en lassen fluid and crystal mechanics (attrition) as well as of
sich Abb. I1 entnehmen, in welcher die mittlere kinetics. Kinetics means growth and nucleation with
Kristallwachstumsgeschwindigkeit G tier der relativen regard to attrition effects caused by mechanical stress
Ubersdttigung AC/C* aufgetragen ist. Nach diesem applied to the crystals. The combination of all these
Bild liegt die Griipe G im Bereich lop9 m s - '< G aspects results in a design method for crystallizers
-cIO-'m s-‘,.Kristallisatoren werden fast immer bei which is reliable and predictable. Unfortunately, up
einer solchen Ubersiittigung AC betrieben, daj3 gerade until now the kinetic parameters needed for an arbi-
diese Kristallwachstumsgeschwindigkeiten erreicht, trary crystalline product have not been made available.
aber nicht wesentlich iiberschritten werden. Abbildung According to Fig. 1 the modelling of crystallizers is
I I enthtilt oben zweite Abszissen fir die volumenanteil- based on specifications such as the system with its
bezogenen Keimbildungsraten B,/rp fir die sekuna%e equilibrium and physical data and the production
bzw. prim&-e (homogene und heterogene) Keimbildung. capacity.
Setzt man die in Abb. I I dargestellten Raten fur Keim- The flows of masses and energies can be calculated
bildung und Wachstum in GI. (9) ein, ergeben sich from the balances for mass and energy. Production
mittlere Kristallkorngr6jen, wie sie in Abb. 10 im abge- capacity and the operating mode of reactors and the
dunkelten Bereich liegen. Das wesentlichste Ergebnis apparatus in the whole production process are decisive
lautet: Je grojer die relative ijbersiittigung AC/C*, criteria for the determination ofwhether the crystallizer
umso kleiner ist die erzielbare mittlere Korngroje f. is operated continuously or batchwise. Usually the
Deshalb ist bei der Auslegung und dem Betrieb von shape of the solubility or equilibrium curve determines
Kristallisatoren darauf zu achten, daJ die optimale whether cooling or evaporation crystallization is the
Ubersiittigung miiglichst iiberall im Apparat zeitlich more economical process. The type of crystallizers
gleichbleibend aufrecht erhalten wird und obersiitti- (stirred vessel, forced circulation, fluidized bed (see Fig.
gungsspitzen an Einleit-, Misch-, Kiihl- und Heizstellen 2)) must be selected properly since kinetic processes
miiglichst vermieden werden. such as growth and especially secondary nucleation
Die optimale iibersiittigung liegt f;lst immer, also depend on the type and geometry of the crystallizer
sowohl bei Kiihlungs-, Verdampfungs- und Verdriin-
gungskristallisation wie such bei der Reaktionskristalli-
sation im Bereich 0,Ol Mol I-’ < AC < 0,l Mol I-‘.
Die MaJstabsvergroJerung von Kristallisatoren wird
zweckm@ig bei gleichbleibender mittlerer speztjischer
Leistung g durchgefiihrt, obwohl das Suspendieren in
Rkhrwerkskristallisatoren kleinere, das Umwiilzen des
Losungsstromes aber gr$ere spezihsche Leistungen er -
fordern wiirde. Bei konstantem g kann damit gerechnet
werden, da$ die mittlere KorngriJe in der Gro$aus-
fiihrung etwas zunimmt. Handelt es sich urn sehr gro,Be
Riihrwerkskristallisatoren oder urn Fliejbettkristalli-
satoren, bleibt bei gleicher mittlerer speztfischer Leis-
tung E die mittlere Korngr6& Z konstant.
Im Aufsatz wird gezeigt, wie sich unter Umstiinden
experimentell bestimmte kinetische Gr@en (Raten
der Keimbildung und des Wachstums) und mittlere
KorngroJen, welche in einem kleinen MSMPR-
Laborkristallisator ermittelt wurden, auf andere Fig. 1. Modelling of crystallizers.
 215

Shred Vessel Forced Fluidmd Bed unit time of the stirrer or the stirrer power dissipated
3culotion in the suspension. The suspension flow (i, + 4 of the
solution with the concentration c, and of the solid
product (product stream @ = i,m,/@, - mT)) is dis-
charged from the crystallizer. The enthalpy flows fi
correspond to the mass flows i, AL and P respec-
tively. The Table in Fig. 3 contains the balances for
mass and energy. The general case can be simplified if
certain restrictions are valid. It is important to men-
tion that the mass balance (for instance for the restric-
tion CJJ+ 1 and At = 0),
mT=cO-c*-Ac=c,,-C, (1)
Fig. 2. Industrial crystallizers [2].
cannot be solved since the suspension density m, and
the supersaturation AC are unknown (the equilibrium
and on the operating conditions. The population den- concentration c* can be derived from the energy bal-
sity balance determines the crystal size distribution ance). Only crystallization kinetics (i.e. the growth
and the mean crystal size. The purity of the crystalline rate G of the crystals and the rate B of nucleation, see
product is often connected with the growth rate. $4) determine the relationship between the two un-
It is at last possible to calculate the dimensions of knowns AC and m,.
a crystallizer,

3. Fluid dynamics in crystallizers

2. Balances for mass and energy
The fluid dynamics in suspension crystallizers must
Figure 3 shows a stirred vessel which can be used be chosen in such a way that
as a cooling or an evaporation crystallizer. In the case (1) the crystals in all sections of the apparatus are
of evaporation-the heat flux Q,+, is added and the kept in suspension;
vapour flow AL of pure solvent is discharged. When (2) the circulation rate in the loop apparatus is
dealing with a cooling crystallizer the mass flow AL high enough to obtain a desirable residual supersatu-
and the heat flux Qadd are zero. I@,,, is the work per ration at the end of the loop [3];

Restriction Mass balance

General .&,=Ai+i,

PLO = PL,

or (with i, = i, + At)

mT=*-c,

CO
=_-c*-Ac
1 -Al/Lo
rp*1 mT = co - c,
AL=0

(only cooling) mT = c, - c* forAcdc,-c*

with c* = r(S)

e-1--
Liquid Vapour Suspension Energy
(add = added ; drs = dlschargel
Fig. 3. Balances for mass and energy of a continuously operated crystallizer.
216
(3) large differences in concentration and/or
supersaturation are avoided.
This presupposes a certain degree of macro- and
micromixing.
3.1. Suspension of crystals
In the crystallizer the crystals have to be kept in
suspension by the volumetric flow rate of the solution
which is generated by a stirrer or a pump. This implies
that the local average flow velocity of the solution
must exceed the settling velocity w,, of the swarm of
particles. This velocity w,, can be calculated with the
aid of a variety of equations and diagrams published
in the literature [4].
The flow velocity depends on the geometry of the
apparatus. Figure 4 shows a vertical and a horizontal
pipe as well as a fluidized bed, and a large stirred
vessel (left side), a small stirred vessel, and an elbow
bend (right side). Recommendations for the flow ve-
locity wf of the solution are: vertical pipe: up,-> SW,,;
horizontal pipe: wy > low,,.
The relationship wF x w,, is valid in fluidized beds
and also in large stirred vessels (7’JZ > 103). This
means that the mean specific power input Bis inversely
proportional to the vessel diameter Td (E - l/T,)
until the minimum value tin = rpw,g(Ap/p) is
reached. A constant circumferential stirrer velocity,
w, = ~sd = constant, is a reasonable criterion for scal-
ing-up. The situation is quite different in small stirred
vessels (T,/.f < 500) and in elbow bends because of
particle settlement in the narrow loopway which leads
to dunes (see Fig. 4). In these cases a constant specific
power input E is recommended as the suspension crite-
rion. Consequently, it can be said that the larger the
apparatus, the easier is the suspension of crystals.
3.2. Mixing in crystallizers
In order to control the process of crystallization,
the fluid dynamics have to ensure proper mixing. Lo-
cal and mean values of the specific power input
(caused, for example, by the rotational speed of the
Fig. 4. Suspension in crystallizers; left side: fluid&d bed and large
stirred vessel with target efficiency qt -B 0; right side: small stirred
vessel and elbow bend with target efficiency )rl+ 1 [S].
impeller) determine the degree of macromixing and
micromixing. On the one hand, the entire crystallizer
volume must be mixed well so that all its elements
participate equally in the mass transfer process and
hence the entire volume is efficiently utilized. In addi-
tion to this bulk mixing, sufficient micromixing has to
be present in certain parts of the crystallizer in order
to even out quickly any local supersaturation peaks.
Such critical zones in the crystallizer are the region of
the feed inlet and the heat transfer areas (i.e. boiling
and cooling surfaces). The absence of zones with a
supersaturation AC higher than the metastable super-
saturation AC,,, must be aimed at.
When the crystallizer is similar to a loop reactor,
supersaturation is generated at the feed inlet or at the
cooling or evaporation surfaces. It is reduced by crys-
tal growth during one circulation in the loop. Let us
consider a stirred tank of dimensions d/T, = 0.33 and
HIT, = 1. According to ref. 3 the following equation
can be derived for a vessel equipped with a marine
type impeller:
>I (2)
P,aTG
-
0.072 s AC,,,
In Fig. 5 the expression Acme,7 s/mT is plotted against
the term Ac,,,s/p,aTG. It will be pointed out later that
the crystal growth rate G often only varies by approx-
imately one order of magnitude (lo-’ m s-l -=zG <
10m7 m SK’). For given values of the suspension den-
sity mT and the volumetric specific surface a, of the
crystals, the speed s, necessary for macromixing, de-
pends on the residence time 7 and especially on the
metastable supersaturation AC,,,,,.
The smaller this supersaturation and the shorter
the residence time 7, the higher the chosen speed s of
the impeller. Fast growing systems with high values
for mT and a, need large volumetric flqw rates V
based on the crystallizer volume V (s N V/V), espe-
cially in the case of small metastable zone width AC,,.
According to the equation
e
Fig. 5. Minimum impeller speed s,,,~” in order to obtain sufficient
macromixing [3] (see also ref. 6).

10° 10' W/kg lo2
Fig. 6. Mixing time (macromixing for laminar and turbulent flow,
micromixing) plotted against specific power input.
valid for macromixing, the macromixing time 8,,,,
increases with the power f of the vessel diameter Td
for a given mean specific power input E (see Fig. 5).
Dealing with micromixing of low viscous systems, the
time for micromixing emioro is dependent on the local
specific power input E, the liquid viscosity v, and on
the Schmidt number of the solution according to Fig.
6. As can be seen from this diagram the time for
micromixing is short in comparison with the induc-
tion period obtained in measurements of the meta-
stable limit. Hence, undesired nucleation owing to
insulflcient micromixing can be excluded as long as
the feed is introduced into the crystallizer in a region
of high local specific power input. These regions occur
in the discharge flow in the immediate vicinity of the
impeller [7]. However, with increasing solution viscos-
ity micromixing becomes more significant.
It should be mentioned here that the situation is
different in precipitation crystallizers (not discussed in
this contribution). When dealing with precipitation,
micromixing has a tremendous influence on the crys-
tal size distribution and the mean crystal size [8].
4. Heat transfer in crystallizers
Contrary to most heat exchangers applied in chem-
ical engineering, crystallizer heat exchanges display
reasonable limitations of maximum allowable temper-
ature difference AS. The reason for such limitations is
undesired nucleation which occurs in solutions with
concentrations higher than the metastable zone AC,,,,,
4.1. Allowable temperature differences in heat
exchangers
In a cooling crystallizer the heat flux 0 is to be
removed; in the case of an evaporation crystallizer the
heat flux 0 must be added. In order to transfer this
energy the heat transfer area A is necessary for a given
temperature difference A9 :
Q=($+~+~)-‘ALM=~AA~
E for most systems.
217
1peroture
4
Fig. 7. Temperature (9) and concentration (c) profiles in the vicin-
ity of a heat transfer wall for a low (upper part) and a high (lower
part) heat flux density 4.
The meaning of the heat transfer coefficients a, (solu-
tion), and a, (coolant) as well as the wall thickness 6
and the wall heat conductivity 1 can be seen from Fig.
7, in which the profiles of temperature 9 and concentra-
tion c are depicted for the case of cooling crystallization.
In a similar way these profiles can be described for
evaporation crystallizers. For this purpose the solubil-
ity curve c * = f(9) of the system under discussion must
be known. The temperature profile depends on the
local flow and heat transfer conditions.
Incrustation is a quite natural but very often un-
desired crystallization process in heat transfer areas
and apparatus or on pipe walls. Let us consider a
surface over which a crystal free solution flows. At first
heterogeneous nuclei must be generated [9]. Further-
more, it is necessary that these nuclei adhere to the
wall. These processes are prerequisites of incrustation.
The local supersaturation AC then leads to growth of
nuclei which grow together, thus forming a crust with
a certain growth rate. In order to avoid incrustation
caused by heterogeneous nucleation the local supersat-
uration AC must be smaller than the metastable zone
width AC,,,, hst for heterogeneous nucleation:
AC < AC,,, bet = g A%,,,, bet (5)
The upper portion of Fig. 7 depicts the case when the
difference ch - c* in the concentration layer near the
wall is smaller than the critical or metastable difference
Acmef,bet (ct, - c* < Ac,~, ,.,&, in which c,, is the bulk
concentration of the turbulent solution flow assumed.
The above picture in Fig. 7 is valid for small.heat flux
densities 4 = k AS. However, with increasing flux den-
sities 4 or increasing total temperature differences A9
the difference c,, - c* becomes larger than Ac,,,,,,~~~
(cb - e* > Ae,t i,st); see lower part of Fig. 7. In this
case the probability of incrustation is very high. Unfor-
tunately, up until now the metastable zone width
(4) Ac,,t, hct =f kmt, ,,omrwith 0 c f -K1, is not known
218

Only the metastable zone width AC,,,, ,,,,,,, for pri-

mary homogeneous nucleation can be evaluated ac-
cording to ref. 10 for given values of the surface
tension ysL between a cluster and the surrounding
solution (see Fig. 8). However, when dealing with
industrial crystallizers, the incrustation on vertical
and especially on horizontal walls of heat exchangers
in the presence of crystals, i.e. in suspensions, is the
more severe problem because the metastable zone
width AC,,,. sec for secondary nucleation is smaller
than AC,,, bet:

For inorganic systems the zone width A&,,,, often lies

in the range OS K c AS,,, c 5 K. Data on AS,, pub-
lished by Mullin [ 1 l] have proven to be very reliable
for the prediction of incrustation of heat exchanger
surfaces of cooling crystallizers.
In suspension crystallizers nuclei and/or particles
must at first impinge or settle on the wall. This process
depends on the collision frequencies and contact ve-
locities of the particles involved. For incrustation it is
then necessary that these particles are not swept away
by the flow of the solution but adhere to the wall. This
process is governed by the reciprocal action of the
forces of adhesion and the forces exhibited by the
flow. Adhesive forces are smaller on smooth surfaces
than on rough areas. Polishing may be advisable [9].
Dealing with horizontal surfaces there is a certain
probability that larger particles settle on the wall (see
$2.1). If settled particles grow together, a crust is built
up. On the one hand these particles may be removed
by large flow velocities but, on the other hand, mass
transfer coefficients are increased which leads to
larger mass flux densities to the crust in cases where its
growth is controlled by diffusion.
Usually, it is not possible to avoid incrustation
completely, but a large heat transfer area A with a
smooth (and, in the case of inorganic systems, hydro-
phobic) surface, a suitable fluid velocity of the solu-
tion and a certain limitation of the temperature
difference A9 (i.e. small heat flux densities) may lead
to a small growth rate of the incrustation layer and
consequently to a long operation time of the crystal-
lizer between two successive cleaning procedures.
Relotlve supersatumtton f
Fig. 8. The dimensionless rate of homogeneous primary nucleation
&Ill
CD=
3B,a(c~.J”3(3vsJt3kF) “‘(J@/P.NA)
plotted against the relative supersaturation AC/C*. The expression
is a parameter which mainly contains physical data of the system.
With respect to the properties of systems (F z 7) and nucleation
rates occurring in crystallizers (CD< lo--2o), the working range is
correspondingly marked.
4.2. Heat transfer coeJ&ients
In the case of small volumetric hold-up (rp 6 0.05)
of the crystals, heat transfer coefficients are not heav-
ily influenced by the presence of crystals impinging on
the heat transfer area. The approximate design of the
heat transfer area A with heat transfer coefficients
calculated for the crystal free solution is, therefore,
allowable. As a rule equations for the heat transfer
in pipes or at plates can be used. For instance, rela-
tionships based on theoretical or semitheoretical
equations derived for the heat transfer at plates can be
applied for stirred vessels (see Table 1 [ 12)).

TABLE 1. Heat transfer in stirred vessels according to ref. 12

Boundary Forced convection Transferred to Experimentally determined Range of validity

layer transfer from a plate stirred vessels

0.18
Laminar Nu = 0.664 Ret/* P@ Nu = 1.18 RetI Prt/3 Nu = 1.0 Re’i*pr’is -? Rec2Sx 102
0 %v
0.14
Transition Nu = 0.18 Re213Pr’/’ Nu = 0.38 Rez13 Pr113 Nu = e Re2/s RI/’ 1. 2.5 x 10a=zRe<7x IO5
range 0 KV
c = O.rO.4 without bafiles
c = 0.7-0.9 with bat&s

Turbulent Nu = 0.0766 Re314Pr*/” Nu = 0.18 Re314Prs@ 7 x 10’ < Re

 219

Similar equations for the calculation of heat trans- from measured crystal size distributions shows that
fer coefficients can be found in the literature for other the operation of ‘mixed suspension mixed product re-
types of crystallizers (forced circulation or fluidized moval’ (MSMPR) crystallizers is most appropriate
beds). for this purpose.
The population density n depending on the crystal
size x is defined as the number dN of crystals per unit
5. Crystallization kinfztics volume suspension in a size interval dx:

The crystal size distribution of a product obtained @) = dN(x)

in a crystallizer mainly depends on: dx
growth rate G, According to the comprehensive study of particu-
effective rate of nucleation B,, late processes by Randolph and Larson [ 131 the com-
and on processes such as plete population density balance valid for well-mixed
attrition or abrasion and/or breakage of crystals, crystallizers can be formulated (see Table 2). Death
dissolution of crystals, rates D(x) and birth rates B(x) may be caused by
agglomeration of crystals, processes such as attrition, breakage, agglomeration
mixing of the solution, and and/or dissolution. When employing MSMPR crys-
mixing of the suspension. tallizers, crystallization experiments are carried out in
The crystal growth rate and the rate of nucleation such a way as to try to avoid the occurrence of such
are the main kinetic parameters, both of which are processes or at least ensure that they only have a
dependent on supersaturation AC. Principally speak- negligible effect upon the final crystal size distribu-
ing, these parameters can be determined in batch- tion. In addition, the volume Y of the suspension is
operated and in continuously operated crystallizers, kept constant. If the crystallizer runs in a steady state
A comparison of the operation modes and of the and if its contents are ideally mixed and only a repre-
methods for the calculation of kinetic parameters sentative product sample is removed, the population

TABLE 2. Population density balance

Population density
dn d(Gn)
balance F +D(x)+ B(x)+n
z+
Moment Significance

General MSMPR

mo= n(x) dx Total number N7 = me NT = n,,Gr

m, =
J
0
xn(x) dx

cc
m2 = x%(x) dx Total surface area aT = k,m, a, = 2k,n,,(G~)~
s
0
m
m, =
J
0
x%(x) dx Volumetric hold-up cp = k,m,
II
cp = m&, = 6ksdW

Results of the ideal MSMPR model

Crystal size

Jxh(x)
dx
distribution n(x) = n,, exp( --x/G?) i

Mean crystal size 2 = 3.67 Or according to ’ = 0.5

m3

48
_=-_
1 _(3.67)3 (3.67)‘G tith cp =3
Rate of nucleation zzzp
9 6k,G”s4 6k& 6k>’ P.
220

density balance can be simplified (see Table 2). For

size independent growth a straight line on a semiloga-
rithmic graph is obtained (In n(x) plotted against x).
Table 2 contains the various moments of the popula-
tion density and their significances. Furthermore, the
direct relationship between the rate of secondary nu-
cleation based on the volumetric hold-up B&p, crystal
growth rate G, mean crystal size _?and mean residence
time z for the volume shape factor k, = 7r/6 of spheres
2
is described according to the ‘simplified MSMPR
10-g ” s
model’. 103 10-2 10-l 100
Relative
supersaturatlon G= $

5.1. Crystal growth rate Fig. 9. Crystal growth rate plotted against relative supersaturation
Larger crystals in industrial crystallizers are usu- for 23 systems. Note: the capital letters denote the metastable limits
of the systems according to refs. 14 and 15.
ally rounded due to attrition and do not display dis-
tinct faces. The mean mass flux density RB or the
mean crystal growth rate G depends on supersatura- ties can have a great influence on growth (PbCl, on
tion AC, temperature T and on crystal size X. In the KC1 [ 161, ferrocyanate on NaCl [ 11, etc.). In some
case of diffusion controlled growth the relative veloc- cases temperature dependent growth was observed.
ity w,, between solution and crystal plays a certain This behaviour is usually explained by a temperature
role. Impurities and additives (add.) usually have an dependent surface integration which is often de-
important influence: scribed by an Arrhenius expression (see Table 3). But
in reality when dealing with impure systems an inter-
G = 2 = f( Ac, T, x, add., w,,) (8) pretation of AE in the context of an adsorption energy
\ Y I of the foreign substance may be more appropriate
surface
megration than an explanation of an activation energy. Since the
\ I / purities of the systems according to Fig. 9 are un-
ditiuaion known it is not reasonable to compare their crystal
growth rates. However, when dealing with industrial
Figure 9 shows the crystal growth rates G of vari- crystallization, the relative supersaturation AC/C* is
ous systems plotted against the relative supersatura- usually chosen in such a way that for inorganic sys-
tion AC/C* for a temperature of approximately 30 “C. tems a growth rate of IO-* m s-i <G < 10m6 m s-l
The curves are mainly valid for a crystal size range is achieved. This may be mainly due to the desire to
100 pm < x < 2000 ,um. As can be extrapolated from obtain economical size enlargements A_x = Gt of
Fig. 9, the growth rate differs over nine orders of the crystals for reasonable residence times r
magnitude for AC/C* = 0.01. It is known from the (lOOOs<r~lOOOOs; 10-8x104=10-4mcGz~
literature that small amounts of additives or impuri- 1OV x lo3 = 10e3 m).

TABLE 3. Growth rate models [ 181

Overall rate Mass flux density R 8 =k B(c-c’)’ with c-c*=Ac

Physicochemical Only convection + Rd = kd(c - c,)

models diffusion
Only surfaoe R,=k,(c,-c’)’ with
integration

Elimination of c,

Special case z = 1

Specialcaser=2

Surface integration BtSmodel

models

BCF model
 221

In the case of pure systems (without any traces of

foreign substances) it is possible to calculate the
growth rate for diffusion controlled systems since the
mass transfer coefficient kd is predictable. Dealing
with systems controlled by surface integration the
models according to Table 3 can be used to predict
growth rates for other supersaturations AC and tem-
peratures T if reliable data for certain AC and T
values are available. However, there is no reasonable
way of calculating the constants K,, K’, K2 and K” of
the B + S or BCF model or the frequency factor k,
and the true kinetic order of reaction t of the physico- Relotlve supersatml~an 6 =bc/c’=S-I
chemical model. The extrapolation of data obtained
Fig. 10. Maximum obtainable mean crystal size f plotted against
for large crystals to small crystals below x < 100 pm
relative supersaturation 0 for 17 systems according to Table 4.
is not admissible.

5.2. Nucleation rates 0.001 up to 100. However, nearly all systems were
crystallized at supersaturations between 0.01 and
According to the equation 0.1 mall-‘. Figure 10 shows the maximum mean
crystal sizes f,,, as a function of the relative supersat-
uration AC/C*. Such a diagram was introduced in a
’ = 3x37 [ 6k,,(&)]‘4
previous paper [ 31. A generalized result would be: the
valid for MSMPR crystallizers, the mean crystal size higher the relative supersaturation, the smaller is the
,? depends on the growth rate G and on the rate of mean crystal size, probably in accordance with in-
nucleation B,/cp based on the volumetric crystal creasing nucleation rates. According to the relation-
hold-up. Both of the kinetic parameters G and B, are ship for the mean crystal size 2 (eqn. (9)), the decrease
strongly dependent on supersaturation. Conse- of the mean crystal size 2 with increasing AC/C* is
quently, the mean crystal size is a function of super- caused either by a decrease of G or an increase of B,,Jq
saturation. or by a combination of both effects. In Fig. 11 the
Table 4 contains the molar mass a, the tempera- growth rates G are plotted against AC/C*. It is again
ture 9 and the solubility c* of 17 aqueous systems. important to keep in mind that this diagram describes
According to results in the literature and our own a comparison of various systems. As can he seen the
experimental data, the supersaturation AC at which growth rates decrease only by approximately
the systems were crystallized and the maximum mean G = 5 x lo-’ m SK’ valid for AC/C* < 1 to G = 0.5 x
crystal size Xmax are listed. Further information is 1O-8 m s-i for sparingly soluble systems. Therefore
given in the literature cited. As can be seen from this the decrease of the mean crystal sizes f against AC/C *
Table the solubility ranges from 4.6 mol l- ’ to is mainly caused by an increase of the rate of nucle-
lo-’ mol I-’ and the relative supersaturation from ation (B,/p) based on the volumetric hold-up rp.

TABLE 4. Kinetic data of 17 aqueous systems crystallized by cooling, evaporation, drowning out and reaction

Aqueous system R Temp. c* AC AC/C* G x IO* f, c or Reference

(kg kmol-‘) (“C) (mol I-‘) (mol I-‘) (ms-I) Olm) b”

A KC1 74.6 24 4.2 0.0042 0.001 5.0 1000 c 1191

B NaCl 58.5 50 4.6 0.0138 0.003 3.7 500 c [171
C (NH,),CS 76.1 25 2.0 0.0140 0.007 4.8 1000 c WI
D (NH&SO, 132.1 21 4.1 0.0286 0.007 7.5 800 c [21,221
E KN09 101.1 20 2.8 0.0420 0.015 4.8 700 c [2325]
F Na,SO, 142.0 40 1.2 0.0720 0.06 7.5 500 c 1261
G K,SO, 174.2 30 0.72 0.0430 0.06 4.6 170 c ~271
H NH,Al(SO,), 237.3 22 0.23 0.0161 0.07 3.3 270 c 128,291
I K,Cr&, 294.2 - 0.42 0.0420 0.1 8.0 200 c [301
J KAWU, 258.1 25 0.35 0.0157 0.45 3.0 350 c 131, 321
K KCIO, 138.6 0.16 0.0096 0.6 - 46 b (331
L NiSO, (NH&SO., 286.7 25 0.27 0.162 0.6 - 330 b 134, 351
M BaF, 175.4 2&50 9.2 x 1O-3 0.0660 7.2 _ 4.2 b I361
N CaCO, 100.I 25 2.5 x 1O-4 0.0024 9.6 0.60 41 c 137, 381
0 TiO, 80.0 25 3.0 x lo-’ 0.0960 32 0.25 2.8 c I391
P CaF, 78.1 18 2.0 x 10-d 0.0120 60 _ 2.0 b WI
Q BaSO, 233.4 22 1.0 x 10-S 0.0010 100 0.1-3.0 3.5 b [411

a~ = continuous; b = batch
222

Nucleotcon Rote, ($I,,,, do 16” lb” lb” l?-& iO’BC

Fig. 11. Growth rate G plotted against relative supersaturation 0 109La.

0 a2 OX 0.6 08 IO mm 14
for 17 systems according to Table 4.

Fig. 12. Population density n depending on particle size for ammo-

Since mean crystal sizes x and growth rates G are nium sulphate according to the experimental results of Tengler 1211.
given in Figs. 10 and 11, the rates of secondary nucle-
ation B,/cp can be calculated from eqn. (9). In Fig. 11
second abscissae are plotted for the rate of nucleation
based on the volumetric hold-up. Calculations of 5.2.2. Mean eflective rate of secondary nucleation
homogeneous nucleation and considerations for see- In the case of high specific power input E, large
ondary nucleation (only effective in the case of crystals volumetric hold-up rp and a long residence time t, no
larger than 100 pm and accordingly ineffective for straight lines in a population density plot are ob-
relative supersaturations AC/C* > 1, see Fig. 10) lead tained. It is, therefore, recommended to calculate the
to the result that in the case of small relative super- mean ‘effective’ kinetic parameters [43] :
saturation AC/C* < 0.1 secondary nucleation due mean effective crystal growth rate
to crystal collisions is the main source of nuclei. co- Cl 1
Homogeneous primary nucleation dominates for AC/ &=- (10)
3k,p,r O”
c* > 1. In the range 0.1 c AC/C* < 1 heterogeneous
n(x)x’ dx
nuclei and preordered species generated on crystals s
present in the crystallizer may contribute to the rate of 0
nucleation.
Dealing with fast growing systems often crystal- mean effective rate of secondary nucleation
lized at low relative supersaturations AC/C* ( 3.67)4G,ff
(AC/C* < O.l), there is some evidence that attrition l
&dT= 6k&,Br 4= 6k,ZeK4
fragments larger than about 10 pm are the main
source of effective nuclei. In this paper information is
only given for secondary nuclei produced as attrition
fragments after collisions of mother crystals with solid
parts of the crystallizer or other parent crystals.

X2.1. Rates of secondary nucleation in MSMPR

crystallizers
Under certain conditions the particle size distribu-
tion of product crystals obtained in MSMPR crystal-
lizers follows a straight line in a In n = f(x) plot (see
Fig. 12) [21]. The aforementioned conditions are usu-
ally small specific power input B ( to.3 W kg-‘),
small suspension density m, ( ~40 kg m-3) or small
volumetric hold-up cp ( -mJp, < 0.02), and small res-
idence time 7 ( < 2000 s). Figure 13 shows a compari-
son of rates of secondary nucleation based on the
volumetric hold-up, B,,/cp, according to results pub-
lished in the literature [42]. Lines of constant mean
crystal sizes 2 are drawn in this diagram according to
:
the results of the ‘simplified’ MSMPR theory (eqn.
(9)). As can be seen from this Figure, a coarse product
(2 > 0.5 mm) is obtained for some systems, whereas 10
other systems deliver a fine product (2 < 0.2 mm). A
first attempt to explain this behaviour is described in Fig. 13. Relative effective nucleation rate B,_,Jrp plotted against
ref. 3. growth rate G for different substances.
 223

By introducing these mean effective parameters it is

possible to calculate the mean crystal size &:

f& = 3.6X?.& = 3.67 [ 6k”(2:*,rp)]l’4 (12)

The mean effective rate of secondary nucleation com-

prises all attrition fragments which, during their resi-
dence time in the crystallizer, grow to a size that is
essential in the context of an industrial crystalline
product. The small crystal volume V, removed from a
particle with the size x after a collision with the colli-
O-5 Pumpmg
copmly N,

sion velocity v is, according to the theory of Hertz-

Huber [ 441:
/ .. \ 1.2
v,- t
0 x3

cL is the velocity of mechanical waves in the mother

(13)

crystal after contact with a rotor of the crystallizer or

with another crystal, and depends on Young’s mod-
ulus E and on the Poisson ratio v of the crystalline
material: Fig. 14. Factor f. (upper part) and factor fb (lower part) plotted
E 112 against pumping capacity N, for various angles p.
cf_=
0-
PS
f(v)
Pohlisch and Mersmann [43] showed that the volu-
equation for the mean effective rate of secondary
nucleation might be useful in the case AC/C < 0.1
metric rate of attrition of crystals in a suspension, (secondary nucleation dominates) :
dV, & en 1 ma eR
cpVdt ~=----~(eR+KlpeJ
rp kR3m
” a a, tot
based on the crystal volume cpV (volumetric hold-up or
cp times the crystallizer volume V) of all particles in
the suspension is proportional to the sum of the attri- $ eff
-_=-A- 1 m, eff 1
tion intensities eR + erp. The contribution eR is caused cp kC3 m, tot G ‘.2
by crystal-rotor contacts and the contribution erp
K=; 4
refers to crystal-crystal
dV
collisions:
0.’

~~e,+K,e,
rpVdt
or
s2.2d3.2
dV
a
cpVdt
=-$ (“febe%,
e + u&~bttt, b) 7

wu
(16)

(15) In this equation, _?ais the mean size of effective attri-

The number of impeller blades (thickness b, and
breadth bb) is described by a. The geometry of the
impeller with the diameter d is described by the geo-
metrical factorsf, andf, (see Fig. 14). Q, c and ‘I~,b are
target efficiencies which will be explained later. A is a
constant which is unknown with the exception of the
value for the system KNO,-H,O which was investi-
gated by Pohlisch and Mersmann [43, 501. K,,,w 0.2
seems to be a reasonable value. In another paper [451
it is shown that under certain conditions the following
tion fragments (mean size of small particles produced
by attrition with a certain growth rate). Only the mass
fraction ma%Jma, tot of the total mass m, t.,t generated
by attrition shows this certain growth rate and con-
tributes to the rate of effective secondary nucleation.
According to their physical meaning, the factors 1/Za3
and m,, .&n,, tot are strongly dependent on supersatu-
ration AC and can only be calculated if two relation-
ships are known:
(1) the number and size distribution of all frag-
ments produced by attrition;
(2) the growth behaviour of attrition fragments
depending on supersaturation, their sizes and temper-
ature.
224

Supersaturation AC how to transfer laboratory results to full-scale indus-

trial crystallizers with the same (small vessel to
large vessel) or a different geometry (MSMPR stirred
vessel to large fluidized bed or forced circulation
crystallizer).

6.1. Design problems

When dealing with the design of crystallizers, deci-
sions on the fluid dynamics and heat transfer must be
made. For this purpose it is necessary to carry out
laboratory experiments in order to determine the
metastable zone width As,,,,, for a certain induction
period rind, the crystal growth rate G, or Gsi for diffu-
sion controlled or surface integration controlled
systems respectively, and the rate of secondary nucle-
ation for certain operation conditions (see Table 5).
Growth rote G
Further experiments are necessary to determine the
Fig. 1;. Kinetic factor K plotted against the mean growth rate of attrition behaviour of large crystals, which may be
large crystals for four different systems: KC1 [46], KNO, [23], expressed as the linear attrition rate G,. Conse-
(NH&SO4 [21] and (NH&S [20]. quently, the volume V of a crystallizer can be calcu-
lated in order to obtain a desirable mean crystal size
3. It should be kept in mind that the final decision is
In order to elucidate the physics involved and to always a compromise between contradictory require-
give approximate values for m, eR/ma,t0t and -?a, the ments. Owing to the limited scope of this paper, the
factor possibilities of, for instance, classification and/or fine
dissolution are not discussed.

is plotted in Fig. 15 against the growth rate G for the
aqueous systems of KCl, KNO,, (NH&SO, and
(NH&CS. According to our results, larger crystals
with x > 100 pm of these systems grow diffusion con-
trolled. Consequently, there is a linear relationship
between growth rates G and the supersaturations. In
Fig. 15 second abscissae with the supersaturation AC
are drawn for these four systems.
Furthermore, the product ( l/k,.?,3)(m,, Jrn,, ,,,) is
split up into the mass fraction m, eE/ma,tot and the
mean size R, of the effective fragments. The
nomogram beside the ordinate allows m, Jma, fot val-
ues to be read for given 5 data. Assuming _iY= = 10 pm
and G = lo-’ m s-’ we obtain m,.,/m, tOtz 0.004
for (NH&SO4 and m, &m, t,,t NS0.02 for KCl.
It is important to mention that the results pre-
sented in Fig. 15 are based on experimental data ob-
tained in stirred vessels and fluidized bed crystallizers.
In the case of fluidized beds the contribution of sec-
ondary nucleation due to crystal-rotor collisions is
simply zero. Principally speaking, it is possible to ap-
ply eqn. (16) and the results depicted in Fig. 15 also
for forced circulation crystallizers equipped with axial
pumps.
6. Design and scale-up
The reliable design of a crystallizer is not possible
without experimental data. Measurements are usually
carried out in a laboratory crystallizer which is often
operated as an MSMPR crystallizer. Two questions
arise: how to design large-scale crystallizers; and
6.2. Scale-up problems
Let us assume that kinetic data of the rates of
growth and nucleation obtained in a laboratory crys-
tallizer are available and that the mean crystal size f
is known for the system crystallized in this apparatus.
The question of how to choose the geometry and size
of the large-scale crystallizer and its operating con-
ditions then arises. According to #3.1 and 3.2
macromixing demands a higher specific power input
but suspending can be carried out at lower specific
power inputs. As a compromise a constant specific
power input B (.? 3 Es’,,& is recommended for indus-
trial crystallizers. Then eqns. ( 12) and ( 16) allow eval-
uation of the relationship between the rate of
secondary nucleation B,,, eR (and the mean crystal size
2 according to eqn. ( 12)) and the scale-up factor for
systems crystallized at AC/C* < 0.1. This mainly de-
pends on the target efficiencies qt, e and qt, ,,. Figure 16
shows target efficiencies plotted against the Stokes
number
x
* =--P&&
18~ 1,
with lc = b, (edge) and I, = b,, (breadth of the im-
peller). U, is the collision velocity between the crystals
and the impeller [44,45]. The curves refer to the ex-
perimental results of Riebel et al. [47], Schuch [48]
and Longmuir and Blodgett [49]. Three ranges can be
distinguished:
(a) In the case of very small Stokes numbers the
target efficiency approaches zero; this may occur in
very large crystallizers (x/Z, -+ 0).
 225

TABLE 5. Design procedure

Attrition 1 Metastable zone width c,, = s A&, for rind

kinetics
G =k,k,Ae AC ’
Crystal growth rate or G,,2k,
d 3k,p, PS 02
Nucleation rate for s=%lin

Attrition rate 1231

Fluid 5 Minimum impeller speed for suspension (see Fig. 4)

dynamics 6 Minimum impeller speed for macromixing (see Fig. 5).
7 Minimum specific power input for macromixing

Heat a Cooling or evaporation A9,,, < A&,,, (Q heat transfer area)

transfer 9 Evaporation Ac_,r,, i AC,,, (a surface area of solution)

CrystaIhzer 10
design
11 Selection of residence time T for R = R,,, [23]
12 Crystallizer volume V according to desirable f

Crystallizer
scale-up

(b) In a medium Stokes number range the target

efficiency qt increases from small values (q, x 0) to
unity (Q + 1).
(c) In the range of large Stokes numbers the target
efficiency is unity (QT,= 1); this may be valid in small
crystallizers conlaining a suspensidn of large crystals
(x/l, %-0). (17)
For geometrically similar crystallizers eqn. (16)
can be simplified to

Fig. 16. Target efficiency plotted against Stokes number according to Schuch [48], - - -, and to Biebel et al. [471, -, with various
values of x/l,.
 226

kinetic constant for secondary nucleation

Boltzmann constant, J K-’
overall heat transfer coefficient, W m-* K-’
mass transfer coefficient, m s-’
variable reaction rate constant
shape factors
liquid flow rate, kg s-*
vapour flow rate, kg s-’
characteristic length, m
molar mass, kg kmol~ ’
mass of attrition fragments, kg
suspension or slurry density, kg me3
Fig. 17. Rates of secondary nucleation based on the volumetric
hold-up plotted against vessel diameter for two different specific
number of particles per unit volume, m-3
power inputs: -, q, according to ref. 43; - - -, qt according Avogadro constant, kmoll’
to ref. 48. pumping capacity of stirrer
population density, me4
production rate, kg s - ’
with the exponent u = 1 (case (a)), 0 c u < 1 (case heat flux, W
(b)), and I( = 0 (case (c)). Figure 17 shows the rate of heat flux density, W m-*
secondary nucleation based on the volumetric crystal mass flux density of growth, kg m-* s-’
hold-up, B,,.&, plotted against the vessel diameter supersaturation ratio
Td for two different specific power inputs. According speed of rotor (impeller or stirrer), s- ’
to eqn. (16) the curves are valid for Za = 10 pm, temperature, K
m,, efflm = 0.01, Z?= 500 pm, cp = 0.033, cL = diameter of vessel, m
2.7 x IO”‘: s-‘, HIT, = 1 and d/Td = 213. The con- time, s
tribution caused by crystal-impeller collisions de- velocity of particles relative to stirrer blade,
creases with the scale-up factor whereas the con- ms-’
tribution due to crystal-crystal contacts remains volume of crystallizer, m3
constant. As a general result of these relationships a volumetric flow, m3 s ~ ’
small increase of the mean crystal size can be expected volume of attrition fragments, m3
for a medium range of scale-up factors when E re- velocity of collision, m s- ’
mains constant. In very large crystallizers 2 remains energy flux or power, W
constant for a constant specific power input E, since velocity of fluid, m s *
the contribution due to crystalcrystal collisions settling velocity (single particle, swarm),
dominates. ms’
particle size, m
mean particle size, m
Nomenclature

A constant heat transfer coefficient, W rnp2 K-’

a number of blades system property parameter
specific area of crystals, m* m-3 interfacial tension, J m-*
aT
nucleation rate, mV3 s- * wall thickness, m
BO
birth rate, me4 s-’ specific power input, W kg- ’
B(x)
b breadth, m mean specific power input, W kg- ’
concentration, kg m-3 or mol 1-l dynamic viscosity, N s m-*
f\c supersaturation, kg m- 3 or mol 1~ ’ target efficiency
velocity of shock waves, m s- ’ temperature, “C
CL
specific heat capacity, kJ kg-’ K-l heat conductivity, W m-’ K-’
CP
D diffusivity, m* s - ’ Poisson’s ratio
D;:) death rate, me4 s-’ density, kg mp3
d diameter of rotor, m density difference, kg me3
E Young’s modulus, N m-* = AC/C*, relative supersaturation
intensity of stress or attrition, ml,* s-*,* residence time, s
volumetric hold-up of crystals
; factor
G growth rate, m s-’ dimensionless rate of primary nucleation
Stokes number
G, _ d V, x/cp V dt, linear attrition rate, m s- ’
g acceleration due to gravity, m ss2
H height of stirred vessel, m = aT,/I, vessel Nusselt number
A enthalpy tlux, W = r)cp/;l, Prandtl number
K,, K’, variable constants in B + S and BCF 1 = sd p/q, stirrer Reynolds number
K,, K” equations = v/D,,, Schmidt number
 227

Indices 18 S. J. Jancic and P. A. M. Grootscholten, Industrial Crystalliza-

tion, D. Reichel, Dordrecht, 1984.
attrition 19 W. D. Beer, Untersuchung zur MalJstabsvergrXIerung der
t breadth or bulk Chargenkiihlungskristallisation von Kaliumchlorid in Leit-
coolant werkkristalliitoren, Ph.D Thesis, Tech. Univ. Munich, 198 1.
: diffusion 20 K. Bornhiitter, Diploma Thesis, Lehrstuhl B fur Verfahrenstech-
e edge nik, Tech. Univ. Munich, 1986.
eff effective 21 T. Tengler, Experimentelle Untersuchungen zum Wachstum
und zur Keimbildung von Ammoniumsulfat in w&tiger
f fluid
Losung bei der Ktihlungskristallisation, Thesis, Tech. Univ.
growth
Munich, 1988.
iet heterogeneous 22 R. Ploss, T. Tengler and A. Mersmann, Secondary nucleation
horn homogeneous and crystal growth in continuous cooling crystallizers, in S. J.
ind induction time Jancic and B. J. de Jong (eds.), Industrial Crystallization 84,
L liquid or solution North-Holland, Amsterdam, 1984, p. 271.
met metastable 23 J. Pohlisch, EinfluD von mechanischer Beanspruchung und
particle Abrieb auf die KomgrijBenverteilung in Kiihlungskristallisa-
P
R rotor toren, Tkesis, Tech. Univ. Munich, 1987.
24 J. B. Helt, Effects of supersaturation and temperature on nucle-
s solid
ation and crystal growth in a MSMPR crystallizer, Ph.D Thesis,
SeC secondary
Iowa State Univ., 1976.
si surface integration 2s P. Juzaszek and M. A. Larson, Influence of fines dissolving on
tot total crystal size distribution in an MSMPR crystallizer, AZChE J.,
0 inlet 23 (1977) 46CM68.
I
outlet 26 W. Fleischmann, Untersuchungen zur Verdrangungskristallisa-
* equilibrium tion von Natriumsulfat aus wiissriger Liisung mit Methanol,
Ph.D Thesis, Tech. Univ. Munich, 1985.
27 H. N. Rosen, The crystallization of potassium sulphate, nucle-
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