ooo?-2509m/050l-065 I Mr.

2 00/o

THEORETICAL STUDY OF THE INACTIVATION OF

PHOSPHATASE DURING SPRAY DRYING OF SKIM-MILK

A E WIJLHUIZEN,? P J A M KERKHOFS and S BRUINO

Department of Food Process Engmeenng, Agncultural Unrverslty. Wagenmgen, De IkelIen 12. 6703 BC
Wagenmgen, The Netherlands

(Recetoed 1 June 1978. accepted 25 August 1978)

Abstract-A theoretical calculatron IS presented of the drymg hlstory of skun-nulk droplets under spray drymg
condxtlons From the unsteady state dtiuslon equation the water concentration dlstnbution 1s calculated as a
function of time, slmukaneously the thermal degradation of the enzyme alkalme phosphatase IS calculated and
Integrated over the paticle Effects accounted for are the temperature and concentration dependence of the water
Muslon coefficient and of the degradation rate constant, and the sbnnkage due to water loss Droplet geometnes
consldered are the “sohd sphere” model (fully hqmd droplets) and the “hollow sphere” model (with au bubble m
the centre) The effect on final phosphatase retention of the followmg process vanables was mvesugated dissolved
sohds content of the feed, au temperature, particle size, and gas bubble size

lNTRODlJCTION calculations of drymg rate and of thermal degradation

Spray drymg 1s one of the most Important dehydration However, an important feature of this modelhng IS that It
processes for liquid foods, such as dauy products and enables the investiganon of the effect of and the relative
coffee extract In additton to qualtty requuements hold- sensitivity for process vanables, which wdl be of
mg for all dned products hke a desved moisture content conslderabk help m improving an extstmg lay out or a
and a desired bulk density, for dned food products also choice of process con&tions, based on a clear concept
other factors may play a role In parWular retention of From various stu&es, also concemmg the retention of
volatie flavour components and mmunal thermal volaNe Ravour components, it has become clear that m
degradation of heat-sensltrve components are favorable au drymg hqmd foods the transport of water, as well as
In order to meet such requrrements expenence with the that of volattles, mslde the liquid phase IS over a large
product in practtcal drying circumstances IS essenttal, part of the process governed by molecular dlfFuslon[l-31
however for the interpretation of expenmental results with a water concentration-and temperaturedepen-
and for the selection of optunal process conditions and dent dtffusion coefficient Mentmg et al [Z] established
equipment design a fundamental m&t mto the various quantttatwe agreement between expenmentai drymg
processes takmg place in the product dunng drying 1s results and theoretical calculations in Isothermal drymg
also requued It IS the obJectlve of the present paper to of gelled slabs of aqueous maltodextnn solutions at 21°C.
contnbute to this fundamental knowledge of the spray usmg a relatlonshlp. determmed by Independent expen-
drymg process by means of a theoretical study of the mental methods, between the water dfiuskon coefficient
thermal mnactivatton of the enzyme alkaline phosphatase and water concentration at this temperature Smular
durmg spray drying of a smgle droplet of skim-nulk stu&es by Chandrasekaran and Kmg[3] for sugar solu-
A quantitative comparison between expenmental and tlons at various temperatures also showed quantltattve
theoreucal work m spray drymg 1s hmdered on one hand agreement between theorettcal and expenmental results
by the lack of data on dtlTuston coefficients, and on the Approximate computer calculations of droplet drying
other hand by the complexity of the processes takmg were mven by Rulkens[41 The first theoretical treatment
place in the spray dner Due to the stochastic nature of of the drymg of droplets with concentration- and
the atomtzatlon process parttcles of various sues are temperature-dependent ddfuslon coefficient, mcludmg
formed, m which tierent enclosed volumes of au may volume change dunng drymg, was gven by Van der LlJn
be entrapped, and also the release velocity and mltlal et al [S] for aqueous maltose solutions Based on
duectlon of the droplets are subject to stochastic vana- expenmental musron measurements, his theoretlcal
tions This senes of physical phenomena lead to dtierent calculations showed good agreement unth expenmentally
droplet trajectones through the dner and thus, from the observed drymg hlstones of smgle droplets[6] Van der
viewpomt of a travellmg droplet, dtfferent w conditions Ltln also performed calculattons for droplets in which atr
in its direct surroundings As a consequence modellmg IS, bubbles were Included
wtthm realistic bmits, probably not to lead to exact In analogous calculations Kerkhof and Schoeber[71
extended the “sohd droplet” model (vvlthout ~LTbubble)
tPresent address Central Institute for Nutntlon and Food ~tb transport of volatie flavour components and
Research, CIVO. Zeist, The Netherlands
*Netherlands Institute for Dauy Research NIZO. Kemhem- degradation of heat-sensitive components For the
seweg 2. Ede, The Netherlands tiusion coefficient of water again the maltose-water
bTo whom correspondence should be addressed data of Van der Lqn were used, for the d&usion of

651
652 A E WULHU~ZEN et al

volatdes a hypothetical relation was used because of lack

of physlcal data, for the degradation kmetlcs a relation
was used denved from the data of Verhey[8] for the
mactlvatlon of phosphatase m slum-rmlk The quahtative
agreement between these calculatrons and expenmental
observations was very encouragmg
Later correlation methods were denved from these
theoretical models for the calculation of drymg
hlstory[9] and of the length of the constant-rate penod
and aroma retentlon[lO], methods which were also found
m agreement wth expenmental results
In recent studies the dlffuslon kmetlcs of water m
skim-mdk were determined from drying curves of single
droplets[lll according to a method designed by
Schoeber [9] Daemen [ 121 extended the measurements of
degradation kinetics of phosphatase m skim-r&k, and
performed spray drying expenments on ths system
Because of these developments the various physlcal
data and reactlon-kmetlcs for one real food hqmd were
known, and so tt was thought useful to explore the (a) SolId sphere
theoretlcal modellrng of this system further In the cal-
culatrons the programs of Van der LlJn[6] were used,
extended with the thermal degradation reaction
our
TEEOREIICAL MODEL * = *out
Only a bnef outline of the various assumptions 1s pW=p, b

given here, for an extended dlscusslon the reader 1s

referred to Van der LlJn[6] In Fig 1 a schematic !r=Re
representation of the droplets considered 1s given The
droplets are assumed to be perfectly spherical and to
consist either totally of liquid (“sohd sphere” model) or
to contam a central akr bubble (“hollow sphere” model)
For the ease of comparison m the calculations of the
hollow-sphere model a number of values of uutml hqmd
mass of the droplets were chosen and kept constant,
whrle varying the amount of entrapped ;llr Thus vanatlon

Jz
IS expressed by the ratio PW,l
r&v2
p- 0

t--=---- . Pvvl jpw2

.---__ Pwb

i-=0 r=Rg r=Rt

-et-
tn which R,,, IS the uutlal radius of the air bubble, and Rio ( b 1 hollow sphere

1s the uutlal value of the so called “hqmd radius” the

Fig 1 Schematic representation of drymg droplet (a) “Sohd
radius of a droplet with the same liquid mass contammg sphere” model, (b) “Hollow sphere” model
no air bubble
In all cases the air m the dner was assumed to be
ideally nuxed with moisture content p& and at a effectively be described by a binary ddfuslon equation
temperature T,,, for the system water-dissolved solids In the absence of
The droplets shnnk dunng drying because of the loss molecular volume contractron then holds
of water The uutml radms of the droplets IS R. For the
“sohd sphere” model R. = RIO for the “hollow sphere” II, = - D,Vp, + v”p, (2)
model R. = (R:,-+ Rio)“’
The droplets have an mltlal water concentration pwo, with respect
to a stationary coordinate system Herein
solids concentration p. o and enzyme concentration pc o D, IS the mutualdiffusion coefficient, v” 1s the volume
In all calculatrons the uuhal radius R. was so small that averaged velocity which 1s zero for the solid sphere and
dunng the whole drying penod heat- and mass transfer caused for the hollow sphere by expansion or shnnkage
coefficients for the air phase can be described accurately of t’le au bubble, as given by
by Sh=Nu=2
evp dR 3
=B
Water transport and transfer dt
It IS assumed that water transport Ins&de the droplet 1s
sphencally symmetnc and mslde the hqmd phase can The equation of contmmty applied to the water m the
 The macuvatlon of phosphatase dunng spray drymg of skun-mdk 653

hquld phase reads following mitral condmon

t = 0, R,, s r s (R&+ R;o)“3, pw = pwo
WV
,=-v+,)=-;$(?n,.) (4)
(hollow sphere) Wa)
t =o, 0 6 T c Rio, pw = pwo
It IS further assumed that mechamcal eqmhbnum exists
between the pressure mslde the gas bubble and outside (lob) (sohd sphere)
the droplet, and that the rate of water transfer to or from Heat transfer
the gas bubble mslde the hquld droplet only causes a In view of the low Blot-number for heat transfer the
neghgble concentration gradlent m the bqmd phase near droplet temperature may be assumed to be homogeneous
the Internal phase boundary Further the transport of leadmg to the heat balance
water mslde the gas bubble 1s assumed to be so rapid that
vu%uaUy equdibnum exists between the water vapour -dT ^
mC, ~=4~R.2iaS(TOu,- T)- k,(p& pLb)AHuJ
concentration m the bubble and the liquid phase water
concentration at the internal mterface, Indicated by the (11)
subscnpt “1” Thus the foliowmg boundary condltlons
are obtamed for the hollow sphere (5a) and the solid where rneP IS the heat capacity of the droplet, T,,, IS the
sphere (Sb) respectively bulk gas temperature, a, IS the contmuous phase heat
transfer coefficient, and A&, IS the heat of evaporation
1 >o, r = &?(0, &WI = 0 @a) Therem It has been assumed that the amount of heat
corresponding to the internal evaporation or conden-
r=o, a&L, sation can be neglected Both the heat and mass transfer
Vb)
ar-
coefficients are corrected for the effect of net mass
transfer
m which nwrl LS the water flux with respect to the
Internal Interface The water vapor concentration at the
Thermal degradatron of the enzyme
rnterface IS
For the descnption of the thermal degradation reactlon
It 1s assumed that the enzyme, mdlcated with subscnpt e,
, a, IP~‘&
pwg=- (6) 1s lmmoblle with respect to the dissolved sohds, and that
BT
the reaction is first order The contmmty equation for the
enzyme reads
with the water actlvlty given by a sorption Isotherm
equation p A 6% =-v J’+r
c 0 (12)
“dt 0 P.
a,] =f@~,, T) (7)
where J*' IS the flux of enzyme with respect to the sobds,
In eqn (6) pl*rg is the water vapour concentration m the which IS assumed to be zero The source term r, = - k,pC,
gas bubble, a,, IS the water actlvlty at the internal so eqn (12) becomes
interface P,” IS the saturated water vapour pressure at
droplet temperature T, 632IS the gas constant and M, 1s ---
dp= p= !h,!!&,_kGe
the molecular mass of water For the radius R, of the gas dt ps dt dt
bubble holds
In which the total time denvatlve (dldt) 1s taken relative
R’ T Pr-Pwo to a coordmate movmg with the total dissolved sohds
F$=T, P*-P,
(8) velocity v.

in which Pwo IS the water vapour pressure at the mltlal $=$+& v (13a)
temperature To and P, IS the total pressure
At the external Interface, which we ~111 indicate by The rate constant k, IS a function of water concentration
subscnpt “2” the boundary condltlon reads both for the and temperature In our case the velocity of the sohds vs
hollow sphere and for the sohd sphere has only a non-zero radial component usr This velocity
IS related to the change in sohds concentration by
t>o, r = R,(t), JWZ = k,(P:s - P’,,, (9)

in which Jo,* IS the flux of water with respect to the

(144
(movmg) external interface. and k, IS the contmuous
phase mass transfer coefficient, which IS calculated m for the solid sphere, and
our case from Sh = 2 pLZ and p,,+ denote water vapour
concentrations at the external Interface and m the bulk
ur. = u,--+-j;@ $2) dr (14b)
gas phase respectively
As already menttoned above, a umform concentration
orofile
rm -~~~~ m
~~~ the
~~~ lmmd
_X~ bhase
r is assumed which eaves the for the hollow sphere Because the enzyme concen-
654 A E WIJLHUIZEN et al

tration IS very small with respect to the sohds concen-

tratlon (pJp, = 0) we can neglect pc d(ln p,)/dt m the
1 h s of eqn (13)

Numerical sol&ton
For the solution of this system of equations, trans-
P
0
formatlon IS apphed to a coordmate system based on
Increments m radial dtrectlon of the amount of non
transfemng components m the gas bubble the reference
i
IS the amount of dry au, m the hquld the amount of dry
f
sohds IS taken as reference The resultmg set of equa- 0;’ I

hons IS then solved by means of an rmphclt firute- 0 02 04 c)i

difference technique, taking unequal space and trme m-
Fx 2 Water vapour sorption Isotherm of skun-~-,“z 34°C
tervals Deb& of the coordinate transformation
ok = water content on dry basis (kg water/kg dry solrds) 0. Dataof
mentioned and of the numerical method apphed are Berlin et of (141, ----. fit wrth Halsey equation
given by Van der LlJn[6] Numerical computattons were
performed on the DEC-10 d1glta.l computer of the Agn-
cultural Unlverslty of Wagenmgen A typlcal computa- skim-milk 7
tlon time was 70 s per run

FWYSICAI DATA

Most of the data used In the computation are tabulated

m Table 1 The water vapour sorptton isotherm was
described by fittmg the data of Berlm et al 1143 mth
Halsey’s equation [15] to gve

a, = exp (- 3 106 X lo-‘(or,)-* ‘“) (15)

‘m which ok IS the amount of water per kg of dry sohds,

the relation IS plotted m Fig 2
The drffuslon coeffictent of water, as denved from
drying curves of single droplets IS plotted m Ftg 3 For
the computations at two temperatures the followmg
equations were fitted

38 912 + 323 39w,

D,,. = exp -
1+15840,
(T = 30°C)
UW
0 05
, r 1 I I
1
(kgwaterl kg total)
-WV+
35 968+310 570,
D, =exp - (T = XPC) Fe 3 Molecular dfiuslon coeficlent of water m skim mdk, as
1+ 15 4670, > determmed from drymg expenments with smgle droplets[12], m
(16b) dependence of water concentrahon and of temperature

Table I Physlcal data used In the calculations

1 Heat of evaporation (Ail") 2500-2 25(T-273 15) (J/kg)

2 Dlffuslon coeffxient of water I” a,~ (0’) 5 28*10-gT3’2 (m2/g)

3 Thermal conductivity of air (h) 4 5*10S3+7 26*10e5T (J/msK)

4 Heat capacities

water vapour (t 8 ) 1930 (J/kgK)

a,r (^cP/, 1000 (J/kgK)

water (ep’a) 4200 (J,‘kgK)

dned milk (q:) 964 (J/kgK)

5 Vapour pressure of water

2
Pi= exp (I Ei T’-1 + E3 1nT)
1=0
E,= -7 246582’103.E,=77 6412,E2=5 744714.

E3= -8 2470
 The mactwabon of phosphatase durmg spray drymg of slum-mdk 655

The values of D, at other temperatures were calculated remams close to unity, causing a high water flux Some-
by means of interpolation or extrapolation usmg the what later m the process water concentration profiles
Arrhemus equatron To the expenmentally determmed butid up mslde the droplet, profiles which become very
data of Daemen1121 on the thermal degradation of al- steep m the region close to the surface because of the
kaline phosphatase m slum-rmlk the following equation strong decrease of the dtiuslon coefficient with decreas-
was fitted mg water concentration When the mterfactal liquid side
water concentration becomes lower than about 20wt%
k,=exp(A-B/T) (17) the water acttvlty decreases from Its value of umty and
where as a consequence also the water flux decreases When a
low level of the mterfaclal water concentration IS
3513x10-’ 356Ox1o-3
reached, the concentration profile starts to penetrate
ow ----Z---
further towards the centre of the droplet Due to the
8923~10~
U7a) decrease m water actlvlty the droplet temperature nses
-0,’ >
and in the simulation deplcted m Fig 5 the thermal
1 569 x 1o-3 1 570 x 1o-3 degradatton reaction sets in after approximately 04s
ow
---Z-- Due to the low water concentration near the surface the
6 297 x lo+ reactlon rate there IS relatively low compared to that at
Wb)
---z--- > the centre of the particle This becomes very clear at
later hmes m a thm dry region near the paticle surface
In Ftg 4 the reactton rate constant IS gven as a function the enzyme IS retamed, while over a small distance
of temperature and dissolved sohds concentration It IS inward the enzyme actlvlty drops to zero
mterestmg to note the large influence of the concen- Figure 6 gives the concentration profiles for a “hollow
trauon on both the dtffusion and the degradation kmettcs, sphere ‘, I e a droplet contauung entrapped air with the
which vary by several orders of magmtude dunng a same nut& hquld mass and a value of &I = 0 5 It IS
typlcal drying process seen that the water concentratton profiles are conslder-
ably flatter than m the case of a solid sphere This IS
RESULTSAND DISCUSSION caused by the lower mass transfer coefficient m the gas
Concentration profiles phase and the smaller dtiuslon distance inside the dro-
In Fig 5 calculated concentration profiles are presen- plet Because of the more umform water concentrations
ted for a droplet contammg no au bubble, the “sold dunng drymg also the profiles of the enzyme rest activity
sphere” Irutmlly the water activity at the surface are not as steep as m the case of the solid sphere From
the figure also the behavlour of the size of the gas bubble
I dunng drymg can be followed Imttally the bubble size
10’. T=8o’C

slum- milk decreases because of coolmg from feed temperature

towards wet-bulb temperature and consequently a lower
water vapour pressure mstde the droplet Due to the
Increase m the temperature of the bubble after the untlal
constant-activity penod the vapour pressure m the gas
bubble rises and the bubble sue mcreases again Only at
low water concentrations at the end of the drymg
process does the bubble size decrease again because of
r0-‘_ T= 70-C
the water Fusion out of the bubble The external radtus
of the hollow droplet first decreases because of water
loss, then mcreases by the just mentloned expansion of
the gas bubble, and subsequently the external radms
decreases agam when also the mtemal gas bubble
lo-*-
shnnks This 1s also dlustrated m Fig 7 m which the radu
are pven as a function of time It should be remarked
here that the shnnkage at the final state of drying 1s a
duect consequence of the assumption of pressure equd-
lbnum between the mslde and the outslde of the droplet,
thus neglectmg possible stresses m the dned matenal In

‘O-1: \I
practtce no such homogeneous shnnkage 1s observed,
but some particles may show an unploslon-hke ap-
pearance, as could be expected for particles of which the
-_ \ I 1
temperature IS lowered and the water vapour pressure
lo ! mslde the au bubble IS decreased, either by dehydration
0 02 04 06 08 10
- ws = l-ww (kgsollds/kgtotal) or by the coohng[M] process durmg product collection
Fig 4 Rate constant for the thermal macttvanon of alkaline Also particles may look hke egg-shells, probably the
phosphatase as a function of water concentmnon and expanded particle has dned very raptdly and formed a
temperature [ 131 mechamcally strong crust
656 A E WIJLHUIZEN et al

07
0 5 10 15 20 25 30 35
- rtpm)
Fig 5 Calculated water and enzyme actrvlty profiles for “sohd sphere” model Imtlal droplet radms 35 pm, air
temperature lOOT, air humtdtty 0 0273 kgH*O/kg dry au, mtttal mass fractton of water 0 55 -. Wetght
fractton of water, - - - -, phosphatase retentton parameter drymg ttme (s)

Fig 6 Calculated water and enzyme actlvlty profiles for “hollow sphere” model Droplet with same hqmd mdss as
m Fig 5, but with uutml gas bubble radms equal to hqwd radms Same condrtlons as m Fig 5 -, Mass
fraction of water, - - - -, phosphatase retention parameter drymg time (s)

Dryrng and thermal mactwatlon history

In Fig 8 the average water content, droplet tempera-
P ture and phosphatase retention are given as functtons of
2 40:.
time, for the sohd droplet under the same condltlons as
above The uutlal coolmg from feed to wet-bulb
i temperature and the subsequent constant-actlvlty or wet-
30. R, (t) bulb penod can be observed, after which the droplet
temperature gradually nses towards dry-bulb tempera-
ture The thermal degradation 1s seen to set m at a
ac- R, (t) temperature of about 70°C and to proceed rapidly to a
final value, due to the strongly lowered reactlon rate at
htgh dissolved sohds concentration
lo- Figure 9 gives the temperature and degradation hlstory
for droplets contammg gas bubbles, for different values
of the ratio & ,, at constant mltlal hqmd mass It IS seen
0, 1 that wxth tncreasmg values of doi the temperature nse
0 2 4 6 6 10
--Dt (5)
after the constant-actlvlty penod shows a somewhat
Rg 7 Internal and external radnts of drymg parWe as a more “rectangular” behavlour the temperature first m-
function of drymg time, same condltrons as m Fig 6 creases slowly and then nses more sharply towards
 The macnvatlon of phosphatase dunng spray drymg of skim-milk 6.57

103 loo

^y G
T!:E- 0
5s P

tt - t

\
\ 50
\

----__________

I
0’ a2 ’ 04 I 06 08 10 12 14 _ I .\
i

Rg 8 Average water concentration, droplet temperature and phosphatase retention as a function of drying time
for sohd sphere Same condltlons as m Fig 5

I I
, ooJ_______ loo

3 - 6
52
__----~~~-~~~o’~-___--__- - ci
7
o!m- 50
*--- -_-__- ----P_________

6 0.5 lb t’5 2’0-

-t (5)

Fig 9 Droplet temperature (- ) and phosphatase retention (-----) for droplets contauang gas bubbles of
varymg size as function of drying trme Condtlons of the au and hquld mass equal to Rg 6

dry-bulb temperature The thermal degradation remams water flux durmg the constant-activity penod, leading to
lower, because the same dissolved sohds concentration LS steeper water concentration profiles Therefore the end
reached at a lower temperature level with mcreasmg of thts penod 1s reached faster, and the layer in which
radms of the bubble, as mdlcated also m Fig 10 Also m enzyme IS protected by the low water concentration 1s
this figure the ultimate limit 1s aven for an mfimtely large thinner Since on top of this the temperature nse is
gas bubble, I#~, +m, which case can be calculated from faster, thermal degradation increases
the water vapour sorptron Isotherm, and the psych- -1ncreasmg the mltlal sohds concentration, as, leads
rometnc chart, smce then the dlffuslon hrmtatlon inside
the hqmd phase vanishes
Calculations for other values of process vanables - T ti = 1Owc
G
z- loo- RI3 I 35pm
showed a sumlar behaviour I-

Final phosphatase retentron as a functron of process EO-

t
vanables
In Table 2 the condlttons are given for which cal- 60-

culations were performed A sensltlvlty analysis for

vanations m process vanables around a “base case” set
of vanables was set up The results of this analysis for
the phosphatase retention are plotted m Figs 11 and 12
In general the followmg conclusions can be drawn
-1ncreasmg the av temperature, T,,,, leads to higher
enzyme degradation This can be explained as follows Rg 10 Temperature-sohds concentration hlstory of drymg
Increasing the au temperature causes a higher mttlal droplets Parameter IS & 1
658 A E WULHUUEN et al

Table 2 Values of process vmables used m the calculations of the base case

1 “Solid 5 here” model

Drying alt- perfectly mixed. Inlet air completly dry

Inlet air temperature (OC) 175

Liquid feed Inlet temperature (‘C) 50

Inltlal mass fraction of water (-) 0.55

Drying a1 r temperature (OC) 100

Imtlal droplet radius (*IO-%) 35

2 “Hollow sphere” model

The same base casecondltlons as for the “solld sohere” model are valid.
while for every droplet size an lnltlal qas bubble radius 1s taken of
25%. 50% and 75% of the lnltlal liquid drool& radius

GO60
--Increasing the ratio I$,,, of the gas bubble and dro-
e pIet size leads, as discussed before, to a faster drying
m
process due to shorter dlffuslon distance resulting m
lower degradation
It IS mterestmg to note that the effect of dissolved
sohds concentration on phosphatase retention becomes
mcreasmgly more nnportant with mcreasmg values of
040-
NC1 X,) -
&a1 from &, = 0 (see Fig 12 when we go from A to B)
9% but at higher values of &, apparently becomes lower
agam (B to C) where the retention is already close to
umty The physIcal explanation of this 1s quite comph-
0 3Oq-s 90~
-100 cated, here only an approxlmatlon will be discussed
FIN 11 Phosphatase retention as function of process vanables
From the calculation it follows that the thermal degrada-
for sohd sphere model Base case retention IS0 36 tion reaction sets m only when there IS already a
considerable devlatlon from the wet-bulb temperature,
to a small Increase m thermal degmdatlon At constant under the au condltlons chosen here The drymg process
mlt1a.l hquld volume droplets with higher dissolved solids IS already after a short time m the so called “regular
concentratmn remam larger durmg the drymg process, reqme” In tbs stage of drying the rate of water removal
and consequently have longer drying times, which results IS independent of the mltlal water concentration and IS,
m a higher degree of enzyme mactlvatlon for gtven air conditions, only dependent on the average

060-110-
6 hollow sphere
<
B
i
a50-
t

Fig 12 Phosphatase retention as function of process vanables for hollow sphere model Base case retentions
A = 0 39, B = 0 61, C = 0 945 Aa temperature (-), mltml droplet radms (-----), mrt~al sohds weight fraction
(_.-_-)
 The mactwatlon of phosphatase dung spray drying of skrm-mrtk 659

motsture content, and on a charactenstrc “sohd thrck- reductrons of phosphatase acttvrhes from 30 to 85% The
ness”, here denoted by L, The temperature and mois- macuvatron increased with increasing au temperatures m
ture content can consequently be scaled on a time scale the exhaust au at a constant feed rate and this increase
7 = f/L,*, m which t’ 1s the tune after r,,, when a certam m macttvatron decreased with au mlet temperature at
temperature or average moisture content has been vanable feedrate but constant exhaust au temperature
reached For a sohd sphere L, IS the radius of the These results are basrcly confirmed by our calculatrons
partrcle at complete dryness, assunung homogeneous although a more quantitative comparison IS not quite
shnnkage For a hollow sphere with only a thm shelf L. possible Daemen[i2] wtIl present a more detaded
IS the shell thickness after complete dehydration comparison of expenmental results m a laboratory spray
Assuming now that the important part of the thermal dryer and the model we described here It suffices here to
degradahon takes place dunng the “regular regrme”, at a say that generally the predIctron from Rgs 11 and 12
given place m the droplet the following equation must were m line with expenments, mcludmg the influence of
hold enclosed gas bubbles
The calcutatron scheme described here can be used to
study other first-order chemical conversrons dunng spray
drying and m pnncrple can be readily extended to non-
(18) first order reactrons Also the mterpretatron of the type
of expenments envisioned by Verhey and Daemen,
From the theoretrcal consrderatrons of Schoeber[9] also namely to deduce time-temperature hrstones of droplets
follows that in this “regular regrme” the water concen- dunng spray drymg by measurement of mactrvatron of
tratron m the particle can be described as a functron of a enzymes and kdhng of nucro-orgamsms of known
coordinate y, which IS defined as the ratro of the mass of kmettcs IS greatly enhanced
dissolved sohds within a certain regron and the total
mass of dissolved sohds Therefore k, IS a function of y
and r, and d r IS chosen large enough to let k, be NOTATION

neghgrble again at the end of the drying process, the actrvity

mtegral m eqn (18) can be wntten as a fun&on of y constant defined by eqn (17a)
constant defined by eqn (17b), K
In WP. 0) = - B(Y)J%* (19) heat capacity at constant pressure, J/kgK
dfiusron coefficient, m2/s
Of course the function /3(y) IS dependent on the constants m vapour pressure eqn (Table 1)
geometry of the system Constdenng now the value of L, heat of vaponzatron, J/kg
for the cases of the solids sphere and the hmmng case of mass flux density with respect to solids,
a hollow sphere with an extremely thrn shell (“egg-shell” kg/m’s
model), we can wnte for L, respectrvely mass transfer coefficient, m/s
Sohd sphere pseudo first order reactron rate constant,
l/S
L,‘= R:op.ovs (2W charactenstrc length, m
mass of droplet, kg
Egg-shell
molecular mass, kg/km01
L, = R:op,otiBR:o (20b) mass flux vector, kg/m’s
component of mass flux vector, kg/m’s
Thts leads to the following expressrons for the rest Nusselt number outside droplet
actrvrty of phosphatase pressure, Pa
Solid sphere saturated water vapor pressure, Pa
radial coordinate, m
ln WP.O) = - Bdy)R& (pso%32’3 (21a) reaction rate of enzyme degratron, kg/m3s
radius, m
Egg-shell
gas constant, J/mol K
la @JP~o) = -/MY)RP~@,o~‘S*/~R~O Wb) Sherwood number outside droplets
trme, s
It follows from these equatrons that the influence of the time measured from reference time to, s
mural Qssolved solids concentratron 1s much larger for temperature, K
the egg-shell model, than for the sohd sphere Thus effect velocity vector, m/s
1s also found after mtegratron of the rest enzyme actrvlty radial component of velocrty vector, m/s
over the droplet volume, as IS observed m the figure parttal specdic volume of sohds, m3/kg
conversron of degradation reaction of the
CONCLUSIONS enzyme
Verhey [17l and Daemen[12] measured inacuvatron of coordinate defined as ratio of mass of drs-
enzymes dunng spray drying m order to deduce solved sol& m a region and total mass
temperature-trme htstones of droplets Verhey measured of drssolved solids
660 A E WULHUUEN
et al

Greek symbols vector dot product

a, beat transfer coefficient, W/m2K dldt substantml derlvatlve
@l(y), &(y) geometry factors defined by eqns (21a) and
@lb) REFERENCES
p part& density of component I, kg/m3
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o mass fraction, kg/kg Technof 1970 5 111, 127
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