Chemical

Engineering 3

Lecture 9: Spray drying

 Outline
•  Principles of spray drying
•  Macroscopic view: mass and enthalpy balance

•  Microscopic view: single droplet evaporaAon

•  Control of parAcle properAes

 Spray drying process

liquid spray powder

GEA Niro spray congealing systems

Spray drying process

Closed-cycle spray drying process Spray cooling

Feed

Cyclone Bag filter HEPA Condenser

Heater
HEPA

Co-current, flat base

atomizer, for special
Also suitable for spra

Main Fines Solvent

powder
fraction
N2 out
N2 in
 Spray drying process
Laboratory scale Pilot plant scale
 Spray drying process
Industrial scale
 ParAcle morphologies
polymer soluAon (chitosan) colloidal dispersion (colloidal SiO2)

parAcle slurry (lactose) salt soluAon (NaCl) milk powder dried at different temperatures
 Process parameters
!  Feed concentraAon
ParAcle size
!  Droplet size (atomisaAon pressure)
and
!  Choice of solvent* morphology
!  Choice of addiAves

!  Feed flowrate
!  Drying gas flowrate Product
temperature
!  Drying gas humidity and residual
!  Drying gas temperature* moisture
 Mass and enthalpy balance
X in Yin A … solvent assumpAons:
B … dry gas 1)  non-volaAle solids
m˙ C m˙ B C … dry solids 2)  non-condensible gas

mA
€ € moisture content in solids X=
mC
€ vap € mA
m˙ A moisture content of gas Y=
mB
€
moisture mass balance:

€ m˙ C ( X in − X out ) =
€m˙ B (Yout − Yin ) = m˙ Avap
X out Yout
⇒  evaporaAon rate m˙ vap
m˙ C m˙ B€ ⇒  gas consumpAon
A
m˙ B
 Mass and enthalpy balance
X in TC ,in TB,in Yin TB,ambient assumpAon:
isenthalpic drying
m˙ C m˙ B
specific enthalpy of wet solids
H A + HC
Q˙ J= = (Xc p,A + c p,C )T
€ € € € € mC
specific enthalpy of wet gas
€ €
m˙ vap I=
HA + HB
= (Yc pg,A + c p,B )T + YΔhvap,A
A € € mB

enthalpy balances:
€ m˙ B Iin = Q˙ + m˙ B Iambient
€ m˙ C J in + m˙ B Iin = m˙ c J out + m˙ B Iout
X out Yout esAmate of minimum heaAng duty
€
m˙ C TC ,out = TB ,out m˙ B Q˙ = m˙ Avap Δhvap,A
€
 Mass and enthalpy balance
Condi&on: RelaAve humidity at outlet < 100 %

HA + HB
specific enthalpy [kJ/kg] I= = (Yc pg,A + c p,B )T + YΔhvap,A
mB

mA
moisture content [kg/kg] Y=
€ mB
M
pA xA P P nA P Y M ww ,B,A
relaAve humidity [%] ϕ = sat = = =
pA (T) pAsat (T) pAsat (T) n A + n B pAsat (T) 1+ Y MM ww ,B,A
€

sat b
saturated vapour pressure [Pa]
€ log10 p A =a−
c +T

(Antoine equaAon)

€
Graphical representaAon: Ramzin diagram
Step 1:
1)  Take air at 20 °C
and 60 % RH
2)  Find Y and I

Step 2:
1)  Take air from step 1
2)  Heat it up to 120 °C
3)  Find I

Step 3:
1)  Take air from step 2
2)  Find its adiabaAc
saturaAon
temperature
 ProperAes of wet solids
Equilibrium moisture sorpAon isotherm Same material, different temperatures

DVS (Dynamic Vapour SorpAon)

Same temperature, different materials

“sAcky point” temperature!

 Process parameters
!  Feed concentraAon
ParAcle size
!  Droplet size (atomisaAon pressure)
and
!  Choice of solvent* morphology
!  Choice of addiAves

!  Feed flowrate
!  Drying gas flowrate Product
temperature
!  Drying gas humidity and residual
!  Drying gas temperature* moisture
 Single droplet drying
Drying curve 1st period of drying:
PRODUCT DRYING CURVE EvaporaAon from free surface
Wet bulb temperature
VOLATILE CONTENT POWDER TEMPERATURE

2nd period of drying:

Diffusion across solid shell
FormaAon of hollow core

Time
 Single droplet drying
Wet bulb temperature evaporaAon rate

mass transfer (
m˙ A = km S pAsat (Tsurf ) − pAbulk )
droplet
heat-transfer rate
boundary layer
€
( )
Q˙ = kq S Tbulk − Tsurf = m˙ A Δhvap,A

heat transfer Ranz-Marshall correlaAon

1 1
€ Sh = 2.0 + 0.6Re 2 Sc 3

1 1
Nu = 2.0 + 0.6Re 2 Pr 3

udρ
Reynolds number Re =
€
η
k d € ηρ
Sherwood number Sh = m Schmidt number Sc =
D D
€ kq d η
Nusselt number Nu = Prandtl number Pr =
λ λ cp
€ €
 Droplet morphology evoluAon
Fig. 1. Example of the evolution of RH and sample mass of physical mixture of amorphous Valsartan and PVP during a single DVS measurement.
media were aqueous buffers at pH 6.8 with 0.001% (w/v) SDS
(sodium dodecyl sulphate) and pH 2 with 0.001% (w/v) Tween 20.
The rotational speed was 75 rpm at pH 6.8 and 100 nuclea7on
rpm at pH 2. The
dissolution profile was obtained at 37 C by the paddle method from
!
the powder. The concentration of Valsartan in the solution was
non-skin forming
determined using the UV technique at predetermined time points
(2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90 min and at pH 2 also 100,
110 and 120 min). The wavelength of 250 nm was used for
measurements.
3. Results and discussion
3.1. Characterisation of solid dispersions “strong” skin A water sorption isotherm provides information about th
SEM micrographs of spray dried solid dispersions and physical
mixtures of microparticles are shown in Fig. 2. SEM analysis
revealed a particle size distribution between 2 mm and 30 mm and
skin forming
a hollow spherical particle shape of the spray dried particles. The
amorphous form of Valsartan in the solid dispersions was
buckling
“puffing”
“weak” skin
confirmed by XRD porous par7cles
analysis as shown in Fig. 3. The spray drie
samples were compared with the reference sample of semicrys
talline Valsartan. The stability of the amorphous form unde
storage conditions was also measured after 45 days. No crystallin
form of the API was noticed in the stability study of the soli
dispersion after this period. Pure Valsartan used in the physica
mixtures was prepared by milling step and the volume-mea
particle diameter of the amorphous semi-crystalline particles wa
34 mm and 82 mm, respectively.
smooth par7cles
3.2. Sorption of water
affinity between the material and water. The water sorptio
isotherms of pure polymers are shown in Fig. 4. From the teste
polymers, the most hygroscopic character was revealed by PVP K3
(87.7% change of mass at 95% RH). The polymer Soluplus also show
a hygroscopic character with 37.6% change of mass at 95% RH
However, the water sorption of Eudragit EPO shows a hydrophobi
collapsed shells
 Droplet morphology evoluAon

Skin forming vs. Non skin forming Strong vs. weak shell

CompeAAon:
-  EvaporaAon rate
-  Internal diffusion rate

dS dt
α=
Deff

“baAscafo” equaAon
TECHNOLOGICAL BREAKTHROUGH condiAon for shell buckling
€ Direct observaAon:
-  AcousAc levitaAon
-  High-speed camera
-  Contactless thermometer
-  Raman spectroscopy

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