rm2technologies LLC
Applications of Reaction Calorimetry in the Chemical Process Industry
Reinaldo M. Machado
20 May 2105
ppt00 2
fundamentals of scale-up
© R.M.Machado, 2015
Numerous physical and chemical processes interact during a manufacturing or synthesis process. New manufacturing processes require fundamental information for scale-up and safety analysis
Kinetics
Heat
transfer
Thermodynamics;
Equilibrium
Mass transfer
Mixing
Physical property
changes
ppt00 3
fundamentals of scale-up
© R.M.Machado, 2015
Heat is Evolved or Consumed by Most Chemical Reaction Processes
Chemical reactions
Phase changes – Crystallization
– Vaporization/Condensation
Sensible changes
Mixing, solution
Viscous dissipation Friction of fluid elements “rubbing” together
ppt00 4
fundamentals of scale-up
Heat Generation and Heat Removal Form the Basis of Reactor Scale-up and Safety Analysis
20 40 60 80 100 120 0
200
400
600
800
1000
1200
Temperature, C
Heat
Flo
w/V
olu
me,
watt
s/lit
er
Heat Generation :
qgen/Vrctr= A* e{-Ea/RT} f(CA,CB)
Heat Removal :
qcool/Vrctr= (UA/Vrctr){Trctr-Tjacket}
Increasing UA/Vrctr
& Lowering Tjacket
© R.M.Machado, 2015
ppt00 5
fundamentals of scale-up
Traditional Heat Flow Calorimetry Using The Mettler RC1
Reactor temp., (Tr) is controlled by adjustment of jacket temp. (Tj)
Jacket flow is sufficiently high that Tj is virtually constant, ±0.1OC
QFLOW = U A ( Tr - Tj )
Calibration U A = QCALdt
(Tr - Tj)dt
Temperature
Controller
QCAL QFLOW
Tr Tj
© R.M.Machado, 2015
ppt00 6
fundamentals of scale-up
Profiles for a Simple Batch Co-Polymerization
0 50 100 150 200 250
-10
-5
0
5
10
0
20
40
60
80
100
120
140
Time, minutes
Tr-
Tj,
oC
Tr,
oC
© R.M.Machado, 2015
ppt00 7
fundamentals of scale-up
Reaction Exotherm Profile for a Polymerization Process
0 50 100 150 200 250 300 -60
-40
-20
0
20
40
0
20
40
60
80
100
120
140
Time, minutes
Heat
Pro
du
cti
on
, w
att
s
Tr,
oC
© R.M.Machado, 2015
rm2technologies LLC
Heat Transfer Characterization
ppt00 9
fundamentals of scale-up
Heat Transfer in CSTR’s Can be Correlated According to Empirical and Fundamental Models
Nu
Pr
Re
hTk
Cpk
ND
2
Nu Pr Rewall
C 1 3 2 3
014/ /
.
1 1 1U U h *
© R.M.Machado, 2015
ppt00 10
fundamentals of scale-up
Heat transfer characteristics of RC1 MP10 is similar to large scale reactors
0 1 2 3 4 5 6 -1
0
1
2
3
Log (Re) L
og
[N
u/(
Pr0
.33)]
Slope = 0.69
0.14
wall
32
31
RePrCNu
fluid
Number NusseltNu
Number ReynoldsRe
Number PrandtlPr
fluid
DiameterTankfluid
fluid
fluid
fluid
fluidfluid
k
Th
μ
NDρ
k
Cp
2
© R.M.Machado, 2015
ppt00 11
fundamentals of scale-up
© R.M.Machado, 2015
Heat Transfer Characterized By a Single Correlation Equation for a Stirred Tank Reactor
14.0
3/2
*111
wall
rctroN
NZVCUU
31
22
rctr
rctrrctrrctr gCpk
Material Heat Transfer Parameter
3/1
3
24
TgND o
Reactor Geometric Parameter
ppt00 12
fundamentals of scale-up
© R.M.Machado, 2015
Wilson Plot Reveals Heat Transfer Resistances
3.0
2.5
2.0
1.5
1.0
0.5
0.0 0 1 2 3 4 5 6 7 8
(No/N) 2/3
1/U
Resistance of
Reactor Fluid
Resistance of Reactor
Wall and Jacket Fluid
Intercept = 1/U*
Slope = 1/(C V Z)
ppt00 13
fundamentals of scale-up
© R.M.Machado, 2015
Wilson Plot For Glycerol Reveals Impact of Temp. on Heat Transfer Coefficient
3.0
2.5
2.0
1.5
1.0
0.5
0.0 0 1 2 3 4 5 6 7 8
25oC
40oC
55oC
U* = 120 W/(m2 K)
1.5 liter Lab Reactor
K)W/(mU 2
100
32
100
rpmN
ppt00 14
fundamentals of scale-up
© R.M.Machado, 2015
Material Heat Transfer Parameter for Various Fluids at 30oC
Water 27,100
Toluene 7,710
Sulfuric Acid 8,820
Isopropanol 5,960
Glycerol 1,690
Polymers 100 to ~10,000 cp 5,000 to ~500
Material V, W/(m2 K)
ppt00 15
fundamentals of scale-up
Deviations From Wilson Plot Indicate Mixing Problems
1/U
1/U*
(N/No)-2/3
Decreasing N(rpm) • High Wall Viscosity
• Poor mixing
• Pseudoplastic Fluid
Stagnant
Zone
Mixed
Zone
© R.M.Machado, 2015
ppt00 16
fundamentals of scale-up
© R.M.Machado, 2015
Heat transfer with anchor impeller at 100 rpm with glycerol in MP10 lab reactor (1.5 liter, heat load = 25 kW/m3)
V hr U
TroC
cp
W/(m2 K) r
mm
TjoC
TrwoC
cp
w)0.14
25 940 1400 115 58.1 2.4 14 19 1600 0.93
40 274 2100 169 68.4 1.6 31 36 380 0.96
55 89 3000 276 83.7 0.9 48 53 100 0.98
U* = 120 W/(m2 K) Measured values
ppt00 17
fundamentals of scale-up
© R.M.Machado, 2015
Comparisons of VisiMix predictions and Experiments for Heat Transfer with Anchor Impeller at 100 rpm with Glycerol in the Mettler Toledo RC1 MP10 glass lab reactor
Inlet
Jacket
Temp. oC
Reactor
Temp. oC
Reactor
fluid
, cP
Re Overall Heat
transfer coeff. U
W/(m2 K)
Heat
removal
rate, W
Experiment 14 25 940 13
58.1 25.0
VisiMix 59.5 27.0
Experiment 31 40 274 43
68.4 25.0
VisiMix 70.5 26.2
Experiment 48 55 89 133
83.7 25.0
VisiMix 80.0 23.2
ppt00 18
fundamentals of scale-up
Review article for coils in Agitated Vessels
© R.M.Machado, 2015
ppt00 19
fundamentals of scale-up
Tranter Prime Surface Heat Exchangers can serve as both baffles and heat exchangers
Plate coils are fabricated by
embossing channels on
opposing plates and
welding plates together.
Uniform temperature
distribution.
© R.M.Machado, 2015
Photos from Tranter Inc. product brochure www.tranter.com
rm2technologies LLC
Reaction Rate Analysis: Hydrogenation
ppt00 21
fundamentals of scale-up
© R.M.Machado, 2015
Examples from a Hydrogenation/Oxidation process development laboratory
ppt00 22
fundamentals of scale-up
Process Rates for Reductive Alkylation Help Identify Interaction of Feed Rate and Mixing
R-NH2 + 2 H2C=O + 2 H2 R-N(CH3)2 + 2 H2O + Q heat
1 1 2 2 3 3
.35
.30
.25
.20
.15
.10
.05
.00
800
600
400
200
0
0 2 4 6 8 10 12
Time, hrs.
No
rma
lize
d
Ra
tes
, 1
/hr
RP
M
Formaldehyde Hydrogen
Heat
© R.M.Machado, 2015
ppt00 23
fundamentals of scale-up
© R.M.Machado, 2015
No baffle Baffle
ppt00 24
fundamentals of scale-up
© R.M.Machado, 2015
RC1 MP10 hydrogen mass transfer correlation in MeOH and IPOH
Isopropanol/H2
V*kLa = 0.2009*N - 98.949
R2 = 0.9667
Methanol/H2
V*kLa = 0.3077*N- 130.11
R2 = 0.9325
0
50
100
150
200
250
300
350
400
450
500 700 900 1100 1300 1500 1700 1900
rpm
Vliq
uid(c
m3)*
kLa
(s-1
)
ppt00 25
fundamentals of scale-up
Lets take a look at developing a semi-batch process chemistry for Nitrobenzene hydrogenation to Aniline : The Engineer’s View!
NO2 + 3H2 NH2 + 2H2O
Hreaction = -537 kJ / mole
© R.M.Machado, 2015
ppt00 26
fundamentals of scale-up
Semi-batch operation can be used to simulate features of continuous operation under specific conditions
= Qin Cin - Rate VR dN dt
dN dt
= Qin Cin - Qout Cout- Rate VR
at high conversion
Continuous
Semi-batch
with small volume changes
dN dt
= Qin Cin - Rate V(t)
© R.M.Machado, 2015
ppt00 27
fundamentals of scale-up
Feed rate affects reaction rate during multi-ramp feed experiments. Lessons: 1) Calorimetry is a convenient method for measuring the overall reaction rates, 2) Programing feeds allow rapid kinetic characterization.
0 20 40 60 80 100 120 140
320
240
160
80
0
Time, minutes
Rea
cti
on
Rate
, w
att
s
Theoretical Feed Controlled Rate (~Infinitely Fast Reaction) =
Q = Feed rate x DHreaction
Reaction Rate
© R.M.Machado, 2015
ppt00 28
fundamentals of scale-up
Recall that the reduction of nitrobenzene can take two paths! Maybe changing conditions change between the paths.
NO2 NO H2
NOH H
H2 NH2
H2
Nitrobenzene Nitrosobenzene Phenylhydroxylamine Aniline
Phenylhydrazine Aniline
N + N
O -
H2
N N
H2
N H
N H
H2 2 NH2
Azoxybenzene
Azobenzene
© R.M.Machado, 2015
ppt00 29
fundamentals of scale-up
Nitrobenzene
When the feed rate was too fast for conditions (catalyst type, catalyst amount, pressure) nitrobenzene and intermediates accumulated to “poison” catalyst. Lesson: Engineers really do need Chemists!
0 20 40 60 80 100 120 140
Rea
cti
on
Rate
, w
att
s
Wt%
In
term
ed
iate
s
240
200
160
120
80
40
0
Time, minutes
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Azoxy-
benzene
Azobenzene
© R.M.Machado, 2015
ppt00 30
fundamentals of scale-up
Pressure increases the maximum rate which can be achieved. Identical programed multi-ramp feed experiments used to characterize process capability. Lesson: Use programed recipes to test conditions, catalysts, raw material quality.
0 40 80 120 160 200
200
160
120
80
40
0
Time, minutes
Rea
cti
on
Ra
te,
wa
tts
Ma
ss o
f F
eed
Ad
ded
, g
ram
s
Total Reactor Pressure
11 barg
8 barg
Feed Addition 50% Aniline/ 50% Nitrobenzene
200
160
120
80
40
0
© R.M.Machado, 2015
ppt00 31
fundamentals of scale-up
© R.M.Machado, 2015
Programmed “ Disturbance ” Patterns Can Be Used to Screen Catalyst Performance
200
0 2 4 6 8 10
Reaction Time, hrs
Reacti
on
Exo
therm
, W
att
s
Three Increasing Feed Ramps; Repeated
150
100
50
0
1a 2a 3a 1b 2b 3b
ppt00 32
fundamentals of scale-up
© R.M.Machado, 2015
ppt00 33
fundamentals of scale-up
Biazzi Impeller and mixing system
© R.M.Machado, 2015
rm2technologies LLC
Reaction Rate Analysis : Soybean oil hydrogenation
ppt00 35
fundamentals of scale-up
© R.M.Machado, 2015
Mass transfer tells us how fast we absorb H2
H2 (gas) H2 (liquid)
Rate of Absorption = kLa (sec-1) { [H2]sat.- [H2]bulk }
“Rate”
Constant
Increases with Agitation
Intensity and H2 Flow
Driving
Force
Increases with Pressure
and Usually Increases with
Temperature
ppt00 36
fundamentals of scale-up
© R.M.Machado, 2015
Hydrogenation of Soybean Oil
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
O H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C C H
O H H H H H H H H H H H H H H H H H H
C R’
H
H C O
H C O
H C O
H
GLYCEROL GLYCEROL
FATTY ACID FATTY ACID C R’
O
Approximately 50% of double bonds are
Polyunsaturates
ppt00 37
fundamentals of scale-up
Olefin Hydrogenation Reactions
H2 +
Catalyst
+ ~23 kcal/mole H2
R' R R' R
cis
H2 +
R R'
Catalyst
+ ~23 kcal/mole H2
R R'
trans
H2
Catalyst R R'
trans
R' R
cis
© R.M.Machado, 2015
ppt00 38
fundamentals of scale-up
Process Conditions Impact Soybean Oil Hydrogenation Rates: Calsicat E-479D
Reaction Time, minutes
0
50
100
150
200
250
0 30 60 90 120 150 180 210 240
Rate
, w
att
s/k
g
30 psig, 180oC, kla=0.013 /sec
30 psig, 180oC, kla=0.2 /sec
45 psig, 180oC, kla=0.013 /sec
30 psig, 200oC, kla=0.013 /sec
© R.M.Machado, 2015
ppt00 39
fundamentals of scale-up
0
50
100
150
200
250
% Conversion
Rate
, w
att
s/k
g
Polyunsaturate Monosaturate
100 80 60 40 20 0
30 psig, 180 C, kla=0.013/sec
30 psig, 180 C, kla=0.2/sec
45 psig, 180 C, kla=0.013/sec
30 psig, 200 C, kla=0.013/sec
Various Process Conditions Reveal a Consistent Transition @ ~50% Conversion
© R.M.Machado, 2015
ppt00 40
fundamentals of scale-up
Catalysts can be Screened for Selectivity and Activity
0
50
100
150
200
250
% Conversion
Rate
, w
att
s/k
g
Selective Catalyst
w/ High Activity
Non Selective
Catalyst
100 80 60 40 20 0
© R.M.Machado, 2015
ppt00 41
fundamentals of scale-up
Key Spectral Features of Soybean Oil
3011 cm-1
cis-isomer Virgin Oil
1749 cm-1
ester
50% Hydrogenated
965 cm-1
trans-isomer
100% Hydrogenated
3000 2500 2000 1500 1000
Wavenumber, cm-1
© R.M.Machado, 2015
ppt00 42
fundamentals of scale-up
FTIR Profiles Track trans - Formation
Wavenumber cm-1
1050 1000 950 850 800 750 700 900
200
150
100
50
0 Time,
min. 0.30
0.35
0.40
0.45
Ab
so
rban
ce
© R.M.Machado, 2015
ppt00 43
fundamentals of scale-up
FTIR Profiles Track cis- Disappearance
Wavenumber cm-1
3100 3050 2950 2900 2850 2800 3000
Time,
min. 0.30
0.50
0.90
0.70
Ab
so
rban
ce
200
150
100
50
0
© R.M.Machado, 2015
ppt00 44
fundamentals of scale-up
cis -trans -isomer Fraction during Soybean Oil Hydrogenation : Calsicat E-428D
% Conversion
Fra
cti
on
0.0
0.2
0.4
0.6
0.8
1.0
30 psig, 180oC
kla = 0.013 sec-1 (1000 rpm)
cis-isomer trans-isomer
100 80 60 40 20 0
© R.M.Machado, 2015
ppt00 45
fundamentals of scale-up
trans- Formation for Selective Calsicat E-428D is Not Sensitive to Process Variables
0
20
40
60
80
% Conversion
% T
ran
s i
n U
nre
acte
d
Do
ub
le B
on
ds
30 psig, 180 C, kla=0.013 /sec
30 psig, 180 C, kla=0.2 /sec
45 psig, 180 C, kla=0.013 /sec
30 psig, 200 C, kla=0.013 /sec
7 psig, 160 C to 215 C, Breen [1]
60 40 20 0
© R.M.Machado, 2015
rm2technologies LLC
Reaction Rate Analysis : Propoxylation of an aromatic amine
ppt00 47
fundamentals of scale-up
MDA Propylene Oxide Reactions to Mono-, Di-, Tri- and Quad- Substituted Products
N H 2
N H 2
O 1.
N H 2
N H O H
198.27 58.08 256.35 A
PO M
1
N H 2
N H O H
O
N H O H
N H
O H 314.43 D12
2 M
N H O H
N H
O H
O
N H O H
N O H
C H 2
O H
4.
372.51
D12 T
4
© R.M.Machado, 2015
ppt00 48
fundamentals of scale-up
Symmetry and Similarity Suggest Kinetic Models with 2 Independent Rate Constants
Rate 1 = k1 CA CPO
Rate 2 = k2 CM CPO
Rate 3 = k3 CM CPO
Rate 4 = k4 CD12 CPO
Rate 5 = k5 CD11 CPO
Rate 6 = k6 CT CPO
k2 = k1/2
k4 = 2 k3
k5 = k1/2
k6 = k3
k1 = A1 exp{-E1/RT}
k3 = A3 exp{-E3/RT} © R.M.Machado, 2015
ppt00 49
fundamentals of scale-up
Typical Rate Profile at 85oC
0
10
20
30
40
50
60
70
80
0 2 4 6 8 10
Time, hr
Reac
tio
n R
ate
, w
att
s
0
1
2
3
4
5
PO
Ad
ded
, g
mo
les
Propylene Oxide
Reaction Rate
© R.M.Machado, 2015
ppt00 50
fundamentals of scale-up
© R.M.Machado, 2015
Comparison of Actual and Simulated Rate Profiles
0 1 2 3 4 5 6 7 8 9 10
Time, hrs
Reacti
on
Rate
, Q
r, w
att
s
85oC
100oC Lines = Simulation
Points = Data
70oC
ppt00 51
fundamentals of scale-up
© R.M.Machado, 2015
Final Rate Parameters Show Primary Amines ~10 x’s Faster than Secondary Amines
k1 = k1(To)exp{E1/RTo(1-To /T)}
k3 = k3(To)exp{E3/RTo(1-To /T)}
k1 = 6.29 x10-6 m3/(mol s) exp{48.2 kJ/mol /RTo(1-To /T)}
k3 = 6.45 x10-7 m3/(mol s) exp{48.5 kJ/mol /RTo(1-To /T)}
To = 85oC
ppt00 52
fundamentals of scale-up
Comparison of Predicted and Observed Component Mass at all Temperatures
0.00
0.10
0.20
0.30
0.40
0.00 0.10 0.20 0.30 0.40
Component mass (observed), kg
Co
mp
on
en
t m
as
s
(pre
dic
ted
), k
g
Mono Di
Tri Quad
Parity
© R.M.Machado, 2015
ppt00 53
fundamentals of scale-up
© R.M.Machado, 2015
Impact of PO Stoichiometry on Selectivity at 85oC
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Moles Propylene Oxide/Mole MDA
Mo
le F
rac
tio
n A
min
e G
rou
ps
Primary Tertiary
Secondary
rm2technologies LLC
Reaction Rate Analysis: Oxidation of an alcohol
ppt00 55
fundamentals of scale-up
© R.M.Machado, 2015
Discrimination of Kinetic Models
Composition analysis alone is an incomplete method of
determining accurate kinetic models
Analysis of continuous rate measurement in
combination with composition is the best way to
discriminate various kinetic models
ppt00 56
fundamentals of scale-up
© R.M.Machado, 2015
Model Discrimination: CA0=100 gmole/m3, CB0=80 gmole/m3
A+B C
0
20
40
60
80
100
120
0 20 40 60
Time, minutes
Co
nce
ntr
ati
on
of
A,
gm
ole
/m 3
0.0
0.4
0.8
1.2
1.6
2.0
Reac
tio
n R
ate
, g
mo
le/(
m 3
min
)
0-order
1st-order
2nd-order
0-order
1st-order
2nd-order
Lines = Rate
Points = Concentration
ppt00 57
fundamentals of scale-up
© R.M.Machado, 2015
Case History: Alcohol Oxidation with Heterogeneous Catalysis
OH
R+ O2 + M
+OH
-
R
CO-M
+
O
+ 2 H2O
OH
R + M+OH
-
R
CO-M
+
O
+ 2 H2
Cat.
Original research determined that this reaction was 1st
order in the alcohol. The batch kinetics data was
based exclusively on composition samples,
approximately 10 samples per experiment. Oxygen
pressure was held constant.
ppt00 58
fundamentals of scale-up
© R.M.Machado, 2015
Batch Alcohol Oxidation to Carboxylate Salt
0
50
100
150
200
250
0 50 100 150 200
Time, minutes
Rate
, w
att
s
0
1
2
3
4
5
Pre
ssu
re,
barg
Rate
Pressure
OH
R+ O2 + M
+OH
-
R
CO-M
+
O
+ 2 H2O
ppt00 59
fundamentals of scale-up
© R.M.Machado, 2015
Typical Reaction Characterization of Alcohol Oxidation with a Slurry Catalyst indicates more complex Kinetics
Substrate Concentration (based on thermal conversion)
Rate
, m
ole
/[se
c m
3]
Pre
ssu
re,
barg
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0% 10% 20% 30% 40% 50% 0
1
2
3
4
5
6
Rate
Pressure
1st order region
Ost order region
ppt00 60
fundamentals of scale-up
© R.M.Machado, 2015
Typical Heterogeneous Kinetics: Oxidation of Substrate S
catalyst Weight%% where,
O & S inorder -1st ,%
0@
O inorder -1st S, inorder -Zero ,%
@
Transfer, Masshigh With
1
%
2.,1
2
.,1
.,
1
2
2
22
2
wt
CCwtkRate
C
K
CwtkRate
C
CC
CK
CCwtkRate
satOS
S
satO
S
satOO
S
OS Simple model
explains results!
rm2technologies LLC
Thermal Safety Analysis: Propoxylation of an aliphatic amine
ppt00 62
fundamentals of scale-up
© R.M.Machado, 2015
Illustration Problem: Propylene Oxide Addition to an Amine; A(amine) + B(propylene oxide) C
Homogeneous Liquid Phase
The amine is in large excess over propylene oxide
– Reaction is 1st-order in propylene oxide
Reactor volume can be assumed constant
Propylene oxide is added at a constant rate over time,
tadd
OR1 NH2 + R1 N
HOH
ppt00 63
fundamentals of scale-up
© R.M.Machado, 2015
Heat Evolution is a Function of Reactor Temperature and Feed Rate, 60oC
0 200 400 600 800 0
5
10
15
20
Time, minutes
Heat
Evo
luti
on
, w
att
s
50
150
200
100
Mass o
f P
O, g
ram
s
PO + Amine Alcohol
ppt00 64
fundamentals of scale-up
© R.M.Machado, 2015
Accumulated propylene oxide can be considered “Stored Energy” during semi-batch addition
time, minutes 0 200 400 600 800
0.0
0.5
1.0
1.5
2.0
2.5
no
rmali
zed
reac
tio
n
rate
(W)/
tota
l h
ea
t (J
),
(s-1
) x
1000/6
0
Stored reaction
energy @ end
of PO addition
Time
Tem
p.
This is what could happen
if we loose cooling at the
end of the addition! End of addition
ppt00 65
fundamentals of scale-up
© R.M.Machado, 2015
Increasing addition time reduces maximum exotherm and stored reaction energy
0 200 400 600 800 0
2
4
6
8
10
time, minutes
120 min. addition time
for propylene oxide
480 min. addition time
for propylene oxide
no
rmali
zed
reacti
on
rate
(W)/
tota
l h
eat
(J),
(s-1
) x
100
0/6
0
ppt00 66
fundamentals of scale-up
© R.M.Machado, 2015
Increasing reactor temperature reduces stored reaction energy
0 200 400 600 800 0.0
0.5
1.0
1.5
2.0
2.5
time, minutes
60oC
75oC
105oC
no
rmali
zed
reacti
on
rate
(W)/
tota
l h
eat
(J),
(s-1
) x 1
000/6
0
ppt00 67
fundamentals of scale-up
© R.M.Machado, 2015
MTSR After Cooling Loss Just at the Point of Complete Propylene Oxide Addition (120 minutes)
Limiting
Temp. 110oC
37oC
80oC
Reactor Temp.,oC, During Addition of PO
0 50 100 150 75 25 125 0
50
100
150
25
75
125
Fin
al R
eacto
r Tem
p.,
oC
Net Adiabatic DT = 100oC
ppt00 68
fundamentals of scale-up
© R.M.Machado, 2015
MTSR After Cooling Loss Just at the Point of Complete Propylene Oxide Addition
120 min.
Reactor Temp.,oC, During Addition of PO
0 50 100 150 75 25 125 0
50
100
150
25
75
125
Fin
al R
ea
cto
r Te
mp
.,oC
30 min.
480 min.
Addition Rate
rm2technologies LLC
General Conclusions
ppt00 70
fundamentals of scale-up
Reaction Calorimetry
Realtime rate feedback allows investigators to
interact and optimize processes online
Addition Strategy and Feed Rates are key process
design variables
Thermal Reaction Profiles generated to
– compare process strategies
– screen raw materials with programmed “Disturbance” patterns; temperature, feed rate, pressure. agitation
– “process thermal spectra”
Heat transfer characterization of difficult materials
and intermediates © R.M.Machado, 2015
ppt00 71
fundamentals of scale-up
Reaction Calorimetry
Characterizes Kinetics, Mass Transfer, Heat
Transfer, Thermodynamics, Physical Property
Changes
Thermal Data Allows Efficient Development of
– Optimized processes
– Scaleable process
– Safe processes
© R.M.Machado, 2015
ppt00 72
fundamentals of scale-up
Online FTIR
Monitors Selectivity in Complex Reaction Sequences
ConcIRT Provides Rapid Analysis without Standards
© R.M.Machado, 2015
ppt00 73
fundamentals of scale-up
© R.M.Machado, 2015
Semibatch Processes at High Temperature Can be Advantageous
Lower reaction mass viscosity
– Improved mixing
– Improved heat transfer
Higher heat removal driving force, Tr-Tj
Increased kinetic reaction rates
– Shorter batch times
Improved reagent and product solubility
Reduced risk of reagent accumulation
– Lower stored exotherm energy
ppt00 74
fundamentals of scale-up
© R.M.Machado, 2015
Semibatch Processes at High Temperature may also create unwanted results
Increase rate of by-product formation
– Lower selectivity due to by-product formation
– Color problems
Increase pressure from increased solvent vapor
pressure
Longer cool down time
ppt00 75
fundamentals of scale-up
Reinaldo “Ray” Machado
phone: (484) 553-3612
E-mail: [email protected]
Website: www.rm2tech.com
Ray is the instructor of short course
“Fundamentals of Scale-up”, which may be offered at your site.
Reinaldo (Ray) Machado is the developer and instructor of a popular industrial short course, “Fundamentals of
Scale-up” which he teaches part time. Proceeds from the course supports EWB, Engineers Without Borders.
Ray is also currently employed by Air Products and Chemicals, Inc. in Allentown, PA where he serves as a
senior process engineer supporting both the Electronics and Performance Materials Divisions. He also serves
as a senior consultant specializing in gas/liquid reaction engineering and electrochemical engineering and
provides global support for hydrogenation and oxidation applications for both internal and external customers.
Ray has broad technical experience in applied reactor engineering, scale-up of chemical reaction processes,
mass transfer, heat transfer, applied reaction calorimetry, hydrogenation, electrochemical engineering,
sulfonation, amination, propoxylation, polymerization, and plastics recycling.
Ray received a Ph.D. in chemical engineering with a concentration in chemistry from the University of
Wisconsin, Madison, and a B.A. in chemistry and mathematics from Frostburg State University. He has served
as a part-time instructor of a short course, “Scale-Up Considerations in Chemical Processes,” at Lehigh
University and currently teaches industrial courses on the fundamentals of scale-up. He holds 17 patents, has
collaborated on 17 publications, and is a member of the American Institute of Chemical Engineers and the
American Chemical Society. © R.M.Machado, 2015
ppt00 76
fundamentals of scale-up
(c) Reinaldo Machado; rm2technologies LLC 2011
Titration by Reinaldo Machado
Into the acid brew, fall bitter drops of base.
Whirling pink ribbons, consumed without a trace.
Each fresh drop gives life, to stronger crimson swirls. A spinning fatal dance, in twisting eddy whirls.
A hesitant drop descends, into the vortex roll. A fiery flash of red transforms the mixture whole. © 2011 Reinaldo Machado
Top Related