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SYNTHESIS
OF PROPYLENE
OXIDE
FROM PROPYLENE
CHLOROHYDRINS-I
KINETIC
S Cm,
Ishtuto
da Chlmlca
E SANTACESAlUA,*
F~s~ca del
reactlons
mvolved
OF THE
M
30 October
1978, accepted
IIIthe mdustnal
PROCESS
MORBIDELLI
Pohtecmco
dr Mtlano. bCentro
Energetrca, Socleta Euteco,
(Recewed
Abstrac-The
ASPECTS
production
Nazlonale
Mdano
I6 Jun~ory
of propylene
and L CAVALLI
Tecnologla
della
Prop&lone
ed
1979)
have been
kmetlcally mvestlgated The kmetlcs of dehydrochlonnatlon of propylene chlorohydnns have been studied, both In
the presence of slaked hme and of caustic soda, by potentlometnc techmques The kmetic parameters of the
reactions have been determined The propylene oxide hydrolysis has been studled by measurmg the decrease of the
reagent dunng the time usmg NMR analysis
INTXODUCTION
CH,-CH-CH,
CH, = CH-CH,
dH
+ HClO
dl
CH,-CH---CHz
L1
AH
CH3YH-YH2
dH
-CH2-_CH--CH,
CH,+H-_CHz
+ Cl- + Hz0
+OH-
EXPERIMENTAL
\/
41 AH
+ HzO-
tOH-J
CHz-CH-CHs
d I-I
OH
Equipment,
reagents and operating condltrons
The dehydrochlormatron
of propylene chlorohydrms
in
aqueous basic solution 1s a fast reaction occurrmg with
the ehmmatlon
of hydrogen
chloride
As previously
mentioned,
the basic envuonment
can be obtamed by
usmg slaked lame or caustic soda In the present paper
the kmetlcs of propylene oxide formation, both in the
presence of slaked lune and of caustic soda, have been
studied
In the first case, the reaction rate has been
determined by contmuous
potentlometr?c
evaluation
of
the amounts of chlonne
released dunng the reactlon
accordmg to the method described m[S, 71 A concentration electrochermcal
cell, with two Ag/Ag Cl electrodes has been used for the determmation
One electrode
was unmersed m the reaction solution and the other m
a K2S04 saturated solution, separated from the reaction
solutlon by a porous disk of fntted Pyrex glass, which
allows electrlcal continuity
The electrodes
were prepared by anodlc attack of a salver rod m a 0 1 N HCl
solution at very low current mtenslties. as suggested by
Ives et al [S] The AgCl coatmg was renewed before each
run m order to prevent the effects of electrode agmg[8]
1123
1124
S CARR.4et al
RESULTS
the propylene
oxide formation
occurs m the
presence of slaked hme, Ca CIZ IS formed and the solution 1s buffered In fact, If we consider the relations
When
ICa*][OH-]*
[Cal=
It
IS
possible
= k, solublhty
product
(1)
(2)
to write also
[Ca]
(3)
- 2K, = 0
(4)
The concerttratton
of hydroxyl
Ions decreases
very
slowly after the uutlal stage of the reaction Therefore, m
this case, we can consider the hydroxyl concentratttlon
during the reaction as constant
The Ag/AgCl electrodes,
described
m the previous
sectlon, give potentlometrlc
curves which can be used for measuring the increase of
the chloride ton concentration
as a result of the reactlon
These curves can be easily rearranged m order to obtam
the conversion
degree as a function of time In Fig 1 the
experlmentaI
values
of conversion
versus
time are
reported for several temperatures
The experImental data
reported In Fig 1 are well fitted, as shown m the Fig,
assummg pseudo first order krnetlc reactton model of the
type
(5)
[PC] bemg the concentration
of propylene chlorohydrm
The use of this slmphfied model 1s Justified because the
solution,
as already mentioned,
IS buffered
and the
hydroxyl concentration
can be considered
nearly constant
The kmetlc parameters obtained from the experlmental
runs are reported tn Table 1 In Fig 2, an Arrhenms type
plot, IS reported for this reaction
If the dehydrochlormatlon
IS made
m the presence of
caustic soda, the hydroxyl ion concentration
decreases
rapidly during the reaction
The change of hydroxyl
concentrat!on
dunng this tame has been determined by a
glass electrode
Smce the reaction rates slow down with
the decrease of pH, they depend on the hydroxyl concentration
The experlmental
results,
m fact,
can be well
represented
by assuming a second order kmetm model,
of the type
r<d,, = kz[OH-][PC]
(61
The experimental
data obtained
for runs made m
different operating condmons
are reported m Table 2
The kmetrc constants have been calculated on the basis
Synthesis
Table
1 Kmetwz parameters
Basw
of propylene
klnetlc
rlItTI~
lune
= kl
= A1
r soda
02x
= k2 [PCllOH-1
503x10
-E2/RT
k2
EI
[PC]
3
109s
-1
12
(kcal/mole)
15
860
16
422
moks
2
tlmc
Rg
I
--
1125
soda
= x2
chlorohydrms--I
model
-E,/RT
k,
Caustic
reactton
soda
Adopted
mednun
Slaked
37 C
3
( m~nules)
reaction of propylene
I Trend of conversIon vs time for the dehydrochlonnatlon
lime suspension
chlorohydrms
made m slaked
Fig 2 The Arrhemus plot for the kmetlc constants of the dehydrochlonnatlon reaction in the presence of slaked lime
of the second
order
kmetlc
model
The kmetlc
parameters are summarrzed m Table 1 In Fig 2, an
Arrhenms plot for this reaction IS also reported
From
Ftg 2 one can compare the kmetlc constants obtamed for
the reaction made m the presence of slaked hme and
caustic soda The relation between the two constants ks
and k, IS
ka = k, [OH-]
(7)
S Cm
1126
et al
RUTI
iOH-10
(%
moles/l
(sex)
30
27
5
10
01
20
30
40
0
10
20
30
40
50
0
10
20
30
40
=L
01
01
25
28
45
-q--g-
---I-?
0
01
3
55
10
---l-e
7
Table 3 A comparison
59
between
I
---i-T-
28
01
01
20
30
40
2
33
4
(Cl
0
0
0
0
0
043
174
261
043
086
0 167
0 178
0 184
0 197
0 203
608
695
261
608
869
0 203
0 214
0 205
0 197
0 197
739
608
043
043
0
0
0
0
130
131
130
131
089
109
123
132
0
0
0
0
190
180
175
168
856
461
269
002
339
!
I
1
1
I
223
226
237
130
390
787
a04
374
730
952
0
0
0
0
0
232
229
221
217
214
265
374
826
030
134
3
3
3
2
2
244
223
650
930
700
set
251
262
265
266
257
values,
at several temperatures
K,'K2
3 595
90
5631x
x 10 -2
10 -2 (y)
3 277 x 10 -2
2
110x
10 -2
data
087
956
034
626
913
50
x Extrapolated
0
1
1
3
3
3
0
13
22
28
33
36
0
1
2
3
3
3
0
14
23
29
33
0
0
0
0
0
0
1
2
3
4
4
0
1
2
3
3
3
0
2
3
3
4
4
k2
l/mole
I
T
Conversions
I
0
Time
1
(8
1127
m caustic
= 5 03 x 10 e-
soda solution,
follows
422/RT [PC][OH-]
the
(9)
kn = kk + kc,, [OH-]
Propylene
oxide hydrolysis
lowers the yields of the
process
It 1s therefore unportant to know the kmetlc
parameters
of thts reaction
Runs made with an NMR
spectrometer
at several pH and temperatures
show that
hydrolysis IS a first order reaction
An effective kmetlc
constant can be evaluated by the determmatlon
of the
half life time
In Tables
4-7 the percentages
of
hydrolyzed
propylene oxide for several operatmg conditions are reported as a function of tune The effective
kinetic constants k, are reported for each run in the same
tables
Figures 3 and 4 show the values of -In (I -x) vs tune
for runs made at dtierent temperatures
The linearity of
the curves justdies the assumption of the iirst order for
the orgamc reagent In Fig 5, the values of the effective
kinetic constant, obtamed for the runs made at the same
temperature
#WC), but at different
pH values,
are
reported as a function of hydroxyl concentration
As can
be seen there IS a linear trend between ks and [OH-]
Moreover, the presence of an intercept m Fig 5 and
T1XTI.Z
(mmutes)
36
45
62
[PO1
COlWer6lOZl
65
76
25
100
27
145
34
205
45
308
63
407
69
10
35
16
65
25
120
42
150
50
lb
11
30
18
60
36
90
46
150
bb
190
74
10
30
22
55
72
33
42
79
52
85
62
89
10
13
lb
0
5
18
(12)
Q(IWC
1)
28
(11)
Table 4 Expertmental data obtamed for the propylene oxtde hydrolysis performed at a hydroxyl concentrahon of
0 I moles/l, changmg the temperature
I-to3
(10)
31
43
50
-5
067
IO
49
10
208
10
103
lO-4
602
10
061
10
-5
-4
-4
52
41
63
13
78
19
89
25
94
-3
S Cma.4 et al
Table 5 Expertmental
data obtamed
tC)
at hydroxyl
concentration
IPOI
TIIYW
Conversion
(mmutes)
%
90
1050
2500
25
5443
13395
28
105
60
46
28
35
456
10
36
27
40
5I
0
387
10
82
115
49
26
30
37
40
I
95Y
10
-4483
10
197
244
-5
382
20
45
67
75
83
86
50
63
75
70
96
79
13
28
23
34
45
58
9
5
44
67
48
73
-5
-4
I
-4
15
10
x
5
7
05
0
a
100
300
200
t Ime
( mmutes
LOO
oxide hydrolysis
reactlon
performed
at pH = 12
of
Synthesis
Table 6 E!xpc wmental
T
of propylene
data obtamed
oxide hydrolysis.
?C)
1129
chlorohydrms-I
at low hydroxyl
concentration
(pH = 6-10)
l-4
Conversion
%
56
10
56
-6
IO
56
I
10
56
10
75
10
90
Table 7 Expertmental
-6
-6
data obtamed
T(OC)
[OH-I
66
7
5
11
270
35
38
83
9
27
3
7
33
320
39
1355
81
40
166
24
250
33
340
39
79
I335
14
49
17
120
37
175
49
61
12
245
11
25
27
48
43
66
54
87
64
(mmutes)
427
126
10
10
-5
-5
-5
000
10
913
10
439
10 -5
1 961
10
performed
[PO1
COI-lVf2rSlOn
Tame
moles/l
31
29
255
-4
26
90
177
1
8
185
---l-fL
-5
9
18
-5
-4
at several
(6.X
k3-
1)
25
60
16x
10
-4
60
60
60
10
98
708
10
10
-2
-2
15
175
26
370
47
1357
86
22
-3
63
24
10
-5
34
74
161
13
26
5
5
378
249
49
36
71
12
17
25
32
42
4
3
53
56
60
63
36
21
15
30
23
48
31
60
39
6~
03
10 -5
646
10 -4
558
10
-4
hydroxyl
concen-
1130
CARRAetal
2
z
z
5
1
ml
ltme
200
(mm&r)
Fig 4 A plot of -In (I - X) vs tune for the propylene oxide hydrolysis reactlon performed at pH = 13
Fu 5 The trend of the effective lunehc constant k~with the hydroxyl concentration for runs performed at 60C
DlSCUS!%ON
experiments
described m this paper, allowed the
determination
of the kinetic parameters of the reactions
involved m the propylene ox&de production process The
scheme of the reactions studied IS as follows
The
CH~-CHXHI
&l
AH
yH,TH-CH3
\
-HCl
/
CH\YH-CH
0
+I-ZtCB
~-------,CH2-_CHXH,
3
AHAH
1131
-,C-C<+Cl-+HzO
The reaction
(13)
Ill k,
12 -
CHOH
0 + OH-m
10 r
HO-
+H*CJ
___,
ci HOH
I
+OH-
8-
6-
20
25
30
35
lO/l
Wg
The probabdlty
of mtermedlate
Ion formation
1s
evidently the same
The dlfferenees
m actlvatlon
energy values for the
reaction m the presence of slaked lime and of caustic
soda 1s due to the solublllty
of Ca(OH)*, which
decreases
when the temperature
IS increased
The
effective constant m the presence of slaked lime could be
expressed as
kr-kK+Ks
(14)
{kh + kchW-1HRl
(17)
preexponentlal
factors
uutlal concentration
of chlorohydrms
m water
apparent
actlvatlon
energy for the synthesis
performed m slaked hme solution
actlvatlon
energy for the synthesis
EZ apparent
performed m caustic soda solution
E true activation energy for the propylene oxide
synthesis
Ai
C
El
1132
S CARRA et al
k,
kh
k ch
K, Ke
k, k:,,
KS
kl
k2
rw
[PO1
r
R
T
X
effective
kinetic constant
for the hydrolysis
reaction
effective kinetic constant for the non catalyzed
hydrolysis
effective kinetic constant
for the acid-base
catalyzed hydrolys:s reaction
equlhbrmm
constants
for the intermediate
ions
in the synthesis and in the hydrolysis of propylene oxide respectively
kinetic constants for the synthesis and hydrolySISof propylene oxide respectively
solublhty product of slaked hme
kinetic constant
for the propylene oxide synthesis m slaked lime solution
kmetlc constant
for the propylene oxide synthesis rn caustic soda solutlon
propylene chlorohydrms
concentration
propylene oxide concentration
reaction rates
general constant of gases
absolute temperature
degree of advancement
of the reaction
Greek symbols
AHn
AHs
Ion formation
hydroxide
dls-
solution
REFERENCES
Wllev-Interscience.
New York (1975)
A , The Chemistry .of Heterocyclrc Compounds
Interscience, New York 1964
[41 Pam S , The Chemistry of Functronol Groups InterscIence,
New York 1967
PI Smrth L , Zertschr f Physlk lo18 93 59
[61 Carra S Santacesarra E , Morbldelh M Schwarz P and DIVO
C , SubmItted to Ind Engng Chem Proc Des Dev
r71 Carra S , Santacesarla E , Morbldelh M , Schwarz P and
DIVO C , Submitted to Ind Engng Chem Proc Des Dee
PI Ives D J G and Janz G J , Reference Electrodes Academic
Press, New York (l%l)
of Znorgonrc and Organrc Comr91 Stephen H , Sohbhtres
pounds Pergamon Press, Oxford 1964
[31 Wersiberger