0009-2509179/0901-1123/$0200/0

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)

oxide from chlorohydnns

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

Propylene oxide IS still mamly prepared m industry from

the chlorohydrmatlon
of propylene, followed by dehydrochlonnatlon
of propylene chlorohydrms,
according to
the followmg scheme [ 1,2]

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

The basic medmm necessary for the second reaction can

be obtamed
by using slaked hme or a caustic soda
solution
In spite of the fact that this process 1s quite old, very
httle mformatlon
IS avadable
on the kmetlcs of the
dehydrochlonnatlon
reactlon[3,4]
Together
with the
reactlon of propylene oxide formatlon, hydrolysis always
occurs, according to the scheme
CH2-CH-CH,
\/
0

propylene oxide IS flashed out with stream to shorten the

contact tune and to prevent hydrolysls[l,
2]
Designing the dlstdlatlon
column and choosmg
the
optimal operating condltlons requires the determination
of kmetic parameters for the reactions Involved in the
process and the evaluation
of vapor hqmd equdlbrmm
data
In the present
paper the kmetlcs
of dehydrochlormatlon of propylene chlorohydnns
and the propylene
oxide hydrolysis have been studled
A subsequent paper wdl study the vapor-hquld
equdlbrla By combmmg
such mformatlon
with kmetlc data,
the stmulatlon of a continuous mlcropdot unit for propylene oxide production wdl be made The results of the
calculations wdl be compared with the experimental data
obtamed by a mlcropdot plant

+ HzO-

tOH-J

CHz-CH-CHs
d I-I

OH

The kmetlcs of this reactlon IS also poorly described m

the literature [4,5] Smce the hydrolysis reaction lowers
the yields, propylene oxide must be removed as quickly
as possible from the reaction envuonment
For these reasons, the mdustrlal productIon of propylene oxide IS performed
m a dlstdlatlon
column, and

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

Before each experiment,

the response of the electrodes
to the chloride ion concentration
was calibrated by adding measured quantltles of HCI to an aqueous solution
contammg
an excess of Ca (OH)* at the reactlon temperature
In the presence of caustic soda, the reactlon rate has
been determined
by usmg a glass electrode to measure
the decrease
of the hydroxyl
Ion concentration
as a
consequence
of the reaction
In this case, a saturated
calomel electrode was used as reference electrode
In both cases, the reaction took place m a thermostated stirred batch reactor Fifty cm of basic solution contammg
about
4g
of Ca(OH)z
or 10e3 10-l moles/l of NaOH was put mto the reactor When the
reaction temperature
was reached, 1 cm3 of the organic
reagent was InJected into the soiutlon with a glass synnge,
and the potentlometrlc
response was recorded
This response was quick m both cases and the dead
time IS negligible with respect to the time of the reaction
Runs made with the two pure chlorohydnns
isomers
have shown IdentlcaI reactivity
The kmetlc data collected
m this papel refer to an mdustnal
mixture of the two
Lsomers mentloned
These mixtures contam secondary
and primary alcohol m a ratlo of about 9 1 [l]
The hydrolysis of propylene oxide was studied wrth a
different procedure, because there 1s no ehmmatlon
of
chloride ions or change of pH, and the reaction IS rather
slow
The reaction rate, m this case, has been determmed by
using an NMR spectrometer
Jeol JNM-C-4OHL
to
measure the decrease of propylene oxide concentration
Runs were made at several temperatures
and pH
NaOH 1 N was added to 50 cm3 of aqueous solutlon
contammg
6% m weight of NaCl m order to adJust the
PH
Then, 20mg of CHKOONa
were added as Internal
reference to 2 cm3 of this solution and, after freezing at
about 0C 70~1 of propylene
oxide was introduced
0 5 cm of this solution were then transferred to a test
tube and submitted
to NMR analysis, at a given temperature
The dead time for reaching this temperature
IS neghgrble with respect to the reactlon time
For long runs, the NMR test tube was kept soaked m a
thermostated
vessel and analyzed from time to time at
regular Intervals
The spectral peaks used for analytical
purposes
were those related to the methyl protons of
propylene
oxide (doublet at 6 = 1 33) and the smglet
methyl of CHsCOONa at 8 = 1 97 Also the peaks of the
propylene glycol at 6 = 1 15 have been determmed
The measurements
were performed m the 3 Hz for cm
expanded range
The hydrolysis reactlon rates have been determmed by
observing the decrease m the mtenslty of the regstered
peaks of the propylene oxide
Runs were made in the pH range 6-13 and m the
temperature
range 25~90C The experrments at low pH
values (610) were made m the absence of CH,COONa,
cahbratmg
with accuracy
the uutlal concentration
of
propylene oxide

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

i [OH-] + k [Cl-] electroneutrahty

(1)
(2)

to write also
[Ca]

= l/2 {[OH-] + XC}

(3)

where X IS the degree of advancement

of the reactlon,
and C the uutlal concentration
of the organic reagent It
follows that
[OH-l3 + XC0[OH-]2

- 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

for the dehydrochlormatlon

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

of slaked hme and causttc

I
--

1125

soda
= x2

chlorohydrms--I

made m the presence

model

-E,/RT
k,

Caustic

reactton
soda

Adopted

mednun

Slaked

oxide from propyIene

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

and cawhc soda soluhon

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)

Therefore kl/kl = [OH-] IS the hydroxyl oncentratlon m

the Ca(OH)z saturated solution, at a given temperature
In Table 3 the ratios k2/kl and the related [OH-] concen-

S Cm

1126

et al

Table 2 Kmetlc data obtamed for the dehydrochlormatron

reachon made m caustic soda solutions The kmehc
constants have heen calculated assummg a second order kmetx model The mrtud concentration of chlorohydrm IS
0 23 moles/l
I

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

values are compared at several temperatures

The
values of [OH-] concentrations m saturated Ca(OI-02
solutions have been calculated by usmg the data reported
by Stephen[7] As, can be seen from the data reported m
Table 3, the ratios k$k,
and the correspondmg hydroxyl
concentrations are not much different Thus confirms the
kmetlc models adopted
The dfierences m the actlvatlon energies observed m
trataon

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

the ratios &Jkl and the related [OH-] concentration

I
T

Conversions

I
0

Time
1

the two basic media must be attibuted to the Ca(OH)z

solubdlty, whrch decreases when the temperature IS
Increased 191
We can then conclude that the propylene oxide reactlon rate m the presence of slaked hme can be expressed
as
rlime= 3 02 X lo e-5B60RTCpCJ

(8

1127

Synthesis of propylene oxide from propylene chlorohydnns--I

The same reaction,

kmetlc model
rda

m caustic

= 5 03 x 10 e-

soda solution,

follows

422/RT [PC][OH-]

the

the fact that at low hydroxyl concentratrons

@H = 6 10) the kmetlc constant becomes
independent
of this
concentration,
allow us to write

(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

Hence the hydrolysis

of propylene
oxide obeys the
general acid-base catalyzed kmetlcs
The relation of the reaction rate becomes, m this case
rhyd.

Ikh + kch [OH-W01

T1XTI.Z
(mmutes)

Trh ydr = 2 68 X 108 e-6Z3RT[PO][OH-]

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)

Tlus slmphfied kmetlc model IS important for mdustnal

purposes, because the pH of the solutlon m the reactor
always IS kept higher than 12

Q(IWC

1)

28

(11)

where [PO] = propylene oxide concentration

The kmetlc parameters
have been determined
by a
no&near
regression
calculation
and are k,, = 1, 48 X
kk =268X
Wexp(and
lo exp (- 16,388)IRT)
l6,253/RT)
If the pH IShigher than 12, k,, becomes newble
and the
kinetic expression can be srmpldied as follows

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)

for the propylene oxide hydrolysis performed

0 01 moles/l, changmg the temperatures

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

Fig 3 A plot of -In (l-x)

300

200

t Ime

( mmutes

vs time for the propylene

LOO

oxide hydrolysis

reactlon

performed

at pH = 12

of

Synthesis
Table 6 E!xpc wmental
T

of propylene

data obtamed

oxide from propylene

for the propylene

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

for the propylene oxide hydrolysis

tratlons

(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

In Fig 6, an Arrhenrus type plot

constant of this reaction IS drawn

for the effective

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

The rates of reactions 1 and 2 are identical, as has been

seen experimentally
For the epoxlde formation, the rmg closure reaction,
occurs, as described
by Patit
and Weissberger [31,
according to an mtemal nucleophdlc
substitution (Z&2)
mechanism
preceded by a base catalyzed
drssoclatlon
equlhbrmm
The reactzon mechanism
can be represented
as fol-

CH~-CHXHI
&l

AH

yH,TH-CH3

\
-HCl
/

CH\YH-CH
0

+I-ZtCB
~-------,CH2-_CHXH,
3

AHAH

1131

Synthesis of propylene oludc from propylene chiorohydrms-I

lows

-,C-C<+Cl-+HzO

The reaction

rate, m this case, IS

r = kK[R][OH-]

(13)

where [R] IS the reagent concentration,

k IS the kinetic
constant and K IS the equdtbrmm constant for the formation of the intermediate Ion

Ill k,

12 -

and the activation energy depends also on the enthalpy

change of calcium hydroxide dissolution
That IS
(15)
E ,-E+AHR+1/3AH.
where E IS the true activation energy, AHn IS the enthalpy
change m intermediate ion formation. AH, IS the enthalpy
change of calcmm hydroxide dlssolutlon
The last term of
this expression does not appear m the actlvatlon energy for
the reaction In caustic soda solution
The rmg opening or hydrolysis
reaction IS a base
catalyzed reaction occurring accordmg to the scheme
suggested by Patai [4]
CHOH

CHOH
0 + OH-m

10 r

HO-

+H*CJ
___,

ci HOH
I

+OH-

For this mechamsm, a kinetic law of the followmg type IS

Justified
rhydr = kLXJR][OH-1
(16)

8-

6-

20

25

30

35

lO/l
Wg

6 An Arrhemus type plot for the effective kmettc constant

k3

The reaction rate strongly depends on this equlhbrmm

constant
and therefore depends also on the enthalpy
change for the mtermedlate ion formation
The two chlorohydrm
isomers which can give propylene oxide have, as already mentioned, the same reactivity This IS due to the mductive effect of the methyl
group, which favours the reaction m either case, mcreasmg the chlorine mobMy or the negative charge on the
oxygen

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)

where kih IS the kinetic constant, K, IS the equdlbrmm

constant,
and R IS the organic reagent concentration
This kinetic equation IS true for pH values higher than
12 When the pH IS lower than 10, the reaction rates
hardly change with the hydroxyl concentration
A kmetrc
model of the followmg type can then be suggested
rhydr

{kh + kchW-1HRl

(17)

which shows the mterventlon

of a parallel uncatalyzed
first order reaction This reactlon IS also present m the
acid catalyzed hydrolysis, as reported by Patal[4], and
we can conclude that the reaction obeys the general
acid-base catalyzed kinetics Finally, if we consider that
at IWC, which IS the reactton temperature
of the mdustraal process, the ratio between the rmg closure and
the rmg opening reaction rates IS 830 we can conclude
that, for low contact time, yields of propylene oxide are
hardly affected by the hydrolysis
NOTATION

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

enthalpy change m intermediate

durmg the synthesis reaction
enthalpy change for the calcium

Ion formation
hydroxide

dls-

solution
REFERENCES

111 Horsley H L , Encycfopedra of Chemical Technology (Edited

by Othmer K ). p 595 Wiley, New York (1965)
El Lowenhelm F A, Moran M K , Industnal Chemrcals, p 692

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