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Abstrac-The reactlons mvolved IIIthe mdustnal production of propylene 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
1123
1124 S CARR.4et al
to the chloride ion concentration was calibrated by ad- When the propylene oxide formation occurs m the
ding measured quantltles of HCI to an aqueous solution presence of slaked hme, Ca CIZ IS formed and the solu-
contammg an excess of Ca (OH)* at the reactlon tem- tion 1s buffered In fact, If we consider the relations
perature
In the presence of caustic soda, the reactlon rate has ICa*][OH-]* = k, solublhty product (1)
been determined by usmg a glass electrode to measure
the decrease of the hydroxyl Ion concentration as a [Cal= i [OH-] + k [Cl-] electroneutrahty (2)
consequence of the reaction In this case, a saturated
calomel electrode was used as reference electrode
It IS possible to write also
In both cases, the reaction took place m a ther-
mostated stirred batch reactor Fifty cm of basic solu-
[Ca] = l/2 {[OH-] + XC} (3)
tion contammg about 4g of Ca(OH)z or 10e3 -
10-l moles/l of NaOH was put mto the reactor When the
where X IS the degree of advancement of the reactlon,
reaction temperature was reached, 1 cm3 of the organic
and C the uutlal concentration of the organic reagent It
reagent was InJected into the soiutlon with a glass synnge,
follows that
and the potentlometrlc response was recorded
This response was quick m both cases and the dead
[OH-l3 + XC0[OH-]2 - 2K, = 0 (4)
time IS negligible with respect to the time of the reaction
Runs made with the two pure chlorohydnns isomers
The concerttratton of hydroxyl Ions decreases very
have shown IdentlcaI reactivity The kmetlc data collected
slowly after the uutlal stage of the reaction Therefore, m
m this papel refer to an mdustnal mixture of the two
this case, we can consider the hydroxyl concentratttlon
Lsomers mentloned These mixtures contam secondary
during the reaction as constant The Ag/AgCl electrodes,
and primary alcohol m a ratlo of about 9 1 [l]
described m the previous sectlon, give potentlometrlc
The hydrolysis of propylene oxide was studied wrth a
curves which can be used for measuring the increase of
different procedure, because there 1s no ehmmatlon of
the chloride ton concentration as a result of the reactlon
chloride ions or change of pH, and the reaction IS rather
These curves can be easily rearranged m order to obtam
slow
the conversion degree as a function of time In Fig 1 the
The reaction rate, m this case, has been determmed by
experlmentaI values of conversion versus time are
using an NMR spectrometer Jeol JNM-C-4OHL to
reported for several temperatures The experImental data
measure the decrease of propylene oxide concentration
reported In Fig 1 are well fitted, as shown m the Fig,
Runs were made at several temperatures and pH
assummg pseudo first order krnetlc reactton model of the
NaOH 1 N was added to 50 cm3 of aqueous solutlon
type
contammg 6% m weight of NaCl m order to adJust the
PH (5)
Then, 20mg of CHKOONa were added as Internal
reference to 2 cm3 of this solution and, after freezing at [PC] bemg the concentration of propylene chlorohydrm
about 0C 70~1 of propylene oxide was introduced The use of this slmphfied model 1s Justified because the
0 5 cm of this solution were then transferred to a test solution, as already mentioned, IS buffered and the
tube and submitted to NMR analysis, at a given tem- hydroxyl concentration can be considered nearly con-
perature stant
The dead time for reaching this temperature IS negh- The kmetlc parameters obtained from the experlmental
grble with respect to the reactlon time runs are reported tn Table 1 In Fig 2, an Arrhenms type
For long runs, the NMR test tube was kept soaked m a plot, IS reported for this reaction
thermostated vessel and analyzed from time to time at If the dehydrochlormatlon IS made m the presence of
regular Intervals The spectral peaks used for analytical caustic soda, the hydroxyl ion concentration decreases
purposes were those related to the methyl protons of rapidly during the reaction The change of hydroxyl
propylene oxide (doublet at 6 = 1 33) and the smglet concentrat!on dunng this tame has been determined by a
methyl of CHsCOONa at 8 = 1 97 Also the peaks of the glass electrode Smce the reaction rates slow down with
propylene glycol at 6 = 1 15 have been determmed the decrease of pH, they depend on the hydroxyl con-
The measurements were performed m the 3 Hz for cm centration
expanded range The experlmental results, m fact, can be well
The hydrolysis reactlon rates have been determmed by represented by assuming a second order kmetm model,
observing the decrease m the mtenslty of the regstered of the type
peaks of the propylene oxide
Runs were made in the pH range 6-13 and m the r<d,, = kz[OH-][PC] (61
temperature range 25~90C The experrments at low pH
values (610) were made m the absence of CH,COONa, The experimental data obtained for runs made m
cahbratmg with accuracy the uutlal concentration of different operating condmons are reported m Table 2
propylene oxide The kmetrc constants have been calculated on the basis
Synthesis of propylene oxide from propyIene chlorohydrms--I 1125
Table 1 Kmetwz parameters for the dehydrochlormatlon reactton made m the presence of slaked hme and causttc
soda
Adopted
Basw mednun A EI (kcal/mole)
klnetlc model 1
= kl [PC]
rlItTI~ -1
Slaked lune 3 02x 109s 15 860
-E,/RT
k, = A1 e
r soda = k2 [PCllOH-1 I
12
Caustic soda 503x10 -- 16 422
-E2/RT
moks
= x2 e
k2
37 C
0
0 1 2 3
tlmc ( m~nules)
Rg I Trend of conversIon vs time for the dehydrochlonnatlon reaction of propylene chlorohydrms made m slaked
lime suspension
Fig 2 The Arrhemus plot for the kmetlc constants of the dehydrochlonnatlon reaction in the presence of slaked lime
and cawhc soda soluhon
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
iOH-10 Time X
RUTI
I T (%
moles/l 1 (sex)
0
Conversions
0
%
k2
l/mole set
I 5
10
1
1
087
956
0
0
251
262
0 01
20 3 034 0 265
30 3 626 0 266
40 3 913 0 257
=L
0 0
10 13 043 0 167
20 22 174 0 178
2 30 01
30 28 261 0 184
40 33 043 0 197
50 36 086 0 203
0 0
10 1 608 0 203
20 2 695 0 214
3 27 0 01
30 3 261 0 205
I 40 3 608 0 197
3 869 0 197
0
14 739 0 130
4 25 -q--g- 23 608 0 131
29 043 0 130
33 043 0 131
0
0 089 0 190
5 28 0 109 0 180
0 123 0 175
---I-?
0 132 0 168
0
1 856 ! 223
I
3 2 461 I 226
4 45 0 01
55 3 269 1 237
10 4 002 1 130
---l-e
4 339 I 390
0
1 787 0 232
I
20 2 a04 0 229
7 28 0 01
30 3 374 0 221
40 3 730 0 217
---i-T-
3 952 0 214
0
2 265 3 244
2 3 374 3 223
8 I 59 o 01
33 3 826 3 650
4 4 030 2 930
4 134 2 700
Table 3 A comparison between the ratios &Jkl and the related [OH-] concentration values, at several temperatures
I I I I
I T (Cl I K,'K2
50 3 595 x 10 -2 3 277 x 10 -2
x Extrapolated data
trataon values are compared at several temperatures The the two basic media must be attibuted to the Ca(OH)z
values of [OH-] concentrations m saturated Ca(OI-02 solubdlty, whrch decreases when the temperature IS
solutions have been calculated by usmg the data reported Increased 191
by Stephen[7] As, can be seen from the data reported m We can then conclude that the propylene oxide reac-
Table 3, the ratios k$k, and the correspondmg hydroxyl tlon rate m the presence of slaked hme can be expressed
concentrations are not much different Thus confirms the as
kmetlc models adopted
The dfierences m the actlvatlon energies observed m rlime= 3 02 X lo e-5B60RTCpCJ (8
Synthesis of propylene oxide from propylene chlorohydnns--I 1127
The same reaction, m caustic soda solution, follows the the fact that at low hydroxyl concentratrons @H = 6 -
kmetlc model 10) the kmetlc constant becomes independent of this
concentration, allow us to write
rda = 5 03 x 10 e- 422/RT [PC][OH-] (9)
kn = kk + kc,, [OH-] (10)
Propylene oxide hydrolysis lowers the yields of the
process It 1s therefore unportant to know the kmetlc Hence the hydrolysis of propylene oxide obeys the
parameters of thts reaction Runs made with an NMR general acid-base catalyzed kmetlcs
spectrometer at several pH and temperatures show that The relation of the reaction rate becomes, m this case
hydrolysis IS a first order reaction An effective kmetlc
constant can be evaluated by the determmatlon of the rhyd. = Ikh + kch [OH-W01 (11)
half life time In Tables 4-7 the percentages of
hydrolyzed propylene oxide for several operatmg con- where [PO] = propylene oxide concentration
ditions are reported as a function of tune The effective The kmetlc parameters have been determined by a
kinetic constants k, are reported for each run in the same no&near regression calculation and are k,, = 1, 48 X
tables lo exp (- 16,388)IRT) and kk =268X Wexp(-
Figures 3 and 4 show the values of -In (I -x) vs tune l6,253/RT)
for runs made at dtierent temperatures The linearity of If the pH IShigher than 12, k,, becomes newble and the
the curves justdies the assumption of the iirst order for kinetic expression can be srmpldied as follows
the orgamc reagent In Fig 5, the values of the effective
kinetic constant, obtamed for the runs made at the same Trh ydr = 2 68 X 108 e-6Z3RT[PO][OH-] (12)
temperature #WC), but at different pH values, are
reported as a function of hydroxyl concentration As can Tlus slmphfied kmetlc model IS important for mdustnal
be seen there IS a linear trend between ks and [OH-] purposes, because the pH of the solutlon m the reactor
Moreover, the presence of an intercept m Fig 5 and always IS kept higher than 12
Table 4 Expertmental data obtamed for the propylene oxtde hydrolysis performed at a hydroxyl concentrahon of
0 I moles/l, changmg the temperature
25 8 2
100 27 6
145 34 9 -5
28 5 067 x IO
205 45 4
308 63 0
407 69 9
10 6 b
35 16 6
-5
36 65 25 8 7 49 x 10
120 42 9
150 50 3
lb 11 1
30 18 5
60 36 0 -4
45 1 208 x 10
90 46 6
150 bb 0
190 74 7
10 30 1
22 55 3
72 0
62 33 6 103 x lO-4
42 79 5
52 85 0
62 89 3
10 2 31 0
43 0 -4
65 13 0 7 602 x 10
lb 5 50 2
18 3 52
5 41 3
9 63 0
-3
76 13 78 5 2 061 x 10
19 89 4
25 94 4
S Cma.4 et al
Table 5 Expertmental data obtamed for the propylene oxide hydrolysis performed at hydroxyl concentration of
0 01 moles/l, changmg the temperatures
90
1050
25 2500
5443
13395
28
105
-5
60 197 46
28 35 I 5 456 x 10
244
382
20
45
-5
67 75 36
27 5I I 9 387 x 10
82 40 0
115 49 6 I
26 30 4 I
37 40 5
-4
83 50 63 9 2 95Y x 10
75 70 4
96 79 5 I
13 28 0
23 45 9
-4
86 34 58 5 -4483 x 10
44 67 0
48 73 0
I
15
10
x
5
7
05
0
a 100 200 300 LOO
t Ime ( mmutes )
Fig 3 A plot of -In (l-x) vs time for the propylene oxide hydrolysis reactlon performed at pH = 12
Synthesis of propylene oxide from propylene chlorohydrms-I 1129
Table 6 E!xpc wmental data obtamed for the propylene oxide hydrolysis. at low hydroxyl concentration (pH = 6-10)
T ?C) l-4
Conversion
%
9 1
18 8
-5
56 26 5 I 427 x 10
31 1
66 7
90 11 5
185 29 8
-6 -5
56 10 270 35 2 2 126 x 10
38 7
56
---l-fL
IO
-5
177
255
83
27
33
9
4
3
7
4 2 000 x 10
-5
320
I 1355
39
81
1
8
40 8 3
166 24 7
I
-4 -5
56 10 250 33 2 1 913 x 10
340 39 8
I335 79 7
14 5 a
49 17 4
-6 6 439 x 10 -5
75 10 120 37 2
175 49 8
245 61 0
11 12 7
25 27 1
-6 -4
90 10 48 43 5 1 961 x 10
66 54 3
87 64 8
Table 7 Expertmental data obtamed for the propylene oxide hydrolysis performed at several hydroxyl concen-
tratlons
25 I 5 2
63 15 6
-4 -5
60 3 16x 10 175 26 4 24 x 10
370 47 0
1357 86 5
22 J 34 I
60 10
-3
74
161 I 13
26
5
5 I 3 03 x 10 -5
378
249 I 49
36 71 I
12 17 3
25 32 4
-2 42 3 2 646 x 10 -4
60 3 98 10 36
53 56 8
60 63 0
8 21 1
15 30 7
-2 -4
60 708 10 23 48 4 4 558 x 10
31 60 3
39 6~ 5
1130 s CARRAetal
z
z
5
0
0 ml 200
ltme (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 for the effective The rates of reactions 1 and 2 are identical, as has been
constant of this reaction IS drawn seen experimentally
For the epoxlde formation, the rmg closure reaction,
DlSCUS!%ON occurs, as described by Patit and Weissberger [31,
The experiments described m this paper, allowed the according to an mtemal nucleophdlc substitution (Z&2)
determination of the kinetic parameters of the reactions mechanism preceded by a base catalyzed drssoclatlon
involved m the propylene ox&de production process The equlhbrmm
scheme of the reactions studied IS as follows The reactzon mechanism can be represented as fol-
CH~-CHXHI
&l AH \ +I-ZtCB
-HCl ~-------,CH2-_CHXH,
yH,TH-CH3
/
CH\YH-CH
0
3
AHAH
Synthesis of propylene oludc from propylene chiorohydrms-I 1131
lows
-,C-C<+Cl-+HzO
The reaction rate, m this case, IS and the activation energy depends also on the enthalpy
change of calcium hydroxide dissolution
r = kK[R][OH-] (13) That IS
E ,-E+AHR+1/3AH. (15)
where [R] IS the reagent concentration, k IS the kinetic
where E IS the true activation energy, AHn IS the enthalpy
constant and K IS the equdtbrmm constant for the for-
change m intermediate ion formation. AH, IS the enthalpy
mation of the intermediate Ion
change of calcmm hydroxide dlssolutlon The last term of
this expression does not appear m the actlvatlon energy for
Ill k, the reaction In caustic soda solution
The rmg opening or hydrolysis reaction IS a base
catalyzed reaction occurring accordmg to the scheme
12 - suggested by Patai [4]
I I I
CHOH CHOH
10 r 0 + OH-m +H*CJ
HO- ___, ci HOH +OH-
I
in the synthesis and in the hydrolysis of pro- 111 Horsley H L , Encycfopedra of Chemical Technology (Edited
pylene oxide respectively by Othmer K ). p 595 Wiley, New York (1965)
k, k:,, kinetic constants for the synthesis and hydroly- El Lowenhelm F A, Moran M K , Industnal Chemrcals, p 692
Wllev-Interscience. New York (1975)
SISof propylene oxide respectively [31 Wersiberger A , The Chemistry .of Heterocyclrc Compounds
KS solublhty product of slaked hme Interscience, New York 1964
kl kinetic constant for the propylene oxide syn- [41 Pam S , The Chemistry of Functronol Groups InterscIence,
thesis m slaked lime solution New York 1967
PI Smrth L , Zertschr f Physlk lo18 93 59
k2 kmetlc constant for the propylene oxide syn-
[61 Carra S Santacesarra E , Morbldelh M Schwarz P and DIVO
thesis rn caustic soda solutlon C , SubmItted to Ind Engng Chem Proc Des Dev
rw propylene chlorohydrms concentration r71 Carra S , Santacesarla E , Morbldelh M , Schwarz P and
[PO1 propylene oxide concentration DIVO C , Submitted to Ind Engng Chem Proc Des Dee
r reaction rates PI Ives D J G and Janz G J , Reference Electrodes Academic
Press, New York (l%l)
R general constant of gases r91 Stephen H , Sohbhtres of Znorgonrc and Organrc Com-
T absolute temperature pounds Pergamon Press, Oxford 1964
X degree of advancement of the reaction