11 - Chapter 3 PDF

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CHAPTER 3
CATALYTIC DECOMPOSITION OF CYCLOHEXANOL
3.1 INTRODUCTION
Catalytic dehydrogenation of cyclohexanol to cyclohexanone is an

industrially important reaction. Cyclohexanone is the raw material for the
manufacture of adipic acid (starting material for the manufacture of nylon-6,6)
and for the manufacture of caprolactum (raw material for nylon-6).
Cyclohexanone is also an important industrial solvent for PVC polymers, lacquers
and also used as a building block in the synthesis of many organic compounds
such as pharmaceuticals, insecticides etc. Cyclohexanone is used in the
manufacture of magnetic video tapes (Kirk Othmer, 1979).
Cyclohexanone is manufactured by dehydrogenation of cyclohexanol

which is produced either by hydrogenation of phenol or by air oxidation of
cyclohexane. A number of catalysts are reported in literature, most of which are
based on copper, nickel and some metallic oxides either alone or as combination
of two or mote with or without support. The dehydrogenation of cyclohexanol
has been earned out over oxides of copper and zinc (Yu-Ming Lin et al 1988)
and oxides of copper and magnesium, Ni-Sn-Sn02, Cu-Zn0-Al203,
Cd-Cu-Al203 (Sivaraj et al 1988, Sideltseva and Erofeev 1986). However, these
oxides are susceptible to sintering and limit the temperature of the reaction well
below 300°C.
Hence, the dehydrogenation of cyclohexanone has been a subject of

intensive research by major caprolactum and adipic acid producing industries with
a view to achieve higher conversion, selectivity, improved catalyst life time and
lower operating temperature.
Dehydrogenation of cyclohexanol is an endothermic reversible

reaction. (Dake et al 1990).
C6HnOH C6H10O + H2 AH = 14.5 k.cal/mole

35
The decomposition of cyclohexanol leading exclusively either to

cyclohexene or cyclohexanone has often been used as a model reaction in
studying the mechanism of dehydration or dehydrogenation and in the evaluation
of the catalysts (Morita et al 1970). It has also been reported that the quantity of
cyclohexene formed depends on the density of Bronsted acidic sites
(Bezouhanova and Al Zihari, 1992).
Scheme 3.1 gives the different decomposition reactions of

cyclohexanol (Richardson and Lu 1976) yielding a variety of products in single
or multistages.
1. Dehydrogenation of cyclohexanol to cyclohexanone.
2. Dehydration of cyclohexanol to cyclohexene.
3. Dehydrogenation (nuclear) to phenol.
4. Self condensation of cyclohexanone to different oxidation products

(BePskaya 1982).
5. Carbon skeletal isomerisation of cyclohexene to methyl cyclo pentene

isomers.
According to the above scheme, cyclohexanol may undergo

dehydrogenation to phenol over platinum catalyst. The formation of
cyclohexanone from phenol might occur through the formation of
cyclohexene-l-ol as the intermediate. Hydrogenoiysis of phenol may give
benzene (Manninger et al 1977). Cyclohexanol dehydrates on platinum-alumina
catalyst to give cyclohexene over the acidic sites of alumina and cyclohexene
disproportionates to benzene and cyclohexane. Cyclohexene also undergoes
carbon skeletal isomerisation to methyl cyclopentene isomers over the acidic sites.
The hydroxyl group of cyclohexanol interacts with platinum metal via oxygen
atom leading to cleavage of O-H bond and formation of O-M bond simultaneously
giving rise to adsorbed C = O-M species. This surface carbonyl species is held by
the metal either by its x-bond or one of the lone pairs of electrons of oxygen.
The alcoholate then transforms to a n bonded ketone and is desorbed as
cyclohexanone. The cyclohexanone thus formed may be converted to benzene
through cyclohexene.
36
0
Benzene
Pt
OH 0
o
Cyclohexane
Cyclohexene Methyl Cyclopentene isomers
Scheme 3.1 Different decomposition reactions of cyclohexanol

37
In addition to the above products, high boiling products like

2-{l-cyclohexenyl)-cyclohexanone (A), 2-cycIohexyliden cyclohexanone (B) and
l-{l-cyclohexenyl)-cyclohexen (C) were also reported to have formed (Gut and
Jaeger 1982) as shown in Scheme 3.2.
(c)
Scheme 3.2 High boiling products obtained from cyclohexanone
Metals catalysing the decomposition of cyclohexanol have been

classified into two types (i) dehydrogenating metals (Os, Co, Fe, Ru, Re) and (ii)
aromatizing metals (Pd, Pt, Ni) (Dobrovlszky et al 1981). Chen and Lee (1992)
investigated the transformation of cyclohexanol over Cu-Zn0-AJ203 and Cu-Fe
and reported that the dehydrogenation of cyclohexanol proceeded on metallic
copper and dehydration on acidic sites. However, Fridman etal (1988 and 1992)
reported that monovalent copper ions are the active sites for the dehydrogenation
of cyclohexanol over copper-chromium catalysts.
Sivaraj et al 1990 reported that Cu-Al203 catalysts prepared by

coprecipitation using the urea hydrolysis procedure found to be highly active for
the reaction of cyclohexanol to cyclohexanone and cyclohexene. They have also
adopted ammonia chemisorption to assess Cu-A1203 catalysts for their relative
selectivity to cyclohexanone and cyclohexene. Sideltseva and Erofeev (1986) have
studied the dependence of the metal deposition procedure on the specific surface
3B
and catalytic properties of Cu/MgO catalysts. Wen-Shing Chen et al (1992)

observed that dehydrogenation of cyclohexanol to cyclohexanone proceeded
mainly on reduced metallic copper in Cu-Fe304 system. They found that
Cu-Fe304 gave much higher yields to 79% at 663K than Cu-ZnO (ca.56%).
Hsiu-Fuchang et al (1994) correlated the catalytic activity with acidity and surface
area of copper of the Cu/A1203 catalyst in the dehydrogenation of cyclohexanol.
Stoklosa et a/ (1996) studied the influence of zinc ions on the rate of cyclohexanol
dehydrogenation by a copper catalyst. Raja and Santhanalakshmi (1996)
obtained higher percentage conversion and yield of 2-methyl cyclohexanone in
the dehydrogenation of 2-methyl cyclohexanol with calcined 3:1 Ni-Fe layered
double hydroxide. Mg3(P04)2. yields cyclohexene preferentially and some
cyclohexanone when modified by the addition of sodium carbonate in gas phase
conversion of cyclohexanol (Aramendia et al 1996). Kuriacose et al (1968)
illustrated that selectivity is determined not by the catalyst alone, but by both, the
adsorbate and the catalyst. Athappan & Srivastava (1980) applied Langmuir-
Hinshelwood kinetics to determine the mechanism of parallel dehydrogenation
and dehydration of cyclohexanol on Ni0-Al203 systems and found that the model
with ‘dual site’ surface reaction with cyclohexanol adsorbed’ found to fit for
dehydrogenation and ‘dual site surface reaction with cyclohexene not adsorbed’
for dehydration. However, Gut and Jaeger (1982) discriminated the models by
fitting the data to different kinetic models and suitable model was found to be a
Langmuir-Hinshelwood model, involving associative adsorption of cyclohexanol,
cyclohexanone and hydrogen on the same of kind of sites.
3.2 DECOMPOSITION OF CYCLOHEXANOL ON MIXED

METAL OXIDES
As mentioned in section 1.1, the noble metals and some metal oxides
are susceptible to sintering and capable of forming volatile metal oxides at high
temperatures.. Hence, stabilization of the metal ions in a suitable environment
becomes necessary. Different ways may be adopted for stabilizing the metal ions.
A2B04 oxides stable complex oxides with A and./ B sites partially

substituted. It seems meaningful to understand first the significance of such partial
substitution in the light of solid state chemistry. If the cations are replaced by
divalent A' cation, the charge compensation will be achieved by the stoichiometric
formation of either trivalent B cations (or positive holes) or oxide ion vacancies.
However, these are two extremes and a mixture of these possibilities seems to
appear in practice.
39
1. A2-x3+ A'x2+ B2+ B3+x O4 (Trivalent B3+ ion creation)

2. A2-x3+ A'x2+ B2+ Ofrx/2) Vcxx/2) (Oxide ion vacancies)
3. A2-x3+ Ax'2+ B2+!.2y B3+2y 0(4^2) + y Vo(x/2-y) (Both)
Introduction of abnormal valence causes a change in electronic

properties, while that of oxide ion vacancies increases the mobility of oxide ions
and the ionic conductivity. Since oxide ion vacancies can act as accommodation
sites for extra oxygen, the latter also leads to a variation of non-stoichiometric
compositions depending on temperature and oxygen partial pressure. This
chapter discusses the decomposition of cyclohexanol by mixed metal oxides of
the types A2B04 and AB03. As both of them possess catalytically active B site
ion, they show catalytic activity towards the decomposition of cyclohexanol.
In addition to the above mentioned features, these oxides are

extremely stable even at high temperature.
Decomposition of cyclohexanol has been carried out on rare earth

mixed metal oxides of the following types
(a) (i) Metal oxides of A2B04 type with K2NiF4 structure
Ln2Cu04 (Ln = La - Gd,) and

La2Ni04
(ii) Srx La2.x Cu04_y (x = 0, 0.2, 0.3, 0.5, 0.7 and 1.0)
(b) Metal oxides of ABQ3 type with perovskite structure
LaM03 (M = Co, Ni & Mn).
Both K2NiF4 and AB03 type oxides were prepared by ceramic

technique. They were prepared by the reaction between the intimate mixtures of
the constituent binary oxides or their precursors (nitrates, carbonates, etc.) as
described in section 2.2.2.
XRD patterns of the above mentioned compounds established the

crystal structure and the single phase. The d-spacings were calculated from 20
values. The observed and calculated d values for the representative samples are
4D
Table 3.1
Calculated and observed d-spacings of A2BO4 & ABO3

type compounds
d(cal)(f) d(obs)Cfo Intensity d(cal)<ft d(obs)^ Intensity

La2Cu04 Pr2Cu(>4
3.6670 3.6281 m 3.7000 3.7365 m
3.2689 3.2632 w 2.8062 2.8335 vs
2.8731 2.8578 vs 2.0466 2.0589 s
2.7150 2.6900 s 1.9636 1.9603 vs
2.1790 2.1826 w 1.7416 1.7368 m
1.6778 1.6793 m 1.5900 1.6120 m
1.5855 1.5869 w 1.3948 1.6937 m
1.4366 1.4290 w 1.2493 1.2409 m
1.1557 1.1543 w
Nd2Cu(>4 Sm2Cu04
3.7250 3.7325 s 3.6773 3.7090 m
2.7700 2.7787 vs 2.7791 2.7840 vs

2.0361 2.0220 m 2.0205 2.0269 s
1.9592 1.9670 m 1.9314 1.9533 s
1.6224 1.6357 s 1.6145 1.6163 s
1.6052 1.6143 s 1.5861 1.5993 s
1.4156 1.4116 w 1.2210 1.2212m
Gd2CuC>4 Lai.8Sr0.2CuO3.9
---------------- 1---------------- 1----------------
3.6769 3.6281 m 2.8587 2.8630 m
2.7332 2.7384 vs 2.6584 2.6639 ms
2.0146 2.0180 s 2.2138 2.2034 m
1.9327 1.9328 s 2.1694 2.1639 m
1.6074 1.5974 s 2.0753 2.0742 m
1.5850 1.5856 s 1.8790 1.8840 s
1.2256 1.2301 m 1.7012 1.6882 m
1.5718 1.5729 vs
41
Table 3.1 (continued)
d(caI)W d(obs)(&) Intensity d<cal)(A) d(obs)(A) Intensity
La2NiC>4 LaCo03
3.6707 3.6929 m 3.8200 3.7939 ms
2.8463 2.8494 vs 2.7110 2.7064 vs
2.7203 2.7291 vs 2.6790 2.6739 vs
2.1188 2.1188 m 2.2130 2.2077 s
2.0670 2.0684 s 1.9090 1.9058 vs
1.9236 1.9298 s 1.5630 1.5606 ms
1.7040 1.7104 m 1.5420 1.5420 ms
1.6704 1.6701 m 1.3560 1.3576 ms
1.5937 1.5979 s
1.2249 1.2205 m
LaNiQ3 LaMn03
2.7320 2.7246 vs 2.7390 2.7204 vs
1.9200 1.9277 s 1.9510 1.9357 s
1.7080 1.7086 m 1.5960 1.5843 s
1.5765 1.5964 m 1.3700 1.3762 ms
1.3640 1.3637 w
t
SdO
■a
</>
0)
a>
cvi
s>Q)CP
Fig.3.1 Pow der XRD p attern of L a2C u04

42
150
120 -
-06
co
Q_
O 6CH
30 -
10 25 40 55 70
2 0 (degrees)
Fig.3.2 Powder XRD pattern- of Sro.2Lai.8Cu03.9

43
150
Sd 0
2 0 ( degrees)
Fig.3.3 Powder XRD pattern of Sm 2 CuC>4

44
150
120
SdD
40 55
2 © {degrees )
Fig.3.4 Powder XRD pattern of Gd2Cu04

45
150
SdO
10 25 40 55 70
2 0 ( degrees )
Fig.3.5 Powder XRD pattern of Nd2Cu04

46
2 6 ( degrees )
R g. 3.6 Powder XRD pattern of La2Ni04

47
SdO
Fig.3.7 Pow der XRD p attern of LaCoOa
48
t
49
IR spectra for Ln2Cu04 (Ln = La to Gd) showed an absorption band

at 690 cm*1 which can be assigned to the stretching vibration of the short La-Oj
bond in La2Cu04 which confirmed the crystal symmetry to be orthorhombic
(Singh and Ganguly 1984) whereas for the other system Ln2Cu04 (Ln = Pr to
Gd), the absence of absorption bands in this region indicated that the compounds
were tetragonally distorted. The appearance of two prominent bands in the
regions (i) 505 - 515 cm*1 and (ii) 360-370 cm'1 have been assigned to the
stretching vibrations of Cu-0 and the deformative bending mode of square planar
Cu04 group in the D4h symmetry. The band occurring at 320 cm*1 has been
assigned to the internal modes of vibration of Ln202 layers.
In the La2_x Srx CuO^ (x = 0.2 to 1.0) system, absence of IR

absorption band at 690 cm*1 indicated that except for the parent compound
La2Cu04, all the compounds of SrxLa2.xCu04l/ (x = 0.2 to 1.0) were tetragonally
distorted due to the substitution of strontium at the A site. The change in the
orthorhombic to tetragonal symmetry may be attributed to the change in the
position of O, atom from a linear La-0|-Cu linkage along the c axis in the
orthorhombic phase to a tetragonal interstice of the lanthanum bilayers of the
tetragonal phase (Ogitaeta/ 1987). The IR absorption bands around 510-520
cm*1 and 315-390 cm*1 have been assigned to the asymmetric stretching and
bending modes respectively of strong Cu-On linkages in the basal planes.
Three IR absorption bands around 650, 510 and 375 cm*1 observed
for La2Ni04 have been attributed to the shortest La-O stretch of the La-O-Ni
bridges, short Ni-0 bonds in the equatorial position and superposition of several
vibrations contributed by the deformation of La-O-Ni bridges respectively (Odier
et al 1986).
IR spectra of LaM03 (M = Co, Ni & Mn) perovskites show atleast two

strong absorption bands in all the cases, one around 600 cm*1 and the another
around 400 cm*1 which have been assigned to M06 vibration. IR spectra
representative samples are given in Figures 3.8 and 3.9.
Thus, both XRD patterns and IR spectral data have confirmed the
phase purity of the compounds prepared in the present study.
51
Transmittance (•/•>
Transm ittance (V.)
Wavenumber ( cm-1)
Fig.3.9 IR spectra of (a) La2NiC>4; (b) LaCo03

52
3.3 SURFACE AREA OF THE CATALYSTS
The surface areas of the catalysts were determined by BET method

using nitrogen as adsorbate at liquid nitrogen temperature. The data are shown
in Table 3.2. The surface areas for all the compounds are relatively low in the
range of 0.97-3.41 m2/g. The observed low values for these catalysts may be
attributed to the high temperature employed in the synthesis of these materials.
Table 3.2
Surface area values of the mixed metal oxide catalysts
S.No. Catalyst Surface area

<m2/g)
1. 1.36
2. Pr2Cu04 1.40
3. Sm2Cu04 1.21
4. Nd2Cu04 0.97
5. Gd2Cu04 1.24
6. Sr0 2Lai.8Cu03 9 1.42
7. Sro.3La1.7CuO3.g5 1.40
8. ^r0.5^-a1.5^'u®3.75 1.34
9. Sr0 7Laj sCuO^g 1.50
10. SrLaCu035 1.40
11. La2Ni04 2.07
12. LaCo03 3.41
13. LaMn03 2.86
14. LaNiOg 3.05
53
3.4 CATALYTIC ACTIVITY AND KINETIC STUDIES ON K2NiF4

AND ABOs TYPE OXIDES
3.4.1 Flow reactor technique
The catalytic activities of K2NiF4 and AB03 type oxides towards the
dehydrogenation of cyclohexanol have been investigated in vapour phase by the
flow reactor technique. The catalyst samples were first pretreated with hydrogen
at 673 K for 4 hours. The reaction was investigated for the conversion of
cyclohexanol in the temperature range of 473 - 823 K with constant flow rate
(W/F = 53.0 g.hr./g.mole). The flow rate of cyclohexanol was controlled by a
syringe model infusion pump. A constant weight (0.5 g) of the catalyst of mesh
size 60-80 was packed in the reactor zone of the pyrex reactor which was then
plugged tightly with the help of asbestos wool. The products were collected by
condensing them and subjected to gas chromatographic analysis. The
quantification of the product analysis was achieved from the peak areas calculated
by the integrator attached to gas chromatograph.
Among the catalysts synthesised and tested, only La2Cu04 and

Sr^La^CuO^ were found to be selective towards the cyclohexanone formation
in the temperature range of 553 - 648 K and all others in the series Ln2Cu04
(Ln = Pr - Gd), La2Ni04 and LaM03 (M = Co, Ni & Mn) gave a mixture of
products. Hence, kinetic studies were carried out only for La2Cu04 and
SrxLa2_xCu04^ (x = 0.2, 0.3, 0.5, 0.7 and 1.0).
3.4.2 Activity studies on l^CuO^
The effect of temperature on the conversion of cyclohexanol on

La2Cu04 (0.5 g pretreated) is shown in Figure 3.10. It was found that the
selectivity towards the formation of cyclohexanone on La2Cu04 was maximum
in the temperature range from 553 - 613 K. Beyond 653 K, the formation of
cyclohexene was found to increase. Therefore kinetic studies were limited to the
temperature range of 553 - 613 K.
The kinetics of catalytic vapour phase dehydrogenation of

cyclohexanol to cyclohexanone was studied quantitatively by varying the (i)
contact time (by varying the reactant flow rate) and (ii) temperature. Fresh,
pretreated catalyst (0.5 g) was used for every run.
O
O CD
O
Conversion (%)
T>
O
<
?
C
O
VJ
550 630 710 790

Temperature ( K )
Fig.3.10 The plot of the effect of temperature on the

decomposition of cyclohexanol over La2Cu04;
a : Cyclohexene; b : cyclohexanone; c : unreacted
cyclohexanol; d : percentage selectivity towards
cyclohexanone.
55
The percentage selectivity of cyclohexanone was calculated by using

the formula
Percentage selectivity of cyclohexanone =
Percentage of Cyclohexanone ^qq

Percentage of cyclohexanol converted
3.4.2.1 Effect of contact time
The effect of contact time on the catalytic conversion of cyclohexanol

was investigated by varying the factor W/F (where W is the weight of the catalyst
in grams and F is the flow rate of the reactant cyclohexanol in g. mole/hr). The
conversion of cyclohexanol to cyclohexanone was found to increase with
increasing W/F for all the compositions in La2Cu04 system. The particle size of
the catalyst and the flow rates of cyclohexanol were chosen from preliminary trial
experiments so as to eliminate the mass transfer effects. Considering the fact that
the surface area of these mixed oxide catalysts were only about 1 - 3.4 m2/g (60
- 80 mesh), the diffusion effect may be neglected. These low values of surface
area also indicate that the catalysts prepared are nonporous.
3.4.2.2 Effect of temperature
The effect of temperature on the conversion of cyclohexanol to

cyclohexanone at constant catalyst weight was carried out in the temperature
range 573 - 613 K for each of the catalyst compositions. The conversion in the
above temperature range was found to increase with increasing temperature as
expected. For heterogeneous catalytic reactions, the overall apparent effect of
temperature is both due to the effect of temperature on adsorption and also the
effect on the reaction velocity. The adsorption of the reaction generally decreases
with increasing temperature. It is not possible to deduce independently the relative
magnitude of these two factors on the basis of simple experimental studies.
However, the advent of computational methods has paved the way for
determining the relative importance of these factors.
3.5 ANALYSIS OF EXPERIMENTAL DATA
The experimental data of conversion as a function of temperature at

constant W/F value and as a function of W/F were analysed at fixed temperature
in order to calculate the kinetic parameters of the reaction.
56
The experimental data have been analysed by two different

approaches:
i) Integral method and
ii) Method based on reaction mechanism.
3.5.1 Analysis using integral method
The design equation for the differential flow reactor (catalytic) may be
written in the form
W dx'
(3.1)
F r
where W is the weight of the catalyst in gram; F is the flow rate of the cyclohexanol
in g.mole/hr. and r is a function of concentration of the reactant Ca which may
be expressed as
dx' = kCAn
r (3.2)
d (W/F)
where n is the order of the reaction
The value of ‘n’ can be evaluated by plotting r vs CA or by assuming

a value for n, solving the equation (3.2) and then testing whether the value of K
remains constant. In this study, an integral method was used assuming a first order
reaction for the dehydrogenation of cyclohexanol. The concentration of
cyclohexanol can be calculated from the knowledge of the percentage conversion
by the following method.
Let the molar flow rate of cyclohexanol be F g mole/hr.
Let the fractional conversion be x'. The molar flow rates of the
components were evaluated by using the following equation.
( 3.3 )
57
The molar flow rates of different components at the exit end of the
reactor will then be
Na (l-x')F (3.4)
Nb - x' F (3.5)
Nc - x' F (3.6)
The total flow rate at any time will be
NTotal (1 + x') F (3.7)
Assuming that the ideal gas law is applicable at the reaction conditions,
the concentration at any time is
Na Na Pt
c - — NTotel RT
y
where, V = Volume of cyclohexanol
PT = Pressure of cyclohexanol at the temperature of the reaction
R = Gas constant
T = Temperature of the reaction,
F (1 - xO PT
(3.8)
F (1 + x') R T
The rate of the. first order reaction can be expressed as
dx * . n
r ~ d (W/F) " k Ca (3.9)
substituting for CA in equation (3.2) from (3.9)
d x' _ , (1 - x') *t
(3.10)
d (W/F) " (1 + x') RT
Integrating the equation within the limits 0 to x'

58
x'
» d x'
q-*).
(l+x) J d (W/F) (3.11)
gives the equation
-x' - 2 In (1 -x') (3.12)
The value of the rate constant was determined from a plot of -x' - 2
In (1-x') vs W/F for the first order reaction.
3.5.1.1 Evaluation of kinetic and thermodynamic parameters
The rate constant values were obtained from the slope values of the
linear plot of -x'-21n (1-xO vs W/F. The linear dependance of In k us 1/T gave
the activation energy (Ea). By knowing rate constant and activation energy values,
Arrhenius frequency factor values were calculated from the equation
log k = log A - (3.13)

2.303 R T
The values of heat of activation (AH) were also found out from the
general equation
AH = Ea - RT (3.14)
The validity of the integral equation was checked by substituting the

values of the frequency factor (A) and activation energy (Ea) in the equation.
-E
___a p
-x' - 2 In (1-xO = AeRT (W/F) ^ (3.15)
and back calculating W/F values as a function of x' at a given temperature. The
calculated W/F and experimental W/F values fall on the same curve for a given
temperature which confirmed the validity of the integral equation.
59
3.5.2 Analysis based on reaction mechanisms
The integral rate equation has limitations in that it assumes a very

simple expression for the concentration dependence of the reaction rate.
However, catalytic reactions are quite complex and take place in a number of
steps, both physical and chemical in nature. In addition, the temperature
dependence is a combined effect of temperature on the adsorption equilibrium
constant and the reaction velocity constant. Hence, to obtain the rate equations
which could be applied over a wider range of conditions, all the steps through
which the reaction takes place on the surface of the catalyst must be given due
consideration.
The general scheme for a surface catalysed reaction involves five

stages of physical and chemical processes for the conversion of reactant A into
a product B (Langmuir - Hinshelwood mechanism).
1. Diffusion to surface
2. Adsorption of reactant (A) on to surface
3. Chemical conversion on surface
4. Desorption of product (B) from surface
5. Diffusion from surface
In general, the rate of any one of these stages can create a bottleneck,
such that the kinetic dependences of that stage are imposed on the overall
reaction.
The chemical steps involved are considered to be the three consecutive

steps based on Langmuir - Hinshelwood mechanism, namely adsorption, surface
reaction and desorption. The experimental conditions were so chosen as to
eliminate the physical steps. Internal diffusion was negligible because of the small
surface area of the catalyst and absence of pores. The dimension of the reactor
and the catalyst bed height precluded the influence of external diffusion and
transport phenomena on the rate of reaction.
Assumptions have also been made that all active centres (or catalyst
sites) function identically and that each molecule is adsorbed regardless of
interaction between molecules of the same and different kinds.Under these
conditions, it was fair to assume that the rate of the reaction was influenced only
by any one of the chemical steps.
60
The five possible rate controlling chemical steps and the

corresponding rate expressions are given below :
A ^ B+C
1. Adsorption rate controlling
_ ______ k(CA-CB Cc /Keq)

r " KaCbCc (3.16)
1+ K + KBCB + KcCc
*\q
2. Surface reaction - single site rate controlling
Adsorbed A reacts to give B (adsorbed) and C (not adsorbed)
^C /Keq)
r " 1 + KaCa + KbCb (3.17)
3. Surface reaction - dual site rate controlling.
3a. Adsorbed A forms a transition state complex with a neighbouring free, active
centre which reacts to give adsorbed B and adsorbed C (without
dissociation of C)
»<a(Ca-Cb Cc /KJ
(3.18)
(1+kaca + kbcb + Kcty2
3b. Adsorbed A forms a transition state complex with a neighbouring free, active
centre which reacts to give adsorbed B and dissociatively adsorbed C
k â (â ~ CB Cc/Keq)
r (3.19)
(1 + KaCa+KbCb + Kc
3c. On an active centre, z, adsorbed A forms with a neighbouring free,, active

centre, s, of other species a transition state complex which reacts further
to give B (on z adsorbed) and C (on s adsorbed without dissociation)
k KA (CA CB Cc/KCg)
r (3.20)
(1 + KA CA + KB CB) (l+KcCc)
61
3d. On an active centre, z, adsorbed A forms with a neighbouring free, active

centre, s, of other species a transition state complex which reacts further
to give B (on z adsorbed) and C (on s adsorbed with dissociation)
k ( CA ~ CB CC/êq)
r (3.21)
(1 + KaCa + KbCb) (1 + KcC(i)2
4. Surface reaction - dual site with negligible adsorption of

products rate controlling.
â(CA-CB CC /Keg)
(3.22)
(i + kaca)2
5. Desorption rate controlling
r = êg ^ ( CA / CB - CB / K^)
(3.23)
l + KACA + KeqKc^
The true rate expression based on the reaction mechanism that

governs the heterogeneously catalysed reaction was determined by statistical
methods of parameter estimation and model selection. Two methods of modelling
possible are : (i) from the integral data without extracting point rates, which
involves estimation of the parameters in a system of first order differential
equations that may be linear or non linear and (ii) from rate data obtained directly
from a differential reactor or by differentiation of integral data (concentration vs
W/F), which involves estimating the parameters in a system of linear or non
linear algebraic equations. In the present study the second method was followed.
A broad outline of the method involved the following steps.
(a) estimation of'initial rates
(b) estimation of thermodynamic equilibrium constant for the overall reaction.
(c) estimation of gas phase concentrations of reactant and products.

62
(d) Numerical analysis of the algebraic equation of the rate expression for
determining rate constant and the adsorption equilibrium constant.
(e) Discrimination of the models.
Detailed methodology of these steps is given in the following

subsections.
3.5.2.1 Estimation of initial rates
The rate of the reaction was obtained from the experimental

conversion vs W/F curve by regression analysis of the second degree polynomial
of the form
x' = a(W/F) + b(W/F)2 (3.24)
and therefore
r = a + 2b (W / F) (3.25)
the zero power term of (W/F) was excluded from the polynomial to satisfy the
boundary conditions, that at (W/F) = 0, x' = 0. A model calculation of the initial
rates using the above polynomial by least squares method and the computer
program adopted to solve the co-efficients of polynomials are given in Appendices
1 & 2.
3.5.2.2 Estimation of thermodynamic equilibrium constant
The equilibrium constant for the uncatalysed reaction was calculated

from specific heat data. The methodology involved the following steps.
The specific heat data for the cyclohexanol dehydrogenation reaction

was calculated by using the group contribution method (Lyman et al 1982). The
data so obtained was used for calculating the free energy change of the reaction
using the equation.
AG° = AH° - Aa T (InT) -1 Ab T2 -1 Ac T3 + I.T (3.26)

4 6
The AH° value in the above equation was obtained from the known
values of AHT, Aa, Ab and Ac at the standard temperature of 298°K. The
63
thermodynamic equilibrium constant, K was calculated from AG° value by using

eq
the equation 3.28.
AG° = - RT In K (3.27)
eq
A model calculation is given in Appendix 3.
3.5.2.3 Estimation of gas phase concentrations
The gas phase concentrations of cyclohexanol CA, cyclohexanone CB

and hydrogen Cc were calculated from conversion data.
(1-x ) PT
(1+X)
(3.28)
RT
t
X PT
(3.29)
(1 + X) RT
/
X PT
(1+X)
(3.30)
RT
3.5.2.4 Numerical analysis of the rate expression
The conventional method of analysing Hougen-Watson models (Yang

and Hougen 1951) consists of transforming the non linear rate expression into
a linear equation and solving it by the standard regression method. However, not
all the Hougen-Watson models are linearised especially those involving dual site
surface reaction mechanism. Further, linearisation results in a rate equation in
which the concentration term becomes simultaneously dependent as well as an
independent variable. Estimation based on such model violates the assumptions
for which linear regression is valid. In linear methods, the results of conventional
unweighted analysis can be quite misleading. Models can be rejected on the basis
of negative adsorption constants even though these apparent inadequacies can
be caused by the type of data analysis rather than by the true behaviour of the
experimental data. Lastly, the linear least square analysis allows to fit the data to
Hougen-Watson mechanism at isothermal conditions only.
Non linear estimation methods allow the analysis of the data even at
non isothermal conditions. A non linear estimation of the rate data can result in
the estimation of the parameters which are compatible with the problem, because
the sum of squares of residual rates are minimised directly instead of minimising
the residuals of a combination of variables involved in the rate.
A comparison of the results obtained on the basis of the linear least

squares analysis of isothermal data and those of non linear least squares analysis
of both isothermal and non isothermal data has shown that the non linear least
squares procedure was better for a rational selection of an acceptable model and
estimation of its parameters (Kittrell et al 1965). The non linear estimation
method has been used for the kinetic analysis of dehydrogenation of ethanol and
isomerisation of n-butene reactions as reported in literature (Peterson & Leon
Lapidus 1966).
In the present study, the rate data have been analysed by non linear
least square method of analysis through a computer program.
The program consisted of three sections.
1) Input section - for feeding the reaction model equation, and experimental
data.
2) Refinement section - consisting of an algorithm for solving the non linear

objective function by iterative method from given initial estimates to
generate a sequence of new estimates, each of which represents an
improvement over the previous one.
3) Regression section - algorithm for obtaining least square estimates of the

parameter.
The pattern search technique proposed by Hooke and Jeeves (Swann

1972) was used in the program. This method attempts to define and pursue a
direction which lies along the local principal axis of the contours of the function
using a combination of exploratory moves and patterns moves to generate a
sequence of improving approximations. Exploratory moves examine the local
behaviour of the function and seek to locate the direction of any sloping valley
present. Pattern moves utilise the information yielded by the exploratory moves
for further progressing along such valleys. The procedures continue until
convergence is achieved.
A list of the program is included in Appendix 4.

65
3.5.2.5 Model discrimination
The selection of the reaction mechanism was based on the following

criteria.
1. That all the coefficients must be positive and significantly different from
zero.
2. That the reaction velocity constant and adsorption equilibrium constant

must be temperature dependent.
3. If more than one mechanism satisfied the conditions given above, then
whichever mechanism gives the best fit between experimental and
calculated reaction rates was selected as the correct mechanism.
3.6 KINETIC STUDIES ON La2Cu04
To find the effect of contact time( W/)F on the conversion of

cyclohexanol, four different values of W/F were taken and the variation of
conversion of cyclohexanol with W/F is shown in Figure 3.11.
The flow reactor data for the dehydrogenation of cyclohexanol over

La2Qi04, calculated by integral method is given in Table 3.3.
The plots of -x'-21n (1-x') versus W/F at different temperatures are

shown in Figure 3.12. Straight lines passing through origin were obtained
indicating the reaction to be first order with respect to the concentration of
cyclohexanol. The values of rate constants k, at different temperatures were
obtained from the slopes of the straight lines in the Figure 3.12. The activation
energy Ea is obtained from the slope of the plot of log k vs 1/T (Figure 3.13) and
the activation energy was found to be 39.8 K.J/mole. The rate constant and
activation energy values were substituted in the equation 3.12 and the Arrhenius
factors for all the three temperatures were calculated. From the equation 3.13
AH values were also calculated and tabulated in Table 3.3. The Ea and frequency
factor (A) were substituted in the equation 3.14 and W/F values were back
calculated. The values of (W/F)^ and the experimental (W/F)exp values fall in the
same curve. The effect of time on stream on the conversion of cyclohexanol over
La2Cu04 was studied in the temperature range of 573 - 613 K for 3 hrs. Figure
3.14 shows the effect of time on stream at W/F = 53 g. hour/g. mole.
W/p ( g r hr / g. mole )
Fig.3.11 The plot of effect of contact time on the conversion of

cycloliexanol over La2Cu04 (1st hour) at different
temperatures.
a : 613K; b: 593K; c : 573K.
67
Table 3.3
Flow reactor data obtained by using integral method for the

dehydrogenation of cyclohexanol over La2Cu04
W/F k
x' at -x'-2ln(l-x') (lit. atm./ A AH
(g-hr/ (1/h) (kJ/mole)
g. mole (1st hour) g. hr.)
Temperature 613 K
21.2 0.227 0.2879
26.5 0.280 0.3770
37.9 0.373 0.5606
53.0 0.436 0.7094 0.6539 2.289xl03 36.5
Temperature 593 K
21.2 0.200 0.2463
26.5 0.238 0;3056

37.9 0.294 0.4023
53.0 0.405 0.6334 0.5157 2.378xl03 36.7
Temperature 573 K
17.7 0.112 0.1256

26.5 0.175 0.2055
37.9 0.242 0.3121
53.0 0.310 0.4321 0.3709 2.296xl03 36.8

Activation energy Ea = 39.8 kJ/mole.
Reaction conditions :
Catalyst Weight = 0.5 g.
Data taken after 1 hr. of time on stream.
68
(2 In 1-X*)
Fig.3.12 Kinetic plot for the dehydrogenation of cyclohexanol

over La2Cu04 at different temperatures
a : 613K; b : 593K; c : 573K
69
( lit. atm./g.hr)
log k
Fig.3.13 Arrhenius plot for the dehydrogenation of

cyclohexanol over La2Cu04
Fig.3.14 Plot of the effect of time on stream on the conversion
of cyclohexanol over La2CuC>4 at W/F = 53 g.hr. / g.
mole.
a : 573K; b : 593K; c : 613K.
71
All the possible mechanisms based on the Langmuir-Hinshelwood and

Hougen-Watson models namely,
1. adsorption
2. surface reaction - single site
B adsorbed and C not adsorbed
3. Surface reaction - dual site
A adsorbed on same types of active centres
3a. Both B and C adsorbed without dissociation
3b. Both B and C adsorbed but C dissociatively adsorbed
A adsorbed on different types of active centres (z and s)
3c. B adsorbed on z and C adsorbed on s without dissociation
3d. B adsorbed on z and C dissociatively adsorbed on s
4. surface reaction with negligible adsorption of products
5. desorption
were considered as rate controlling steps for the catalytic conversion of

cyclohexanol to cyclohexanone catalysed by La2Cu04. The rate constant k and
adsorption equilibrium constant of the reactant KA as well as of the products KB
and Kq were calculated by using the computer program. The flow reactor data
used for the model descrimination and the parameter values obtained for different
models for the dehydrogenation of cyclohexanol to cyclohexanone catalysed by
La2Gi04 are given in Tables 3.4 and 3.5
3.7 KINETIC STUDIES ON La1<8Sr0'2 Cu03 9

The kinetic studies of the dehydrogenation of cyclohexanol was
investigated in the temperature range of 573 - 613 K. The experimental data is
given in Table 3.6. Figures 3.15 to 3.17 show various plots for the evaluation of
kinetic parameters. The initial rates derived from W/F us x' plot and the gas phase
concentration derived from the conversion data (Table 3.7) were used for
deducing the rate determining step. The computed values for all the possible
mechanisms are listed in Table 3.8.
72
Table 3.4
Flow reactor data used for the model descrimination for the
dehydrogenation of cyclohexanol on La20uO4
W/F t CA cB cc
S*hr/ X
g. mole g. mole r
g.mole g. mole
Temperature - 613 K
21.2 0.227 0.01252 0.00368 0.00368 0.00922
26.5 0.280 0.01118 0.00435 0.00435 0.00829

37.9 0.373 0.00908 0.00540 0.00540 0.00631
53.0 . 0.436 0.00781 0.00604 0.00604 0.00369
Coefficients for the polynomial: a = 1.29 x 10'2 b = -8.69 x 10'5
Temperature = 593 K
21.2 0.200 0.01370 0.00343 0.00343 0.00802

26.5 0.238 0.01265 0.00395 0.00395 0.00753
37.9 0.294 0.01121 0.00467 0.00467 0.00646
53.0 0.405 0.00870 0.00592 0.00592 0.00506
Coefficients for the polynomial: a = 9.995 x 10'3 b =-4.6582 xlO'5
Temperature = 573 K
17.7 0.112 0.01699 0.00214 0.00214 0.00633

26.5 0.175 0.01493 0.00317 0.00317 0.00587
37.9 0.242 0.01298 0.00414 0.00414 0.00529
53.0 0.310 0.01120 0.00503 0.00503 0.00451
Coefficients for the polynomial: a = 7.237 x 10'3 b = -2.572 x 10'5
73
Table - 3.5
Parameter values obtained for different models for the

dehydrogenation of cyclohexanol on La2Cu04
Tempe CONSTANTS
Model No. rature
K k KA Kb Kc
1 613 0.650 -1.7138 -1.8952 -1.9525
593 0.600 3.0327 3.4657 2.9250
573 0.425 5.6294 5.6310 5.6000
2 613 1.200 0.550 -2.1475 -
593 1.200 0.500 4.4560 -
573 1.025 0.400 -4.8560 -
3a 613 1.200 0.550 -0.8314 -0.9000
593 1.150 0.500 -1.3377 -1.3000
573 1.025 0.400 -1.6727 -1.6500
3b 613 1.100 0.550 -0.6918 -0.4906
593 1.100 0.500 -0.3708 -0.4136
573 0.979 0.400 -0.0760 -0.2107
3c 613 1.200 0.5020 -0.7438 -0.2002
593 1.122 0.5000 -3.8831 -3.8237
573 1.127 0.4000 -1.2046 -1.1516

74
Table - 3.5 (Continued)
Tempe CONSTANTS
Model No. rature
K k ka kb Kc
3d 613 1.116 0.5983 0.5032 -.0.3500
593 1.100 0.5000 0.0064 -0.5398
573 1.014 0.3996 -1.0578 -1.0000

4 613 1.156 0.5750 - -
593 1.183 0.5000 - -
573 0.981 0.4250 - -
5 613 0.022 1.4540 - 3.2580

593 0.022 1.5280 - 3.0634
573 0.019 1.5420 - 3.3204
Model No.l Adsorption rate controlling
Model No.2 Surface reaction - single site rate controlling
Model No.3 Surface reaction - dual site -

A adsorbed on same types of active centres
3a. Both B and C adsorbed without dissociation -
rate controlling
3b. Both B & C adsorbed but C dissociatively adsorbed-
rate controlling
A adsorbed on different types of active centres
3c. B and C adsorbed on different types of active centre
(C - without dissociation) - rate controlling
3d. B and C adsorbed on different types of active centre
(C - with dissociation) - rate controlling
Model No. 4 Surface reaction with negligible adsorption of products -

rate controlling
Model No.5 Desorption - rate controlling

75
Tabic 3.6

dehydrogenation of cyclohexanol over Lai.sSr0.2CuO3.9
W/F k
-x'-21n(l-x') (lit. atm./ A AH
(S-br/ x' at
(1st hour) (1/h) (kJ/mole)
g. mole g. hr.)
Temperature 613 K.
15.1 0.206 0.2553
17.7 0.226 0.2864

26.5 0.275 0.3682
35.3 0.351 0.5136 0.8047 6.020xl03 40.37
Temperature 593 K
15.1 0.171 0.2041
21.2 0.203 0.2508
26.5 0.259 0.3408
35.3 0.295 0.4041 0.5839 5.901xl03 40.54
Temperature 573 K
17.7 0.155 0.1818
18.9 0.165 0.1956

26.5 0.220 0.2769
35.3 0.268 0.3559 0.4278 5.966x103 40.71

Activation energy Ea = 45.47 kj/mole.
cyclohexanol over Lai.8Sr0.2CuO3.9 (1st hour) at
different temperatures,
a : 613K; b: 593K; c : 573K.
77

over Lai.8Sro.2Cu03.9 at different temperatures
a : 613K; b : 593K; c : 573K
7B
)
tit. atm /g.hr
k (
tog
Fig. 3.17 Arrhenius plot for the dehydrogenation of

cyclohexanol over Lai.8Sr0.2CuO3.9*
79
Table 3.7
dehydrogenation of cyclohexanol on Sro^Lai.sCuOa.g
W/F CB Cc
g.hr/
9 CA
X
g. mole g. mole g. mole r
g.mole
Temperature = 613 K
15.1 0.206 0.01309 0.00340 0.00340 0.01053

17.7 0.226 0.01255 0.00366 0.00366 0.00970
26.5 0.275 0.01130 0.00429 0.00429 0.00690
35.3 0.351 0.00955 0.00516 0.00516 0.00410
Coefficients for the polynomial a = 1.5339 x 10'2 b =-1.5925 x 1O'4
Temperature = 593 K
15.1 0.171 0.01455 0.00300 0.00300 0.00902

21.2 0.203 0.01356 0.00347 0.00347 0.00750
26.5 0.259 0.01209 0.00409 0.00409 0.00617
35.3 0.295 0.01119 0.00468 0.00468 0.00396
Coefficients for the polynomial a = 1.2806 x 10'2 b =-1.2524 xlO4
Temperature = 573 K
17.7 0.155 0.01556 0.00285 . 0.00285 0.00761

18.9 0.165 0.01525 0.00301 0.00301 0.00745
26.5 0.220 0.01360 0.00384 0.00384 0.00641
35.3 0.268 0.01227 0.00450 0.00450 0.00520
Coefficients for the polynomial a = 1.00346 x 10'2 b = -6.8484 x 10~5
an
Table - 3.8

dehydrogenation of cyclohexanol on Sro^LaigCuC^g
Tempe CONSTANTS
Model No. rature .
K
k ka KB Kc
1 613 0.650 -1.1411 -1.1594 -1.1250
593 0.525 4.5575 4.5750 4.5500
573 0.475 2.5512 2.4249 2.4000
2 613 1.175 0.5500 -3.0349 —
593 1.025 0.5000 -5.2513 -
573 1.075 0.4500 5.3615 -
3a ' 613 1.200 0.5500 0.1871 0.1750
593 1.000 0.5000 -1.7530 -1.8000
573 1.075 0.4500 0.8354 0.8500
3b 613 1.163 0.5409 -0.2039 -0.4898
593 1.063 0.4369 -0.5265 -0.5478
573 1.002 0.4000 -0.8632 -0.3068

B1
Tempe CONSTANTS
Model No. rature
K k ka KB KC
3c 613 1.146 0.5957 -3.9275 -3.9744
593 0.999 0.4984 -2.6724 -2.6519
573 1.137 0.4279 2.1831 2.1048
3d 613 1.187 0.5802 -1.0988 -0.5884
593 1.063 0.4776 -0.4079 -0.4433
573 1.177 0.4000 -0.9507 -0.3500
4 613 1.195 0.5500 - -
593 1.025 0.5000 - -
573 1.002 0.4750 - -
5 613 0.022 1.3590 -

2.8999
593 0.022 1.5200 -

3.3179
573 0.022 0.2990 -

3.2252
B2
3.8 KINETIC STUDIES ON LaL7 Sr0 3 Cu03>85
x' vs W/F, kinetic plot and Arrhenius plots for the system
Lai 7Sr03CuO3 85 are Siven in Figures 3.18 to 3.20 and Table 3.9 gives the
experimental data for the cyclohexanol decomposition over Lax 7 Sr0 3 Cu03 85.
The values of CA, CB, Cc and r used to descriminate the models are given in
Table 3.10 and the parameter values obtained from different models for the
catalyst Lai 7 $ro 3 Cu03 85 are given in Table 3.11.
3.9 KINETIC STUDIES ON Laj 5 Sr0 5 Cu03 75
The corresponding plots for the system Lai 5 ^r0 5 Cu03 75 are given
in Figures 3.21 to 3.23 and Table 3.12 shows the experimental data for the
cyclohexanol decomposition over Lai 5 ^ro 5 Cu03 75- The values of initial
reaction rates obtained from the polynomials and the gas phase concentrations
derived from the conversion data are given in Table 3.13. These values were used
as input for solving the reaction rate expression based on mechanisms with the
help of the computer program. The adsorption equilibrium constants for reactants
and for the products are given in Table 3.14.
3.10 KINETIC STUDIES ON Lax 3 Sr0 7 Cu03 65
Figures 3.24 to 3.26 shown for the system Lai 3 SrQ 7 Cu03 65 were
used for evaluating kinetic parameters and Table 3.15 shows the experimental
data for the cyclohexanol decomposition over Laj 3 Sr0 7 Cu03 65. The values
of the initial rates of reaction derived from the polynomials are given with the
corresponding concentrations of reactant and products in Table 3.16. The values
of the rate constant (k), adsorption equilibrium constant (KA, KB and Kc) calculated
from various mechanistic steps are given Table 3.17.
3.11 KINETIC STUDIES ON LaSrCu03 5
Kinetic studies were carried out in the temperature range of 593 to

643 K. the experimental data pertaining to LaSrCu03 5 is shown in Table 3.18.
The corresponding x'vs W/F, x' vs -x' - 21n (1-x'), log k vs 1/T are shown in
Figures 3.27 to 3.29. The values of CA, CB, Cc and r are given in Table 3.19
and Table 3.20 shows the values of k, KA, KB and Kc for all the possible reaction
mechanisms.
83

cyclohexanol over Lai.7Sro.3CuC>3.8 (1st hour) at
a : 603K; b: 593K; c : 583K1
84

over Lai.7Sro.3Cu03.8 at different temperatures
a : 603K; b : 593K; c : 583K
05
5
( lit. atm /g.hr
log k

cyclohexanol over Lai.7Sro.3CuO3.8S
86
Table 3.9

dehydrogenation of cyclohexanol over La1.7Sro.3CuO3.s5
W/F k
(s-W x' at
(1st hour) g. hr.) (1/h) (kJ/mole)
g. mole
Temperature 603 K
17.7 0.215 0.2691
26.5 0.285 0.3859
35.3 0.368 0.5497
53.0 0.470 0.7997 0.6926 0.839xl03 30.58
Temperature 593 K
21.2
0.213 0.2661
26.5 0.250 0.3253

35.3 0.305 0.4226
53.0 0.415 0.6572 0.6082 0.830xl03 30.67
Temperature 583 K
17.7 0.171 0.2041
21.2
0.185 0.2241
35.3 0.280 0.3770
53.0 0.370 0.5540 0.5381 0.832xl03 30.75

Activation energy Ea = 35.6 kj/mole.
Catalyst Weight - 0.5 g.
87
Tabic 3.10
dehydrogenation of cyclohexanol on Sro.3La1.7CuO3.85
W/F 9 eA CB
g.hr/ X g. mole g. mole r
g. mole
g.mole
Temperature = 603 K
17.7 0.215 0.01305 0.00358 0.00358 0.01033

26.5 0.285 0.01125 0.00448 0.00448 0.00887
35.3 0.368 0.00934 0.00544 0.00544 0.00741
53.0 0.470 0.00729 0.00646 0.00646 0.00447
Coefficients for the polynomial a = 1.3265 x 10'2 b = -8.295 x 105
Temperature 593 K
21.2 0.213 0.01333 0.00361 0.00361 0.00844

26.5 0.250 0.01233 0.00411 0.00411 0.00779
35.3 0.305 0.01094 0.00480 0.00480 0.00671
53.0 0.415 0.00850 0.00602 0.00602 0.00455
Coefficients for the polynomial a = 1.1026 x 10'2 b =-6.1132 x lO’5
Temperature 583 K
17.7 0.171 0.01480 0.00305 0.00305 0.00805

21.2 0.185 0.01438 0.00326 0.00326 0.00769
35.3 0.280 0.01176 0.00457 0.00457 0.00586
53.0 0.370 0.00961 0.00565 0.00565 0.00366
Coefficients for the polynomial a = 1.0246 x 10'2 b = -6.216 x 10'5
aa
Table-3.11

dehydrogenation of cyclohexanol on Sro.3La17CuO3.s5
Tempe CONSTANTS
Model No. rature
K k Ka Kb Kc
1 603 0.750 0.5282 0.5161 0.5500
593 0.550 -5.1926 -5.2349 -5.2500
583 0.475 -4.1762 -4.2101 -4.1750
2 603 1.225 0.6000 -4.6220 -
593 1.075 0.5750 4.2181 -
583 1.050 0.4750 4.7491 -
3a 603 1.225 0.6000 -1.4929 -1.5000
593 1.075 0.5750 0.6603 -6.5000
583 1.050 0.4750 0.7199 -0.8000
3b 603 1.170 0.5691 -0.4015 -0.5293
593 1.091 0.5000 -0.5361 -0.7144
583 1.016 0.4375 -0.6961 -0.4862

89
Tempe CONSTANTS
Model No. rature
K Ka Kg KC
k
3c 603 1.101 0.6000 -1.5904 -2.5128
593 1.093 0.5972 5.8800 2.3916
583 1.025 0.4467 2.9757 3.0821
3d 603 1.195 0.5954 0.0660 -0.7064
593 1.089 0.5000 0.0598 -0.9091
583 0.969 0.4694 -0.4675 -0.4250
4 603 1.260 0.6000 - -
593 1.064 0.5750 - -
583 1.036 0.4750 - -
5 603 0.022 1.3080 -

2.8381
593 0.022 2.1020 -

3.1475
583 0.022 4.8010 -

3.5049
V
90

cyciohexanot over Lai.5Sro.5CuO3.75 (1st hour) at
a : 648K; b: 623K; c : 613K.
91

over Lai.5Sro.5CuO3.75 at different temperatures
a : 648K; b : 623K; c : 613K
• 3
92
)
lit. atm ./g.h
(

cyclohexanol over Lai.5Sro.5CuO3.75
93
Table 3.12

dehydrogenation of cyclohexanol over La1.5Sro.5CuO3.75
W/F k
(g.hr/ x' at
(1st hour) g. hr.) (1/h) (kJ/mole)
g. mole
Temperature 648 K
26.5 0.298 0.4096
35.3 0.377 0.5694
53.0 0.475 0.8137 0.8188 0.999xl03 32.9
Temperature 623 K
26.5 0.266 0.3525
35.3 0.356 0.5241
53.0 0.451 0.7480 0.6645 1.079xl03 33.1
Temperature 613 K
26.5 0.248 0.3220
35.3 0.331 0.4729
53.0 0.402 0.6263 0.5684 1.042xl03 33.2

Activation energy Ea = 38.3 kJ/moIe.
94
Tabic 3.13
W/F CB
g.hr/ X/
CA CC
g.mole
Temperature = 648 K
26.5 0.298 0.01017 0.00432 0.00432 0.00898
35.3 0.377 0.00851 0.00515 0.00515 0.00739
53.0 0.475 0.00669 0.00606 0.00606 0.00420
Temperature = 623 K
26.5 0.266 0.01134 0.00411 0.00411 0.00856
35.3 0.356 0.00929 0.00514 0.00514 0.00734
53.0 0.451 0.00740 0.00608 0.00608 0.00489
Coefficients for the polynomial a = 1.223 x 10'2 b =-6.9264 xlO5
Temperature = 613 K
26.5 0.248 0.01198 0.00395 0.00395 0.00763
35.3 0.331 0.00999 0.00494 0.00494 0.00623
53.0 0.402 0.00848 0.00570 0.00570 0.00340
Coefficients for the polynomial a = 1.186 x 10'2 b = -7.9835 x lO:5

95
Table - 3.14
Tempe CONSTANTS
Model No. rature
K k Ka Kb KC
1 648 0.800 0.7063 0.7423 0.7667
623 0.767 4.6289 4.4670 4.4667
613 0.533 -3.8420 -3.7409 -3.8000
2 648 1.167 0.6670 -3.2450 -
623 1.230 0.6000 0.6660 -
613 1.033 0.5330 -0.9047 -
3a 648 1.167 0.6670 -1.1648 -1.0670
623 1.233 0.6000 -0.1578 -0.1000
613 1.067 0.5330 -0.5492 -0.5330
3b 648 1.274 0.5869 -0.7927 -0.5256
623 1.093 0.5464 -0.8074 -0.7653
613 1.081 0.4806 -0.5894 -0.6172

?6
Tempe CONSTANTS
Model No, rature
K k Ka Kb KC
3c 648 1.278 0.6932 2.1408 2.2372
623 1.110 0.6000 -0;3704 -2.0000
613 1.022 0.4934 -0.6168 -0.5900
3d 648 1.295 0.5947 -1.6852 0.6888
623 1.195 0.6000 -1.7657 -0.5660
613 1.012 0.4120 -1.1504 0.6667
4 648 1.239 0.6670 - -
623 1.196 0.6000 - -
613 1.046 0.5330 - -
5 648 0.021 1.3710 -

3.0418
623 0.021 1.3550 -

2.9510
613 0.021 1.6430 -

3.6439
97

cyclohexanol over Lai.3Sro.7CuC>4 (1st hour) at
a : 633K; b: 613K; c : 593K.
-1 ) UI2 98
Fig.3.25 Kinetic plot for the dehydrogenation of cyclohexano!

over Lai.3Sro.7CuC>4 at different temperatures
a : 633K; b : 613K; c : 593K
99
atm /g.hr )
lit.
(
log k
1.58 1.62 1.66 1.70

cyclohexanoi over Lai.3Sr0.7CuO4
1DD
Table 3.15

dehydrogenation of cyclohexanol over Lai.3Sro.7CuO3.65
W/F k A AH
x' at -x'-21n(l-x') (lit. atm./
(g.hr/ (1/h) (kJ/mole)
g. mole (1st hour) g. hr.)
Temperature 633 K
13.3 0.375 0.5650
17.7 0.451 0.7483
26.5 0.575 1.1363
53.0 0.772 2.1848 2.0775 1.153xl06 64.36
Temperature 613 K
14.1 0.292 0.3986
26.5 0.405 0.6334
35.3 0.500 0.8862
53.0 0.622 1.3237 1.2574 1.074xl06 64.52
Temperature 593 K
14.1 0.180 0.2168
17.7 0.240 0.3089
26.3 0.357 0.5262
35.3 0.415 0.6573

1.239xl06
53.0 0.540 1.0131 0.9147 64.69

Data taken after 1 hr. of time on stream
101
Table 3.16
Flow reactor data on the dehydrogenation of

cyclohexanol on Sro.7La1.3CuO3.g5
W/F Qb Cci
g.hr/ X
9 Ca. r
g. mole g. mole g. mole
g.mole
Temperature = 633 K
13.3 0.375 0.00875 0.00525 0.00525 0.02249

17.7 0.451 0.00728 0.00598 0.00598 0.01983
26.5 0.575 0.00519 0.00703 0.00703 0.01450
53.0 0.772 0.00248 0.00839 0.00839 -0.01755
Temperature = 613 K
14.1 0.292 0.01089 0.00449 0.00449 0.02711

26.5 0.405 0.00842 0.00573 0.00573 0.00417
35.3 0.500 0.00663 0.00663 0.00663 -0.01210
53.0 0.622 0.00463 0.00762 0.00762 -0.04483
Temperature = 593 K
14.1 0.180 0.01428 0.00314 0.00314 0.01260

17.7 0.240 0.01259 0.00398 0.00398 0.01190
26.5 0.357 0.00974 0.00541 0.00541 0.01020
35.3 0.415 0.00850 0.00603 0.00603 0.00851
53.0 0.540 0.00614 0.00721 0.00721 0.00509
102
Table-3.17

Tempe CONSTANTS
Model No. rature
K k Ka Kb KC
1 633 0.250 -1.2575 -1.7972 -1.8000
613 -2.025 -0.7694 -0.6186 -0.5844
593 0.920 -1.7742 -1.9150 -1.8980
2 633 2.025 0.3250 -5.5166 -
613 1.725 -0.750 -1.9634 -
593 1.360 0.7000 -1.5705 -
3a 633 2.000 0.3000 -1.9528 -1.9500
613 1.650 -0.7500 -1.9547 -2.2750
593 1.520 1.1750 -0.6855 -1.7250
3b 633 1.800 0.9796 -0.7119 -1.0296
613 1.415 0.9760 -1.1020 -1.0688
593 1.302 0.6954 -0.6260 -0.3452

103
Tempe CONSTANTS
Model No. rature
K k Ka Kb KC
3c 633 1.9302 0.7906 -2.3781 -2.3412
613 2.6933 3.3858 -2.4485 -2.3880
593 1.4060 0.6976 2.8239 2.9042
3d 633 1.7692 0.8295 -1.4041 -1.3560
613 1.3974 1.1342 -1.7340 -1.0099
593 1.3483 0.6411 0.0994 -0.4780
4 633 1.9900 1.4000 - -
613 1.7620 1.3000 - -
593 1.3660 0.7000 - -
5 633 0.6670 92.2200 -

3.4600
613 0.0280 -82.1500 -

1.6600
593 0.0320 -14.6640 -

3.1837
104
Table 3.18

dehydrogenation of cyclohexanol over LaSrCu03.5
W/F k
-x'-2in(l-x') (lit. atm./ A AH
(g-hr/ x' at
(1st hour) (1/h) (kJ/mole)
g. mole g. hr.)
Temperature 643 K
21.2 0.410 0.6450
26.5 0.492 0.8773
29.4 0.534 0.9930
35.3 0.600 1.2330
44.2 0.611 1.2770 0.2576 2.868xl016 194.16
Temperature 633 K
21.2 0.274 0.3664
26.5 0.320 0.4513
35.3 0.401 0.6240
53.0 0.505 0.9014 -0.0551 2.540xl016 194.24
Temperature 613 K
21.2 0.119 0.1344
26.5 0.128 0.1459
35.3 0.172 0.2055
53.0 0.334 0.4789 -0.4746 3.330xl016 194.4
0.75

cyclohexanol over LaSrCu04 (1st hour) at different
temperatures.
a : 643K; b: 633K; c : 613K.
1D6

over LaSrCu04 at different temperatures
a : 643K; b : 633K; c : 613K
107
)
/ g.hr
lit. atm
k (
log

cyclohexanol over LaSrCuC>4
108
Table 3.19
dehydrogenation of cyclohexanol on SrLaCuOs.s
W/F t CB Cc.
g.hr/ X
g.mole
Temperature = 643 K
21.2 0.410 0.00793 0.00551 0.00551 0.01455
26.5 0.497 0.00637 0.00629 0.00629 0.01174
29.4 0.534 0.00576 0.00660 0.00660 0.01019
35.3 0.600 0.00473 *0.00711 0.00711 0.00708
44.2 0.611 0.00458 0.00719 0.00719 -0.00237
Coefficients for the polynomial a = 2.5776 x 10"2 b = -2.6486 x 10-4
Temperature = 633 K
21.2 0.274 0.01097 0.00414 0.00414 0.01061
26.5 0.320 0.00992 0.00467 0.00467 0.00952
35.3 0.401 0.00823 0.00551 0.00551 0.00773
53.0 0.505 0.00633 0.00646 0.00646 0.00412
Coefficients for the polynomial a = 1.4929 x 10'2 b = -1.0192 x 10"4
Temperature = 613 K
21.2 0.119 0.01565 0.00211 0.00211 0.00455
26.5 0.128 0.01536 0.00226 0.00226 0.00416
35.3 0.172 0.01404 0.00292 0.00292 0.00353
109
Table - 3.20

dehydrogenation of cyclohexanol on SrLaCuC>3.5
Tempe CONSTANTS
Model No. rature
K k Ka Kb KC
1 643 1.460 -1.2465 -1.7172 -1.7600

y
633 0.900 2.7317 2.6642 2.6473
613 0.300 18.5468 21.4050 21.4660
2 643 1.540 0.9400 -0.0826 -

633 1.300 0.6750 -0.1896 -
613 0.899 0.3000 -1.9766 -
3a 643 1.520 0.9400 -0.6855 -0.6800
633 1.300 0.6750 -0.3274 -2.8750
613 0.899 0.3000 -1.1398 -1.1667
3b 643 1.481 0.9233 -0.9620 0.9199
633 1.293 0.6943 -0.8584 -0.4750
613 0.829 0.3000 -0.8284 -0.2000

110
Tempe CONSTANTS
Model No. rature
K k Ka Kb Kc
3c 643 1.6976 1.0932 0.5434 0.5866
633 1.1303 0.6135 0.3995 0.3804
613 0.8856 0.3000 2.8736 2.8079
3d 643 1.5413 0.9892 -0.0824 -0.9480
633 1.0842 0.5562 -1.3373 -1.1915
613 0.8831 0.3000 -1.1136 -0.0667
4 643 1.5150 0.9600 - -
633 1.3110 0.6750 - -
613 0.9120 0.3000 - -
5 643 0.0260 -86.6680 -

2.8293
633 0.0220 3.8440 -

2.8028
613 0.0120 1.2590 -

4.1008
111
3.12 SUMMARY AND COMPARISON OF RESULTS OF THE

CATALYTIC ACTIVITY OF La2.x Srx Cu04.y SERIES
(x=0.0, 0.2, 0.3 0.5 0.7 & 1.0)
The investigation made for the different compositions of the series

La2_x Srx Cu04.y (x=0.0, 0.2,0.3 0.5 0.7 & 1.0) by flow reactor technique have
indicated that all the compositions are selective towards the dehydrogenation of
cyclohexanol in the temperature range investigated (573 to 648 K). However,
beyond 648K, all the catalysts favour dehydration of cyclohexanol yielding
cyclohexene with decreasing percentage of cyclohexanone.
All the compositions require identical activation and pretreatment

procedures involving evacuation and treatment with hydrogen at 573 K for 4
hours.
Integral method of analysis was adopted which was based on the

assumption of first order kinetics. By plotting - x' - 21n (1-x') vs W/F, the rate
constants of the catalytic reactions were obtained and the rate constants found
to obey the Arrhenius equation for all compositions. The Ea values obtained for
the different compositions in the series La2_x Srx CuO^ are given in Table 3.21.
A comparison of the catalytic activity in the series La2_xSrx Cu04_y

(x=0.0, 0.2, 0.3 0.5 0.7 & 1.0) shows interesting features. These include
(i) Existence of a compensation effect
(ii) Variation of activation energy Ea with strontium concentration.
(iii) Variation of heat of activation with strontium concentration.
(iv) Variation of rate constant with strontium concentration.
3.12.1 Compensation effect
Linear variation of Ea with logarithmic Arrhenius frequency factor has

been observed for La2.x Srx Cu04^ (x=0.0, 0.2, 0.3 0.5 0.7 & 1.0) series. This
compensation effect is shown in Figure 3.30. The linearity in the figure indicates
that the active sites responsible for the catalytic conversion of cyclohexanol to
cyclohexanone are same for the all the compositions in the temperature range
investigated.
112
Table 3.21
Ea, AH and InA values for the system SrxLa2-xCu04^,
Energy of Heat of Logarithmic

Compound activation (Eq) activation (AH) frequency
kJ/Mole kJ/Mole factor (InA)
41.60 36.67 7.75
45.47 40.54 8.69
^LTÔjCliOg g5
35.60 30.06 6.73
38.30 33.06 6.95
69.60 64.52 13.96
LaSrCuOs 5 199.50 194.26 37.90

In A 113
Fig.3.30 Plot of compensation effect on the dehydrogenation of

cyclohexanol over La2-xSrxCu04-y
114
3.12.2 Variation of activation energy Ea with strontium

concentration (x)
The relative activities of the composition can be compared on the basis
of the variation of the energy of activation as a function of strontium concentration
(Figure 3.31). From the figure, it is observed that the activation energy is found
to be minimum for the composition x - 0.3 in the series La2-xSj'xCu04 and
thereafter it increased with x. This increase in the activation energy with strontium
concentration indicates that the different compositions in the series La2-xSrxCu04
are energetically different or it can be attributed to the change in surface
composition i.e., surface enrichment of A site cations (Sr) which was also
supported by increase in coke deposition as strontium content increased.
3.12.3 Variation of AH values with strontium concentration (x)
The variation of AH with strontium concentration is also plotted in

Figure 3.31. A similar trend is observed for AH values vs strontium concentration
as that of activation energy.
The magnitude of AH of a reaction on a given catalyst depends on
a) The affinity of the adsorbate for the active site which in turn depends on
the nature of the active site and
b) On the quantity of reactant adsorbed i.e., the concentration of surface

adsorbed-spedes. Since the nature of the sitesandhence the affinity towards
the adsorbate are almost constant within the series La2-xSrxCu04-y, it is
apparent that increase in AH values may be attributed to the increased
concentration of surface adsorbed species.
3.12.4 Variation of rate constants with respect to strontium

concentration
The rate constants for the different compositions in the series

La2-xSrxCu04^ which catalysed the dehydrogenation of cyclohexanol is
presented in Table 3.22. The rate constants increased with temperature
indicating the assumption made (1st order) was correct. However, a plot of rate
constant vs strontium concentration at 593 K (figure 3.32) shows a trend in
which the increase in rate constant is observed from the compositions x = 0 to
x = 0.7 and rate constant decreases for the composition x =1. A similar trend
o)
(0
O Ea KJ / mole
O
Activation energy (Ea) KJ/mole l
• AH KJ / mole
)
Is
O
-
•(
/mole
KJ
Ah
Strontium concentration ( X )
Flg.3.31 Plot showing the variation of activation energy (Ea) and

heat of adsorption AH with strontium concentration.
116
Tabic 3.22
Variation of rate constants with temperature for the different

compositions in the series La2-x®rxû^4-y
(x - 0.0, 0.2, 0.3, 0.5, 0.7 & 1.0)
Rate constants (k)

Compound Temperature (K) lit. atm. / g.hr.
La2Cu04 613 0.6539

593 0.5157
573 0.3709
Lal^Sr0.2CuO3.9 613 0.8047

593 0.5839
573 0.4278
*-ai.7Sro.3<-'u03.85 603 0.6926

593 0.6082
583 0.5381
La1.5Sr0.5ûO3.75 648 0.8188

623 0.6645
613 0.5684
^l.SÔjCllOa 65 633 2.0775

613 1.2574
593 0.9147
LaSrCu035 643 1.8096

633 0.8809
613 0.3353
(Rate constant ( k ) lit atm /g.hr )
Fig.3.32 Plot showing the variation of rate constant with

strontium concentration at 593K.
11B
is observed at other temperatures also. The increase in rate constant values upto
x - 0.7 can be attributed to the increase of the oxide ion vacancies (or) trivalent
copper ions at the catalyst surface. Increase in x brings about an increase in
oxidising power (dehydrogenating) but a decrease in reoxidation ability. A
maximum activity at x - 0.7 would thus be obtained for which the redox cycle
proceeds most readily (Nakamura et al 1981 and 1982). The third explanation
possible is increase in oxide ion mobility with increasing x, facilitates the supply
of active oxygen from the bulk to the surface catalytic sites. Thus increasing
availability of oxygen, coupled with decreasing specific reactivity of oxygen brings
about maximum activity at x = 0.7.
3.12.5 Conclusions based on reaction mechanisms
The values of k, KA, KB & Kc obtained for different module for

different catalysts were used to arrive at the best model which fits the rate of the
overall reaction. The models namely adsorption and desorption steps as rate
controlling (model Nos. 1 & 5) were discarded because the k values obtained in
most cases were not temperature dependant. The models 2, 3a, 3b, 3c and 3d
were not accepted because of both negative values of KB and Kc (in some cases
Ka also) and discrepancy in the trend of KA values with temperature. The model
‘surface reaction - dual site with negligible adsorption of products’ was selected
as the best model on the basis of following criteria.
1) The k & Ka values obtained for all the catalysts at all the temperatures is
positive and significantly greater than zero and
2) The reactant velocity constant and the adsorption equilibrium constant

values are temperature dependant.
3.13 DECOMPOSITION OF CYCLOHEXANOL CATALYSED BY

Ln2Cu04 (Ln = Pr to Gd) AND La2 Ni04
The vapour phase decomposition of cyclohexanol was also

investigated for the following rare earth cuprates and nickelate.
Pr2Cu04
Nd2Cu04
Sm2Cu04
Gd2Cu04 and La2Ni04.
119
They were investigated in the temperature range of 593 - 773 K using

the flow reactor described in section 2.6. Invariably all the catalysts of the type
Ln2Cu04 (Ln = Fr - Gd) yielded cyclohexene and cyclohexanone as the main
products. However cyclohexene is the predominant product obtained which
increased with temperature and low levels of dehydrogenated product was
obtained. The percentage conversion and the distribution of products is given in
Table 3.23. The corresponding figures for all the catalysts are given in Figures
3.33 to 3.37.
3.14 DISCUSSION ON THE CATALYTIC ACTIVITIES OF

CUPRATES OF LANTHANIDES
The different behaviour of La20uO4 with that of cuprates of other

lanthanides may be explained as follows.
The compound La2Cu04, alone adopts the K2NiF4 (orthorhombic)

structure in the true sense of it whereas for the other cuprates of lanthanides
exhibit slight distortion. In Nd2Cu04 and Gd2Cu04, Cu2+ has been shown to
have square planar coordination. Further, in Ln2Cu04 series, La2Cu04 alone
crystallises in orthorhombic symmetry which is known to involve two long Cu-0
e o
distances (2.4A) and four short Cu-0 distances (1.9A) whereas the Ln2Cu04 (Ln
= Pr - Gd) system have four long and two short Cu-O distances (Shaplygin et al
1979). The short Cu-0 distances (1.9 A) are found to be responsible for the
dehydrogenation of cyclohexanol. The same is true in the case of copper oxide
in which the Cu-0 distance is 1.95A. Hence, it can be concluded that since there
are more number of short Cu-O bonds in La2Cu04 than the other cuprates, this
may be the reason for the effective dehydrogenation of cyclohexanol over
La2Cu04.
However, an acceptable reason for the different behaviour of

La2Cu04 is explained by Wolkenstein Theory (Wolkenstein 1960). According to
his electronic theory of dehydrogenation and dehydration, dehydrogenation is an
acceptor reaction and dehydration is the donor reaction and the reaction path
mainly depends on the mode of attachment of alcohol molecule to the surface.
According to him the scission of O-H bond favours dehydrogenation and C-0
scission favours dehydration. Here the catalytic activity depends on the adsorption
of cyclohexanol on copper. This adsorption will take place in a facile manner
only when the electron density around copper is low. The fact that there are no
outer most electrons in La3+ makes the net availability of copper for cyclohexanol
adsorption through O-H scission favouring cyclohexanone formation.
120
Table 3.23
Percentage conversion of cyclohexanol catalysed by cuprates of

lanthanides (Pr, Nd, Sm and Gd) and La2Ni04
Percentage of Products
Compound Temperature
(K) %of %of
Cyclohexene Cyclohexanone
Pr2Cu04 573 1.8 1.8
593 6.9 5.8
613 8.9 8.2
633 14.3 10.6
673 41.5 10.2
698 70.2 6.4
723 77.6 3.2
748 89.9 3.2
Nd2Cu04 573 3.4 0.2
593 7.1 0.8
633 22.3 3.9
673 62.2 4.4
698 73.2 5.5
723 76.2 7.7
748 79.4 7.5
773 88.4 5.3
Sm2Cu04 573 3.0 0.3
593 8.0 0.7
613 9.0 0.2
633 21.8 1.1
673 43.5 3.3
698 42.3 5.5
723 71.3 3.4
748 91.5 5.0
773 93.4 3.5
121
Table 3.23 {Continued)
Percentage of Products
Temperature
Compound
<K) %of %of
Cyclohexene Cyclohexanone
Gd2Cu04 593 6.8 0.4

633 22.2 7.9
673 37.1 5.3
698 47.9 7.8
723 72.9 4.5
748 90.5 5.4
773 95.5 1.3
La2Ni04 593 7.3 0.8
613 18.8 . 2.2
633 46.5 3.7
673 69.5 3.7
698 70.9 7.4
723 89.9 2.4
748 90.8 5.7
773 93.2 4.1
Catalyst Weight = 0.5 g. Flow rate = 2 ml/hr.
1 —I--------- 1----------- 1--------- L______ 1_______ l______ 1
570 610 650 690 730
Temperature ( K )
Fig.3.33 Plot of effect of temperature on the decomposition of

cyclohexanol over Pr2Cu04
a : cyclohexene; b : cyclohexanone; c : cyclohexanol
0 ________i_____________ i_____________ i__
600 680 760
Temperature ( K )

cycloliexanol over Nd20uO4
a : cyclohexene; b ; cyclohexanone; c : cyclohexanol
124
O
O
O
00
Conversion (%
01
O
O
20 -
600 680 760

Temperature ( K )

cyclohexanol over Sm2Cu04
a : cyclohexene; b : cyclohexanone; c s cyclohexanol
____ 1_________I_________L_
680 760
Temperature ( K)

cyclohexanol over Gd2CuC>4
12G
Conversion {%)
600 640 680 720 760
Temperature (K )

cyclohexanol over La2Ni04
127
Whereas, as the rare earth ion is changed to Pr3+, Sm3+, Nd3+ and Gd3+, the
f-Pz orbital interaction between the rare earth ion and the oxide ion of the lattice
would increase and consequently, the electron density around copper (Cu )
increases which retards the effective adsorption of cyclohexanol through O-H
scission (Sivakumar and Sivasankar 1996). Hence the cuprates of other
lanthanides favour C-O bond scission and thus dehydration.
3.15 DECOMPOSITION OF CYCLOHEXANOL BY ABOs

TYPE OXIDES
The following catalysts of the type AB03 were tested for the catalytic
activities with respect to the cyclohexanol conversion.
1. LaCo03
2. LaNi03
3. LaMn03
3.15.1 Catalytic activity of LaCoOg
The catalyst (0.5 g) was pretreated with hydrogen at 400°C for 4 hrs.
and packed in the flow reactor. The details of the flow reactor is described in
section 2.6. The effect of temperature on the catalytic conversion of
cyclohexanol was studied in the temperature range of 593 K to 748 K. The
contact time (W/F) was maintained at 26.5 g. hr./g.mole. The percentage
conversion is given in Table 3.24 and Figure 3.38 shews the selectivities towards
cyclohexanone and cyclohexene.
It is clear from the Figure 3.38 that LaCo03 favoured both

dehydration and dehydrogenation equally. However, among the catalysts studied
(of the type ABO3), LaCo03 is found to give maximum conversion to
cyclohexanone (as high as 42%).
3.15.2 Catalytic activity of LaNiOg

*
The effect of temperature for the pretreated LaNiOg catalyst on the

conversion of cyclohexanol is given in the Table 3.25. The contact time is 26.5
g. hr./g. mole.
128
Table 3.24
The effect of temperature on the decomposition of cyclohexanol

catalysed by LaCo03
Tempe %of %of %of Selectivity

rature towards
Cyclohexene Cyclohexanone Cyclohexanol Cyclohexanone
(K)
593 8.1 0.7 91.0 7.7
633 25.4 18.3 55.9 41.5
673 27.7 27.4 44.9 49.7
698 27.5 29.2 41.4 49.8
723 27.6 31.6 39.1 51.9
748 41.0 42.1 8.3 45.9

129
Conversion (%!
01wLI;;I
590 650 710 770
Temperature ( K )

cyclohexanol over LaCo03
a ; cyclohexene; b : cyclohexanone; c : cyclohexanol
130
Table 3.25
Effect of temperature on the decomposition of cyclohexanol

catalysed by LaNiOa
Temperature %of %of % of unreacted

(K) Cyclohexene Cyclohexanone Cyclohexanol
593 5.9 4.4 89.6
633 14.2 6.5 79.0
673 43.3 12.1 43.5
698 80.2 10.0 8.6
723 84.2 10.6 2.4
748 90.6 7.3 0.8
Catalyst Weight = 0.5 g. How rate = 2 ml/hr.
131
Dehydrated product is predominant in the products. On increasing the

temperature, all catalysts of the type AB03 give dehydration product in the
temperature range studied between 593 and 823 K. LaNi03 catalyst gives
maximum yield of cyclohexanone (12.1%) at 673 K.
3.15.3 Catalytic activity of LaMn03
The experimental data for the conversion of cyclohexanol catalysed

by LaMn03 is given in Table 3.26.
From the conversion values, it is concluded that LaMn03 did not

favour dehydrogenation reaction significantly. Only 10.3% of cyclohexanone was
obtained at 748 K.
3.15.4 Summary and comparison of the results on the catalytic

activity of ABO3 type compounds.
The studies made for the mixed oxide catalysts of the type AB03 by
flow reactor technique have indicated that all catalysts lack selectivity. These
AB03 type catalysts yielded both cyclohexene and cyclohexanone as products of
which only cyclohexene predominates.
However, LaCo03 favours both dehydrogenation and dehydration

equally.
132
Table 3.26

catalysed by LaMn(>3
Temperature %of % of % of unreacted

(K) Cyclohexene Cyclohexanone Cyclohexanol
, 593 8.6 0.6 90.6
633 33.8 0.7 64.9
673 22.9 1.8 74.7
698 32.6 7.0 59.5
723 71.2 4.8 21.4
748 75.6 10.3 10.6
773 84.8 7.2 2.2
133
3.16 CATALYTIC DECOMPOSITION OF CYCLOHEXANOL BY

MODIFIED ZEOUTE-Y
As discussed in Chapter 1, impregnation and / or exchange of metal

ions over zeolite-Y is also one of the methods of stabilizing the metal ions from
sintering. In the present investigation, both metal impregnated zeolites and metal
exchanged zeolites were taken. They were characterised by different physico
chemical techniques and their catalytic activities were evaluated for the conversion
of cyclohexanol.
3.16.1 Characterisation of metal impregnated and metal

exchanged zeolites
The sodium form of zeolite prepared by hydrothermal synthesis was

found to have Si02/Al203 ratio of 2.57. The phase formation and the crystallinity
were established by X-ray diffractometry using CuKa radiation and the patterns
were compared with those of Linde-Y sample (Fig. 3.39). The BET surface areas
for NaY, metal impregnated and exchanged zeolites were measured at liquid
nitrogen temperature using nitrogen as adsorbate (Table 3.27). Using the flame
photometer, thermo gravimetric analyser, inductively coupled plasma and wet
chemical analyses, the unit cell formula for the synthesised zeolite-Y was arrived
Na54 (A102)54 (Si02) 138
The moisture content of sodium form of zeolite found out by using

thermo gravimetric analyser was 21.8%.
Acidity of zeolites can be investigated by a number of techniques such

as IR, DSC, TFD (using probe molecules such as ammonia, pyridine or amines)
and more recently by solid state NMR spectroscopy (Kenaston et al 1994, Gil et
al 1994, Pfieter et al 1991).
In the present investigation, acidities of both metal impregnated and

metal exchanged zeolites were determined by Differential Scanning Calorimetric
technique (DSC) which involved pyridine adsorption, followed by thermal
desorption adopting Aboul Gheit’s (1987) nullifying technique as described earlier
in section 2.4.6.
4.00
2.00
SdO
0
20 30 40 50 60
2 0 (degrees )
Fig.3.39 XRD pattern* of NaY

134
135
Table 3.27
BET surface area of metal impregnated and metal

exchanged zeolite-Y
Surface area
S.No. Catalyst m2/s
1. 494.2
NaY
2. 446.6
Cu(22)NaY
3. 438.5
Cu(26)NaY
4. 425.8
Cu(29.3)NaY
5. 420.8
Cu(34.8)NaY
6. 362.7
Cu - 5 - NaY
7. 323.9
Cu-10-NaY
8. 314.1
Cu -15 - NaY
9. 385.1
Co - 5 - NaY
10. 372.4
Co -10 - NaY
11. 363.3
Co -15 - NaY
12. 393.6
Ni - 5 - NaY
13. 369.1
Ni -10 - NaY
14. 351.5
Ni -15 - NaY
The numbers in the bracket indicate the percentage of exchange.

iis
3.16.1.1 Acidity characterisation of copper impregnated and

exchanged zeolites
Pyridine adsorbed on copper impregnated / exchanged zeolites (12

to 14 mg.) were taken in the sample cell and an equal weight of pyridine-free
samples were taken in the reference cell of DSC. Samples were investigated in
the temperature range of 50-600°C and no purge gas was used.
« Figure 3.40 shows the DSC thermograms of 5,10 & 15 % of copper

impregnated zeolites and the Figure 3.41 shows the DSC thermograms of
different levels of copper exchanged zeolites. The DSC data for copper
impregnated and exchanged zeolites are given in Tables 3.28 and 3.29.
3.16.1.2 Acidity studies on cobalt and nickel impregnated zeolites
Cobalt and nickel impregnated zeolites were also characterised for

their acidity using DSC. Figure 3.42 shows the DSC thermograms of cobalt
impregnated zeolites and Figure 3.43 for nickel impregnated zeolites and their
corresponding data are given in Tables 3.30 and 3.31.
3.16.1.3 Summary and discussion on the acidity of zeolites
The DSC thermograms of Cu, Co and Ni impregnaed zeolites and

copper exchanged zeolites indicate that pyridine had been chemisorbed over the
acidic sites of these zeolites. Acidic sites should have been introduced during
impregnation / exchange of metal ions which can be explained by considering
the equations 3.31 and 3.32.
nM(H2OpM + ===^1
(M(H20)X + IM(H20)2+]v Nax.2yZ+(Na+)2y (3.31)
A ^
(M(H20)2+)n^, + [M(H20)2+1v Nax.2yZ+ (Na+)2y •«? ...... ....
(MO)m + [M(OH)]+y + Na20 (3.32)
Bronsted acidic sites
(y « n)
Fig.3.40 DSC thermograms showing pyridine desorption from
5, 10, 15% copper impregnated zeolites
138
exo
Heat flow
IOO 300 500

Temperature ( °C)
copper exchanged zeolites
a : Cu(22)NaY; b : Cu(26)NaY; c : Cu(29.3)NaY;
d : Cu(34.8)NaY
139
Table 3.28
Differential scanning calorimetric data and their assignments

for copper impregnated zeolites
. S
Peak
AH Assignment
Sample code Temperature
(°C) (J/s)
Cu-5-NaY 86.7 12.4 PPY + WPY

197.7 85.7 HPY
403.5 995.3 CuPY
Cu-10-NaY 80.4 9.7 PPY + WPY

197.7 58.1 HPY
396.0 859.0 CuPY
Cu-15-NaY 63.3 10.9 PPY + WPY

213.3 73.3 HPY
387.8 540.8 CuPY
PPY - Pyridine desorption from physisorbed pyridine
WPY - Pyridine desorption from weak acidic sites
HPY - Pyridine desorption from hydrogen bonded pyridine
CuPY - Pyridine desorption from copper - pyridine complex

140
Tabic 3.29

for copper exchanged zeolites
Peak AH
Sample code Temperature (J/s) Assignment
(°C)
Cu(22)NaY 159.3 135.5 HPY

230.0 27.3 WLPY
454.9 3308.0 SLPY + CuPY
Cu(26)NaY 162.0 164.0 HPY

230.0 20.2 WLPY
448.0 3252.0 SLPY + CuPY
Cu(29.3)NaY 167.0 160.0 HPY

224.0 13.0 WLPY
448.0 3164.0 SLPY + CuPY
Cu(34.8)NaY 167.0 142.0 HPY

234.0 12.0 WLPY
447.0 3124.0 SLPY + CuPY
WLPY- Pyridine desorption from weak Lewis acidic sites
SLPY - Pyridine desorption from strong Lewis acidic sites
CuPY - Pyridine desorption from copper - pyridine complex

exo
Heat flow
Temperature { C)

5, 10, 15% cobalt impregnated zeolites
143
Table 3.30

for cobalt impregnated zeolites
Peak AH
Sample code Temperature Assignment
<°q (J/g)
Co-5-NaY 89.5 25.2 PPY + WPY

203.7 51.2 HPY
407.5 1206.3 CoPY
Co-10-NaY 71.5 18.3 PPY + WPY

190.0 38.3 HPY
400.6 1183.0 CoPY
Co-15-NaY 66.3 11.7 PPY + WPY

182.4 35.9 HPY
379.7 1006.6 CoPY
CoPY- Pyridine desorption from cobalt - pyridine complex

144
Table 3.31

for nickel impregnated zeolites
Peak
Sample code Temperature AH Assignment
(°C) (J/g)
Ni-5-NaY 63.5 27.4 PPY + WPY

198.9 70.9 HPY
444.6 1229.6 NiPY
Ni-10-NaY 79.8 15.2 PPY + WPY

196.9 65.3 HPY
450.5 988.2 NiPY
Ni-15-NaY 81.6 11.9 PPY + WPY

184.3 61.5 HPY
438.0 774.8 NiPY
NiPY - Pyridine desorption from nickel - pyridine complex

145
According to Equation (3.31), during impregnation, there could be the

possibility of exchange of some of impregnating metal ion with sodium ions
present in zeolite and upon calcination, all the metal ions that are impregnated
except those of exchanged would have been converted into oxides. Thus, during
aqueous impregnation of metal ions, a smaller amount of metal ions (say y) (y «
n) is exchanged for sodium ions and (n-y) quantity of metal ions and 2y sodium
ions remain on the surface of the zeolite. Equation (3.32) denotes the introduction
of Bronsted acidic sites in to the lattice upon impregnation. These exchanged
metal ions (although they are small in number), due to their polarisation power
over the adsorbed water, could promote the formation of H+ ions which could
interact with the framework oxygens producing OH groups bound to the
structure, introducing the Bronsted acidity in the zeolite. This was supported by
Ward as early as 1968 and also by Pietri de Garcia et al (1989). At the calcination
temperature, due to dehydroxylation, Lewis acidic sites were also generated.
As far as exchange of metal ions is concerned, M(H20)Z2+ Nax.2zZ is

obtained in Equation (3.31) where z » y when compared. However,
M(H20)n_z2+ and (Na+)2z are washed during exchange. Hence the metal ions will
be available only in their exchanged form. Scheme 3.3 explains the exchange of
metal ions and subsequent formation of Bronsted and Lewis acidic sites.
Hence, when pyridine was adsorbed over these zeolites, it could adsorb
over the different acidic sites of zeolites that were generated during impregnation
followed by calcination and also over the exchanged metal ions which form
metal-pyridine complex. To confirm the exchange of metal ions further, thermo
gravimetric analyses of pyridine adsorbed, metal impregnated zeolites were made.
The Figure 3.44 shows the TGA thermograms of pyridine adsorbed, copper,
cobalt and nickel impregnated zeolites. Figure 3.45 shows the TGA thermogram
of copper exchanged sample. In the thermogram, the weight loss around 400°C
is due to decomposition of pyridine from metal pyridine complex. This was further
confirmed by complexing metal ion with pyridine and investigating its
decomposition using TGA. This metal could be from that of exchanged and the
remaining metal ions are converted to metal oxides which cannot form complex
with pyridine.
The heterogeneity of acidic sites of both metal impregnated /

exchanged zeolites discussed above can also be determined by titrimetry, IR
spectral and DSC studies. However, quantitative information about the strength
and the density of acidic sites could be obtained only by DSC technique. In the
146
© ©
Na Na
0 Ov 0 0
\ / \0/\ / \ / \o/
Si At Si Si Al
/ \/ \/ \/ \/ \
Cu (NOj )2 * 2H20
Scheme I
2+
[CulHîQ
v 0 Ov 0 0 l ✓
\ / \o/ \ / \ / V./
^ Si Al Si Si M
/\/\/\/\/\
Scheme II
[Cu ( OH ^
H
I
\ /0 0
/\ 0
/\ 0
/°\o/
s Si Al Si Si Al
/ \/ \/ \/ \/ \
( Bronsted )
A
A 450 C
Scheme 111
Dehydroxylation
v 0 0 O ,
\ © / \ / \ / v>/
Si Al Si Si Al *
/\/\/\/ \/ \
l Lewis )
Scheme 3.3 Exchange of metal ions and subsequent formation of

Bronsted and Lewis acid sites
147
4)
>
+
WEIGHT GAIN
axis
O
DTG
a>
>
i
200 400 600 800

Temperature (°C)
Flg.3.44 TGA thermograms showing pyridine desorption from

metal impregnated (5%) zeolites
a : copper; b : cobalt; c : nickel
148
DTG axis
__|__________ j__________ |__________ |_

200 400 600 800
Temperature (°C)
Fig.3.45 TGA thermograms showing pyridine desorption from

a : 22%; b : 26%; c : 29.3; d : 34.8
149
DSC thermograms, the number of peaks indicate the number of acidic sites, the
peak temperature indicates the strength of acidic sites, and the magnitude of
AH gives information about the density of acidic sites.
The DSC thermograms of Cu, Co and Ni impregnated zeolites (Table

3.28, 3.30 and 3.31) show three distinct desorption signals in the temperature
ranges of
(i) 63.3 —89.5°C
(ii) 182.4 —213.3°C
(iii) 379.7 — 450.5°C
The desorption peak observed at 63.3 — 89.5°C is a weak signal

which may be due to desorption of pyridine from very weak acidic sites or from
physisorbed pyridine, the peak obtained at 182.4 — 213.3°C may be due to the
desorption of pyridine from hydrogen bonded pyridine which is also an indirect
measure of Bronsted acidic sites and the sharp signal observed at 379.7 —
450.5°C is due to pyridine desorption from metal-pyridine complex. The third
signal clearly indicates that some amount of metal ions had been exchanged in
zeolite and these exchanged metal ions are responsible for the formation of acidic
sites (Sivakumar and Sivasankar 1996a).
However, the DSC thermograms of copper exchanged zeolites (Fig.

3.4-1) are quite different from that of impregnated zeolites. The DSC
thermograms of copper exchanged zeolite show two distinct peaks in the
temperature ranges
(i) 159 — 167°C (small) and .
(ii) 224 — 234°C (small)
and a broad but unresolved peak, the first one approximately corresponding to
320°C and the second corresponding to the temperature range of 447 — 455°C
are observed. The desorption peak obtained in the temperature range of 159 —
167°C may be assigned to the desorption of hydrogen bonded pyridine
(Sivakumar and Sivasankar 1995). The peak observed in the temperature range
of 224 — 234°C can be explained as follows. Since the zeolite has higher Si /
150
AI ratio (equal to 2.57), there may be the possibility for the presence of different
aluminium environments. Literature shows evidences that isolated aluminium
frame work atoms (having no next nearest aluminium neighbours) have the
highest strength and as the number of next nearest aluminium atom increases,
the acid strength is likely to decrease (Barthomeuf 1987, Barthomeuf and
Beaumont 1973, Dempsey 1974 & 1975). There could be four such different
acid strengths corresponding to aluminium atoms 0, 1, 2, or 3 Al nearest
neighbours (Mikovsky and Marshall 1976, Peters 1982).
This study has indicated that there are two such different aluminium
topologies existing in the samples/ of which one is weak from which pyridine
desorbs in the temperature range of 224-234°C and the slightly stronger one
from which pyridine desorbs in the temperature range of 447 - 455°C along with
desorption from copper pyridine complex. The third peak obtained at 447-455°C
is the unresolved broad peak which may be the mixture of two desorption signals
comprising of strong Lewis acidic site as discussed above and the pyridine
desorption signal from copper pyridine complex (Sivakumar and Sivasankar
1996b). The desorption signal from the strongest Bronsted acidic site is not
observed in the temperature range investigated as it requires very high
temperature (>600°C).
The thermograms of both metal impregnated and exchanged zeolites

show a decreasing trend in their AH values as the percentage of the metal ion
increases. This could be explained pn the basis that, as far as impregnation is
concerned, the exchange of metal ions into the lattice is small. Therefore, they
are not readily accessible to pyridine molecule. The lack of exposure to pyridine
molecule would be more, when more and more metal ions are converted to metal
oxides which mask the exchanged metal ions. In the case of copper exchanged
zeolite also, the same trend in AH values is obtained, despite the fact that there
is no copper oxide on zeolites. This could be explained as follows.
The third thermogram obtained in the case of copper exchanged

zeolite is actually a mixture of two signals namely from strong Lewis acidic sites
and copper - pyridine complex. The copper ions occupy the inaccessible sites at
low levels of exchange and as exchange level increases, they occupy the accessible
sites (super cages) within the zeolite where it can interact with the acidic sites and
decrease the acidity. This decrease in acidic strength is more inspite of increasing
copper ions at high levels of exchange. The trend of decreasing acidic strength
151
is also observed by Ward (1975) with various levels of nickel exchanged hydrogen
zeolites.
Thus, the DSC studies of metal impregnated and metal exchanged

zeolites confirm the presence of different types and densities of acidic sites. The
confirm this further, IR spectra of pyridine adsorbed, copper exchanged samples
were recorded using IR spectrophotometer (Perkin-Elmer 983G). IR spectra of a
representative sample is given in Fig. 3.46 and the observed wave numbers along
with their corresponding assignments are given in Table 3.32.
The conversion of cyclohexanol to cyclohexene is a model reaction

most used to study the zeolite acidity particularly Bronsted sites. Since no
information could be obtained about the Bronsted acidity from the DSC studies,
cyclohexanol dehydration was studied over copper exchanged zeolites at 190°C
(W/F = 53 g.hr/g.mole). Cu(22)NaY yielded cyclohexene as much as 90% with
98% selectivity and as the percentage of copper increased from 22% to 34.8%,
the conversion decreased to 82% with same percentage of selectivity.
Hence, DSC, IR spectral and catalytic activity studies confirmed the

presence of different types of acidic sites with varying strengths.
3.17 EVALUATION OF CATALYTIC ACTIVITIES OF METAL

IMPREGNATED AND EXCHANGED ZEOLITES
The catalytic decomposition of cyclohexanol was investigated for the

following catalysts.
i) 5, 10, 15% of copper impregnated zeolites,
ii) 5, 10, 15% of cobalt impregnated zeolites,
iii) 5, 10, 15% of nickel impregnated zeolites and
iv) copper exchanged zeolites.

80
(%)
T ransm ittance
40
1800 1600 1400
Wavenumber (cm~*}
Fig.3.4 6 IR spectra of pyridine adsorbed copper exchanged

zeolites.
153
Table 3.32
IR wavenumbers and their corresponding assignments of

pyridine adsorbed copper exchanged zeolite
Observed IR wave number (cm"*) Assignment
1446 HPY + LPY
1490 HPY + LPY + BPY
1550 BPY
1599 BPY
1631 LPY + BPY
HPY - Hydrogen bonded pyridine
LPY - Pyridine adsorbed on Lewis acid sites
BPY - Pyridine adsorbed on Bronsted add sites.

154
3.17.1 Catalytic decomposition of cyclohexanol catalysed by

copper impregnated zeolites
The catalytic activities of 5, 10, 15% copper impregnated zeolites

have been investigated for the dehydrogenation of cyclohexanol by flow reactor
technique.
The copper impregnated zeolites were first pretreated with hydrogen

at 673K for 4 hours. The catalytic activities were investigated by taking 0.5 g of
catalyst in the temperature range of 473K to 823K. Samples collected at the first
hour were subjected to chromatographic analysis. The temperature effect on the
catalytic conversion of cyclohexanol over 15% copper impregnated zeolite-Y is
given in Table 3.33. From the Table, it was found that the yield of cyclohexanone
was found to be low at low temperature whereas the dehydrated product
cyclohexene which was insignificant at low temperatures increased abruptly and
reached its maximum at 773K and decreased from 773 to 823K. At high
temperatures, in addition to the predominent product cyclohexene, small
amounts of methyl cyclo pentene isomers and benzene were also form©!. At
823K, the dehydrogenated product cyclohexanone which was low (8%) at the
initial hours found to increase and reaches the maximum of 31.2% at the 8th
hour (but at low temperatures the % conversion decreased with time).
Hence, for the other samples (5% and 10% copper impregnated
zeolites), investigations were made only at 823K. The effect of time on stream
on the conversion of cyclohexanol catalysed by 5,10,15% copper impregnated
zeolites at 823 K is given in Table 3.34.

cobalt impregnated zeolites
The effect of temperature on the catalytic conversion of cyclohexanol

over 15% cobalt impregnated zeolite is given in Table 3.35. The effect of time
on stream on the conversion of cyclohexanol catalysed by 5, 10, 15% cobalt
impregnated zeolite is given in Table 3.36.
155
Table 3.33

catalysed by 15% copper on sodium form of zeolite
Temperature K
Products
523 573 598 623 673 723 773 823
4-Methyl cyclo - - - - - - - 0.8

pentene
3-Methyl cyclo - - - - - -
1.1 4.3
pentene
1-Methyl cyclo - - - -
0.8 1.0 1.2 1.1
pentene
Cyclohexene 3.1 12.9 10.1 14.6 39.0 72.0 87.6 70.8
Benzene — — *
0.9 1.34 2.5 10.6
■- .
Cyclohexanone 9.6 12.1 16.8 4.1 5.7 9.8 2.7 8.0
Catalyst Wt. = 0.2 g
Row rate 2 ml /hr.

156
Tabic 3.34
Effect of time on stream on the conversion of cyclohexanol

catalysed by copper impregnated zeolites at 823 K
% Yield of Cyclohexanone
Time in hours
5% 10% 15%
1 3.6 1.1 8.0
2 9.9 8.7 15.3
3 15.2 18.6 15.1
4 18.8 26.0 21.3
5 24.8 30.3 27.8
6 26.2 33.4 29.3
7 29.7 35.2 29.4
8 31.5 35.8 31.2
Flow rate 2 ml /hr.

157
Table 3.35

catalysed by 15% cobalt on sodium form of zeolite
Temperature K
Products
523 573 623 673 723 773 823
4-Methyl cyclo - - - - -
0.8 2.3
pentene
1.2 2.3 4.7
pentene
1-Methyl cyclo ~. - - - 1.7 3.7 7.8

pentene
Cyclohexene 3.21 8.1 77.6 93.7 88.6 79.0 68.7
Benzene — — — — 6.9 8.4 12.7
Cyclohexanone 1.6 18.3 1.4 1.2 0.96 2.1 3.0
Flow rate 2 ml /hr.

150
Table 3.36

catalysed by cobalt impregnated zeolites at 823 K
Time in hours
5% 10% 15%
1 1.3 1.7 3.0
2 8.0 12.7 18.3
3 11.3 21.0 24.6
4 , 15.4 22.8 25.3
5 17.2 23.9 27.8
6 23.3 24.9 26.3
7 29.7 23.4 28.1
8 28.9 26.3 27.9
Flow rate 2 ml /hr.

159

nickel impregnated zeolites
Tables 3.37 shows the corresponding effect of temperature for 15%

nickel impregnated zeolites and Table 3.38 shows the effect of time on stream
on the conversion of cyclohexanol catalysed by 5, 10, 15% nickel impregnated
zeolites at 823K.

The exchange of copper in the sodium form of zeolite has been carried
out as described in section 2.3.4. The effect of temperature on the catalytic
conversion of cyclohexanol catalysed by a representative copper exchanged
zeolite is given in Table 3.39. But the copper exchanged zeolite found to favour
dehydration and carbon skeletal isomerisation. A small increase in the percentage
of cyclohexanone was observed on increasing time on stream.
3.18 SUMMARY AND DISCUSSION ON THE CATALYTIC

DECOMPOSITION OF CYCLOHEXANOL BY METAL
IMPREGNATED AND METAL EXCHANGED ZEOLITES
The metal impregnated zeolites catalysing the decomposition of

cyclohexanol yielded both cyclohexene and cyclohexanone at low temperatures
and the percentage of cyclohexene increased from a low value at 553K to a high
value at 673K. This can be explained by considering the fact that the acidic sites
introduced during impregnation are not easily accessible at 553K as they were
masked by metal oxites and as temperature increased to 673K, the acidic sites
became accessible and hence favours dehydration. Whereas, for the copper
exchanged zeolites, since there is no coverage of metal oxides, the acidic sites
are accessible even at 473K which favours dehydration to cyclohexene. However,
both metal impregnated (673K onwards) and metal exchanged zeolite (473K
onwards) show a decreasing trend in the percentage of cyclohexene. This is
because of diminution of Bronsted acidic sites observed as temperature increased.
This decrease in Bronsted acidic sites is more and more on increasing time on
stream. Hence, at high temperature, on increasing time on stream the percentage
of cyclohexanone increased and reached its maximum.
160
Table 3.37

catalysed by 15% nickel on sodium form of zeolite
Temperature K
Products
523 573 623 673 723 773 823
4-Methyl cyclo - - - . - - -
0.8
pentene
1.4 1.9 2.3
pentene
0.9 2.3 3.6
pentene
Cydohexene 7.07 12.8 61.03 78.9 76.3 71.8 76.3
Benzene 13.4 14.3 15.1
Cyclohexanone 0.8 13.3 3.3 1.3 0.8 1.2 1.4
Row rate 2 ml /hr.

161
Table 3.38

catalysed by nickel impregnated zeolites
Time in hours
5% 10% 15%
1 0.89 1.09 1.4
2 1.3 3.1 16.3
3 7.3 11.8 27.9
4 13.4 23.6 29.4
5 19.3 21.4 32.1
6 23.6 27.8 33.3
7 24.2 29.8 38.1
8 24.8 31.4 38.9
9 29.38 38.3 41.2
Flow rate 2 ml /hr.

162
Table 3.39

catalysed by copper exchanged zeolite (34.8% exchange)
Temperature K
Products
473 523 573 623 673 723 773 823
4-Methyl 0.35 2.54 8.4 10.3 5.68 4.13 2.01 1.01

cyclo pentene
3-Methyl 0.26 0.58 2.17 5.2 9.53 8.71 9.07 4.49

cyclo pentene
1-Methyl 0.93 2.77 8.9 17.2 24.3 21.57 21.41 10.4

cyclo pentene
Cyclohexene 90.6 87.94 77.77 62.9 56.84 62.4 57.4 54.01
Benzene 0.06 0.18 0.57 0.57 0.6 4.6 7.01
Cyclohexanone 0.43 0.47 0.45 0.32 0.5 1.27 2.52 15.92
Flow rate 2 ml /hr.

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34

CATALYTIC DECOMPOSITION OF CYCLOHEXANOL

Catalytic dehydrogenation of cyclohexanol to cyclohexanone is an

Cyclohexanone is manufactured by dehydrogenation of cyclohexanol

Hence, the dehydrogenation of cyclohexanone has been a subject of

Dehydrogenation of cyclohexanol is an endothermic reversible

C6HnOH C6H10O + H2 AH = 14.5 k.cal/mole

The decomposition of cyclohexanol leading exclusively either to

Scheme 3.1 gives the different decomposition reactions of

1. Dehydrogenation of cyclohexanol to cyclohexanone.

2. Dehydration of cyclohexanol to cyclohexene.

3. Dehydrogenation (nuclear) to phenol.

4. Self condensation of cyclohexanone to different oxidation products

5. Carbon skeletal isomerisation of cyclohexene to methyl cyclo pentene

According to the above scheme, cyclohexanol may undergo

Cyclohexene Methyl Cyclopentene isomers

Scheme 3.1 Different decomposition reactions of cyclohexanol

In addition to the above products, high boiling products like

Scheme 3.2 High boiling products obtained from cyclohexanone

Metals catalysing the decomposition of cyclohexanol have been

Sivaraj et al 1990 reported that Cu-Al203 catalysts prepared by

and catalytic properties of Cu/MgO catalysts. Wen-Shing Chen et al (1992)

3.2 DECOMPOSITION OF CYCLOHEXANOL ON MIXED

A2B04 oxides stable complex oxides with A and./ B sites partially

1. A2-x3+ A'x2+ B2+ B3+x O4 (Trivalent B3+ ion creation)

Introduction of abnormal valence causes a change in electronic

In addition to the above mentioned features, these oxides are

Decomposition of cyclohexanol has been carried out on rare earth

(a) (i) Metal oxides of A2B04 type with K2NiF4 structure

Ln2Cu04 (Ln = La - Gd,) and

(b) Metal oxides of ABQ3 type with perovskite structure

LaM03 (M = Co, Ni & Mn).

Both K2NiF4 and AB03 type oxides were prepared by ceramic

XRD patterns of the above mentioned compounds established the

Calculated and observed d-spacings of A2BO4 & ABO3

d(cal)(f) d(obs)Cfo Intensity d(cal)<ft d(obs)^ Intensity

2.7700 2.7787 vs 2.7791 2.7840 vs

Table 3.1 (continued)

d(caI)W d(obs)(&) Intensity d<cal)(A) d(obs)(A) Intensity

Fig.3.1 Pow der XRD p attern of L a2C u04

Fig.3.2 Powder XRD pattern- of Sro.2Lai.8Cu03.9

Fig.3.3 Powder XRD pattern of Sm 2 CuC>4

Fig.3.4 Powder XRD pattern of Gd2Cu04

Fig.3.5 Powder XRD pattern of Nd2Cu04

R g. 3.6 Powder XRD pattern of La2Ni04

IR spectra for Ln2Cu04 (Ln = La to Gd) showed an absorption band

In the La2_x Srx CuO^ (x = 0.2 to 1.0) system, absence of IR

IR spectra of LaM03 (M = Co, Ni & Mn) perovskites show atleast two

Fig.3.9 IR spectra of (a) La2NiC>4; (b) LaCo03

3.3 SURFACE AREA OF THE CATALYSTS

The surface areas of the catalysts were determined by BET method

Surface area values of the mixed metal oxide catalysts

S.No. Catalyst Surface area

3.4 CATALYTIC ACTIVITY AND KINETIC STUDIES ON K2NiF4

3.4.1 Flow reactor technique

Among the catalysts synthesised and tested, only La2Cu04 and

3.4.2 Activity studies on l^CuO^

The effect of temperature on the conversion of cyclohexanol on

The kinetics of catalytic vapour phase dehydrogenation of

550 630 710 790

Fig.3.10 The plot of the effect of temperature on the

The percentage selectivity of cyclohexanone was calculated by using

Percentage selectivity of cyclohexanone =