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Raney catalysts for the hydrogenation of substituted anthraquinones
Catalysis, 6 (1983) l-9 Elsevier Science Publihers B.V., Amsterdam - Printed in The Netherlands
Applied
RANEY CATALYSTS
A.B. FASMAN,
FOR THE HYDROGENATION
S.D. MIKHAILENKO,
OF SUBSTITUTED
N.A. MAKSIMOVA,
ANTHRAQUINONES
ZH.A.
IKHSANOV,
V.YA. KITAIGORODSKAYA
and L.V. PAVLYUKEVICH
Institute
of Organic
Catalysis
and Electrochemistry,
Alma-Ata,
480100,
K. Marx Street,
(Received
2 April
1982, accepted
Kazakh SSR Academy
of Sciences,
142, USSR.
13 December
1982)
ABSTRACT Raney nickel displays low selectivity in hydrogenation of substituted anthraquinones for hydrogen peroxide production. It was found that the selectivity may be increased by catalyst modification. Using the experiment planning method, effective catalysts for the selective hydrogenation of alkylanthraquinones have been found. The structure and phase composition of the catalysts have been determined using physical methods. It was shown that, for selective reduction of quinone groups in anthraquinones, catalysts with high hydrogen adsorption heats are required. The properties and methods of formation of such catalysts were established.
INTRODUCTION At present, for hydrogen of hydrogen
the anthraquinone
peroxide peroxide
the respective catalysts
One of the important
in anthraquinone of the quinone
H202
is reintroduced
the anthraquinones the reaction
anthraquinones proceeds
mixture,
anthraquinone
is minimized.
non-selectively
hydrogenation
decrease
to make hydrogenation 0166-9834/83/$03.00
to be obtained
allows
[2]. The latter the
In the case when the reduction of rings are involved,
etc., accumulating
is discussed with quinone
rings takes place.
so that only quinone
0 1983 Elsevier Science Publishers B.V.
in the
The problem of
in a number of papers groups
reduction,
the
It is known [IO] that hydrogen-
loosely bound hydrogen.
selective,
separation
cycle is formed wherein
the yield of the product.
on nickel catalysts
of the side aromatic
ation of the latter requires
i.e. hydroanthra-
and side aromatic
It was shown [3,4] that, simultaneously
in
for the process.
product,
i.e. tetrahydroanthraquinone
gradually
Raney nickel
by the oxygen of the air and further
and thus a closed
to
used as
It should be noted that
is necessary
, and the initial anthraquinone
products,
in the technology
Cl] have been mostly
the reaction
route
of anthraquinones
of nickel catalysts,
hydrogenation
groups,
into the reactor
loss of expensive
saturation
stages
reduction
Noble metals
The employment
is easily oxidized
the product,
[3-g].
as the most effective
has been limited due to its low selectivity.
100% selectivity
reaction
is recognized
is the selective
hydroanthraquinones.
After reduction quinone,
production. production
in this process.
particular,
method
To inhibit this process and groups
should be involved,
2 we require catalysts
with a sufficiently
high heat of adsorption
with Pd, Rh, Ru, etc) [II]. Increase of the strongly the nickel catalyst partial oxidation into oxidized
surface
is promoted
and Ni-Al alloy modification
on Raney nickel and the influence Fe and Mn additives strength
by such factors
exerted
have been studied
is, to a great extent,
Thus, V and Nb are completely on the state of the hydrogen
[13-183.
as they oxidize
to various
in 2-ethylanthraquinone
additives
into its composition
the strongly
in the leaching
bond
of the catalyst.
[15,16] and their influence
is insignificant,
increase
The present work is aimed at determining changes
It was shown that the hydrogen
by the phase composition
in the catalysts
degrees
that are transformed
The forms of sorbed hydrogen
from the alloys
MO [17], Cr [19] and Cu [20] additives
on surface
on them by V, Nb, Ta, MO, Rh, Ti, Cr,
determined
leached
content
Cl21 as the nickel
by the metals
forms during the process of leaching.
(Pt and its alloys
bound hydrogen
whereas
Fe and
bound hydrogen
content,
process.
the causes of Raney nickel selectivity due to the introduction
hydrogenation
and thus the formation
of alloying
of highly selective
catalysts.
EXPERIMENTAL Choice of catalysts On the basis of the literature additives
have been chosen.
macrostructure, complicated.
degree of dispersion
Nevertheless,
to some degree and, hence, genation
data [l-20],
Their influence
of quinone
groups.
Fe, Cu, MO, Cr and other modifying
on the leaching depth, micro-
and Raney nickel defect
all of them decrease increase
Based on the literature,
vary. Choice of the best catalysts
variation
TABLE
in the selected
in initial alloys can
simplex planning
factors
content
in the hydro-
we have chosen the range in
and nickel
was made using the experiment
In the present case, the method of consecutive The range of the variation
of the catalyst
and
is rather
the loosely bound hydrogen
the selectivity
which the content of the above stated additives
structure,
planning
method.
[21] was used.
is shown in Table
1, where the
in nickel was from 10 to 50 wt %.
1
The range of variation for anthraquinone
of alloying
Range of variation
Catalyst
of metal/Ni(%)
selectivity method
several
independent
Cr
Fe
MO
cu
O-8
O-25
O-50
O-20
and activity were the functions 1213, a regular
the origin of coordinates. withstand
in the choice of the optimal
catalyst
hydrogenation.
Element
conventional
additives
turnovers
variables.
simplex
to be optimized.
Using the
has been plotted with its centre
in
The simplex volume has been chosen so that it could without
Catalysts
intersecting
with minimum
the boundaries
selectivity
of the space
were rejected
and the
3 initial
alloy
composition
was mirror-symnetrical subsequent between
search
for the next catalyst
to the rejected
for an extreme
the three best points.
are given simplex,
in Table
number
Initial alloy compositions
2, where the first seven compositions
10 corresponds
as a point which turnovers,
value was made by the error method
the next two compositions
and point
was determined
one. After two simplex
correspond
for all the catalysts correspond
to two catalysts
to the experiment
the
in the region
carried
to the initial
of the symplex
out near the extreme
value.
TABLE
2
Initial
alloy
selectivity
compositions
(wt %, the balance being aluminium),
of anthraquinone
hydrogenation
number
Ni
Fe
Cr
MO
Activity/ml H2 -1 min g Ni-'
cu
Selectivity/%
1
21.6
0.7
2.4
4.9
2.0
24
40
2
31.6
1.1
3.5
7.1
2.9
25
80
3.
26.5
0.9
2.9
6.0
2.4
30
55
4
26.6
1.6
2.9
6.0
2.4
46
60
5
26.1
1.0
4.8
5.9
2.4
25
70
6
25.5
1.0
3.2
9.6
2.3
25
98
7
26.1
1.1
3.3
6.5
3.8
32
50
8
41.4
1.9
5.9
11.3
4.0
27
95
9
32.3
1.2
3.6
6.4
0.5
29
IO
20.0
0.2
1.0
10.0
1.0
35
Catalyst
preparation
All alloys
and testing
were prepared
homogenizing
annealing
then crushed
and screened,
of the alloy was treated The catalysts 20% alkaline experiment,
the catalysts
introduced
95 100 [223
hydrogenation
LPZ-67 furnace
and underwent
on the composition.
u fraction
with 25% KOH solution
being isolated.
The alloys were A weighed
for 3.5 h in a boiling
into the autoclave,
portion
water bath.
immersed
in a fresh
and held there at 160°C for 5 h [83. In the course of the
other catalyst
of the initial
depending
the 63-100
were subsequently solution
for anthraquinone
in a high frequency
at 600-8OO"C,
and
catalysts.
Element
Alloy
activity
cast alloy, obtained
preparation
procedures
or catalyst
were
inferior
treatment
were also tested, with ammonium
to those given
e.g. leaching
formate
[231, but
in Table 2, both in selectivity
and activity. Catalyst hydrogenation solvent
activity
and selectivity
in a laboratory
at 40°C. Anthraquinones
from the solvent
were determined
unit described were
and their purity
during
the 2-ethylanthraquinone
in [24] in octanol-xylene
preliminarily
was controlled
cleaned by melting
(1:l)
by recrystallization temperatures
and IR
4
spectra.
Reaction
products
cell which provided atmosphere.
were analyzed
the reaction
Table 2 contains
was determined
process
data on catalyst
by the rate of hydrogen
the selectivity
using a LP-7 polarograph, on a mercury
was determined
electrode
activity
and selectivity.
uptake at the commencement
by the hydroquinone
in a special
in an inert
content
The activity
of the reaction;
in the reaction
products
at the end of the process.
RESULTS The search for correlations
between
ivity, as well as the determination require a detailed
catalyst
composition,
activity
of the Raney nickel promoting
study of these catalysts
using various
and select-
mechanism,
physical
and chemical
methods. The chemical
composition
atomic absorption was carried
of initial alloys
spectroscopy
method.
out using URS-50 and Dron-2 apparati.
gated on an EMR-100 electron
diffractometer
Before being placed on a collodion in a UZDN-1 ultrasonic diffractometer
apparatus
column where
given in Table 3, where The atomic absorption
support,
to the composition
and was transferred
data indicate
in order of decreasing
and free aluminium
in molybdenum,
under alcohol
in brackets.
analyses
with those
and electron
diffraction
content of the phases revealed.
are
in Table
2.
of aluminide
pattern
in all cases.
was also found. could not be ascribed
to any
to which the identification interplanar
(7); 1.37 (12); 1.36 (12), relative compounds
are
In alloy number 6, the richest
NiMo5Al,0
since in the ASTM file, according
These might be complex
analysis
The X-ray analysis
in the initial alloys,
carried out, there were no phases with the following (5); 4.30 (80); 4.27
in alcohol
to the electron
diffraction
are identical
Some of the lines of the X-ray diffraction known compounds
voltage.
was dispersed
that the initial alloy composition
were also identified.
a small quantity
were also investi-
of the charge.
data show that NiA13 and Ni2A13 were present Ni4MoA1,4
by the
10m3 Pa vacuum.
X-ray phase and electron
The results of the X-ray phase analysis tabulated
The catalysts
the catalyst
initial alloy numbers
analysis
was determined
error was +5%. X-ray analysis
at 75-100 kV acceleration
it was dried under
The results of the chemical,
corresponds
and catalysts
The realtive
containing
distances:
intensity
was 4.40
being given
Cr, Fe, Cu and other
elements. Data on the chemical is leached,
transfers
The X-ray analysis comprehensive
present
into the solution
due to their extremely
Thus, alumina
to identify and bayerite
in almost all the catalysts
indicate
that almost no nickel
and MO is oxidized
on leaching
[25].
data on the phase composition
it was possible
analysis.
of the catalysts
Fe and Cr are lost in small quantities
and partially
method,
composition
of Raney catalysts
fine dispersion.
cannot
By the electron diffraction
a number of phases that are amorphous are found and spine1
be
in all the catalysts.
to X-ray
Moo3 is
is found in the catalyst
from alloy
5 number
6. Iron oxide and NiMoO4 spine1 are also present.
Ni2A13 phase, easily diffraction
identified
patterns.
not transparent
by the X-ray analysis,
Probably due to its coarse
to electrons,
It can be seen that
is absent on electron
crystal
rings have been found
structure,
here which are not identified
by the ASTM file: 3.60 (20); 2.66 (50); 1.81 (10); 3.33
(40); 2.85 (10); 2.40 (80);
1.95 (80); 2.77 (40); 1.97 (80) and 1.51 (40). Apparently, initial
alloy destruction
density
of defects are formed in the catalysts.
by alkali, extremely
pure form as well as their intermetallic initial metals with different active
phase carriers.
mechanism
of catalyst
valence degrees,
formation
in the initial
the vacuum surfaces
samples were pressed
in the apparatus
has been recorded.
were exposed
chamber.
which,
metals
alloy leaching
into tablets
compositions
serve as the
of the complex
process.
was determined
spectrometer.
in
and oxides of
in some cases,
is an evidence
of
with a high
alloying
Also, for
by Auger
The working
in alcohol
The spectra of the freshly
The chemical
after surface cleaning
structures
solid solutions
composition
using a Leybold-Heraeus
in the process
They contain
A great number of spinels
a number of samples the surface chemical electron spectroscopy -3 was 10 Pa. Catalyst
complex
compounds,
this phase is
vacuum
and dried under
leached catalyst
of the deeper
layers that
by an Ar ion beam have been studied.
All the
data are given in Table 4. The shape of the aluminium
peaks indicates
that on the surface
in A1203 and Ni2A13 compounds.
As seen from Table 4, the catalyst
enriched
judging
with aluminium
oxidized,
which,
and also with copper,
catalyst
layers,
larger amounts
surface.
Other elements
by the amount of oxygen,
Al is contained surface
is considerably
this being in conformity
with
of nickel and molybdenum
are present
are distributed
rather uniformly
is
[26].
In the deeper than on the
along the catalyst
section.
DISCUSSION A number of physical structure,
chemical
to be elucidated. catalysts
of investigation
As was required
in all cases represented
the greater
Comparison
of the results surface
a metal-oxide
by diffraction
of a study of catalyst
in the bulk. From electron
that molybdenum
is completely
Chemical
in the catalyst compositions
structure, activity
therefore,
diffraction
studied
could not be essentially
and selectivity
of the studied
surfaces
of the experiment,
sublimation
uniformly
and Ni and Mo
data (Table 3), it follows that these oxides,
for other structural
were mainly different.
catalysts
of oxides,
and bulk has shown
having minimum
and it is possible
bulk, serve as a carrier
of the catalysts
the
methods.
Fe is distributed
are predominant
oxidized
planning
system with a complex
layers are rich in elements
i.e. Al and Cu (Table 4), while
present
used in this work allowed
of the bulk and surface of the catalysts
for the mathematical
part of which was identified
that catalyst heats,
methods
and phase composition
increase
components.
similar and their It can be noted that in the following
order:
TABLE 3 Catalyst
phase and chemical
copy, X-ray and electron Alloy
Chemical
compositions
diffraction
composition/wt
according
to atomic
absorption
spectros-
Electron
diffraction
data. X-ray diffraction
%
number
Element
Catalyst
Alloy
1
Ni
73.2
NiA13
Ni
Ni
Cr
1.5
Ni2A13
Ni2A13
NiO
Al
NiO
Moo3
Fe
7.9
MO
8.5
cu
6.6
Al
3.2
Ni
65.8
Cr
1.1
Fe
8.4
MO
13.1
NiA1204
NiA13
Ni
Ni;Ni,Fe
Ni2A13
Ni2A13
NiO
Ni4MoA1,4
NiO
NiMo04
cu
7.2
NiMo5A1,O
6.1
Al
Ni
66.7
Cr
1.5
Fe
18.4
MO
10.0
5.3
(40% Fe)
Fe3O4 y-A1203.3H20
NiA13
Ni
Ni
Ni2A13
Ni2A13
NiC
Ni4MoA1,4
NiO
y-A1203.3H20 Moo3
Al
8.6
Al
y-A1203.3H20
Ni4MoA1,4
Al
cu
10
Catalyst
Ni
Ni
59.3
NiA13
Ni
Fe
12.6
Ni2A13
Ni2A13
Ni0,Mo03
MO
14.1
Ni4MoA1,4
NiO
A12Fe206
cu
Al
6.9
Al
NiMo04 NiA1204
7.1
1 < 7 < 6 < IO (Table 2). In catalysts
of the same series,
of Cu, Fe and Al increases. the selectivity is interesting the catalyst
of the catalysts
the studied
correlates
to note that these elements
granule
amount of the element properties
the nickel content
Thus, within
sections
or enrich
their surfaces
Mo is small on the surface,
IO and thus catalyst
in the catalyst
activity
decreases
and that
with the Fe, Cu and Al content. are either
turns out to be more complicated
that the amount of oxygen
somewhat
range of concentration
uniformly
distributed
It along
(Tables 3 and 4). If the
its influence
on the catalytic
(Table 4). It follows also increases
and selectivity
changes
from Table 4
in the order
are dependent
1 < 7 < 6 <
upon the oxygen
TABLE 4 Chemical
composition
electron
spectroscopy
Catalyst
of the surface and deeper
1
6
a
Element
catalyst
layers obtained
b
7
a
b
10 b
a
a
b
Ni
40
70
35
65
40
63
40
69
Al
13
4
15
5
14
6
15
6
3
7
2
7
4
8
3
3
29
6
27
8
24
8
20
6
MO
cu
by Auger
(in wt %).
Cr
traces
traces
traces
traces
Fe
7
7
10
8
9
9
6
5
Oxvqen
5
3
7
4
5
4
10
5
abefore catalyst cleaning b after catalyst cleaning
content on the surface. maximum
amount of surface
oxide system
molybdenum
oxides
hydrogenation
phase is distributed
having high values of hydrogen
reactant
adsorption
and activation
ized by considerably is confirmed
on which
represents
literature
of the strongly
treatment
identical
is confirmed
the typical
catalyst
by the
adsorption
reports
heats and participating
adsorption
[27,28].
catalyst
bound hydrogen
was 90%. Figure
It is evident sharply
up to 90%. Meanwhile,
to [29], Such
kJ mol-'
, whereas
-1 . on the catalysts
programmed prepared
desorption.
catalyst
Its selectivity
lb represents
with the Figure
without
la
additional
during E-ethyl-
the TPD curve of the
Its selectivity
that were thoroughly
was 100%. These
washed with water of 25°C
of 70°C for 1 h.
that, after treatment increases.
themselves
cell undera vacuum of 1O-3 Pa at a temperature
for 2 h and then at a temperature
fraction
of 100-200
kJ mol
treatment.
from the samples
in the apparatus
than the metals
Thus, according
fraction
by the temperature
after the additional
have been recorded
and dried
of 500-800
TPD curve of the freshly
hydrogenation
in the
The fact that metal oxides are character-
with alkali at 160°C in the autoclave.
anthraquinone
while
oxides
stages.
have heats of adsorption
activity
can be presented
is precipitated,
is distinguished
higher heats of hydrogen
by numerous
The increase highest
catalysts
nickel
on the surface of the developed
as Cr, Fe, Cu and MO have heats of adsorption
their oxides
the
has the best developed
all the investigated
conglomerates
anthraquinone
fact that its active
curves
forming
10, contains
serve as the main carrier.
Thus, the optimal
system,
i.e. number
oxygen and, as was expected,
(Table 3). Apparently,
as a system of oxides
metals
The best of the catalysts,
of the catalyst,
The surface
the total hydrogen
becomes content
the strongly
bound hydrogen
covered with this form of hydrogen slightly
drops from 28 ml to 20 ml
a
100 FIGURE
1
200
Catalyst
the treatment
so0
400
TPD curves;
with alkali
b
T"C
100
(a) without
in the autoclave
200
the treatment
300
400 T"(:
with alkali and (b) after
at 160°C.
per g of catalyst. The energies equation, strongly
of activation
are as follows:
for desorption,
bound form, 80 kJ mol-'.
catalysts
provides
calculated
Thus, the presence
for the increase of the strongly
is the main cause of their high selectivity. hydrogen was accomplished
using the Polayni-Vigner -1 and for the
for the loosely bound form, 34 kJ mol
at a temperature
of the oxides
in these
bound hydrogen
content.
The saturation
This
of the samples with
of 40°C.
CONCLUSION Using the experiment
planning
methods,
been chosen and tested under laboratory of alkylanthraquinone. methods
which allowed
These catalysts
of hydrogen
reaction adsorption
of their structure
represent
upon which an active phase is supported. hydrogenation
correlates
Raney nickel catalysts for selective
were studied by a variety
the determination
It was found that the catalysts
effective
conditions
of physical
and chemical
a system of oxides of alloying Catalyst
selectivity
composition. additives
in the anthraquinone
with its degree of oxidation,
on the oxides of the promoting
have
hydrogenation
due to high heats
additives.
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Applied
RANEY CATALYSTS
A.B. FASMAN,
FOR THE HYDROGENATION
S.D. MIKHAILENKO,
OF SUBSTITUTED
N.A. MAKSIMOVA,
ANTHRAQUINONES
ZH.A.
IKHSANOV,
V.YA. KITAIGORODSKAYA
and L.V. PAVLYUKEVICH
Institute
of Organic
Catalysis
and Electrochemistry,
Alma-Ata,
480100,
K. Marx Street,
(Received
2 April
1982, accepted
Kazakh SSR Academy
of Sciences,
142, USSR.
13 December
1982)
ABSTRACT Raney nickel displays low selectivity in hydrogenation of substituted anthraquinones for hydrogen peroxide production. It was found that the selectivity may be increased by catalyst modification. Using the experiment planning method, effective catalysts for the selective hydrogenation of alkylanthraquinones have been found. The structure and phase composition of the catalysts have been determined using physical methods. It was shown that, for selective reduction of quinone groups in anthraquinones, catalysts with high hydrogen adsorption heats are required. The properties and methods of formation of such catalysts were established.
INTRODUCTION At present, for hydrogen of hydrogen
the anthraquinone
peroxide peroxide
the respective catalysts
One of the important
in anthraquinone of the quinone
H202
is reintroduced
the anthraquinones the reaction
anthraquinones proceeds
mixture,
anthraquinone
is minimized.
non-selectively
hydrogenation
decrease
to make hydrogenation 0166-9834/83/$03.00
to be obtained
allows
[2]. The latter the
In the case when the reduction of rings are involved,
etc., accumulating
is discussed with quinone
rings takes place.
so that only quinone
0 1983 Elsevier Science Publishers B.V.
in the
The problem of
in a number of papers groups
reduction,
the
It is known [IO] that hydrogen-
loosely bound hydrogen.
selective,
separation
cycle is formed wherein
the yield of the product.
on nickel catalysts
of the side aromatic
ation of the latter requires
i.e. hydroanthra-
and side aromatic
It was shown [3,4] that, simultaneously
in
for the process.
product,
i.e. tetrahydroanthraquinone
gradually
Raney nickel
by the oxygen of the air and further
and thus a closed
to
used as
It should be noted that
is necessary
, and the initial anthraquinone
products,
in the technology
Cl] have been mostly
the reaction
route
of anthraquinones
of nickel catalysts,
hydrogenation
groups,
into the reactor
loss of expensive
saturation
stages
reduction
Noble metals
The employment
is easily oxidized
the product,
[3-g].
as the most effective
has been limited due to its low selectivity.
100% selectivity
reaction
is recognized
is the selective
hydroanthraquinones.
After reduction quinone,
production. production
in this process.
particular,
method
To inhibit this process and groups
should be involved,
2 we require catalysts
with a sufficiently
high heat of adsorption
with Pd, Rh, Ru, etc) [II]. Increase of the strongly the nickel catalyst partial oxidation into oxidized
surface
is promoted
and Ni-Al alloy modification
on Raney nickel and the influence Fe and Mn additives strength
by such factors
exerted
have been studied
is, to a great extent,
Thus, V and Nb are completely on the state of the hydrogen
[13-183.
as they oxidize
to various
in 2-ethylanthraquinone
additives
into its composition
the strongly
in the leaching
bond
of the catalyst.
[15,16] and their influence
is insignificant,
increase
The present work is aimed at determining changes
It was shown that the hydrogen
by the phase composition
in the catalysts
degrees
that are transformed
The forms of sorbed hydrogen
from the alloys
MO [17], Cr [19] and Cu [20] additives
on surface
on them by V, Nb, Ta, MO, Rh, Ti, Cr,
determined
leached
content
Cl21 as the nickel
by the metals
forms during the process of leaching.
(Pt and its alloys
bound hydrogen
whereas
Fe and
bound hydrogen
content,
process.
the causes of Raney nickel selectivity due to the introduction
hydrogenation
and thus the formation
of alloying
of highly selective
catalysts.
EXPERIMENTAL Choice of catalysts On the basis of the literature additives
have been chosen.
macrostructure, complicated.
degree of dispersion
Nevertheless,
to some degree and, hence, genation
data [l-20],
Their influence
of quinone
groups.
Fe, Cu, MO, Cr and other modifying
on the leaching depth, micro-
and Raney nickel defect
all of them decrease increase
Based on the literature,
vary. Choice of the best catalysts
variation
TABLE
in the selected
in initial alloys can
simplex planning
factors
content
in the hydro-
we have chosen the range in
and nickel
was made using the experiment
In the present case, the method of consecutive The range of the variation
of the catalyst
and
is rather
the loosely bound hydrogen
the selectivity
which the content of the above stated additives
structure,
planning
method.
[21] was used.
is shown in Table
1, where the
in nickel was from 10 to 50 wt %.
1
The range of variation for anthraquinone
of alloying
Range of variation
Catalyst
of metal/Ni(%)
selectivity method
several
independent
Cr
Fe
MO
cu
O-8
O-25
O-50
O-20
and activity were the functions 1213, a regular
the origin of coordinates. withstand
in the choice of the optimal
catalyst
hydrogenation.
Element
conventional
additives
turnovers
variables.
simplex
to be optimized.
Using the
has been plotted with its centre
in
The simplex volume has been chosen so that it could without
Catalysts
intersecting
with minimum
the boundaries
selectivity
of the space
were rejected
and the
3 initial
alloy
composition
was mirror-symnetrical subsequent between
search
for the next catalyst
to the rejected
for an extreme
the three best points.
are given simplex,
in Table
number
Initial alloy compositions
2, where the first seven compositions
10 corresponds
as a point which turnovers,
value was made by the error method
the next two compositions
and point
was determined
one. After two simplex
correspond
for all the catalysts correspond
to two catalysts
to the experiment
the
in the region
carried
to the initial
of the symplex
out near the extreme
value.
TABLE
2
Initial
alloy
selectivity
compositions
(wt %, the balance being aluminium),
of anthraquinone
hydrogenation
number
Ni
Fe
Cr
MO
Activity/ml H2 -1 min g Ni-'
cu
Selectivity/%
1
21.6
0.7
2.4
4.9
2.0
24
40
2
31.6
1.1
3.5
7.1
2.9
25
80
3.
26.5
0.9
2.9
6.0
2.4
30
55
4
26.6
1.6
2.9
6.0
2.4
46
60
5
26.1
1.0
4.8
5.9
2.4
25
70
6
25.5
1.0
3.2
9.6
2.3
25
98
7
26.1
1.1
3.3
6.5
3.8
32
50
8
41.4
1.9
5.9
11.3
4.0
27
95
9
32.3
1.2
3.6
6.4
0.5
29
IO
20.0
0.2
1.0
10.0
1.0
35
Catalyst
preparation
All alloys
and testing
were prepared
homogenizing
annealing
then crushed
and screened,
of the alloy was treated The catalysts 20% alkaline experiment,
the catalysts
introduced
95 100 [223
hydrogenation
LPZ-67 furnace
and underwent
on the composition.
u fraction
with 25% KOH solution
being isolated.
The alloys were A weighed
for 3.5 h in a boiling
into the autoclave,
portion
water bath.
immersed
in a fresh
and held there at 160°C for 5 h [83. In the course of the
other catalyst
of the initial
depending
the 63-100
were subsequently solution
for anthraquinone
in a high frequency
at 600-8OO"C,
and
catalysts.
Element
Alloy
activity
cast alloy, obtained
preparation
procedures
or catalyst
were
inferior
treatment
were also tested, with ammonium
to those given
e.g. leaching
formate
[231, but
in Table 2, both in selectivity
and activity. Catalyst hydrogenation solvent
activity
and selectivity
in a laboratory
at 40°C. Anthraquinones
from the solvent
were determined
unit described were
and their purity
during
the 2-ethylanthraquinone
in [24] in octanol-xylene
preliminarily
was controlled
cleaned by melting
(1:l)
by recrystallization temperatures
and IR
4
spectra.
Reaction
products
cell which provided atmosphere.
were analyzed
the reaction
Table 2 contains
was determined
process
data on catalyst
by the rate of hydrogen
the selectivity
using a LP-7 polarograph, on a mercury
was determined
electrode
activity
and selectivity.
uptake at the commencement
by the hydroquinone
in a special
in an inert
content
The activity
of the reaction;
in the reaction
products
at the end of the process.
RESULTS The search for correlations
between
ivity, as well as the determination require a detailed
catalyst
composition,
activity
of the Raney nickel promoting
study of these catalysts
using various
and select-
mechanism,
physical
and chemical
methods. The chemical
composition
atomic absorption was carried
of initial alloys
spectroscopy
method.
out using URS-50 and Dron-2 apparati.
gated on an EMR-100 electron
diffractometer
Before being placed on a collodion in a UZDN-1 ultrasonic diffractometer
apparatus
column where
given in Table 3, where The atomic absorption
support,
to the composition
and was transferred
data indicate
in order of decreasing
and free aluminium
in molybdenum,
under alcohol
in brackets.
analyses
with those
and electron
diffraction
content of the phases revealed.
are
in Table
2.
of aluminide
pattern
in all cases.
was also found. could not be ascribed
to any
to which the identification interplanar
(7); 1.37 (12); 1.36 (12), relative compounds
are
In alloy number 6, the richest
NiMo5Al,0
since in the ASTM file, according
These might be complex
analysis
The X-ray analysis
in the initial alloys,
carried out, there were no phases with the following (5); 4.30 (80); 4.27
in alcohol
to the electron
diffraction
are identical
Some of the lines of the X-ray diffraction known compounds
voltage.
was dispersed
that the initial alloy composition
were also identified.
a small quantity
were also investi-
of the charge.
data show that NiA13 and Ni2A13 were present Ni4MoA1,4
by the
10m3 Pa vacuum.
X-ray phase and electron
The results of the X-ray phase analysis tabulated
The catalysts
the catalyst
initial alloy numbers
analysis
was determined
error was +5%. X-ray analysis
at 75-100 kV acceleration
it was dried under
The results of the chemical,
corresponds
and catalysts
The realtive
containing
distances:
intensity
was 4.40
being given
Cr, Fe, Cu and other
elements. Data on the chemical is leached,
transfers
The X-ray analysis comprehensive
present
into the solution
due to their extremely
Thus, alumina
to identify and bayerite
in almost all the catalysts
indicate
that almost no nickel
and MO is oxidized
on leaching
[25].
data on the phase composition
it was possible
analysis.
of the catalysts
Fe and Cr are lost in small quantities
and partially
method,
composition
of Raney catalysts
fine dispersion.
cannot
By the electron diffraction
a number of phases that are amorphous are found and spine1
be
in all the catalysts.
to X-ray
Moo3 is
is found in the catalyst
from alloy
5 number
6. Iron oxide and NiMoO4 spine1 are also present.
Ni2A13 phase, easily diffraction
identified
patterns.
not transparent
by the X-ray analysis,
Probably due to its coarse
to electrons,
It can be seen that
is absent on electron
crystal
rings have been found
structure,
here which are not identified
by the ASTM file: 3.60 (20); 2.66 (50); 1.81 (10); 3.33
(40); 2.85 (10); 2.40 (80);
1.95 (80); 2.77 (40); 1.97 (80) and 1.51 (40). Apparently, initial
alloy destruction
density
of defects are formed in the catalysts.
by alkali, extremely
pure form as well as their intermetallic initial metals with different active
phase carriers.
mechanism
of catalyst
valence degrees,
formation
in the initial
the vacuum surfaces
samples were pressed
in the apparatus
has been recorded.
were exposed
chamber.
which,
metals
alloy leaching
into tablets
compositions
serve as the
of the complex
process.
was determined
spectrometer.
in
and oxides of
in some cases,
is an evidence
of
with a high
alloying
Also, for
by Auger
The working
in alcohol
The spectra of the freshly
The chemical
after surface cleaning
structures
solid solutions
composition
using a Leybold-Heraeus
in the process
They contain
A great number of spinels
a number of samples the surface chemical electron spectroscopy -3 was 10 Pa. Catalyst
complex
compounds,
this phase is
vacuum
and dried under
leached catalyst
of the deeper
layers that
by an Ar ion beam have been studied.
All the
data are given in Table 4. The shape of the aluminium
peaks indicates
that on the surface
in A1203 and Ni2A13 compounds.
As seen from Table 4, the catalyst
enriched
judging
with aluminium
oxidized,
which,
and also with copper,
catalyst
layers,
larger amounts
surface.
Other elements
by the amount of oxygen,
Al is contained surface
is considerably
this being in conformity
with
of nickel and molybdenum
are present
are distributed
rather uniformly
is
[26].
In the deeper than on the
along the catalyst
section.
DISCUSSION A number of physical structure,
chemical
to be elucidated. catalysts
of investigation
As was required
in all cases represented
the greater
Comparison
of the results surface
a metal-oxide
by diffraction
of a study of catalyst
in the bulk. From electron
that molybdenum
is completely
Chemical
in the catalyst compositions
structure, activity
therefore,
diffraction
studied
could not be essentially
and selectivity
of the studied
surfaces
of the experiment,
sublimation
uniformly
and Ni and Mo
data (Table 3), it follows that these oxides,
for other structural
were mainly different.
catalysts
of oxides,
and bulk has shown
having minimum
and it is possible
bulk, serve as a carrier
of the catalysts
the
methods.
Fe is distributed
are predominant
oxidized
planning
system with a complex
layers are rich in elements
i.e. Al and Cu (Table 4), while
present
used in this work allowed
of the bulk and surface of the catalysts
for the mathematical
part of which was identified
that catalyst heats,
methods
and phase composition
increase
components.
similar and their It can be noted that in the following
order:
TABLE 3 Catalyst
phase and chemical
copy, X-ray and electron Alloy
Chemical
compositions
diffraction
composition/wt
according
to atomic
absorption
spectros-
Electron
diffraction
data. X-ray diffraction
%
number
Element
Catalyst
Alloy
1
Ni
73.2
NiA13
Ni
Ni
Cr
1.5
Ni2A13
Ni2A13
NiO
Al
NiO
Moo3
Fe
7.9
MO
8.5
cu
6.6
Al
3.2
Ni
65.8
Cr
1.1
Fe
8.4
MO
13.1
NiA1204
NiA13
Ni
Ni;Ni,Fe
Ni2A13
Ni2A13
NiO
Ni4MoA1,4
NiO
NiMo04
cu
7.2
NiMo5A1,O
6.1
Al
Ni
66.7
Cr
1.5
Fe
18.4
MO
10.0
5.3
(40% Fe)
Fe3O4 y-A1203.3H20
NiA13
Ni
Ni
Ni2A13
Ni2A13
NiC
Ni4MoA1,4
NiO
y-A1203.3H20 Moo3
Al
8.6
Al
y-A1203.3H20
Ni4MoA1,4
Al
cu
10
Catalyst
Ni
Ni
59.3
NiA13
Ni
Fe
12.6
Ni2A13
Ni2A13
Ni0,Mo03
MO
14.1
Ni4MoA1,4
NiO
A12Fe206
cu
Al
6.9
Al
NiMo04 NiA1204
7.1
1 < 7 < 6 < IO (Table 2). In catalysts
of the same series,
of Cu, Fe and Al increases. the selectivity is interesting the catalyst
of the catalysts
the studied
correlates
to note that these elements
granule
amount of the element properties
the nickel content
Thus, within
sections
or enrich
their surfaces
Mo is small on the surface,
IO and thus catalyst
in the catalyst
activity
decreases
and that
with the Fe, Cu and Al content. are either
turns out to be more complicated
that the amount of oxygen
somewhat
range of concentration
uniformly
distributed
It along
(Tables 3 and 4). If the
its influence
on the catalytic
(Table 4). It follows also increases
and selectivity
changes
from Table 4
in the order
are dependent
1 < 7 < 6 <
upon the oxygen
TABLE 4 Chemical
composition
electron
spectroscopy
Catalyst
of the surface and deeper
1
6
a
Element
catalyst
layers obtained
b
7
a
b
10 b
a
a
b
Ni
40
70
35
65
40
63
40
69
Al
13
4
15
5
14
6
15
6
3
7
2
7
4
8
3
3
29
6
27
8
24
8
20
6
MO
cu
by Auger
(in wt %).
Cr
traces
traces
traces
traces
Fe
7
7
10
8
9
9
6
5
Oxvqen
5
3
7
4
5
4
10
5
abefore catalyst cleaning b after catalyst cleaning
content on the surface. maximum
amount of surface
oxide system
molybdenum
oxides
hydrogenation
phase is distributed
having high values of hydrogen
reactant
adsorption
and activation
ized by considerably is confirmed
on which
represents
literature
of the strongly
treatment
identical
is confirmed
the typical
catalyst
by the
adsorption
reports
heats and participating
adsorption
[27,28].
catalyst
bound hydrogen
was 90%. Figure
It is evident sharply
up to 90%. Meanwhile,
to [29], Such
kJ mol-'
, whereas
-1 . on the catalysts
programmed prepared
desorption.
catalyst
Its selectivity
lb represents
with the Figure
without
la
additional
during E-ethyl-
the TPD curve of the
Its selectivity
that were thoroughly
was 100%. These
washed with water of 25°C
of 70°C for 1 h.
that, after treatment increases.
themselves
cell undera vacuum of 1O-3 Pa at a temperature
for 2 h and then at a temperature
fraction
of 100-200
kJ mol
treatment.
from the samples
in the apparatus
than the metals
Thus, according
fraction
by the temperature
after the additional
have been recorded
and dried
of 500-800
TPD curve of the freshly
hydrogenation
in the
The fact that metal oxides are character-
with alkali at 160°C in the autoclave.
anthraquinone
while
oxides
stages.
have heats of adsorption
activity
can be presented
is precipitated,
is distinguished
higher heats of hydrogen
by numerous
The increase highest
catalysts
nickel
on the surface of the developed
as Cr, Fe, Cu and MO have heats of adsorption
their oxides
the
has the best developed
all the investigated
conglomerates
anthraquinone
fact that its active
curves
forming
10, contains
serve as the main carrier.
Thus, the optimal
system,
i.e. number
oxygen and, as was expected,
(Table 3). Apparently,
as a system of oxides
metals
The best of the catalysts,
of the catalyst,
The surface
the total hydrogen
becomes content
the strongly
bound hydrogen
covered with this form of hydrogen slightly
drops from 28 ml to 20 ml
a
100 FIGURE
1
200
Catalyst
the treatment
so0
400
TPD curves;
with alkali
b
T"C
100
(a) without
in the autoclave
200
the treatment
300
400 T"(:
with alkali and (b) after
at 160°C.
per g of catalyst. The energies equation, strongly
of activation
are as follows:
for desorption,
bound form, 80 kJ mol-'.
catalysts
provides
calculated
Thus, the presence
for the increase of the strongly
is the main cause of their high selectivity. hydrogen was accomplished
using the Polayni-Vigner -1 and for the
for the loosely bound form, 34 kJ mol
at a temperature
of the oxides
in these
bound hydrogen
content.
The saturation
This
of the samples with
of 40°C.
CONCLUSION Using the experiment
planning
methods,
been chosen and tested under laboratory of alkylanthraquinone. methods
which allowed
These catalysts
of hydrogen
reaction adsorption
of their structure
represent
upon which an active phase is supported. hydrogenation
correlates
Raney nickel catalysts for selective
were studied by a variety
the determination
It was found that the catalysts
effective
conditions
of physical
and chemical
a system of oxides of alloying Catalyst
selectivity
composition. additives
in the anthraquinone
with its degree of oxidation,
on the oxides of the promoting
have
hydrogenation
due to high heats
additives.
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