ACTIVE STRUCTURE OF A NICKEL-HYDOGEN CATALYST

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000200020072-9
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 13
• Document Creation Date: December 22, 2016
• Document Release Date: May 15, 2012
• Sequence Number: 72
• Publication Date: May 21, 1952
• Content Type: REPORT

?deleniye
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i A ~IIU11.~iL""H~i~'VUJ:,Tr CATA'L.~ST
ACTIVE ~')TPUCr ~CJR~ OF '
author L. Kh Freydla.n,
:
N, I. 7iminova
50X1 -HUM
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50X1-HUM
(QNFJJ)ENT[A1
a~a~a
L. Kh. Freydlin and N. I. Ziminova
Institute of Organic Chemistry,
Academy of Sciences USSR
The present investigation reveals the stochiometric ratio between
the consumption of poison and the quantity of promoter - in this case,
dissolved hydrogen removed from the catalyst - and establishes the linear
dependence of the residual activity of the catalyst on the residual
quantity of Hdis in it, thus attesting to the uniformity of its
elementary active structures.
As N. D. Zelinskiy (1) established for the first time, when nickel
is deposited on aluminum oxide its cracking action is decreased while its
selectivity in respect to hydro~enbned?byld~genaian reactions is
considerably increased. This discovery has made it possible in many cases
to employ nickel instead of costly noble metal catalysts. Nickel catalysts
will be even more widely used if their activity and stability can be
increased. It is therefore necessary to devote further research to the
nature of the active structure of a nickel catalyst, particularly its
skeleton form, whose activity frequently approaches the activity of Pt and Pd.
Earlier (2) we showed that the skeleton nickel catalyst is a type which
is promoted by hydrogen, The removal of this hydrogen brings about the
complete deactivation of the catalyst; consequently, there are no other
(3)
promoting admixtures in it, t was also found possible to distinguish
chemically between two forms of hydrogen bonds in the nickel catalyst with
the aid of specially selected easily hydrated organic compovlxlds; some of
these compounds are capable of removing only surface-adsorbed hydro en
g )
1
()NFIDFN1JA I
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ACTIVE STR11CWRF OF A NICKEL. HXDROG 1 CATALYST
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I
(ONFI DEN1IAL
1
while others (emoverdissolved hydrogen (Hdis) as well, In this wai it
was possible to establish that Hdis alone is the necessary component part
of the active structure of the catalyst. The catalyst being investigated
can therefore be correct/Ycalled nickel_hydrogen (NiH, the subscript
denoting the nature of the promoter), in order to emphasize the importance
of both components of the catalyst which together form its active structures.
In the specimen of catalyst which was investigated (prepared from
extremely pure metals, carefully leached out, and well washed), which was
obtained by the leaching out of a 50% Ni-A1 alloy at 105?C, adsorbed and
dissolved hydrogen and nickel were in the following atomic proportions:
?
Hads1 disNi = 1:3.5:9 Since the number of atoms of structural hydrogen in the nickel catalyst
s less than the number of atbm~ of the
ti
me
was very great, altogether only 2-3
ti
were dissolved, there was a basis for regarding the
metal in which they we
solution of hydrogen in metal as a volumetric phenomenon.
The number of atoms of Hdis considerably exceeds the number of atoms of
44
r~
Hails , Evidently the simplest active catalytic structure includes several
the complex which consists
i
'~ SS
4
ng
atoms of settled on consider
H dis We have
ain number of atoms of nickel and Ndis as the simplest element o
of acer;~
the active structure of the catalyst which is capable of adsorbing one atom
of h rogen and transferring it to the substance to be hydrated. The
yd "~~ F
?.
question arises as to whether all elementary structures of the given specimen
active.
f catal st are identically promoted and equally
o y
The quantity Hads (referred to a unit weight of catalyst) characterizes
.
r`71r ,
the concentration of active structures in the catalyst, while the ratio
~uk5 "dis number of atoms of H in each of them under the
.- indicates the dis
-
~
ads
identically promotedc' Active structures which are
condition that they are
identical in composition must also be uniform with respect to activity. ,
r
Therefore, if the catalyst is subjected to depromotion by the graduel removal
it ll also be reduced at the same -
of H from it, the number of Hails in
dis H
time, while the value of the ratio -s will not change. Consequently,
dis
2
Fl DEHT1L
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 ^
a linear dependence must be observed between the activity of the catalyst
the residual content of structural hydrogen in It.
and
In order to test this position we conducted two series of experiments,
In the first of these we investigated the variation in the adsorption
activity of the catalyst in relation to hydrogen as specific quantities of
Hdis e progressively removed from the catalyst.
h
The experimental methods were si' lar to those described previously (3).
The hydrogenation reaction was carried out in a flask fastened to a powerful
rocking device. Dissolved hydrogen was removed from the catalyst with the
aid of the poison 1-methylcyclopentene-1 (rsP) in the absence of free
hydrogen. The space over the liquid being hydrogenated in the flask was
filled with nitrogen.
The poison was introduced into the flask in a quantity corresponding
to the volume of Hdis to be removed. The more Hdrequired to be removed,
~.s
the grelater was the quantity of poison used. All experiments were conducted
200 with the same specimen of freshly prepared skeleton nickel catalyst.
at
One ml of nickel paste (2.33 g) contained 47.4 ml of H and 177 ml of Hdis'
ads
Experiments were 90 min in duration. Preliminary experiments established
.
amount of time was completely sufficient for the quantity of poison
that this
introduced to be fully hydrogenated under the given conditions at the expense
of hydrogen dissolved in the catalyst.
The results obtained in these experiments are cited in Table 1. Along
the ordinate axis in Figure 1 are laid out the volumes of hydrogen which the
catalyst is capable of adsorbing from the gaseous phase. They characterize
its residual activity in dependence on the residual quantities of Hdis in
..
which are laid out along the abscissa. It follows from Figure
the catalyst,
1 that, the more Hdis extracted from a given portion of the catalyst, and
the more broken down the active structure, the less is its capability to
adsorb hydrogen. Finally, after removal of all Hdis the catalyst becomes
completely deactivated.
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 the more broken down the active structure, the less is its capability to
adsorb hydrogen. Finally, after removal of all Hdis the catalyst becomes
completely deactivated.
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(ONEIDENIIAL
a linear dependence must be observed between the activity of the catalyst
and the residual content of structural hydrogen in it.
In order to test this position we conducted two series of experiments.
In the first of these we investigated the variation in the adsorption
activity of the" catalyst in relation to hydrogen as specific quantities of
Hdis e> progressively removed from the catalyst.
h
The experimental methods were slar to those described previously (3)?
The h'drogenation reaction was carried out in a flan: fastened to a powerful
rocking device. Dissolved hydrogen was removed from the catalyst with the
aid of the poison l~methylcyclopentene-1 (MTsP) in the absence of free
hydrogen. The space over the liquid being hydrogenated in the flask was
filled with nitrogen.
The poison was introduced into the flask in a quantity corresponding
to the volume of Hdis to be removed. The more Hdi .s required to be removed,
the greater was the quantity of poison used. All experiments were conducted
at 200 with the same specimen of freshly prepared skeleton nickel catalyst.
One ml of nickel paste (2.33 g) contained 47.4 m1 of Hads and 177 ml of Hdis'
Experiments were 90 min in duration. Preliminary experiments established
amount of time was completely sufficient for the quantity of poison
that this
introduced to be fully hydrogenated under the given conditions at the expense
of hydrogen dissolved in the catalyst.
The results obtained in these experiments are cited in Table 1. Along
the ordinate axis in Figure 1 are laid out the volumes of hydrogen which the
catalyst is capable of adsorbing from the gaseous phase. They characterize
its residual activity in dependence on the residual quantities of Hdis in
the catalyst, which are laid out along the abscissa. It follows from Figure
1 that, the more Hdis extracted from a given portion of the catalyst, and
 activity of a catalyst; as determined by
It may be expected that the
the usual kinetic method, is expressed by an analogous dependence on the
and this has been verified.
number of residual active structures in it;
ti
In the second series of experiments (Table 2) viny1~bUtY1 ether was used
~
as a poison to depromote the active structux'ea of the catalyst. The duration
of treatment of the catalyst with ether in the absence of free hydrogen (in
the gaseous phase over the liquid in the Bask was nitrogen) was 60 min, and
-
the temperature of the experiment was 200. After removal of a specified
quantity of Hdis from the portion of catalyst in question, the nitrogen was
drawn out of the Mask and the catalyst was saturated with hydrogen for 15 min
dissolved in benzene was introduced and
at 200. Then 0.23 g of allYl alcohol
Thus each portion of catalyst was subjected twice
the agitation continued.
eriment to treatment with substances capable of
in the course of the same exp
ether for the purpose of breaking down
being hydrogenated: first vinylbutyl
part of the active structures by depromotion, and then allyl alcohol, which,
as was shown in our work with K. Rudneva, is incapable of promoting, for
determination activity of the catalyst. The quantity
determination of the residual activa.
Hdis extracted from the catalyst was determined from the value of the weighed
portion of ether used. The die ~~'~,~f,;3,rogenation of allyl alcohol after
. ~
rued the residual activity of the catalyst
15 min. at 20? in this case characte
after the breaking down of part of its active structures. From Figures 1 and
2 it is clear that in both series of experiments the linear dependence of
residual activity of the catalyst on the quantity of Hdis it contained was
1 and 2 are superimposed, it will be seen that the
preserved. If Figures
straight lines obtained ' n both series of experiments are mutually parallel.
~
They intersect the abscissa at the same ang3:s, whose tangent has the value
reads i.e., H : Hdis 1 : 3.7. Thus from the
of the ratio h 0.27, ads
ctis
kinetic data it is possible to determine the number of atoms o dis
simplest structure of the catalyst.
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It is evident from Tables 1 and 2 that both poisons (vinyl ether and
eYcloPentene) are consumed during the process in equimolecular quantities
,
which bear a stochiometric relation to the quantities of Hdis being
progressively removed.
Bredig and Alloio (4) remarked that until it was possible to investigate
separately the influences of admixtures and of the structure of the crystalline
lattice it would be impossible to evaluate each's role in the activity of a
nickel catalyst.
Now it is possible to answer this question. If the activity of the
catalyst is determined by the presence in it of a promoting admixture and is
not connected with the structure of the crystalline lattice, then NiH and
dehydrogenated nickel must have identical structures. To verify this
we tbbk x-ray photographs of the nickel catalyst before and after
position
its complete dehydrogenation (Figure 3)? Vinylbutyl ether was used as the
dePromoting agent. The depromotion took place at room temperature by the
methods described previously.
The x-ray photographs, taken by Professor A. M. Rubinshteyn, to whom
we here express our thanks, were exposed with radiation from iron at 30 kv
and 10 ma. Specimens were prepared for exposure under conditions which
excluded the possibility of contact of the nickel with air. Canadian balsam
was added to the nickel, which was dispersed in alcohol; after evaporation of
the greater part of the alcohol in the cold, specimens of a cylindrical shape
were prepared for exposure from the solidifying paste. In no stage of the
preparation of the samples was there heating or contact of the metal with air.
Results of Measurements. The obtained x-ray photographs are shown in
The number of lines in the photograph is 10. From the character of
Table 3
the distribution of the lines it is evident that both the active specimen,
containing Hdis, and the completely dehydrogenated, inactive specimen of the
nickel catalyst have face-centered lattices.
. 5
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 (ONFI DENTI At
Discarding images under small angles, which yield slight deviations,
and using images beginning with 022 as the basis, we obtain the parameter
a = 3.49 , which is charactrristic for the cubic structure of nickel.
CONCLUSIONS
1. The results of our investigation show that both active NIH and
the inactive (dehydrogenated) form possess the same crystalline structure,
namely, cubic.
2. We found a stochiometric ratio between the consumption of poison
and the quantity of the pronioter Hdis which was removed from the catalyst.
By treating the catalyst with specific quantities of poisons (vinylbutyl
ether or 1-methylcyclopentene-l) its activity may be lowered to any
predetermined value.
3. We established the linear dependence of the residual activity of
the catalyst on the residual quantity of Hdjs in it. This dependence attests
to the uniformity of the active structures in the specimen of skeleton
nickel catalyst under investigation; these active structures are at the
same time the source and measure of the catalyst's adsorption and catalytic
activity,
4. The uniformity of the structures in respect to activity permits the
assumption to be made that they are also uniform as to composition. Together
with active structures of composition N1XHY, the catalyst probably also
contains a certain quantity of dehydrogenated and therefore inactive ballast
nickel.
BIBLIOGRAPHY
1. N. D. Zelinskiy, Ber, LVII, 667 (1920
2. L. Kh. Freydlin and N. I. Ziminova, IAN SSSR, OKhN, No 6, 659 (1950).
L. Kh. Freydlin and N. I. Ziminova, DAN SSSR, L )IV. No 5, 955 (1950).
G. Bredig and R. Allolio, Z Phys Chem, 126, 41 (1927).
6
A
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TATJE 1
Effect of Different Quantities of the Poison 1_Methylcyclopentene--1 (MTsP) on
the Change in Activity of a Nickel Catalyst
Amt of MP used Amtof Hd?s removed Amt of H re- Limit of saturat3on
for removal of from catalyst maining In of catalyst with
H (in ) (in ml) catalyst (in ml) hydrogen (Hads)
dis g (in xal )
0
177
35
142
85
92
135
42
177
0
47.4
38.6
25.4 (24.7)*
10.2 (11.0)
0.2 (o.l)
* In parenthesis are cited results obtained in parallel experiments.
TABLE 2
Effect of Different Quantities of the Poison Vinylbutyl Ether on the Change in
~~
Activity of a Nickel Catalyst in the Hydrogenation of Allyl Alcohol
Amt of the ether Amt~of H . removed Amt of Hdis re- Degree of hydro-
used for removal from catalyst maining in genation of a11y1
(in ) in m1) catalyst (in ml) alcohol (in %)
of H?
5
0
0
0.156
35
0.380
85
0.603
135
0.735
165
0,'91
177
177 96.6 (97.4)
142 79.2 (78.1; 80.0)
92 49.4 (51.3; 5o.1)
42 22.2 (23.8)
12 8.3 (7.9)
0 0.1 (0.1)
# In parenthesis are cited results obtained in parallel experiments.
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(ONF1bEi11AL
TAtLE l
Effect of Different Quantities of the Poison 1-Methylcyclopentene-1 (MTsP) on
the Change in Activity of a Nickel Catalyst
Amt of MTsP used
for removal of
Hdis (in g)
Amt of Hd.s removed Amt of Hdis re-
from catalyst maining in
(in ml) catalyst (in ml)
Limit of saturation
of catalyst with
hydrogen (Hads)
(in ml)
.. _ 4 ...... .. . .... . ~~~~._,.~ --.....__n.~..ww~..~.....w..-...---~~..,
0
0.131
0.319
0.507
0.791
* In parenthesis are cited results obtained in parallel experiments.
TABLE 2
t of Different Quantities of the Poison Vinylbutyl Father on the Change in
Eff
ec
A
h
l
lco
o
Activity of a Nickel Catalyst in the Hydrogenation of Allyl
removed Amt of Hdis re- Degree of hydro-
ther Amt of H
f th
A
e e
mt o
di
maining in genation of allyl
sused for removal from catalyst
of Hdj$ (in g) (in ml) catalyst (in ml) alcohol (in %)
0.30 $5 92 49.4 (51.3; 50.1)
0.156 35 142 79.2 (7$.l; E0.o)
0 0 177 96.6 (97.4) #
0.603 135 42 22.2 (23.$)
165 12 ~.3 (7.9)
0.735
0.791 177 0 0.1 (0.1)
* In parenthesis are cited results obtained in parallel experiments.
li)th ilAL
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 Lr;
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(ONFI DE)J AL
{
TA J.,EI J, r
Effect of Different Quantities of the poison 1wMethylcyclopentene-1 (NITsP) on ;r the Change in Activity of a Nicker Catalyst
_
.4
_____..._.....-__._-----,.-~.- --- .-
..
Amt of MTsP used
.
---- ._.........
Amt of Hd s rencved
Amt of His re~
Limit of saturation
for removal of
from catalyst
"mining n
of catalyst with
)
H (in g)
(in ml)
catalyst (in nil)
hydrogen Gads
dis
(in m1)
0
0
177
47.4
0,131
5
142
3.6
0.319
85
.
92
25.4 (24.7)
0?507
135
42
10.2 (11.0)
..w 1:
0,791
177
0
0.2 (0.1)
*In parenthesis are cited results obtained in parallel experiments.
TABLE 2
Effect of Different Quantities of the Poison Vinylbutyl Ether on the Change in Activity of a Nickel Catalyst in the Hydrogenation of Ally1 Alcohol
Amt of the ether
used for removal
of Hdj$ (in g)
Amt of H removed
from di catalyst
in ml)
Amt of Hdis re-
"mining in
catalyst (in ml)
Degree of hydro-
genation of a11y1
alcohol (in %)
0
0
177
96.6
(97.4)
#
0.156
35
142
?.2
(7L1;
$o ? 0)
0.30
$5
92
49.4
(51.3;
50.1)
0.603
.
135
42
22.2
(23.)
~
0.735
165
0,'791
177
0
0.1(0.1)
~,.
* In parenthesis are cited results obtained in parallel experiments.
H
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 11
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(o'ot"11~`
rra
"
oalcat
Data
."".-~' for n ~d3.g
d.e Y ce1
a
1
a
x e
o ?
2
yin
,w.....M.~~-
3.42
0.204
3,42
0,203
0.246
111 ~
1
~
0.246
0,22
4
3,40 .
111
3.4
2
0,261
0,329
002
'
3.44
3
3.43
13
0,31
7
0.52
r
r .
3
4,
002 at
3.42
.
,
0.524
o.b24
Q~2fg
3.4'7
3.49
0,624
0.695
022 a
3.6 ~
3.49
6
0,699
0.760
11.3
3.1.9
3.49
0,760
o.
222
.49`
3.50
0 0~5
0.927
113 ?,
. 3.50
9
0.922
222 a
10
y"
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3
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o \ (7' /1 60 /
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20 1/ r
10 - 20 \" 40 O 12? 160 2O0 4 O 2O 160
i$1
!v it e
b 'r~ 'deb r s j ual uaflt t o ats
catalyst 0t
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1otograpb$ of
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ycke3. caa3,s c ,
M A ~~ - xiac~ive,
e& ? ii abta fea t
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7i
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