SCIENTIFIC ABSTRACT BALANDIN, A. A. - BALANDIN, A. A.
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CIA-RDP86-00513R000103210010-3
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S
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Publication Date:
December 31, 1967
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SCIENCEAB
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Body:
Catalytic Dehydrogenation of Isopropyl Benzene
S/020/60/132/02/27/067
B011/BO02
is illustrated by Fig. 2:. The points of these two dependences are lying on the
same curve. Hence the authors concluded that their experiments took place within
the kinetic range. From S2 and z3 the changes of the liberated snergyA F, the
host content jinffl and. the entropy 68 were calculated in the adsorption dis-
placement from the active centers of dehydrogenation. The degree of the dehydro-
genstion of isopropyl benzene increases with rising temperature. At 5800 and
6070, the yield in 0(-methyl styrene attains 70-5~ and 83~.j respectively (Table 1).
G. M. Marukyan is mentioned. There are 2 figures, 2 tables, and 8 references,
4 of which are Soviet.
ASSOCIATIONs Institut organicheekoy khimil im. N. D~ Zelinskogo, Akademli nauk
SSSR (Institute of Organic Chemistry imeni N. D. Zelinskiy of the
Academy of Soienceaj USSR);
SUBMITTEDs February 8, 1960
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B/020/60/i32/03/24/o66
BOII/BO08
AUTHORS: Balanding A. Aog Academician, Teteni, P.
TITLE: On the Influence of the Nature of Metals on Their
Catalytic Activity
PIRIODICAL; Doklady Akademii nauk SSSR, 1960, Vol. 132, No. 3,
PP. 577-500
TEXT: In the paper under review the authors experimentally studied the
kinetics of the dehydrogtnation of the isopropyl alcohol on metallio
silver, platinum, and palladium. The methods of the kinetic measurements
have been described previously (Refs. 10t11). The rate constants k
were calculated. in accordance with equation
k w (z2 + z3)Ajln Al M - (32 + z3 - 9m. (i). This equation was
Al
obtained from the general kinetic equation which was derived by A. A.
Balandin (Ref. 19)t with Al being the volume rate of the alcohol
Card, 1/3
on the Influence of the Mature of Metals 8/02 60/132/03/24/066
on Their Catalytic Activity BOIIYBO08
passagag a the hydrogen volume separated within I min. and z2 and z
the relative:adoorption coefficients of the acetone and hydrogen. TL
determination Of 22 and s3 was necessary for the calculation of k. This
was done by neane of the reaotion-kinetio method (Ref. 20). For the
methods of the determination and calculation see Refs. 15 and. 16. The
results are given In Tables 2 and 3. The authors carried out separate
experimental series at different temperatures and at a constant volume
rate In order to determine the activation energy Eof the dehydrogenation
of the isopropyl alcohol* The values Aj, m and ( 52 + 3) were inserted
informula (1) for the calculation of the Yalu of k :a 3 increases in
the case of the platinum catalyst with the ri:: of t e perature (Table 3),
2 had therefore to be determined for the desired temperature with the
aid of interpolation from the dependence diagram log !3 of I/T. The true
activation energy was only determined on silve r and p atinum, since the
relative adsorption coefficients of the reaction products were only
available for these catalysts* For palladiumo the approximate activation
energy was only determined from the tangent of the angle of slope of the
straight line in the diagram log m, I/T. The values determined for C are
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On the Influence of the Nature of Metals 3/020/60/132/03/24/066
on Their Catalytic Activity B0111BOOD
shown in Tables 4-6 and Pigs 2* The points come to lie on the straight
line by Arrhenius with sufficient accuracy (Fig* 2). Table I shown the
activation energies,. also those taken from the papers (Refs. 15 and 16).
In the introduction, the authors explain the multiplet, theory by A. A.
Balandin (Ref. 1) and the structural# as well as energetic correspondence
between the chemical compounds reacting in the substrate and In the
catalyst. They state, moreover# that the results mentioned in Table 1
have a sufficiently general charsoters The authors mention A. Us
Rubinshteyu* S. Z. Roginskiyj F. P. Volskenshtsyn and K. D. Zelinskiy.
There are 2 figures, 6 tables, and 20 references, 11 of which are Soviet.
ASSOCIATION: Moskovskiy goeudaretyennyy universitet im. H. V.
Lomonosova (Moscow State University imeni M. V. Lomonosov)
SUBMITTED: September 9, 1959
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PATRIEffW, T.Y.; BALARDIN A*A. akademik; ]aABUNOVSKIT. Te.I.; PARDASHIT,
YU.S.1 MMIA5V.W. T
Selectivity towards optical Isomers of adsorbents fromed in the
presence of bacteria. Dokl.AN SSSR 1132 no.4o.850-852 JS ;~O
(KIRA .53
1, Institut, orgknichookoy khimii I*. II.D.Zolinakogo Almdemii nauk
SSSR.
(Advorbouts) (Isomers)
Mo
AUTHORS:
B/018i'?'jj(0/1 33/0t/36/070
110C
Doi 1 B003
Tolatopyatova, A. A,,9 Bala, , Academician,
KOz6nkOA-- 1* 1, Adini A. L
TITLE: Catalytic transformations of Alcohols and CZolio ftdro-
cairbontion Titaniim Dioxide
PERIODICAL: Doklady Akadesii nauk SSBR, 1960, Vol. 133, No0j,
pp. 130 - 135
TEXT: Although titanium dioxide is easily ayallableg It belongs to the
little investigated astalyslalThe authors wanted to study its oata-
lytio properties with various modes, of preparation# In reactions with
*thyl-, isopropylp and a-propyl alcohol as well as with eyolohexans,
oyolohox*ne# and 1P4-oy*lohex&dien*. Moreover, they wanted to inv*eti-
gat* the kinetics of these reactions and the energies of the bonds of
C-, H-, and O-stome with th: TiO urfaoe, The method of the difteren-
tial thermocouple is used f r thl Nudy of the catalytic reactions._
Fig. i shows the position of the catalyst in relation to the thersto OK
couple. The electromotive force (eaf) was uninterruptedly recorded on
Card 1/3
as
hYdroxide f roperties Uen
r04 TICI On fo Ur
4 w1 th
8172~
1
'Catalytic Transformation* of Alcohol* and 0/133/01/36/070
Cyclic Hydrocarbons on Titanium Dioxide ioll/BO03
waterp No. 2 - the a&&* with ammonia. No. 3 by oxidation of freshly pre-
pared Ti (003 (precipitated from TiC13 with annonia) with airt and No. 4
by hydrolysis of orthoethyl titanate, It was established by X-ray struo-
tural analysis that anataso resulted in No. 1. Table 2 shows the reac-
tion* studied in certain temperature ranges, the activation energies 'C.
as W:11,:Six, of the krrhenius equation; furthermore, the degree of do-
oarb ni t on of each sample surface. It say be seen from these data and
Table 4 that the nod* of preparation exerts a great Influence on the
above-mentioned values and the binding energy. Table 3 shows the d9pen-
depoe of the adsorption coefficient z on AV (heat *out nt) the ontro--
pjFA80, and the change in free *n:r AFO. The binding :ner6 value*
were calculated for the first tie Fuble 4). Thera are i figure,
4z tables, and 11 references: 10 Soviet.
ASSOCIATION: Institut organicheskoy khinii is. N, D, Zelinskogo
Akademit nauk 8839 (Institute of OManic ChouistrZ i
N. D. Zelinskiy of the Academy of Sciences, M
OMITTED: 1pril 2, 1960
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S/020160/t33/03/07/013
B016/BO68
AUTHORS: Balandin, A, At.,.Academician, Bogdanova, Ot Koa,
Shchogloval A. P.
TITLE: Catalytic Dehydrogenatio~n of qyolohexanol~
PERIODICAL: Doklad.y Akademii nauk SSSR, 1960t Vol. 133# No. 3,
pp. 578 - 580
TEXT: It was shown by the authors in earlier publications (Ref. 1)
that several aliphatic alcohol@ can be dohydrogenated over a mixed
oxide catalyst without any noticeable formation of by-products due to
decomposition and dehydration. They showed in this publication that the
same oatelyst may be alett used to dehydrogenate eyolohexanol. This meth-
od cf preparing cyolohexaione is being used in the production of syn -
thotio fibers in which oyclohexanone is applied an a good solvent. Ac-
ooriing to To. V. Turi S. A. Anisimov, and M. S. Platonov (Bef. 2), the
oyoldhexanons jiold is up to 25.3~ over finely disperse rhonium at
3500C. Bonzeae# oyclohexanep and other compounds form as by-products.
The oycloho2anone, yield over a nickel-aluminum catalyst according to
Card 1/3 k__100,
Catalytic Dehydrogenation of Cyclohoxanol S/020160/133/03/07/013
B016/BO68
Zellnekiy and Komarevskiy is about 37A at 3800C, with larger amounts
(allut 48%) of bonsenep and, in addition, phenol, eyolohex*ne, and
pol,raer produats being formed. Moreover, the authors give data obtained
by German and Japanese researchers* They studied the kinetic@ of the
mentioned reaction, and.determined the relative absorption coefficients,
the reaction rate constants together with the activation energies
(Table 3), the changes in free energy, heat content, and the entropies
found for the, adsorptive displacement of the alcohol molecules from the
otive dehydrogenation centers by cyclohexanone (Table 2). Finally, the
:
uthors established the oonditionsof dehydrogenation which asours high
yields of oyl)lohexanone. The continuous method was applied for theme
experiments. They were carried out in an apparatue described previously
(Rer. 0) and over a similar oxide catalyst,sample. The conversion degree
of alcohol in oyolohexanone varies between 16 and 754 of theory
(Table 1). The results of further experiments carried out with binary
cyolohexanol - oyclohsx&nons mixtures (containing 24.6 mole % of the
latter) are shown in Table 2. Prom these results, it follows that the
relative adoorption coefficient of cyclohexanol is 3.03 at 2810C9 and
drops to 0.1)1, if the temperature is raised to 3360. A logarithmic
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Catalytic Dikhydrogenation of Cyclohexanol 8/020160/133/03/07/013
B0161BO66
dependence holds between the adsorption coefficient and reciprocal tem-
perature (Fig. 1). it can be seen from Table 2 that the values of the
mentioned ocefficients retain unaltered, if the temperature in kept
constant and. the rates of passage are varied. From Table 4, it can be
seen that the conversion degree of alcohol increases from 6T.9 to 6841
when the temperature in raised from 333 to 3600C and the rate of passage
per hour is increased. There are 2 figurest 4 tables, and 10 references:
7 Soviet and 3 American6
ASSOCIATION: Institut organicheskoy khimii im, No D. Zelinskogo
Akademii nauk SSSR (Institute of 2rganio Chemistry
imeni No Do Zelinskiy of the.kciaWa
SUBMITTED: March 18, 1960
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3102 60/153/004/036/04OXX
BOI 6YB054
AUTHORSs Bogdanova, 0. K., Balandin, A. A., Academician, and
Belomestn1kh, I. P. ------
TITLEi The Effect of the Conjugation Energy on the Rate of
Catalytic Dehydrogenntion of Alkyl-aromatio and Alkyl-
hexahydro-aromatic Hydrocarbona
PERIODICALs Doklady Akademii nauk SSSR, 1960, Vol. 1331 No- 41
PP- 80-842
TEXTt The authors report on their investigations of the dehydrogenation
of ethyl oyclohexans, and leopropyl cyclohexane on mixed oxide catalyst.
They proceeded from the results of a previous paper (Ref. 1) which showed.
that ethyl benzene and isopropyl benzene are well dehydrogenated on this
catalyst. The rate constant of the dehydrogenation of isopropyl benzene
with a ramified alkyl radical is twice that of ethyl benzene (Table 1).
Apparatus and methods used for the experiment are described in the paper
mentioned (Ref. 1). The amount of catalyst used was 10 ml, the temperature
Card 1/3
The Effect of the Conjugation Energy on the 8/020/60/133/004/036/04OXX
Rate of Catalytic Dehydrogenation of Alkyl- B016/BO54
aromatic and Alkyl-hexahydro-aromutic
Hydrocarbons
was 550 - 6000C, the volume velocity of the hydrocarbon was 1000 ml/l - h
(equal to a rate of travel of 0.5 ml per 3 min). Afer every experiment,
the catalyst was blown through with vapor - air mixture and with air.
Cyclohexane was also used for the experimentol it can, however, not be
dehydrogenated under the above conditions. The dehydrogenation of ethyl
cyclohexane at 5500 was poor ( 1% of vinyl cyclohexnne was formed)l the
Oftme agplies to isopropyl cyclohexane (2,9 of isopropylidene cyclohexane).
At 600 C, these yields were 5.8, and 6.7% respectively. At 6000C, methane#
ethane, and unsaturated hydrocarbons were formed by cracking. The authors
conclude from their results that the rate of catalytic dehydrogenation
depends on the structure of the hydrocarbons used, on that of their alkyl
radicals, and mainly on. the poseibility of formation of a conjugate bond
with the aromatic ring. The dehydrogenation of the alkyl group of the
hexahydro -aromatic ring is rendered diffioult. There are 1 table and 7
references' 5 Soviet, I British, and 1 German.
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The Effect of the Conjugation Energy on the S/02Y60/133/004/036/04OXX
Rate of Catalytic Dehydrogenation of Alkyl- B016 B054
aromatic and Alkyl-hexahydro-aromatic
Hydrocarbons
ASSOCIATIONt Inatitut organioheskoy khimii im. N. D. Zelinakogo
Akademii nauk SSSR (Institute of Organic Chemistry imeni
N. D. Zelinakiy of the Academy of Sciencea USSR)
SUBMITTEDe April 13, 1960
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8/020/60/133/005/031/0-34/XX
,67 le? B016/BO60
AUTHOR: Balandin, A. A., Academician
TITLEi Structural Correspondence in Catalysis
PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol. 133, No. 5,
pp. 1073 - 1076
TEXT: As far back as 1929 (Ref. 2) the author had already defined the
principl* of structural correspondence between catalyst and reacting
molecules. The evidence gathered in the course of time regarding the signi-
ficance of structural factora.for catalysia~ and especially the exper imen-
tal results indicating a sextet model have been collected by the author in
Refs. 7 - 11. Since two years have already passed since the last-mentioned
work., the author now adds further results. Table 1, compiled on the- basis
of the now (Ref. 12,, 1958) detailed collection of interatomic distances,
includes only metals, viz., such as crystallize in simplest systems (Al,
A2, A3, and A4). This shows that the rule earlier established is also valid
for the now values of interatomic distances. The elements known as catalysts
of cyclohexane dehydrogenation actually belong to the metals with lattice
Card 113
Structural. Correspondence in Catalysis S/020/60/133/005/031/034/XX
aoWBo6o
types Ai and A3. These metals including rhenium have the shortest interatomic
distances do The Cyclohexane dehydrogen&tion by Re, predicted by the
multiplet theory, has been.proved by the author jointly-with Te. N.
K&rpoyakay& and A. A. Tolatopyatova (R#f. 13). Th& author further succeeded
in establishing a case of so-called irreversible catalysis of cyclohexone
on Re, which takes place more slowly than the dehydrogenation of cyclo-
hexans, to benzene. This confutes the assumption contradicting the sextet
scheme, uttered by some authors (Rot. 14), according to which the dehydro- ic
genation of cyclohexane proceeds by way of irreversible catalysis. Accord-
ing to Table 1, also technetium belongs to the category of dehydrogenation
catalysts. This would have to be checked experimentally. Cu has proved to
be a catalyst of benzene hydrogenation(according to B. V. Yerofeyev and
N. V. Nikiforova, Ref. 15). Its weak activity Is explained by other, not
structural factors. Thel low-temperature modification of manganese has a
complex lattice U12) and is not givin.in Table 1. According to theory,
cyclohexane, is not dehydrogenated on Kn (Rot. 16). The same holds for Fe.
The author believes that the data by I. E. Anderson and C. Kemball (Ref. 17)
do not contradict Table 1. The mechanism of dehydrogenation discussed here
has been checked from still another angle: the dehydrogenation of 7- and
Card 213
Structural CorreapoAdence in Catalysis 8/020/60/133/005/031/034/XX
B016/BO60
5-membered rings (1), giving rise to non-benzoid aromatic compounds (II)
(Ref. 21). The sextet model is excellently confirmed by the fact that on
Pd (Ref. 22) bicyclo-(0,3,5) decane is dehydrogenated to azulene (III) only
in a small amount. Table I of the article under consideration is intended
to replace the table given in the author's earlier paper (Ref. 2, 1929).
It is also applicable in the case of other catalytic reactions on metals
as, e.g., in the hydrogenation of olefins and aldehydes. Papers by A. Ye.
Agronomov and V. N. Luzikov (Ref. 16), and by the author and I. I. Brusov
(Ref. 20) are mentioned. There are I table and 26 references: 15 Soviet,
3 US, I British, I Swiss, and I German.
ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow State University imeni M. V. Lomonosov),
Institut organicheskoy khimii im. N. D. Zelinskogo Akademii
nauk SSSR (Institute of Organic Chemistry imeni N. D.
Zelinskiy of the Academy of Sciences USSR)
6UBMII'TED: April 29, 1960
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S/020/60/t33/006/007/016
B016/D060
AUTHORS: Shchoglova,_A. P., Dogdanoval Oo st Dalandint A. A.11
Academician
TITLE. The Problem of Dehydrogenating Butane - Butylene Mixtures
-on-an Aluminum Chromium Catalyst I
PERIODICAL-. Doklady Akademii nauk SSSR, 1960, Vol. 133, No. 6,
pp- 1350-1353
TEXT: The present investigation was. carried~out in 1950. The catalyst
was supplied by M. N. Marushkin (Ref. 6). The authors wanted to collect
data concerning the kinetics and mechanism of the 4ehydrQgenation I
mentioned in the title. The dehydrogenation rates of butane and it's
binary mixtures with butylene (Table 2), butadiene, and hydrogen
(Table 3) were measured under optimum conditions. Since butylene and
butadiene are deconpooed on this catalyst, the authors measured the
reaction rates in binary mixtures of these hydrocarbons with ethane in
order to determine the degree of decomposition. In fact, ethane occupies,
Card 1/3
The Problem of Dehydrogenating Butane -
Butylene Mixtures on an Aluminum Chromium
catalyst
5/020/60/133/006/007/016
B016/B060
on the active surface, a part equal to butane, but is neither
dehydrogenated nor decomposed. Figs. I and 2 show the decomposition of
butylene and butadienet respectively, as dependent on temperature.
Experimental results confirmed the assumption previously put forward by
the authors, according to which coal and resins result from the
dehydrogenation mentioned in the title, due to the decomposition of
butylene and, even more, butadionel(Table 3). The authors state in
conclusion that the following reactions take place: 1) dehydrogenation of
butane to butylene; its rate is inhibited by the butylenc that is
present in the initial mixture; 2) dehydrogenation of butane and
butylene to butadiene; 3) decomposition of butane; 4) decomposition of
butylene into light hydrocarbons and coali 5) decomposition of butadiene
into light hydrocarbons, coal, and condensation products. Butadiene
develops in low ykelds at atmospheric pressure. The catalyst is soon
poll-ated with coai. and requires frequent regeneration. A more selective
dehydrogenation o-.r butane to butylene can be attained (Refs. !16) at
lower temperatures. Lose light hydrocarbons and coal are thus formed.
Card 2/3
The Problem of Dehydrogenating Butane - S/020/60/133/006/007/016
Butylene Mixtures on an Aluminum Chromium B016/Bo6o
Catalyst
The authors draw the conclusion that the catalyst used is specific for
the dehydrogenation of saturated hydrocarbons (butane). There are 2
figures, 4 tables, and 6 Soviet references.
ASSOCIATION: Institut organicheskoy khimii im. N. D. Zelinskogo
Akademii nauk SSSR (institute of Organic Chemistry inani
11. D. ZelinaKi_y_of_the Academy of Sciences USsR)
SUDIMITTED. March 26, 1960
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8h577
S/020/60/134/001/036/038/XX
B004/Bo64
AUTHORS., Balandin, A. A., Academiciano RoghdeatXonakaya. Is Lot
a
nd _A.
Blinkin"7r
TITLE: Effect of the Treatment of Chromium Oxide Catalysts With
Gases Under Various Conditions Upon Their Catalytic and
Magnetic Properties
PERIODICAL: Doklady Akademil nauk SSSR, 1960, Vol. 154, Ho. It
pp. 110-113
TEXT; The authors wanted to find a relation between the magnetic sus-
ceptibility X and the catalytic. properties in the Cr 0 catalyst treated
2 3
by various methods. The chromium hydroxide prepared from chromium nitrate,
degree of purity "pro analysill, was treated as follows:
Card 1/5
8h577
Effect of the Treatment of Chromium Oxide S/020/60/134/001/036 /038 /XX
Catalysts With Gases Under Various Condi- B004/B064
tions Upon Their Catalytic and Magnetic
Properties
Cr2 03(VII) H2t5000C
It h 10 h
Cr 203(1)
H
Cr2 03(VIII) h 0
h
H, 20 h ir,500 C
H, 20 h/
~i
10 h
Cr20 3(IX) Cr 203(V)
Cr(OH)3
N 2,5000C air, 500 0C'
10 h 10 h
C
r 2 03(n) Cr 203(111)
OOG
H2,5000C air 600 0C
Ir I
1 h h
rh
C ~r_
Cr 2 03(iv) Cr 2 3 (VI)
Cr 0 was treated with atomic hydrogen in aspectal apparatus (Fig.
2 3
H formed in vacuum at a voltage of 10,000 - 12,000 v and 1 2 mm Hg, and
was sucked through the Cr 203sample. Sabsequently, catalysis was made in
the sum* apparatus under the exclusion of air. Table 1 shows the tempera-
ture dependence of X for the various C 20, preparations.
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8h577
Effeet of the Treatment of Chromium Oxide S/020/60/134/001/036/038/xx
Catalysts With gases Under Various Condi- B004/Bo64
tions Upon Their Catalytic and Magnetic
Properties
No. of
sample )(010
200 C1 500C 800C I 1600CI ff,K1 PB N of
sample X 010()
200cl 50'C1 800CI 1600C
1 24.0 25-3 24-4 23.3 VI 24.4 25.2 23.4 23.0
11 23.0 25.0 23.6 22.9 VII 92.0 - - -
111 340.0 - - - Is 96..o -
IV 28.0 - 25.8 24.0 500 3.7 Ila 21.8 - 2291 20.8
V 22.8 24.3 23.3 22.8
The samples Is. and Ila were prepared from impure Cr 0 The ferromagnetism
of sample Is is caused by impurities. The ferromagniti;m of III is-, hew.
ever, not due to impurities and occurs only when Cr 0 is treated with
2 3
air at 6000C. The nuthors assume that CrO 2' forms in low yields. This now
phase could, however, not be confirmed by X-ray- and electron diffraction
pictures. Table 2 gives the results of the catalytic decomposition of
isopropanol and the dehydrogenation of cyclohexane by means of the samples.
Card 3/5
8h577-
Effect of the Treatment of Chromium Oxide S/020160/134/001/036/038/XX
Catalysts With Gases Under Various B004/BO64
Conditions Upon Their Catalytic and Magnetic
Properties
Different activity, selectivity, and activation energy were found to exist
The dehydrogenation of C 6H12 was reduced both in the ferromagnetie sample
III and the antiferromagnetio sample IX, and the dehydration of I-C 3 H7 OR
increased. Herefrom, the authors infer the presence of hydroxyl groups
on the catalyst surface. Their origin Is, for IX, explained by the chemo-
sorption of atomic H, for III by the interaction of CrO. with H. forming
at the beginning of the reaction. The inactivation of sample I bg treat-
men% with water vapor and subsequent regeneration with H2 at 500 C con-
firmed the inhibiting effect. of the OR group upon the dehydrogenation
of C6Hi2# The authors came to the result that it is not possible to draw
conclusions from the magnetic and electrical properties upon the surface
structure that determines the catalytical properties only. There are
I figure, 2 tables, and 13 references: 5 Soviet, 5 US, 3 British, and
2 German.
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84577
Effect of the Treatment of Chromium Oxide S/020/6O/t34/OO1/O36/O36/XX
Catalysts With Gases Under Various B004/BO64
Conditions Upon Their Catalytic and Magnetic
Properties
ASSOCIATION: Institut organicheakoy kh1m1i im. N. D. Zelinskogo kkademil
nauk SSSR
(Institute of Organic Chemistry imeni N. D. Zelinskiy of
the Academy of ScieRces, USSR)
SUBMITTED: May 17, 1960
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S/020/60/134/002/039/041XX
B0000611
AUTHORS: Vasserberg, V. E., BAlp_ndin, A. As, Academician, and
Georgiyevakaya, Tb V.
TITLE: Conjugate Dehydration of Alcohols in an Adsorbed Layer 3n
Aluminum Oxide Catalysts
PERIODICLLI Doklady kkademii nauk SSSR, 1960, Vol- 134, NO* 2,
PP. 371-373
TEXT; In studying the dehydration of alcohols In A1203 (Refs- 1-3) the
authors observed different reaction rates in catalysts which had been
prepared in different ways. In the present paper, they examined such
catalysts. No. 1: A1203 precipitated by moans of WaOR at pH - 6031
No. 2: A1203 obtained by hydrolysis of aluminum isopropylatel No. 3:
precipitated from aluminate solution by means Of C02 at OOC. First, the
different activities of the catalysts in the dehydration Of C2Hr)OH and
'GO-C3H7OH were confirmed. Furthermore, the dehydration of Isopropanol in
the presence of ethanol. was studied. Since the dehydration of isopropancl
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Conjugate Dehydration of Alcohols in an S/020J60/134/002/039/041XX
Adsorbed Layer on Aluminum Oxide Catalysts B004/BO67
proceeds rapidly already at 120 - 1500C, whereas ethanol d',es not yet
react at this temperature, the dehydration of isopropyl alcohol was
studied on a catalyst whose surface was covered with ethanol which wa*
considered an inert subritance. Furthermore, water and methanol were used
as inert substances. The effects of these Inert substances were fcund tG
be different. Water, methanol, or ethanol adsorbed in equal quantities
reduced the dehydration of isopropanol to a difforont degree) this
reduction depending also on the method of catallyst preparation. Sinco
this could not be explained by a blocking of the catalyst surface, the
authors thoroughly studied the kinetics of ':he joint decomposition of
isopropanol and ethanol. First, ethanol was adsorbed at 120 - 1500C, thon
isopropanol, and the pressure rise of the olefin formed was measured. It
was found that the pressure p oetheor a 0.6 - 0.7 mm Hg calculated fcr a
100% decomposition of isopropanol was mu.,h higher (p 00~'Xp -i.i - i.6mm 11~)
and increased in the course of reaction. H-nce, the authors con~~Iude that
when ethanol and ioopropanol are jointly adsorbed on the catalyst, a
conjugate dehydration occurs. The dekydratlon of ethanol wan strongly
Card 2/3
Conjugate Dehydration of Alcohols in an
Adenrbed Layer on Aluminum Oxide Catalysts
S/020/60/134/002/039/041XX
MOW
accelerated (compared with that of pure ethanol), while that of
isopropanol was delayed. The authors therefore conclude that the complexes
adsorbed on the catalyst surface are not isolated but react with
neighboring molecules, and are capable of forming combinod voml4oxotv
(ethanol-iuopropanol and mothanol-toopropanol aomploxva) which decompose
moro alowly than tho ioopropanol complexes. There are 3 figures and 3
references: 2 Soviet and 1 German.
ASSOQIATION: Inatitut or-anichookoy khimii im. H. D. Zelinskogo A.kadem"i
nauk SSSR ~Inetitute of Organic Chemistry imeni N. D.
I
"elinskiy of the Academy of Sciences USSR)
SUBMITTED: May 17, 1960
Card 3/3
20
S
/0: /60/134/003/030/033/XX
B004/B064
AUTHORS% BalanAin_L_A. A., Academician, ToletopyatoyalA.A., and
__U_8~9 S~ve
TITLE: The Catalytic Activitylof Tungsten Pentoxide 7-1
PERIODICAL: Doklady kkademii nauk SSSR, 19609 Vol. 1~41 No. )I
pp. 625 - 628
TEXT: The authors investigated the dehydration of ethanoll isopropanol,
t-butanol, oyclohexanol, , and Tetralin th W 0 under iso-
.1 m~~anol 1 7w'. 2 5
thermal conditions. Blue W 205 was obtained from tungetic acid at
350 - 4000C in an air current. First, WO was formed and then reduced to
3
W20 5 during the reaction with the alcohols at 200 - 3000C. The reaction
apparatus operated continuously, and the liquid substances were auto-
matically added. The gaseous products were oollected in an automatic
Patrikeyev gasometer, and analyzed with a BTA (VTI) apparatus or ohroma-
tographically, In the liquid produot of catalysis, the amount of
Card 1/4
The Catalytic Activity of Tungsten S/02q6O/134/003/C30/033/XX
Pentoxide B004/BO64
unsaturated hydrocarbons was determined by the method of Kaufman-Gall-
porn. Since the ondothermia effect of reaction affected the results of
measurement,, the catalyst was diluted in a ratio of 2 : 3 with quartz
of the same grain size, the alcohol with water orwith the corresponding
unsaturated hydrocarbon. Under these oonditlona, the process was Iso-
thermal. By determining the apparent activation energy (Table 1) it was
found that the primary alcohols were dehydrated with the same energies
(approximately 30 ktal/mole), that the activation energy of the second-
ary alcohols was about 6 kcal/sole lower than that of the primary onset
and that the activation energy of the tertiary alcohol was approximately
6 kcal/mole lower than that of the secondary ones. The reaction constant
and the relative adsorption coefficients z 2 and z5 of water and the un-
saturated hydrocarbon were computed (Table 2) by Balandin's method
(Rof. 3) with reference to the adsorption coefficient of alcohol. Check-
ing by introduction of the experimental. data into Balandinla equation
confirmed the validity of this equation (Table 31. Table 4 gives the
actual activation coefficients for isopropanol and n-butanol; which are
approximately 3 koal/mole higher than the apparent ones. For the binding
Card 2/4
The Catalytic Activity of Tungsten e/020/60/1 34/003/0 30/C 33/XX
Pentoxide B004/Bo64
"C-C I(CH they affect the binding energy betwein the C, H, and 0
H11 I[H(CH 3) ' atoms and the catalyst. The authors mention a paper by
IH OfH 1. Yo. Adadurov and P. Ta. Krayniy. There are 5 tables
and 8 Soviet references.
ASSOCIATION: Mookovskiy gosudarstvennyy universitet im. H.V. Lomonosova,
(Moscow state University iment X. gonoftay)
SUBMITTED: May 17, 1960
Card 4/4
S/062/60/000/03/02/007
BOOS/B000
AUTHORS: Proydlin, L. Kh., Balandin, A. As, Nazarova, N. Me
kylation of Isobutaae'~~
TITLE: Catalytic Al y Ethylene at High
Ttoporaturis and Under Fr-essure '
PERIODIC-kL-. lavestiya Akademil nauk SBSR* Otdelenlys khimicbeekikh
naukt 1960# No. 3t PPw 409-412
TEET: The alkylation of isobutans in the presence of aluminum oxide at
high temperatures was investigated. The experiments were carried out in
the oontinuous-flow unit described in Ref. 5. The reaction conditions,
degree of ethylene transfornationp and alkylate yields are given in
Table 1. The characteristics of the various alkylats fractions obtained
in experiments No. 2 and 4 are shown In Table 2. The fractionation curve
of the catalyzate obtained In experiment No- 4 is represented In Fig. 1.
Experimental results show that, ethylene and propylene react mainly with
the tertiary carbon atom of isobutane, and only to a lesser extent with
its primary carbon atoms, In these reactions, 2#2-dimethyl butane and
Card 1/2
Catalytic Alkylation of Isobutans, by 8/062j6o/OOO/O3/02/007
Ethylene at High Temperatures and Under BOOS/BOO6
Pressure
2-methyl pentanst respectively, are formed.. An octane fraction was also
obtained, which was identified to consist mainly of an alkylation product
of 2#2-dinothyl butane. Alkylation at this stage, however# proceeds via
the primary carbon atom at the unbranched end of the carbon chain. This
fact confirms the stopwise character of the alkylation process established
previous ly (Ref. 6), It was found that in the presence of aluminum oxide
an olefin (ethylene, propylene) in added to the tertiary carbon atom of
isobutane less easily than to the secondary carbon atom of n-butane.
Yu. Pe Yegorov and K, 0. Gayyoronska analyzed the: fractions by means of
their Haman spectra. There are I figure, 2 tables, and 11 references,
6 of which are Soviet.
ASSOCIATION: Inet1tut organichookoy khisti in. N, D. Zelinskogo Akademii
nauk SSSR (Institute of Organic Chemistry imeni N9 D.---
Zelinskiy of the Academy, of Sciences# USSR)
SUBMITTED: July 16f 1958
Card 2/2
5 13000 05
SO'1/62-60- 1 -51/37
AUTHORS: SteFner, G., Balandin, A. A., Iludenko, A P.
TITALE: Influence of Different Stages of Polycondensation
of the Products of Gataly'.Ilo Deccmposition of Ethyl
Alcohol on the Rate of Carbonizatlon
PERiODICAL: Izvestiya Akademil nauk SSSR. Otdelenlye khtmicheskikh
nauk, ig6o, Nr 1, pp 24-30 (USSR)
ABSTRACT: This Is a contInti3tion of' the author's previous work
(Izv. AN SSSR, Chem. Ed., 1959, 1896) on the mechanism
of carbonization in the dec-omposition of ethyl alcohol
over copper-allIca. Experimental data presented
In thIs paper confIvm previous concluslons (see above
refevence) concerning the mechanism of carbonization
which accompanies catalyt.,Ic decomposition of ethyl
alcohol. Carbon.1,zatlon is considered to be a multi-
stage polycondensation of ethyl alcohol and the pro-
ducts of its catalytic decomposition. The so-called
Card 1/2 low temperature carbonization (below 6000) proceeds
Influence of DIVIerent Stages of
Polycondensat-lon or the Products of'
Catalytic Decomposition of Ethy'A
Alcohol on the Rate of Carbonization
ASSOCIATION:
SUBMITTED:
Y8059
S07/6'2-60- 1 -5/37
through dehydrogenation of ethyl alcohol. Accele-
ratlon or slowing down of' ethy, alcohol decompos',tion
(dehydrogenation and dehydratlon) causes a change In
the rate of carboillzation. There are 4 f,-gure3; and
11 references, 1 German, 10 Soviet.
M. V. Lomonooov Moscow State Uri versity (Ywkovski
gosudav-stvennyy unIversitet Imer! M. V. Lomonosova
May 4.
Card 2_12
5 SoV/6-2-60- & -4/3'7
AUTPORS.- Ft-eylilin. L. Kh., BalandIrl, A. A., BorUnova, N. V.,
Agronomov, A. Ye.
TITLE: Concei-ning Connections Between the Microstructure of'
Aluminum Oxide and Activity of Mckel-Alumina Catalysts
of Various Nickel Content
PERIODICAL: Izvestlya Akademil. nauk SSSR. Otdelenlye khlm'.cheskikh
nauk, 1960, Nr 1, pp 21-2,~ (USSR)
ABSTRACT: This paper presents the results of Investigations of
the connection between the microstructure of aluminum
oxide and activity of nickel-alumlna catalysts of
various Ni content. Th~ catalysts were prepared: by
impregnation of alumina with Nl.(NO,);,, and reduction
0
with Hn at 350 . The alumina for the catalysts 1
and 2 Isee Table) was prepated by Ignition of com-
0
rrercial aluminum oxide at 500 . Alumina for catalyst
I w4th ammonia.
3 was prepared by treatment of klk'NO-,,,
3
Card 1/4 .
Activity of the catalysts was determined by the degree
Concerning ConneCLIOtls Between me
Microstructure of Aluminum Oxide and
Act',vity of Nickel-Alumina Catalysts
of Various Nickel Content
c)-A
SOV/62-60-1-4/37
of' cyclohexane del-,ydrogenation. The results are
shown in T,:_ble 1. The following conclusions were
made! Propertles of' nIckel-alumina catalysts of
various Nt content depend on the character of
microstructure of alumina. Catalyst3 prepared with
large-pore alumina, conta-Ining 5-10% Ni, are of high
'Irld practically the 3ame activity. Activity of the
L
catalyst. containing 50% N1. in considerabl,y lower.
Catalysts prepared with fine-pore alumina, and containing
5, 10, and 30% Ni are of a low activity and unstable.
There are I table; and 9 references, I U.S., and 8 Soviet.
The U.S. reference Is: S. Brunauev, P. Emmet, A.
Teller, J. Am. Chem. Soc., 62, 1723 (1940).
ASSOCIATION: N. D, Zelin.ukiy Institute of Organic Chemistry Academy
of Sciences USSR and M. V, Lorronosov voscow State University
T
Anstitut organicheskoy khtmi! Imen'. N. D. Zelinskogo
Akademil nauk SSSR., Moskovskly gosudarstvennyy universitet
iment M. V. Lomonosova)
SUBMITTED: May 5. 1953 Card 2/4
concel,111111, callnect-jolm the
m1crostmictuve of Almninum OxI(le and
Activity of Nlelwl-Ahnfltm Citnlyst..-,
of Vat,loiju Nickel Conteut
Table 1
sov/62-6o-i-4/37
175 1 oil i tAlk
17 .5 211 -It w I t,2 -f.3
4,8
typ'll
lo W1,2
1.01 2rw too 41, 3. 3
1 .5 U'll
rl-, i v zx 4,7
3M Il- %1 4
20 3711 11 - - it 1 22 3 7 1 48,1
fit? 10 21 X,l V I I -X) 21) 3
211 *_'70
(Key to Table on Cavd
Concerultir, Connections Bet"weet) the 7.5058
Mict-0-11tructure of Aluminum Oxide and sov/62-6o-i-11/37
Activity of' Nickel -A lumina Catnlynts
of Varlou,", Nickel Content
Key to Table 1: (a) numl,er; (b) experiment; (c) sample
of aluminum oxide; (d)-N1 content In % by weight; (e)
duration of reduction with H2 in hr; (f) specific
SUrfACe iU.M2/,,; W range of pore size in A; (h)
maxlrnum distribution of volxunea of pores along the
radlus In A; (1) total amount of benzene absorbed on
saturation, in millimoles/g; (J) degree of cyclohexane
dehydvogenation In % of theoretical,
Card 4/4
5 - -.5200
AUTHORSt Brimov, 1. 1., Polkovulkov, 13. D.
TITLE i Kineticn of' 2-YAnylpyvidine Ilydvoir(,mation Over Raney's
Catalynt
PERIODICAL: Izventlya Akademill nauk SASS11. Otdolonlye Ichimi-
cheakikh nauk, 1960, Ni, 1, PI) 15-20 (IJSSR)
ABSTRACT: Thin paper prenentu experimental data on kinetics of
2-vIny1pyr1dIne hydi-ogenittlon over Rimey nickel In
96% ethyl al(!Ohol at te-tweratures from 5 to 400, under
atmosphertc pressure. 'I'le esultil obtained are nhown
In the figuves, where Aj 0 (a) In the total. volume
t 6V t
of hydrogen absorbed and (b) the volmne
2
Of' 112 absovbed, mid re(hwe-l to ntandard conditions.
Erfect, of rtyvene concentrallon on the vate of lt:i
hYdVOj'Cnn1,IOn Wa9 11,10 -Itlldled; L-110 reSUltS ShOWn
Card 1p In FIF, 6.
Kineticu of 2-Vinylpyvidine Ilydvogena t ton 78057
0-ier Rancylto CntAyst
la
6
Fig . I . Effect of 2-vIn IPYvIdIne concen trat toll oil the
rate or hytivogentat ~- 0.398,1 g; (2) 0.79,16 g;
(3) 1.1949 g (a and b given it) text).
Fig. 2. Effect of the
producta of reaction on the
rate of 2-vinylp vidine
hydrogenation. 11) without
addition of tile Product s;
~21~ on repeated hydilogenation;
3 with ndditioti of 2 rill I'll X V j# Av IV Alv
Card VI of 2-ethylpyi-Iditio (a and 1)
alto explained In text).
Killet-1co of* -'-Vtliy.lpyv1,11,tw
Ovel. Ralley's cat-aly.A.
Fig. 5. ErVect of' inolvent
on hydrogenation of'
2-vitlylpyridine: (1) in
96% 0211 5011; (2) '11 CO(J);
(A. and b given in tcxt~-
v v
fit
a
in w of w rv /a OR
Flg. 4 6
C, 1A I'd 3/ 7 (captlall for loig'. I; oil Cant lilt
Kinet-Ilog of' C-.1-Vinylpyridine Hydvoi-,cuntion
Over Raney's Catilytit SOV;~i), -60-1-3/37
Fig. 4. Kinetica cut-ves of' 2-vinylpyridine hydro-
genatJon at various t~cmpevatuves: (1) 5.40; (2) 100;
(3) 15'; (14 ) 20'; (t . 0 0
.5) 25 (6) 500; (7) 550; (8) 40
(a and b.given itt text). j4 a j
Fig. 5. Dependence of
the log of rate constant
on temperature.
Card
ell
N
N
,V . . . . . . .
J71 rs IV am In ja jul w JR ju ju
I
T
o
Kinetic-11 Or ','-VII'Yl PYPI tilOo 11Y(lV(Wf!W'l 1 11
Ovel. Ratley"I Cat"llyst'181-
.01
SOVA2-6o-i-3/37
u lu
Fi P. 6. Hydro enation or stTrene. (1) 0-3875 V;
L
J2~ O:p7r- 0-7750 9; 4) 0-4155 C,; (5) 0.111 5 gi
6 0 ~5" in this case another cataiyat was ui3edl
a and b given In text).
Card 5P
Kinetics of ~2-Vinylpyrldine Hydrogenation '(8057
Over Raney',; Catalyst SOV/62-6o-1-3/37
The following conclusions were made: Hydrogenation of
2-vinylpyrid1ne proceedo rapidly In 04 ethyl alcohol;
In benzene the reaction is about 1.6 times slower.
The rate of reaction increases about 3 times with in-
0
creasing temperature from 5 to 40 . At these tempera-
turen the reacl.-.Ion follows first order kinetics. The
true energy of' :,:7tivation In equal to 5.6 kcal/mole.
Hydrogenation ol" styrene under similar conditiono is
also a first ordev reaction. Substitution of one
hydrogen atom In ethylene by an CL-pyrldyl radical
has the same effect on the rate of hydrogenation over
Raney nickel as substitution by a phenyl radical.
There are 5 tables; 6 figures; and 7 references., I
U.S., 1 Polish, 5 Soviet. The U.S. reference is: E. C.
D. Craig, J. Am. Chem. Soc., 70, 3138 (1948).
card. 6p GregF
Kinetics of 2-Vinylpyridine Hydrogenation 78057
Over Raney's Catalyst sov/62-6o-i-3/37
ASSOCIATION: N. D. ZelInskly Institute of Organic Chemistry Academy
of Sciences USSR (Inatitut organicheskoy khtmit Imeni
N. D. Zelinskogo Alcademil nauk SSSR)
SUMMED: April 25, 195B
Card 7/7
S/595/6o/ooo/(,)(- c/oi.o/oi Ii
E075/0435
'101,110t?j: Bogdanova, O.K., 11alandin. A.A., VX-Iryshnil,ova, T.11.
TIT LE: Dohydrogenation kinetics of othyl bonzene to styrone
and isopropyl benzene to a-methylstyrono
SOURCE: Vaesoyuz;oyo noveshchaniye po Ichi-miclicskoy
percrabotke neftyanykh uglevodorodov v poluprodulcty
dlYa sintozn volokon i plastichoshild, Tlakui 1957.
Baku, Izd-vo Ali, Azorb. SSR, 1960, 241-247
TZ*,%T: The object of the work is a study of the kinctics of
dchydrogonation of othyl and isopropyl benzene; it is a
continuation or the authors.' investigations on the orract or
molecular structure on dehydrogenation hinotics. The
experimental work was carried out by passage through an
electrically heated glass tube conta:hing an oxide catalyst on a
screen, at atmospheric pressure. Dilution ratios of 1:3 to 5
and 1:2 were used for ethyl and propyl benzene respectively;
the steam was superheated to 3000C. Liquid and gaseous product
fractions were analysed and good agreement between hydrogen and
unsaturated hydrocarbons was found. The kinetics of isopropyl
benzene dohydrogonation were studied at three food rates in the
Card 1/ 4
Dehydrogenation kinetics'...
temperature range of 500 to 5500C, rate
hydrogen produced. A table of reaction
given.. Under identical conditions the
binary mixtures of isopropyl benzene nndits
a-methylstyrono, were studied to obtain
the catalyst from
S/595/60/000/000/010/014
E075/E435
being measured by the
product analysis in
dehydrogenation rate of
reaction product,
adsorption coefficients an
where mo = number of moles reaction product for food of pure
starting material; in w number of moles reaction product for fece,
of mixture; p = % of starting material in mixture.
The relative adsorption coefficient of hydrogen was found to W,
0.7 and was independent of temperature. The relative adsorption
coefficient of a-methylstyrono falls with tomperature, a table and
graph are given. Plotting the log of the adsorption coefficient
against the reciprocal of the absolute temperature gives-a straight
line. The reaction rate was calculated by using the general
equation for catalytic reactions derived by A.A.Balandin Olef.2:
Card 2/4
S/595/60/000/00o/olo/o14
Dehydrogenation kinetics ... E075/E435
ZhOKh, 19420 12, 156)
j2,403(z,+r4)AjjIg- (2)
Al-m
The calculated reaction rate has been plotted against the
reciprocal of the absolute temp .erature and the points lie on a
straight line. The activation energy has been calculated as
30.3 Kcals/mol. A series of experiments with catalyst particles
varying in size from 1*5 to 5 mm was carried out; particle size
had no effect on reaction rAtt. The dehydrogenation of ethyl
benzene was studied in the range or 520 to 5600C. The results
were similar to those obtained with iaopropyl benzene but the
adsorption costricientx and reaction rates were considerably lower.
Figures for picluct analysist adsorption coefficients and reaction
rates are give-t. The higher rates for isopropyl benzene are
considered to ja due to the introduction of a mothyl group into
the alpha position. At higher temperatures there is a
considerable increase in conversion; in,the 58o to 6oo*C range
at rates. of 800 to 1000 ml/litre catalyst/hour, yield of' styrene
Card 3/11
I S/595/60/000/000/010/014
Dehydrogenation kinetics ... E075/E435
and methyletyrone reached 70 to 83%, which is near to
equilibrium. This in of considerable practical interest.
Increase of feed rate towards 1400 to 2000 ml/litro catalyst/hour
led to a slow decrease in yield. At these higher temperatures the
reAction rate~plot changes but the plot of Log K against the
reciprocal of the-absolute temperature still falls on a straight
line of a different slope. The activation energies become 18.8
and'19.5 Kcals for isopropyl and ethyl benzene respectively.
(Abstractor's notes St::m.ldsorption was neglected in all
reaction rate calculati a The dehydrogenation of ethyl
cyclohoxane was investigated. The low rate of reaction sliows
that in tho absonce of conjugation, the dehydrogenation of the
side chain is slowed down, There are 5 figures, Is t.%bles and
5 raferencest 2 Soviet-bloc and 3 non-Soviet-bloc. Tho
reference to an English language publication reads as follows:
ner.4s Gilliland E.K. Chem. Eng. News. 23, 129 (1945).
Card-4/4
s/595/60/000/000/009/014
E134/E485
AUTHORS: JDAjAndin, A.A., nogdanova, O.K., Shcheglova, A.P.
TITLEs Catalytic dehydrogonation of isopentenes to isoprens
SOURCE: Vaesoyuznoye soveshchanlye po khimichaskoy
pererabotke neftyanykh uglevodorodov v poluprodukty
dlya sinteza volokon i plasticheakikh mass. Baku, 1957.
Baku, Izd-vo AN A.zerb. SSR, 1960. 233-239
TEXT: The paper in concerned with the catalytic dehydrogenation
of isopentenes and the conversion of isopentant-isopentenes
inixtures to isoprene as part of the general problem of
ituAnuracture of isoprene rubber from the isopentane fraction in
petroleum. The authors studied dehydrogenation of isopentene and
isopentans-isopentenes mixtures in the presence of steam at
atmospheric pressure. Artificial inixttires eta well as mixtures
obtained by dehydrogenation of isopentane on an Al-Cr- catalyst
were used. The experiments were carried out by continuous flow
over a mixed oxide catalyst. Work on isopentone was concerned
with the effect of temperature, flow rate and steam dilution ratio
on isoprene yield. Yield based on isopentene feed increased from
14-5 to 36% as temperature rose from 540 to 620"C but dropped from
Card I/ I
S/595/60/000/000/009/014
Catalytic dehydrogenation E134/E485
92 to 85% of'the reacted isopentene, Curves showing the effect of
temperature and flow rate on isoprene yield are given (Fig,I and
Beat dilution ratios are It2 or 113 by weight. ;% complete tilass
balance for operation with a 113 ratio at 600'C at a rate of
4500 g/litre ca.taly:it/hour is given. Under these cir:uttistan[-4.%-~
yield is 28 to 30% on feed and 88 to. 92% on reacted Loopentene.
The removal of carbon from the catalyst in the form of carbon
dioxide makes prolonged reaction without regeneration possiblt--
The results show that the catalyst acts selectively.
InvestIgatIons of mixtures 55% isopentarke-45% Isopentene welle
carried out under identizal tonditions to study the effe:t of flo-
rate and temperature. Conversion of mixtur-m and yield of -1joprert
increased with rising temperature but yield of isoprene ba,'-ed -Yi
reacted Isopentene dropped from 94 to 86.5%, A full analyiia is
given, At 600"C, a flow rate of 4400 g/litye cataly&t/hour ard
1;3 dilution ratio yield of isoprene on iaopentent present wa6
38 to 40% and was more than 90% of the rea-ted isopentene. Undt~?-
identical conditions dehydrogenation of isopentana ro iscptnten,,
only took plac--* tc~ the extent of q to ~.I',ere is no dire,,t
Card 2/4 ~
Catalytic dehydrogenation ...
conversion to laoprene. Results with mixtures obtained by
dehydrogonation of isopentane over an Al-Cr catalyst wex-1,
to those with synthetic mixtures. Full analysis sooving efrect
of now rate and toml)orature is given. Tho degree of convc:r!,-.1o,I
decreases with increasing flow rate. The killotica of Uic
reaction were investigated in the 530 to 5300C range with a
stoam dilution ratio of 122 and hourly flow rates of 51.c,,(-;- to
7000 g/litre catalyst/hour. Reaction rate in given by aquation of
the following type
djc
d.v EA,Itz:j A+23 V:
The adsorption coefficients z were deternined axpori?-,entally by
measuring the rato of dehydrogenation of binary mixtures of the
starting material and the reaction products and were calculatcd
Card
E134/L485
Catalytic dehydrogenatio6 ...
where me - nwnbor of mola of reaction prodtict for feed of pure
starting material; m - numbor of mols of reactioli product for
food of mixture; p - percent of reacting material in initial
mixture, The hydrogen adsorption coafficients rcmaincd cn-.i3tant
at 0.83. The isoprene adsorption coefficients droppe(l fro;~, ',^.7 to
2-8 (z2) between 530 and.580-C. The reaction rates were
calculated using tho adsorption coefficients and the plot of log N
against the reciprocal of the absolute temperature gave a str,iight
line. The activation energy was calculated as 23300 calories/
raolecule. The mixtures used in the tests were produced in tl,.c
laboratory of Academician B.A.Kazanalciy and Corresponding
N.I.Shuykin. There are 3 figures, 4 tables and 6 reforences:
2,Soviet-bloc and 4 non-Soviet-bloc. The four references to
English language publications read as follows: Ref.3: U3 Patent
2440471, 1948; C.A.42, 54 4, 1948; Raf.h: US Patent 2442319,
C.A.42, 61o6, 1948; Ref.5: Grosse A., Morell J.C., Navity J.."-*,.
Industr. Engng. Chem. 32, 309, 1940; Ref.6: ',,,avity JJII..
Zetterholm E.E. Trans. Am. Inst. Chem. Engn., 40, 1944, 1;73.
Card" 4/0 11
41
U
V6
v I# f
WANDINs A. A.
*Sow Problams of Use of Catalysis in Chemical Technology*
report presented at the 09neral Conference of the Division of Chemical
Sciences of the Academy of Sciences, USSR; 27-28 October 1960
Sat Izvestiya Akadexii nauk SSSRp otdoloni" khimicbeskikh nauk,,Noe 29
1, MOSCOW, Pages 378-3M'
9p
31
Sol
;Iq
Ral
It
is
-tF
f
gig P. 3
8/062/61/000/001/004/016
B101/B220
AUTHORS: Tolstopyatovaj As Att Konenko, I* R., and Balandin# A. A*
TITLE: Kinetics of dehydrogenation and dehydration of isopropyl
alcohol on titanium dioxid* (anatise)
PERIODICAL: livestiya Akademii nauk SSSR. Otdel*niy* khimiohtskikh naukt
noo 1, 1961t 38-44
TEM By way of introduction the author& offer a survey of reports
dealing with the catalytic efficacy of T102t and then report on the
dehydrogenation and dehydration of leopropyl alcohol on anatass. Regarding
the production of the catalyst they refer to another report published
by then* For the verification of the kinetics of monomolecular
hottrogensous-oat lytic raactionT)mthey roce*d from the equation
k N A1 (Z2-Z3)InA,7(A,,-m)-(Z2+Z,- (13. Al is the volume of alcohol
converted per minute, which is Introduced at the rate vi m is the volume of
propylene (or hydrogen) formed per minutel Z2t Z3 are the relative
adsorption coefficients of the reaction products (hydrogen and acetone
Card 1/3
8/062/61/000/001/004/016
Kinetics of dehydrogenation and dehydration... B101/B220
in the cast of dehydrogonationi propylens and water in the case of
dehydration)l Z2 and Z~. were calculated from Z - (mo/m-')/(Ioo/p-') (2),
where mo, m are the amounts of the reaction products resulting on the
passage of pure alcohol (mo) and on the passage of a p molar mixture with
the reaction product, Sinc# Z is the equilibrium constant of the
displacement of the isopropyl alcohol from the catalytic centers by the
reaction products, it was possible to calculate also A? of the free
energyj 63 of entropy, and AH of the heat content. The adsorption
coefficient Z,, of acetone was found to be highly dependent on temperature
and much less so on the degree to which the catalyst was covered with
carbon. The following is indicated for not carbonized T1021 Za - 2.4 at
2620C1 1.7 at 2940Ct 1o2 at 3100C. For carbonized TiO2 these values
amounted to 2.7, 1.8 and 0,9. The adsorption coefficient Zff, of the
hydrogen remains, constantly 0.9 In the range of 276-3060C. Moreover, it
was found that ZR20 " 1.9 at 2820C, 1.4 at 2940C, and 0.9 at 3100C.
whereas Zpropylene remains a constant 0.2 in the temperature range of
300-33000. A. M. Rubinshteyn and S. 0. Kulikov are mentioned.
Card 2/3
S10621611000100110041016
Kinetics of dehydrogenation and dehydration*.. B101/B220
There are I figurej 6 tables, and 24.r9feroncost 8 Soviet-bloo and 13
non-Soviet-blooo
ASSOCIATIONt Institut organioheskoy khimii im. N'. D. Zelinskogo Akadsmii
nauk SSSR (Institute of Organic Chemistry imeni N. D.
Zelinekiy, Academy of Sciences USSR)
SUBMITTED: June 29t 1959
Card 3/3
S/062/61/000/001/005/016
B101/B220
AUTHORSt Balandin, A. A., Konenko, Is R., and Tolstopyatovat A. A.
TITLE: Effect of the method of production on the catalytic proper-
ties of titanium dioxide In the reaction with ethyl alcohol,
isopropyl alcohol# and. oyclohoxane
PERIODICAL: Isvestlys, Akademli nauk SSSR. Otdoleniye khIm1ch9skIkh nauk,
no. 1, 19611 45-50
TEXT: The authors were concerned with the investigation of the catalytic
properties of titanium dioxide. Here, they studied the dependence of
those properties on the method of TiO 2 synthesis. Four specimens were used.
Catalyst 1 (anatalle), whom# produotion is desorib*d in Refs 1, a previous
report of the authoral catalyst 2, obtained by hydrolysis of TiC14 by mans
of ammonia solution in a weakly &aid medium at room tesperaturel catalyst
3, obtained by precipitation of Ti(OH) 5 from TiCl3 by- means of ammonia
at room temperature and conversion to Ti(OH) 4 which occurred automatically
Cord 1/5
Effoot of the method of productions... 8/062JO/000/001/005M6
B101/B220
while washing the prooipitatel catalyst 4t obtained by kydmjrsisaf ethyl ortho.
tits.nate by means of distilled water at room temperature. The further
treatment of the hydroxides for the purpose of obtaining TIO2 was per-
formed according to Ref. 1. Ethanol reacted with these catalzats accord-
ing to three reactions: a) dehydrogenation, b) dehydration, c) hydrogena-
tion of the, resulting ethylene. Moreover, up to 2A ethyl acetate was
formed on all four catalysts. The reaction of isoprepanol corresponded
to data mentioned in Refs 1. Due to the growing accumulation of carbon
on the catalyst, the rate of dehydration increasest whereas that of do-
hydrogenation deofeases. Cyclohexane is dehydrogenated on all four
catalysts. The differences between the catalysts regarding the activation
energy E and the factor k0 of the Arrhenius equation are listed in Table 8.
The linear function log ko W as + b (a, b - constants) is conserved for
all reactions. A. M. Rubinshtsyn and S. G. Kulikov are mentioned. There
are 2 figures, 8 tables, and 6 referencest 4 Soviet-bloc and 2 non-Soviet-
bloc.
Card 2/5
Effect of the method of production*,. S/062/6i/000/001/005/016
3101/A220
ASSOCIATION: Institut organichookoy khImii im. N. D. Zelinskogo Akademli
nauk SSSR (Institute of Organic Chemistry imetit X. D.
Zelinskiyj Academy of Sciences USSR)
SMITTED: July 9t 1959
Card 3/5
Effeot of the method of produetion... S/06 61/000/001/005/016
BlOIYB220
Bananas two" Spufoloutnut 1100 as staxqRSM sulprok allassuou
4 f, f. ones/ N A.
cw" I"" j X.TvA 9MY"
ta "MAN.
,at". 1 1 2 LS
N. 0. tfNAPMHNSAUXI OTHRODOM OMPTS 22,8 20,4 014
4, 0. MAPATAUR IT"Osom c""PTA 25,0 23,4 0,0
n.0 ericAparaut nionponuowiv cnopTs. 22.0 9.1 26.2
1 4, 0: 1# 11APOremitu"A STMe"s
r 21,2 24.2 13,0
14 M.0 f( erHAPMR11MUIR ttHKAOMCANA
In t9,O H.7 21.0
0: 1 truApommmsaamn ff3onponmaotom
ka
emp" 911 t0.4 -
Vit 0 OeMAPATAtUtit "MPORKAOSOM Cn*PT& 24.4 i5.8 -
411: 0: kAel'"Aporemouitun msonponnikogoro
cnllpT4 11.9 -
it. 0. If Acrupor"onaxt tututomKcau 25,2 -
14. 0* IjJlerAAPOrtwuus npowowo enpra 10.4 -
,y W. 0. AentAP&TSURA M.nPon"09" CIMPTS 12,1 -
Card 4/5
12,4 t.0 - 100 t,040t 1.4-101 1.2-104
t2,5 t,5401 5,6401 3.7-101 4,4. up
17 2 3 7-tO* 9,1-1(P 1.0-1010 2.8-101
10:8 1:8.101 t,0. 101 t 3, 104 2,7.10%
t5,0 8,7. W$ 5340' t,3. tOl 3,5404
- 1.04104 2.2404
- 4,5409 6.240%
I
4',9401 -
2.3. t0l -
4,5. 10t -
Effect of.the method of
4
8/062J61/000/001/005/016
B101IB220
2.84 2,8t 3.01 3.05
2.73 2 90 2 70 2,70
-2.39 2:29 2:54 2.3t
2,9t 301 301 3.10
3,2D 3:12 3:53 3,3.0
2 24 2,40 -
2:53 2.52 -
2,25
3.27 -
271 -
3:05 2,73 2,98 2,80
2,OU
Legend to Table 8t Effect of'tl%e method of preparing the TiO catalyst on
the amounts of activation energies. 1) Condition of catalyst urface,
2~ reaction; 3) catalYstl 4) partially carbonizedl ~) completely carbonizedl
6 not carbonizedl 7) dehydrogenation, of ethanoll 8) dehydration of etbanoll,
9 dehydration of isopropanoll 10) hydrogens tion of ethylene; 11) dehydro-
genation of cyclohexanel 12) dehydrogenation-of isopropanoll 13) dehydro-
genation of propanol; 14) dehydration of n-propanol.
Card 5/5
AAq_.CI[L.Yi;VAt G.Yu.
AcUra maing a chango in tho rochanisms ol' curbon form4tion
during tho eocomposition of hydrocarbons. Izve QT 535ris Otd.
kldm. nauk ro. ItI64-166 Ja 161, (laNA 1412)
1, Mloskovekiy Cosud&rt;tvennyy universitat im. EN. Lomononovi..
(HydroeLrbons) ' (Cubon)
a/603Y61/001/000/050/056
BI 25 104
AUTHORS: Balandin ,-A., Spitsyn, V. I., Duzhenkov, V. I.#
!t~~
Barsovap L. 1.
TITLE: Radioohemical method of preparing metallic catalysts
SOURCE: Tashkentakaya konferentsiya po mirnomy ispolltovaniyu
atomnoy energii. Tashkent, 1959. Trudy. v. 1. Tashkent,
1961, 289-295
TEXT: Platinum and palladium catalyst& are reduced by radiochemical reac-
tions from aqueous solutions of suitable compounds. Cyclohexene is hydro-
genated for a catalytic check reaction. Chloroplatinic acid samples in
Pyrax, glass calla, kept by a thermostat at a con tant temp ratureo were
a Ole :V/cm3
irradiated by means of a lineaa(maximum dose rate 3-1 .400) and
a Co6o source of 400 g-oqu. Re. At integral doses of 2-10 ev/CM3, solid
YtClOH20 and its aqueous solution (0.1-1.0 M) are not reduced to
metal owing to the stability of the PtCl;- ion. in saturated solutions of
N&2[Pt(OH) xC16-,] and.K2[Pt(OH)xC1 6-.1" which were examined because of the
Card 1/i
33120
.s/63ej61/oo1/000/05o/o56
Radiochemioal method of ... B125/B104
lower stability of the hydrocomplexes, irradiation acted indirectly upon
the addends in the inner sphere. The least radiution-resistant Na2lkco~4
decomposes completely at 4-1 el ev/CM3 to form metallic platinum. The
third group of compounds presented in the figure exhibits the least
radiochemical resistance which drops in the sequence Cl-Pt-Cl> ON-Pt-OE>OH-
Pt-Cl. The resulting palladium sharply retards the decomposition of the
compounds produced, The optical density of a K 2PdCl4 solution also
depends largely on the dose rate. Zelinekiy's method was used to compare
the catalytic activities of the metal samples, measured in low-temperature
hydrogenation of cyclohexens in 96% ethanol and in an ethanol solution in
0.1 N H2SOV with the activity of metals obtained by reducing the
corresponding salts with formaldehyde. The platinum catalyst produced by
radiolybis in 4-5 times more active than platinum black produced by
Zelinskiy's method (Table 2). In the radiolysis ofaqueous PdC12 and
X2PdCl4 solution, Pd2+ is completely reduced to metal, the reduction
process being noticeably retarded by metallic palladiums The apparent
activation energies of a platinum catalyst and platinum black, calculated
Card 2/P
33120
5/63ej6i/001/000/050/056
Radiochemical method of ... B125/B104
from the rate constants, of zeroth order, amountto 4.0 and 6.6 kcal/mole,
respectively, and their surfaces, determined from cyclohexane adsorption,
amount to 23 and IS 22/g at OOC. The catalysts produced by the radiation
method are lose active than the platinum black obtained by Zelinskiy's
method. The catalytic action of radiolytic precipitates of PdC12 solution
of different concentrations differs in intensity. The activation energy
of the catalysts in question satiefies the Arrhenius equation .
K;Koe' E/RT . The activity of the resulting metal *&a reduced by adding
H 1 to the irradiated PdC12 solution. Both irradiated and nonirradiated
palladium black samples produced by reduction according to Zelinakly's
method exhibited the same activity. Previous studies did not
reveal the causes underlying the change of catalytic activity in radio-
lytically prepared metal blacks. It is, however, hoped that very active
catalysts can be produced radiolytically. There are 4 figures, 2 tables,
and 12 references: T Soviet and 5 non-Soviet. The four most recent refer-
ences to English-language publications read as follows: Taylor E. H.,
Wethington J. A. J. Am. Chem. S00., 76, 971, 19541 Gibson E. J-9 Clarke
R. W., Dorling T. A.* Pope D. II Intern. Conf. Peaceful Uses of atomic
Energy, alconf), 15 P/63, 19581 Taylor E. H~ J. Chem. Education, 36, 396,
Card 3/Y,/
" 120
8/638 61/boi/ooo/o5o/o56
Radioohemical method of B104
19591 Raldarw B. C., J. Am. Chem. Boo., 4229, 1954,
ASSOCIATION; Institut fizicheakoy khimii AN SSSR (Institute of Physical
Chemistry AS USSR), Moskovskiy gosuniversitat. im. M. V.
Lomonosova (Moscow State University imeni M. V. Lomonosov)
Table 2. Comparison.between activities of Pt black and Pd black,
prepared by chemical reduction using Zelinakiy's method, and by radiolysis
of salts.
Legend: (1) production procesal (2) teat temperature, OCI (3) weighed
portion of oatalystj (4) rate constan.tj (5) specific activity of catalystj
(6) ratio of specific activitioal (7) platinuml (8) palladiuml (9)cbemloaW
preparedi (10) radiolytically preparedl
Fig. Structural formulas of the compounds investigated.
Card 4/,61/
- - -TOLSTOPUTOVA --A.-A-. -j -- -- ---- ---- - -
KONLNXOp IIH,
Energies of the bonds betveen reacting organio compounds and the
catalytio aotive aentorcof titanim *dioxide. Ity. AN SUL Otd.
khiso rAuk noW14-217 F 161. (MIRA 14t2)
19 Inatitut organlohaskoy kb W i lm.N.D.Zolinakogo AN SSSR,
(Titaniua oxide) (Chemioal boade)
20937
12og
8/062J61/000/003/003/013
B117/B208
AUTHORSa Balandin, A. A., Sokolovs., N. P., and Simanov, Yu. P.
TITLEt Nioblum and tantalum pen'toxidea as dehydration catalysts
PERIODICALs Izvestiya Akademii nauk SSSR, Otdolonlys khimicheaklkh
nauk, no. 3, 1961, 415-424
TEXT: The authors studied the dehydration kinetics of Isopropyl alcohol
on niobium and tantalum pentoxides. Ihe experiments with Nb 205 samples
were carried out in a catalytic contiriuous-flow device (Ref. 3s
A. A. Balandin and A. A. Tolatopyatovs., Zh. fis. khimli 30, 1367, 1956)
in a t mperature range of 3600-40000 and at a flow rate of the alcohol
of 0.1; MI/min. The volume of the ca':alyat was 2 ml, and the volume rate
of the alcohol 4.5 hr-1. The activity of Nb2o 5 was found to depend on
temperature and calcination time of the oxide during its formation from
metal, Experiments disclosed that the most active NbjOk samples are
obtained by calcination of metallic niobium at 5300 w t in 1-2 hr.
Although the formation rate of the oxide depends on the form (powder,
Card 1/4
20937
S/06 61/000/003/003/013
Niobium and tantalum pentoxides ... B117YB208
filings, larger parts) of the metal used, and the individual experiments
with Nb205 provide no comparable results, the oatalyBt is active in a.V
case. Activity is maintained for some timej esgs, for ton hours without
regeneration. X-ray phase analyses carried out with a 'OsHHKC' (FenikB)
tube of the SC8 (BSV) type with an iron anode at a voltage of 25 kv and a
charge of e me disclosed that the catalytically most active form of Nb205
is a low-tomperaturZir-modification. The high-temperature modification
of Nb205 is 1088 &c vs. The Nb205 modification remains unchanged during
catalytic dehydration of alcohol. To study the dehydration kinetics of
isopropyl alcohol on T&205, the same continuous-flow system was used, The
experiments were conducted in the temperature range of 3360-3820C at a
flow rate of the alcohol of 0.2 ml/min. The volume of the catalyst was
2 ml, and thavolume rate of the alcohol 6.0 hr- 1. A comparison of the
catalytic activity of Nb205 and Ta2051 prepared at equal temperatures,
suggests that Ta20 is more active than Nb205 under otherwise equal
experimental condizions, particularly in the same temperature range. A
lower activation energy corresponds to the higher activity of Ta 205' as
Card 2/4
209)?
S10621611000100310031013
Riobium and tantalum pentoxides... B117/B206
compared with Nb205- Nb205, on the other hand, remains active for a
longer time and is better regenerable. The catalysts obtained from pure
NbgO5 and T&2C2 May be regenerated by air. The conditions of such a
regeneration were studied. At present, the investigations of the effects,
of temperature and calcination time of Ta205 on its catalytic activity,
and of the effect of these factors on the activity of Nb2o5 and Ta205 with
respect to other reactions, especially condensation, are continued.
A. Yo. Agronomov is thanked for determining the catalyst surface by the
BET method, and V. M. Akimov-for X-ray analysis of Ta 0 The laboratory
2 5*
assistant Z. M. Skullskaya took par'. in the exp6rimental work.
R. A. Zvinohuk and A. V. Topchiyev are mentioned. There are 3 figures,
9 tables, and 10 referenoest 8 Soviet-bloc and 2 non-Soviet-bloo.
ASSOCIATIONi Institut organicheekoy khi/m'i'i im. N. D. Zelinskogo kkademii
nauk SSSR (Ina titut"f I- Organic Chemistry Iment N.D. Zelinskiy,
Academy of Scisnc~p,USSR)- Moskovskiy gosudarstvennyy
universitet im. M. V. Lomunosova (Moscow State University
Card 3/4 imeni M. V. Lomonosov)
----BOGDA.NOVA-- O.K.;I-8AIW;gj._k.Aj SHCHE=VA,, A.P.
Rogularities in the catalytic dehydroganation of primary aW
meanndary alcohols, Isv*AX SSSR Otd,Irh4m,nAjs no,38423-4n W
161* (ORIA Ut4)
I* Inatitut organichookqy Irbiali Imni N.D.Zolinakogo AN SWR.
(Dehyd"gonation) (Alcohols)
225U
S/062/61/000/004/003/008
jo 22,o9, 1114,1297 B118/B20e
AUTHORSo jalarLdAi_&__A. k., Spitsyn, Vikt. I., Dobrosellskayat N. P.*
Mikhaylenko, I. Ye., Vereshchinakiy, 1. V., and
Glazunov, P. Ya.
TITLEs Effect of radioactive radiation of a solid body on its
catalytic, properties
PERIODICALt Izvestiya Akademii nauk SSSR. Otdoloniye khimichookikh nauk,
no. 4, 1961, 565-571
TEXTs There are no data available on the effect of the proper radio-
active radiation of solids on their catalytic properties. The authors of
the present paper investigated the change of catalytic activity as a
result of decay of the radioactive isotope, furthermore whether also the
A-radiation of a foreign element affects the reaction to be studied, and
the effect of irradiating the catalyst by a fast electron beam. The effect
of the radioactive catalysts CaCl2' X9S04' and Na2so 41 containing the
P-emitters S55 and Ca45j on the dehydration of cyclohexanol was studied.
The increased catalytic activity of radioactive catalysts, contrary to
Card 1/3
225U
8/062/61/000/004/003/008
Effect of radioactive ... B118/B208
non-labeled catalysts, which had been previously observed by the authors,
was confirmed in many cases. The catalytic activity decreases with
decreasing radioactivity of the catalyst owing to decay of the isotopes
B35 and C&45. Bombardment of the surface of the non-labeled catalyst with
800-kev electrons has no pronounced effect, contrary to the effect of
P-particles of labeled B35 and Ca45 which are constituents of the catalyst.
Thus not only the labeled S35, but also the labeled Ca45 increases the
catalytic activity of magnesium sulfate in the dehydration of cyclohexanol.
The radioactive isotope need not be a component of the acting catalyst.
It must be concluded that the increased activity of the radioactive
cata.lyste studied is due to a continuous bombardment of the active centers
of the catalyst with P-partioles. The latter tranefer their energy to the
adsorbed cyclohexanol molecules and reduce the activation energy of the
chemical reaction. It may be concluded from the decrease of the catalytic
activity due to the decay of the isotope in the catalyst that the new
elements resulting in the radioactive conversion do not increase the
activity. Apparently, the activation of the catalyst surface takes place
Card 0
22M
Effect of radioactive ...
S/062/61/000/004/003/008
B116/B208
at the expense of the proper radioactive radiation. There are 8 figures,
2 tables, and 4 Soviet-bloo references.
ASSOCIATIONt Institut fizicheskoy khimii Akademii nauk SSSR (Institute of
Physical Chemistry of the Academy of Sciences USSR).
Moskovskiy gosudaretvennyy universitst im. M. V. Lomonosova
(Moscow State University iment. M. V. Lomonosov)
SUBMITTEDe January 16p 1960
Card 3/3
BOGDANOVA, O.K.; SHCIiEGWVAO A.P.1 BALANDINj A.A. VOZNESFMKAYA, I.I.
catal,vtio dehydrogenation of ri-pentenes, Izv.AN SSSR Otd khilL
nauk n0*057&-582 Ap 161. 1414)
I* Inatitut organiche k0 khimii in. N.DZeliwkogo AN SSSR.
(Pent:ns~ (Dehydrogenatior-)
TOI.STOPrATOVA, A.A.; ~DIN, Ak.-j-HATYUSHMOV
Kinetics of the dohydrogenation arA dehydration of alcoholes and of
the debydrogenation of:hydrocarbons over WS2 and MOS2 O&talYbts, IST,
AN SSSR Otd.khimenauk to.4083-590 Ap t6l. (KUU 3A W
1. Institut organiohookoy khinii im. N.D.Zelirwkego AN SSSR,
(Dehydrogenation) (Dehydration (Cheaistry))
(Molybdenum sultide) (Tungsten sulfide)
BAIANDINi--AQ-A*-;-RUDENXOj- A* Pq STEGNER,--G,- ---- ---- - -- -- - -- - -- -- -
Formtion of coal dendrites in the course of'decomposition of
alcohols on nickel, OsT-AN SSSRoOtdAhissnauk uoo5s762-770 )v
161. (KMA 1435)
I* Moskovskiy~ gosudarstyenm urAversitst in, MV. Lomonosovs,
Wcohols) (coal)
RUDUKO.. A.P.1 B&LUMINO A.A.; ZAWWTXAXA. MA
Mechanism of coal formation during the decomposition of methe
oths j ethylene, wad acetylene on silica gole Izv#AN SSSR,Otd.khiao
nauk no.6&98%-995 A 161. (KMA WO
I* Hookovskiy gosudaret"nnyy univ*rsitet is* M,Lomonosovas
(Hydrocarbons) (coal)
RAIANDIN, A,A.; SOKOLOVA* N.P.
Catalytic properties of niobium pentoxide in the vapor phase
aminatian of ethyl alcohol with aniline. Izv. AN SSSR. Otd.khim.nauk
n-7.911543-1548 3 161. (MIRA 14:9)
1. Institut, or anlohnrkoykbimli In. N.D.Zelinskogo AN SSSR.
Moblum oxide) (Ethyl alcobol) (Aniline)
BAIANDIN# A4A*j ISAGULYANTSj O.V.; SMOLOVA# NP.; ZAKITARTGNIEVA, 14.
Mechanism of propane formation in thn decomposition of isopropyl
alcohol on vanadium trioxide. Izv. All SSSR. Otd.khim.nauk
no.9tlYO-1551 S 461. (MIRA 14%9)
1. Institut organicheskoy khimii im. N.D.Zelin akogo AN SSSR.
(Isopropyl alcohol) (Propane)
BALANDINP A.A.1 KLAMNOVSKII, Yo.1.1 LITV1Np Yet?*
Compooition of butenes formed in the catalytic dehydration of
2-butanol, IsvAH =R.,Otd.khim.nauk no.lOsl863-1870 0 161,
(Mnk 14 93-0)
I# Inatitut organichookoy khisil im. N.D.Zelinskogo AN MR.
(Butane) (Dutawl)
BALANDIN, A,A.,- ROUDESTUNSKAYA, 14D#
---------------
Mechanism of cyclohexane dehydroeenation on a crystalline chromium
-oxide. Izv.AN SSSR.Otd.khim.nouk no.11:1955-1961 N 461.
(MIRA 14ill)
1. Institut organicheakoy khImit im. N.D.Zelinskogo AN SSSR.
(Cyclohexane) (Dehydrogenation)
P
BALAINDIN, A.A!; KLABUNOVSKIY, YO.L; ANTIK, L.V-.---
Synthesis and transformations of dihydroxyanthrylene-naphtbohy-
droquinone (stereochomistry of catalysis). Izv. AN SSSR Otd.-
khim.nauk no.l2t2l89-2192 D 161. (MIRA 14.-11)
1. Inatitut organichaskoy khimil Im. N.D.Zolinskogo AN SSSR.
(Anthracene) (Naphthoquinone)
KIABUNOVSKIY, Ye.I.; ULANDIN, A.A.; GOVJNOVA, L.F.
Chromatographie separation of menthol. Izv. AN SSSR Otd.khim.nauk
no.l2t2243-2244 D 061. (MIRA 14:11)
lo Institut organicheakoy khimli im. N.D.Zelinskogo AN SSSR.
(Menthol)
BOGDANOVA,, O.K.; SW.JMGLOVAp A.P.; BAIANDIN, A.A.j BSLDWTNM, I.?.
Cata3jvtIc dehydrogenation of ethyl benzene into otyrene,
NeftekUmiia 1 noo2sl95-200 Hr,-4p- 161. (MIRA 15:2)
1. Inatitut organichookoy khimli AN SSSR im. N.D. Zeliwkogo.
(Benzene) (Styrene)
(Dehydrogenation)
8/195/61/002/001/001/006
BiOl/B2i6
AUTHORS: Balandin, A, A.j Klabunovskiy, Ye. 1.
TITLE: Steric position of atoms, and catalysis on the occasion
of the 100th birthdayof N. D. Zelinskiy~
PERIODICAL: Kinetika i katalit, vs 2l no. 1, 1961, 3-8
TEXT: On the occasion of the 100th anniversary of N. D. Zelinekiyls
birthday, the authors give a survey of problems of catalysis and
stereoohemistry, which had been studied by Zelinekiy and further
investigated by his suocessora. Zelinakly made detailed investigations
of the stereoisomeriam of derivatives of di- and tribasic organic acidep
and studied the optical activation of crystallization of dimethyl
dihydroxy glutaric acid. Basing on stereochemical considerations,.
Zelinskiy arrived at the following concept of heterogeneous ca'-lysis:
"The deformation of molecules occurs under the influence of th., orce
field present on the active surface of the catalyst, this force -'ield
influencing the configuration of particles and rendering them rea-',, to
interact ... 11. From this concept, A. A. Balandin developed his multil~lot
Card 1/5
S/195/61/002/'001/001/006
Sterio position of atoms~ and B101 B216
theory of catalysis (Ref- 5: Dim. nauka i promyshlennost', A, 6559 1959),
which assumes the highest possible agreement between the structure of the
reacting molecules and the surface structure of the catalyst. A multiplet
complex is formed between the reacting atom group and the catalyst without
deformation of valency angles. It is mentioned that K. D. Zelinskiy
discovered the metallic dehydrogenation catalysts with face-centerod
crystal lattices in 1911. The principles of atereochemical influencing
of catalytic processes are illuctratedo using the hydrogenation of cis-
and trans-olefins and the conversion of maleic acid to fumario acid on
palladium as examples. The multiplet theory enables claseifica.tion of
all known catalytic reactions. About 2000 types of catalytic reactions
were laid down, many of which have not been realized so far. The equations
of the multiplet theory permitted advance calculation as to which out
of the 15 possible modes of decomposition of cyolohexanol would be most
likely on activated carbon, the prediction being confirmed experimentally
(nef- 15: A. A. Balandin. et &I. Izv. AN SSSR, Otd. khim. nauk., 1960,
614). The steric specificity of enzyme catalysis is also explained by
the multiplet theory. It is mentioned that Zelinskiy verified the organic
origin of petroleum postulated by reason of the optically active
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Steric position of atomep and ... BlOlyv2i6
substances contained in it, by experimentally preparing similar products
by dry distillation of organic substances of vegetable and animal origin.
The authors stress the versatility of Zelinskiy's scientific activity,
the results of which may be utilized for further development up to the
present day. There are 1 figure and 18 reference&: 17 Soviet-bloc and
I non-Soviet-bloo. The reference to the English-language publication
reads as follows: R. L.Burwellt Jr., Chem. Rev. 51, 895, 1957.
SUBMITTED: December 8, 196o
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---
Pladiochemical ltudy of the mechanism of dehydration catalpis. ?&A 1t
Reactions of CA4 -dinathyl other vith hydrocarbons* Kin. i Jmt, 2
no.116i.65 A-F 161. (MITOlAs3)
1. Inatitut orpniobe k WWI imeni N.D. Zolinsk AN SSSR.
" Oji=.arbon.) (J~ohydratl '
(Ether) 04(chemintry))
----7OISMMT%WA. Aek.;-KONEKOp -- ---
Catalytio properties of yttriua oxide. Conversions of alcobols and
hydrocarbons. M. i kat. 2 no.ItI35-143 J&-JF 161. (HM U:3)
1, Institut organicheekoy khimii imed N.D. Islinskogo IN SSSR.
(Ittrium oxide)
(Alcohols)
(Hydrocarbons)
DIN I-TiDMi-OPYATv-VA---A-.A.-I--DUD;ixI
-BAIAN -,-" I - t *,-
Catalytic properties of thorium dioxide in the dehydrogenation
and dehydration of alcohols,, and in the dehydrogenation of cyclic
hydrocarbons, Kinoi kat. 2 no.2t273-284 Mr-Ap 161.
(MIM 14W
1, Moskovskiy gosudarstvennyy universitet, kafedra organicheskogo
kataliza.
Thorium oxide)
Dehydrogenation)
~Dehydration (Chemistry)
---RUDENKO---".
p 0; . A.
Dehydrocondensation of methane vith the formation of a coal-
yielding cubstance. Kin.i kat, 2 no*4:52,9--533 JI-Aq 161.
'JKURA 14:10)
1. Moskovskiy gosudarstvennyy universitat imeni M.Lomonosova.
(Met.11aale) (Condensation products (Chemiatry))
MUMINS ksk.j SPITSIN, V.I.; RUDMOO L.P.; DOUROSELISKATA, N.P.1
X.Mor 1,19s; PPMOVA, G.1.1 GLAZUNOVp P.Ta.
Apparatus for studylag heterogenooux catalysit at high temperaturo
using radioactive eatalpts and ionizing radiations* Kinei kate
2 no*0626-632 Jl-Ag t6l. (KLU 14,10)
I* ;~wtltut ilsichosimy Irbiall AN SSSR i lbskovskiy goeudantv*MW
uniftraltat imeni M.Momonosova.
(catalyals)
33491
S/195/61/002/005/016/027
S71190 E030/El85
AUTHORSt Isagulyants, G.V., and Balandin, A_A.
TITLEs The use of radiocarbon (in) In studying the mechanism
of parallel.-consecutivo catalytic processes
PERIODICALi Kinetika i kataliz, v.2, no.51 ig6i, 737-740
TEXTt The use of radiocarbon is proposed to determine the
stages and process of forming products in parallel-consecutive
reactions, the general scheme of which is represented bys
W
A B
W W1
C
where A is the initial product, 8 and C the products formed
during the process. Three typical cases aris*i for a reaction
rate W2#:-! 0, C is formed consecutively from A with B as inter-
mediatel for W3 "2'eol B and C are formed from A in parallel but
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The use of radiocarbon (C14) S/195/61/002/005/016/027
E030/E185
independent of each otherl and when all the rates are
commensurable, C is a produot of a consecutive-parallel reaction.
The formulae for the rates Vi ares
W do C2 W I' dot Cl
Tr CL Tz a 7 7
W C3(dy/di) + (y - m)(dC3/dv) dC3
3 P - a --- ; W2 -d-t W3;
where QL, 0, y are the specific activities and Cl, C2 Cz the
concentrations of At 81 C, respectivelyt. T Is the con~ac time.
The authors were able to observe the above discussed cases in
many processes by adding to the initial product A a small
quantity of B or C marked with CA and determining the changes
in concentration and specific radioactivity in relation to
contact time. One of these processes was that of the decompo-
sition of ethyl alcohol investigated by the authors together with
Ye.l. Popov and YU-1. Derbentsev (Ref.3, Izv. AN SSSR, Otd.kh1m.
n., 1958, 233). The decomposition was ctrried out in the
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The use of radiocarbon (C14) ...
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E030/F.185
temperature range 275 - 400 OC with aluminium oxide as catalyst.
It occurs in two directionsi Into ethylene and into ethyl ether.
At the lower temperatures, dooompovition into ethylene was much
slower than the dehydration reaction (reversible) into ethyl
other. As the temperature rose, the decomposition rate of ethyl
alcohol into ethylene rose until at 400 OC it became comparable
with that of the other reaction. Thus, the concentrations of
both alcohol and other show maxima. As the temperature rises the
other maximum is produced not only by the direct alcohol-ethylene
reaction, but also by decomposition of the ether to ethylene.
At 400 OC where there is 100% conversion to ethylene, 80% of the
ethylene ih produced from the alcohol and 20% from the other.
The dehydrogenation of cyclohexane to cyclohexane and to benzene
is another similar process (Ref.5t Yu.I. Derbentsev,
A.A. Balandin, G.V. Isagulyants, Kinetika I kataliz, v.2, 741,
1961). K pure consecutive process occurs in the dehydrogenation
of butane-butane mixtures on chromium catalysts. Both the butane
and butenes are converted directly to butadiano, the conversion
rate from butane boins about 3 times faster than from butane.
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