LITERATURE CITED

i. B . P . Nikol'skii and V. I. Paramonova, Usp. Khim., 4, 1535-1538 (1939).

2. A . T . Davydov and I. Ya. Levitskii, Tr. Khim. Fak. NII Khimii Kharkov. Un-ta, No. 12,
309-312 (1954).
3. K . M . Saldadze, A. B. Pashkov, and V. S. Tinov, lon Exchanging High-Molecular-Weight
Compounds [in Russian], Moscow (1960), p. 37.
4. V . S . Soldatov and L. V. Novitskaya, In: Thermodynamics of Ion Exchange [in Russian],
Minsk (1968), pp. 217-223.
5. V . S . Soldatov and O. F. Kharevich, In: Thermodynamics of lon Exchange [in Russian],
Minsk (1968), pp. 228-233.
6. V . P . Kol'nenkov, "lon exchange equilibrium on a sulfa-styrene cationite in the I+ --
I~--I~+ systems" [in Russian], Candidate dissertation, Minsk (1972).

EXCHANGE OF INFORMATION

PREPARATION OF RANEY NICKEL CATALYST AND ITS USE

IN THE SYNTHESIS OF 3,4-DIMETHYLPHENYL-D-RIBITYLAMINE

T. M. Glushkova, I. P. Serpukhovitin, UDC 615.356:577.164.11].

N. V. Kazanina, M. D. Moskvin, 012.1:66.097.3
A. A. Buimov, G. K. Glushkov, Yu. V. Enyutin,
and N. S. Zolotarev

The intermediate product in the production of riboflavine, 3,4-dimethylphenyl-D-ribityl-

amine (I), is obtained by the hydrogenation of 3,4-dimethylaniline-D-ribopyranoside (II) in
an alcoholic medium over Raney nickel catalyst at a temperature of 40-50~ and at a pres-
sure of 25-30 kg/cm 2 [ 1].

H H OH?_0H

H O~ H [~]]~I~
H30
2: _r
Raney nickel catalyst is usually prepared by leaching a ground nickel--aluminum alloy
(nickel content 25-33%, aluminum 67-75%) with a particle size of 5-10 mm.
In the literature [2-7] it is shown that it is possible to prepare highly active cat-
alysts by leaching either a finely ground alloy or granules obtained by rapid cooling (quenching)
of a melt in water or oil [8]. The authors of [3-7] note the influence of the composition
and the degree of, comminution of the initial alloys on the operational stability of the cat"
alysts.
According to the data of [9-11], during the hydrogenation over the Raney nickel catalyst,
an appropriate solvent must be selected. We therefore studied the production of highly ac-
tive forms of Raney nickel catalyst. We used nickel~luminum dust with a particle size of
0.02-0.4 mm, obtained by mechanically grinding the alloys, and also porous granules 3-15 mm in
size, obtained by rapidly cooling a jet of the melt in water (Fig. i).
Pump (i) circulates water in a closed circuit. Water is pumped from tank (5) into hy-
dro-nozzle head (2). The melt is fed on the water jet emerging from hydro-nozzle head (2)
from crucible (3) through funnel (4).

The Belgorod Vitamin Combine. Translated from Khimiko-Farmatsevticheskii Zhurnal, Vol.

13, No. 5, pp. 87-90, May, 1979. Original article submitted June 12, 1978.

526 0091-150X/79/1305-0526507.50 9 1980 Plenum Publishing Corporation

 ,/ /
z. I

Fig. i. Scheme of installation for com-

minuting the melt by the hydrojet method.
Designation in text.

TABLE i. Comparative Data TABLE 2. Results of

on the Results of Hydrogena- the Hydrogenation of
tion of II at Different Tem- II at Different Charges
peratures over Catalyst A. of Catalyst A.

Charge of Reaction Yield of I, Charge of A,

A,~, ....~mperature, Yield of I, ~7o
07~ 070
10 40--50 82,6 30 88,7
10 40--50 79,0 30 87,9
10 45--70 84,7 15 88,5
10 45--70 85,0 15 86,7
10 45--70 85,3 15 88,2
10 85,3
10 85,1
10 84,7

The water jet breaks the melt into granules and cools them, and the granules are di-
rected into basket ( 6 ) . From the basket water is poured into the tank, and the granules
are directed to drying, and then to the production of the catalyst. The size of the gran-
ules is regulated by the velocity of water emerging from the hydro-nozzle head, and by the
diameter of the outlet of the funnel. Desalinated water is used in the installation.
Each of the given fractions were leached by a 20-22% aqueous solution of sodium hy-
droxide at 50-80~ with a 5-1iter consumption of alkali per kg of alloy. In the catalyst
obtained, we determined the activity, particle size, and the stability on storage. The ac-
tivity of the catalyst samples was judged from the yield of product I and the amount of ad-
sorbed hydrogen.
The catalysts obtained from the dustlike fraction of alloys (A) contain about 200 mg/g
of adsorbed hydrogen. The particle size of the catalyst is about 50 Dm.
Hydrogenation of II over A was carried out in two temperature ranges, 40-50 and 45-70~
Increase in the hydrogenation temperature made it possible to increase the yield of I by
4% at equal catalyst charges (Table i).
By using A, the catalyst charge could be reduced by one fifth of that with the samples
used at present (Table 2), and a used-up catalyst could be obtained with no pyrophorie pro-
perties.
However, we noted that on storage under a layer of water (pH 8.5-8.8), the activity of
catalyst A, i.e., the amount of the adsorbed hydrogen, decreased after i0 days by 70-75%.
When A was stored under a layer of ethanol, isopropanol or water at pH 10.5-11.5, the acti-
vity decreased by 8%, on an average (Table 3).
Moreover, when alloy particles with asize of less than 0.i mm are leached, prolonged
washing with water of the leached alloy is needed to remove the used-up alkali, and the
final pH of the wash-waters is usually 9.8-10.0.
When an alloy which was comminuted by the hydrojet method was used in the process, two
fractions of granules were obtained, 3-15 mm and 3-5 man in size. The catalysts obtained
from the granules, 3-15 mm in size (B), were used for the hydrogenation of II in different
amounts and at a temperature of 45-70~ (Table 4).

527
 TABLE 3. Stability of Catalyst A on
Storage in Different Solvents
-Storage conditions T i m e of storage
3h ] I da.y ] t o d a y s
solvent pH amount of adsorbed hy-
[ drogen, m l / g

Water 8,5 197,5 100 48

>> 10,85 214 210 188,5
>> 11,5 1w 191,5 183,5
Isopropanol 197 189,0 187,5
Ethanol 198,2 198,5 187,4

TABLE 4. Results of Hydro- TABLE 5. Comparative Data on

genation of II over Cata- the Hydrogenation of II over
lyst B Catalysts B and C
Charge Yield of Properties of Granule Amount of Yield of
of B, % I, % used-up catal- size of adsorbed IC"
yst hydrogen, narge, ~o I, %
alloy, mm
ml/g
50 96,6 IPyrophoric
40 9t ,3 F >> 3--15 142 25 86,5
25 90,14 ]Nonpyrophoric 3--15 142 25 85,2
25 86,5 I >5 ~ 3--15 142 25 85,7
25 85,7 3--5 165 20 87,2
25 85,2 >5 55 3--5 165 20 85,3
22,5 76,1 ~ 5> 3--5 165 20 85,8
20 70,15 >~ >>
15 62,3 >> >>
10 59,3 >> >>

80

70

GO

6O ~ 80 80 tO0
Fig. 2. Dependence of yield
on the alcohol concentration
of the solvent. Abcissa)
concentration of alcohol (in
%); ordinate) yield (in %).

528
 100

85

90

B5

75

70 I I I 1 .,.I
25 O0 85 4 0 46 60
Fig. 3. Dependence of
yield on the nickel con-
tent in the initial alloy.
Abscissa) content of nick-
el (in %); ordinate) yield
(in %).

The optimal charge of B is 25% of the weight of ll, and the yield of I reached 86.5%.
The used-up catalyst was not pyrophoric. However, the most active samples of the catalysts
were obtained on leaching granules 3-5 mm in size (C). The content of the adsorbed hydrogen
was 165 ml/g, and the optimal charge for the operation was 20% of the weight of If. The
yield of I reached 87.2% (Table 5).
The particle size of catalysts B and C was in the range of 12.5-100 ~m (catalysts used
at present, the particle size is 16-200 zm).
When the catalysts prepared from the granulated alloy are stored under a water layer
at pH 8.5-8.8, their activity decreases by 4% after i0 days of storage.
During the hydrogenation of II over the catalysts A, B, and C, we used aqueous solutions
of ethanol as the reaction medium. Thus, the optimal concentration of ethanol is 70-80%
(Fig. 2 ).
We studied the influence of the initial alloy on the yield of I. The best hydrogena-
tion results were obtained when catalysts prepared from alloys containing more than 30% of
nickel were used (Fig. 3).
We checked the possibility of the repeated use of regenerated catalysts B and C for
the hydrogenation of If. The best results were obtained when a mixture'of a regenerated
catalyst with a fresh catalyst in the ratio 4:1 was used, and the charge of fresh catalyst
was 15% of the weight of If.
From the data obtained we can conclude that the best effective catalyst during the hy-
drogenation of II into I is one consisting of granules 3-5 m m in size, obtained in the c o m -
minution of an alloy by the hydrojet method. Thus, the content of nickel in the initial
alloy is more than 30%, the concentration of ethanol in the reaction mixture 70-80%, and
the reaction temperature 45-70~ It was thus possible to increase the yield of I by 5-6%,
and to decrease the charge of Raney nickel catalyst by a factor of 2.5.
EXPERIMENTAL
Hydrogenation of IT is carried out in a 2-1iter autoclave with an electromagnetic disk
stirrer. The mixture is stirred by alternating motion over the vertical at a rate of ii0
strokes per minute.

529
 Hydrogenation of II over A, B and C. A 100-g portion of II is stirred with 900 ml of
an alcoholic-aqueous mixture, containing 70-80% of ethanol, until a homogeneous suspension
is obtained, and 10-25 g of a catalyst with a moisture content of about 30% are added.
The hydrogenation is carried out for 5-6 h at 40-70~ at a pressure of 25 kg/cm 2.

LITERATURE C ITED

i. V. M. Berezovskii and E. P. Rodionova, Transaction of the All-Union Scientific-Research

Vitamin Institute [in Russian], Vol. 6 (1959), p. 5.
2. M. A. Borowiak, et al., Przem. Chem., 57, 160-162 (1972).
3. Jap. Patent No. 42801.
4. L. S. Melekhina and D. V. Sokol'skii, Uch. Zap. Kazakhst.-Univ., 44, 26-35 (1958).
5. U. S. Patent. No. 3676364.
6. Isikawa Dzyudzaburo, J. Chem. Soc. Jap. Pure Chem. Sect., 81, 1629-1636 (1960).
7. A. B. Fasman, D. V. Sokol'skii, et al., Inv. Cert. No. 182122 (USSR).
8. N. M. Popova, In: Kinetics and Catalysis [in Russian], Vol. 7, Alma-Ata (1971), pp.
75-92.
9. F. K. Bizhanov and D. V. Sokol'skii, In: Productive Capacities of Southern Kazakhstan
[in Russian], Vol. 3, Alma-Ata, (1966), pp. 128-133.
i0. Iwamoto Issei, Jap. Patent No. 4658-661.

INFLUENCE OF THE SCALE OF TURBULENT PULSATION ON OXYGEN

CONSUMPTION IN FERMENTATION

L. M. Kuz'mina, V. V. Biryukov, and L. S. Gordeev UDC 615.33.012.6

In the culturing of microorganisms, stirring is an important factor wNich appreciably

influences the rate and the end result of the process. In the literature there are data on
experimental investigations on the influence of stirring (at one and the same content of oxy-
gen dissolved in the medium) on the respiration intensity, rate of growth, and other param-
eters of the fermentation process [1-3].
The explanation of the results obtained, i.e., the clarification of the mechanism of
the influence of stirring is of great importance during the solution of problems of scale
transition, selection of the construction of fermenters and stirring devices, and optimal
regulation of stirring in the process.
Figure 1 shows the dependence of the specific rate of growth of the microorganisms on
the partial pressure of the dissolved oxygen during cultivation under conditions of a sta-
tionary continuous process [i]. Usually, dependences of this type are explained by the li-
mitation on the l i q u i d ~ o l i d body boundary, i.e., mass transfer of the liquid--biomass bounda-
ry [i]. In other words, it is believed that the oxygen concentration on the surface of the
cells (cell conglomerates) is not equal to that in the main mass of the liquid, and so this
surface concentration depends on the condition of stirring. Thus, the fact that the ob-
served rate of the process under different conditions of stirring is the same (Fig. i, points
I, 2, 3) indicates that the partial pressure of oxygen c s on the surface of the cells (cell
conglomerates) is also the same, and equal to the value Co which is lower than the concen-
tration of the dissolved oxygen c L = ci, c2, c3 in the main mass of the liquid under three
different stirring conditions. Since the specific rate of consumption is the same every-
where, the oxygen flow to the cells (conglomerates) should be the same in all three cases.
If we assume that the cell (conglomerate) is spherical, we can express the value of the oxy-
gen flow as:
Q ~ 4 ~ R 2 K I . t ( C L --C8), (i)

The D. I. Mendeleev Moscow Chemical-Technological Institute; The All-Union Scientific-

Research Institute of Antibiotics, Moscow. Translated from Khimiko-Farmatsevticheskii Zhurn=
al, Vol. 13, No. 5, pp. 90-97, May, 1979. Original article submitted October 16, 1978.

530 0091-150X/79/1305-0530507.50 9 1980 Plenum Publishing Corporation