Document Type: 
Document Number (FOIA) /ESDN (CREST): 
Release Decision: 
Original Classification: 
Document Page Count: 
Document Creation Date: 
January 3, 2017
Document Release Date: 
July 27, 2000
Sequence Number: 
Case Number: 
Publication Date: 
December 31, 1967
Content Type: 
PDF icon CIA-RDP86-00513R000103210014-9.pdf6.78 MB
2o-119-4-27/6o Iv&novg Pe Ge* Balandin, A. Member, Academy of Sci AUTHORS: ences,t" TITLE: On the Thermal Ionization of Hydrogen and Hydrocarbons in the Presence of Metal Catalysts (0 termiehookoy ionizataii vodoroda I ugleyodorodov v prioutetvii metallicheskikh katalizatorov) SSSR,, PERIODICALt Doklady Akademii Haukiv-1958, Volo 119, Wr 4, PPo 727 - 730 (USSR) ABSTRACT: The aim of the present work is the direct detection of the occurrence of charged particles in the gaseous phase in the presence of metal surfaces with catalytic properties. The con- atruction of the measuring apparatus is discussed on the- asis of a schematical dravring. The device was evacuated to lo ~ ma mercury column before the experiments began. The results obtained by ionization tests were represented in form of time-tempera- ture diagrams (the abscissa stands for the time Ir- and the ordinate for temperature). The more intenne ionization becomes, the more will the course of the curve extend toward the a-va WA downwards. A further diagram Illustrates the result: for Ly-drogen Card 1/4 in the presence of electrodes made from palladium, aluminum and On the Thermal Ionization of Hydrogen and Hydrocarbons 2o-119-4-27/6o in the Presence of Metal Catalysts copper. Accordingly, the number of ions begins to increase noticeably below looO. It must bebme in mind that -with an increase of temperature the Ionization of hydrogen de- pends on the material of the electrodeal it is in all cases reproducible and reversible. Ionizability can, e.(;. be charac- terized according to that temperature at which the inverse discharge velocity amounts to 6o asconde. The lower this amount t6ot the greater ionizability will be. In palladium electrodes this tegperature is very low for hydrogens amounting to only t6oo 90". For palladium and aluminum electrodes it holds that t6o" 1000 and in the presence of copper electrodes it holds that t6o" 1350,In a similar manner also the ionization of the vapors of hydrocarbons of different structure wao studied: H-heptane, 2,214-trimeth.r)- pmtanej- cyclohexane; benzenel decaline, tetra- line and also cyclic ketonol these experiments were carried out with different electrodes. In all these cases ionization occurred. Experiments carried out with hydrocarbons were reproducible Card 2/4 with the exception of cases with hysteresis, Also in this case On the Thermal Ionization of Hydrogen and Hydrocarbons 2o-119-4-27/6o in.the Pressnoe of Metal Catalysts the ionization observed depends in a high degree on the elec- trode material and therefore occurs on the surfact of the metal. Besidesp such an ionization depends on the nature of the gasl and therefore it occurs on the layer of molecules adsorbed on the gas. On the electrodes the electrons rapidly enter into the me- talt and therefore there-is no equilibrium in ionization under the oonditions described. In tetraline and decaline there may be a hysteresis bsoause of the presence of a sterio factor-. The sequence found here is parallel to that, of the catalytic activi- ty of the metals in hydrogenitation and dehydrogenization. The phenomenon found here devel#jh within the same intervals of tem- perature as also the catalytic reactions mentioned. The now effect proved to.%oxist here is important for catalysis. It is not taken into account by hitherto developed electron theories, of catalysis, but this must# without doubt, be done in the case of a further development of the theory. The investigation is continued. There are 4 figures, I table and 2 references, now Of which'are Soviets Card 3/4 On ths, Thermal Ionization of Hydrogen and Hydrocarborin 2o-li9-4-27/6o in.the Presence of Metal Catalysts ASSOCIkTIOH: Moskovekiy goeudaratvennyy universitet im. M. V. Lomonosova (Moscow State University imeni M. V. Lomonosov) SUBMITTED: December 269 1957 Card 4/4 SOV/ 20-120--2 AUTHORSI HnIAnAin, k. A.. Member, Academy of Sciences, USSR. Bogdanovat 0. K., Shcheglova, A. P. T1TLEt The Production of Isoprene by Catalytic Lehydrogenation of Isopentenes (Polucheniye izoprena putem kutaliticheskoy degidrogenizat- sii izopentenov) PER10DICILs Doklady Ikademi.i. Nauk BSBR, 1956, Vol, 12o, Nr 2, pp. 297-300 (USSR) ABSTRACTs This synthetic production in connection with the polyme- rization of isoprene and the production of iaoprene-rub- ber with better properties than natural rubber makes the method of isoprene production a problem of topical inter eat. Cheapest and most promising are mineral oil and its derivatives as raw material. The mineral-oil industry disposes of considerable supplies of isopentane and iso~ pentenes which can be utilized for the above-mentioned purpose by the method mentioned,in the title. The con-, ditione of reaction according to publications (Roferences 1-4) are given. For determining the optimum conditions Card 1/2 the authors investigated this reaction at different tem- The Production of Isoprome by Catalytic Dehydrogvriatiu;. JOV20-1120-2-19163 of Iaopentenes peratures and supply velocities of isopentenes as well as by different dilution with steam. The results are given in table 1 and figures 1-5, The beat conditions for the dehydrogenation of ieopentenes to isoprene aret temperature 580-62oOC, supply velocity per I liter cata.- Vat 5000-8000 ml/hour, and dilution with steam I ' 2,~-5,3 (by weight). The catalyst does not need regeneration for a longer period of time. Experiments of reaults were also made at 6ooOC and supply velocities of 67oo-72oo ml/liter/ hour as vall aa a 3tca-n dilution of 1 t 3. The results are given in table 2., Finally the kinetics of the reao- tion was investigated and a velocity conotant of 4,3 ml/min at 5300C and 12,25 Ml/min at 5900C was determined. The activation energy of the reaction is equal to 23,3 Koal/mol. There are 3 figures, 2 tablesand 5 regerences., 1 of which is Soviet. ASSOCILTIONt Institut organicheekoy khimii im. N~ D. Zelinskogo Akademii nauk SSSR (institute of Organic Chemistry imeni N. D. Zeline kiyJS USSR) SUBMITTED* March 7, 1958 Card 2/~ 1. leopentones-Dehydrogenation 2, loopentenes-Polymerization 3. Synthetic rubber-Produation 4. Mineral oila-Applicationo AUTHORS: .,_Jalaa~Ljn, A._A,,-Xember, Academy of SOV/20-120-4-24/67 Sciences, USSRt Sovalova, L. I., Slovokhotova, T. A. TITLE; Catalytic Transformations of 2-1lethyl-Thiophene Under Steam Influence (Katalitiche 8ki c prevrashcheniya 2-metiltiofena pod vliyaniyem parov vody~ PERIODICAL: Doklady Akademii nauk SSSR, 1958, Vol. 120, Nr 4, PP. 775- 778 (USSR) ABSTRACT: Difficulties were bound to occur in connection with the prob- lem of the applicability of the reaction of the catalytic de- methylation to the thiophene derivatives because of the spe- cifio behaviour of the latter on metallic catalysts in the presence of hydrogen (Refs 6-11) which is known to be a pro- duct of the said reaction. Ni/Al 20 and Co/Al 0 3 :ere used Re catalysts. The velocity and the p4ducts of t9e r action of 2-meth,yl-thiophene with water change gradually if its vapors are allowed to pass above a fresh catalyst (Fig 1, Table 1). 2-mothyl-thlophone separates the mathyl group and in subjected to a small extent to a ring cleavage. The existence of lateral methyl, groups rendere the ring system more reactive. During the Card 1/3 first minutes of the experiment the liquid catalyzed product Catalytic Transformations of 2-Idethyl-Thiophene BOV/20-120-4-24/67 Under Steam Influence contains thiophene which vanishes as soon as the velocity of the gas separation has attained a constant value. The quantity of C02 first exceeds that of the saturated compounds, vanishes then, however, together with thiophene. Unsaturated hydrocar- bons and 1128 occur at temperatures higher than 4000. The co- catalyst has an effect similar to that of Al. Table 2 shows the dependence of the composition of the liquid and Z;aseous products on the temperature, on the quantity of water, and on the composition of the catalyst in the experiment with methyl- thiophene. Within 1 hour of heating in hydrogen the consumed catalyst is restored, unless it had lost its activity com letely before. A longer heating increases its activity (Table 3~. Her qfrom it can-be concluded that methyl-thiophene is demethy~_ lated in the reaction In question. The complete cleavage of the methyl-thiophene molecule which occurs as well may develop with the participation of either hydrogen or water. The dealkylation of methyl-thi.ophene thus determined is a model reaction for the production of thiophene from alkyl.substitukd. The present Card 2/3 paper in principle shows a poasibi34ty of obtaining accessible Catalytic Transformations of 2-Mothyl-Thiophons Under Steam Influence SOV/20-120-4-24/67 raw material for the synthesis on thiophene basis from sul- furous mineral 6ile and slate resins (Ref 12). The reaction can be carried out on a mobile contact mass with a con- tinuous regeneration of the circulatinj; catalyst. There are 2 figures, 3 tables, and 19 references, 12 of which are Soviet. SUBMITTED: February 18, 1958 1. Thiophene aldehydea--Catalysis 2. Metal catalysts-Chemical effects Card 3/3 21(8), 5M AUTHORS: Baland cademician. SOY/2o-121-3-28/47 Dobrosel I skaya, N. P. , Mikhayle.,,_u, i. Ye ., Spitsyn, Vikt.I Academician TITLE: Rn,dionotive Catalyets (Radio&kt1vnyye katall-.ntory) The Dehydration of Cyclohexanol Over the Stiphntes of Magnesium And Sodium(Degidratatslya talklogekennola nad sullfatami magniya i natriya) PERIODICAL: Doklady Akademii nauk SSOR, 1?1W-0, Vol 121, Nr 3, pp 495 - 498 (USSR) ABSTRACT: Some recent investigations used the irradiation by y-rays or neutrons for the influencing of the processes of hetero- geneous catalysis. In the present paper, however, the catalyst itself is used as a source ol" the ionizing radiation for the heterogeneous catalysis of gaseQus substances. This cata- lyat contained various quantities of the radioactive iso- tope (0-radiutor). It is assumed that the continuous bo's- bardment by P-particlea will energetically influence the processes whichoccur on the bounclary solid body-gas. Theren Card 1/4 may be also an influence of the radiation on the structure Radioactive Catalysts. The Dehydration of Cyclo- BOV/2o-121-3-28/47 hexanol Over the Sulphates of Magnesium and Sodium of the catalyzer (especially a change of the, properties of its surface ) and a radiation-chemical influence of radiation on the gaseous reagents even before their contact with the catalyzer. The object of the investigation was the catalytic dehydration of cyolohexanol over the sulphatea of magnesium and sodium, in which the sulphur was subst1puted by various quantities of radioactive sulphu* S*7~~. The investigation was carried out by means of a catalytie apparatus of the flowing type with an inserted, reactor. This apparatus was placed in a tubular furnace with automatic feeding. The radioactive preparations MgSO 4 and the measurement of the radioactivity of the catalysts are then diooussA.No gaseous products were generated by this reaction. The apparatus did not indicate the presence of any radioactive contailininta, The more non-radioactive sodium sulphate in added to the maenesium zul,,)htkte , the more does catalytic activity decrease. Also an"...-.,xas soiium sulphate is a catalyzer for tiie dehydr%tion of cyclohexanol, Card 2/4 although it is rather leso active than mnt;nesium sulphate. R' d1oactive Catalysts. The Dehydration of Cyclo- SOV/2*-121-3-28/47 h:xanol Over the Sulphates of Magnesium and Sodium The degree Aof the conversion of oycloheianol into cyclohexene increases with an increase of the radioactivity of thqcatalyst, but these increases are not proportional which respect to one another. The Arrhenius (Arrenius) equation, can be applied to the cases discussed in this paper. The paper showed experimentally that the radio- active radiation.of the catalyst has an influence on cata- lytic activi.ty and on activation energy. Finally, come possible explanations of the results of this paper art discussed. The discussed phenomena are a completely now effect of simultaneous action of the electrons and active centers of the catalyst. It may be assumed that the P- particles act upon the catalytically active centers which had adsorbed cyclohexanol molecules. The P-particles diminish the activation energy of the dehydrhtian of cyclohexanol. InvestigLtions are being continued. There ara 4 figureep I tabie, and 8 referencea, 5 of which are Soviet. Card 3/4 Radioactive Catalysts.. The Dehydration of Cycle- SOV/'2*-121-3-28/47 hexanol Over the Sulphates of Magnesium and Sodium ASSOCIATION: Mogkovskiy gosudaretvennyy univeraitet im.U.V.Lorionosova (Moscow State Univernity itieni M.V.Lomonooov) Institut fizicheskoy khinii Akademii nauk SSSR (Institute of Physical ChemistryAS USSR) SUBMIJTED: April 23, 1958 Card 4/4 WTHM; Jazarova, N. i4'.,. ~alaniin, A. A,, QCV - 2 01 Member, Academy of_3-c1znrr-s-,U4Sa,_Fj%yd31A# L. Kh. :.'I T L Catalytic Alkylation of n-butnne by Means of .,thylene at High remp3raturea and High rressures (Katalitichookoye alkillrovnniye n-butana etilenom pri vysokikh temperaturoxh i davlaniyakh) P,ORICnICALi Lok1ndy Akadwaii nauk 333,41 1958, Vol. 121, Nr 5, pp. 865-868 (USSR) ABSTRAM The authors already previously found (Refs 5) that a cata- lytic alkylation of normal paraffin hydrocarbons by clefino ible at increased temperatures (450 1, ona incroaned i:e:Oeu8re (500 atmospheres of excess pressure). This work is a P continuation of those referred to above. The tests were carried out under flow conditions. The equipment, the methods of both test and analyses have been described already pre- viously (Ref 1). The results have shown that the reaction re- ferred to in the title yields a complicated mixture ~f hy4ro- carbono. The expected hexane fraction (nNilintion p.,..iu