Vol. 2 (1960) Bulletin of the Japan Petroleum Institute

Vapor Phase Reactions of Alkenes with under Atmospheric Pressure*

by Takeo Yamauchi** and Sumio Matsuda**

Summary: (1) By reacting propylene with ammonia, using cobalt or nickel catalyst, with no regard to the kinds of carrier or promotors, , pro- pionitrile, i-and n- were obtained. Particularly, with nickel catalyst, i-and n-butyronitrile were obtained principally. With cobalt catalyst, by using suitable promoter and under suitable conditions, was obtained to a certain degree. With molybdenum or wolfram sulfide-alumina, acetonitrile was predominantly obtained accompanied by a small amount of propionitrile. With Ni-MgO-K. G., the reaction factors were investigated. (2) By reacting with ammonia in the existence of nickel catalyst, propionitrile was predominantly obtained along with small amounts of acetonitrile. With Ni-MgO-K. G., the reaction factors were studied. (3) By reacting butylene-1 and-2 mixtures with ammonia in the existence of nickel or cobalt catalysts, acetonitrile, propionitrile, n-butyronitrile, sec.-and n-valeronitrile were obtained. And also with i-butylene, acetonitrile, propionitrile, i-butyronitrile, i-and n-valeronitrile were obtained. With nickel catalysts, valeronitrile was obtained predominantly. (4) The order of the reactivity of alkenes to ammonia is ethylene>propylene >butylene, considering from the conversion rate of alkenes to the total .

The reactions of alkenes with ammonia to tained along with it. But it was reported that, yield alkyl nitriles have been reported by J. W. by using nickel-alumina, i-and n-butyronitrile Teter1) and other investigators. J. W. Teter could be obtained under suitable conditions. got many patents on the reactions of alkenes In the author's laboratory, the study on the with ammonia in the existence of cobalt cata- reactions of alkenes with ammonia have been lysts under pressure. For example, the reac- developed for these years6). This paper is tion of olefin fraction containing 37% propylene going to describe the results of the reactions with ammonia over cobalt(23～35%)-magnesia of ethylene, propylene and butylene with

(5～40%)-diatomaceous earth (10～25%), the ammonia in the existence of various catalysts. mole ratio of propylene to ammonia being 1 Experiments to 10, at 700°F and 1,500lb./sq. in., for 1hr. I. Equipments gave 23% yield of containing products of the following composition (wt.%): aceto- Fig. 1 is a schematic flow diagram of the 25.2, propionitrile 44.5, i-butyronitrile 4.4, equipments used in these experiments. n-butyronitrile 17.9, 0.8 and others 7.2. The alkene and ammonia were metered As to the reactions under atmospheric pres- through flowmeter, mixed and then passed sure reports have been made by Wm. I. Den- into a reactor made of stainless steel. The ton and other investigators. In these cases, reactor was consisted of a preheating zone Molybdena-alumina2), metals molybdates3), me- and a reacting zone which was filled with ca- tals phosphates4), nickel alumina5) and so on talysts. were used as catalyst. Temperature control was achieved by im- When propylene was used as alkene, aceto- mersing the reactor in a molten salt bath held nitrile was the principal product and, in at the desired temperature. general, only 5～10% of propionitrile was con- The resulted gas from the reactor was led * Received December 15, 1959. through a water condenser and then a trap ** Faculty of Engineering, Osaka University, Osaka . cooled by ice-salt. Then the liquid products

76 Vol. 2 (1960) Vapor Phase Reactions of Alkenes with Ammonia under Atmospheric Pressure were separated. The mixture of the trapped * cyanide was recovered again by analysis. products and water scrubbers were collected The liquid products were identified and anal after being washed with water and * yzed as described later.

Fig. 1 Apparatus used in Studying the Catalytic Reaction of Alkenes and Ammonia

(2) Cobalt-Alumina (Co-Al2O3) II. Raw materials Cobalt-alumina was prepared from cobalt Ethylene, propylene and i-butylene were nitrate, anhydrous sodium carbonate, and acti- prepared by the dehydration of ethylalcohol, vated alumina (200 mesh). Before using, it i-propylalcohol and tert.-butylalcohol, using was treated as shown in (1). activated alumina as catalyst (the purity of (3) Cobalt-Magnesia-Diatomaceous earth these alkenes was 92～98vol. % by absorption Co-MgO-K. G. I 100-12-200 in 98% sulfuric acid). II 100-80-200 " Similarly, butylene was prepared by the III 100-160-340 " catalytic dehydration of n-butylalcohol, the Cobalt-magnesia-diatomaceous earth was pre- composition of butylene mixtures being buty- pared from cobalt nitrate, anhydrous sodium lene-1 76.5, butylene-2 22.9, and i-butylene 0.6 carbonate, and diatomaceous earth in accord- wt. % (determined by gas-chromatography). ance with Teter's method or Fischer-Tropsch's Propane-propylene, commercial grade, con- process of manufacturing the catalyst7), while taining propylene 70.0vol. %, was used as changing the proportion of the component. raw material. (4) Cobalt-Magnesia-Thoria-Diatomaceous earth Co-MgO-ThO2-K. G. I 100-12-6-200 III. Catalysts " II 100-160-6-340 " (1) Cobalt-Diatomaceous earth (Co-K. G.) These catalysts were prepared in accordance Cobalt-diatomaceous earth was prepared with the method of manufacturing catalysts from cobalt nitrate, anhydrous sodium car- by Fischer-Tropsch from cobalt nitrate, thori- bonate and diatomaceous earth, and then pel- um nitrate, magnesium acetate, anhydrous so- leted and dried. dium carbonate and diatomaceous earth. Before using, this catalyst was reduced by (5) Nickel-Magnesia-Diatomaceous earth passing gas, and then purged com- (Ni-MgO-K. G. ) pletely by ammonia afterwards. Nickel-magnesia-diatomaceous earth was pre-

77 Takeo Yamauchi etc. Vol. 2 (1960) pared from nickel nitrate, magnesium acetate, passing hydrogen at 350℃ for 2～3hrs. anhydrous sodium carbonate, and diatomaceous (11) Wolfram sulfide-Alumina (WS2-Al2O3) earth in accordance with Teter's method. Wolfram sulfide-alumina was prepared from Before use, it was treated as in (1). ammonium tungstate in accordance with (10). (6) Nickel-Magnesia-Thoria-Diatomaceous (12) Molybdenum sulfide-Cobalt sulfide-Alumina earth (Ni-MgO-ThO2-K. G.) (MoS2-CoS-Al2O3) Instead of cobalt nitrate described in (4-II), Molybdenum sulfide-cobalt sulfide-alumina nickel nitrate was used. was prepared from ammonium molybdate, Before use, it was treated as in (1). nickel nitrate, and activated alumina according (7) Nickel-Diatomaceous earth (Ni-K. G.) to the method described in (10). Nickel-diatomaceous earth was prepared IV. Analysis of the reaction products from nickel nitrate, anhydrous sodium car- bonate and diatomaceous earth in accordance The liquid products were identified by their with the ordinary method. boiling points, , the color reac- (8) Nickel-Silicate tion by hydroxylamine-ferric salt, and the Nickel-silicate was prepared from nickel comparison of their retention time with pure nitrate and sodium silicate in accordance with alkyl nitriles in gas-chromatography. the method in the literature8). Liquid products were analyzed using a Shi- (9) Nickel-Magnesium-Silicate madzu G. C.-2A Gas-Chromatography contain- This catalyst was prepared from nickel ing a column packed with a material in which nitrate, magnesium acetate, and sodium carbo- dioctyl phthalate was the stationary liquid nate as in (8). phase. (10) Molybdenum sulfide-Alumina By the reaction of alkenes with ammonia, (MoS2-Al3O3)9) crystalline products were obtained. By the By passing into aqueous result of the qualitative analysis, it was as- solution of ammonium molybdate, and then sumed that ammonium cyanide was contained the precipitate was produced by adding aque- in the crystalline products. ous . After being washed, The aqueous solution of the crystalline pro- the precipitate was impregnated through acti- ducts was titrated with the aqueous solution vated alumina. of silver nitrate using the aqueous solution of Before use, this catalyst was reduced by potassium iodide as indicator and calculated as

Table 1 Reactions of Propylene with Ammonia in the Presence of Cobalt Catalysts

78 Vol. 2 (1960) Vapor Phase Reactions of Alkenes with Ammonia under Atmospheric Pressure ammonium cyanide. Generally, the increase of the temperature caused the increase of the content of ace- Results and Discussion tonitril in the products. I. Reactions of propylene with ammonia When the content of magnesia is high as in (1) Reactions over cobalt catalysts Co-MgO-K. G. III and Co-MgO-ThO2-K. G. II, the Propylene was treated with ammonia over effects of reaction temperature on the composi- cobalt catalysts. tion of nitriles were not clear. The reaction conditions and the results are The increase of the reaction temperature illustrated in Table 1. caused the increase of the conversion of pro- (a) Comparison between the carriers. pylene to total nitriles, but it caused the Diatomaceous earth and activated alumina decrease of the yield of total nitriles based on were used as the carrier of the catalysts. the consumed propylene. It seemed that the In the existence of Co-K. G., propionitrile decomposition of propylene or the produced was contained about 30.0wt. % in the reaction nitriles occured as the reaction temperature products and this quantity was more than the grew high. content when Co-Al2O3 was used (15wt. %). (d) Effects of total space velocity. Also with Co-K. G., i-and n-butyronitrile In the case of Co-MgO-K. G. II, the effect of were obtained to a certain degree, but with the total space velocity on the composition of Co-Al2O3, acetonitrile was the principal pro- nitriles was not observed, but in the case of duct. By using diatomaceous earth, the total Co-MgO-ThO2-K. G. I, the increase of the total content of propionitrile and i-and n-butyronit- space velocity increased the content of i-and rile was more than that of acetonitrile, in ge- n-butyronitrile and decreased that of acetonit- neral. rile. The total conversion of propylene to nitriles The increase of the total space velocity did not show a great difference between the caused the decrease of the conversion of two cases in which both carriers were used. propylene, but the total conversion of pro- (b) Effect of promoters. pylene to nitriles and the yield of the total When magnesia was added as the promoter, nitriles based on the consumed propylene it was observed that the contents of i-and n- showed the maximum at the space velocity butyronitrile in the products were increased. of 300l/hr./l in Co-MgO-K. G. II and 400l/hr./l As the contents of magnesia in the catalysts in Co-MgO-ThO2-K. G. I. increased, the resulted contents of i-and n- (2) Reactions over nickel catalyst butyronitrile were also increased. In general, The conditions and the results of the reac- the order of the contained quantities was Co- tion of propylene with ammonia over nickel MgO-K. G. III>II>I> Co-K. G. catalysts are illustrated in Table 2. When But the less was the content of magnesia in propylene was treated with ammonia over the catalysts, the more was the content of nickel catalysts, ammonium cyanide, acetoni- propionitrile in the products and its order was trile, propionitrile and i-and n-butyronitrile Co-MgO-K. G. I>II>III. were obtained same as when cobalt catalysts The total conversion of propylene to nitriles were used. Above all, the total content of i- increased by adding magnesia to the catalysts and n-butyronitrile was over 50.0wt. % in the used. products. And so, it was assumed that with Co-MgO-ThO2-K. G. II, thoria added Co-MgO- nickel catalysts, the carbon number of the K. G. III, did not show much difference from principal nitrile was one more than that of Co-MgO-K. G. III. It would perhaps be owing alkene used as raw material. to the small amounts of thoria. (a) Comparison of catalyst. With Co-MgO-ThO2-K. G. I, thoria added Co- In the composition of nitriles, the products MgO-K. G. I, the content of propionitrile in the with Ni-MgO-K. G. were not much different products was high at 360℃, but it decreased from those with Ni-MgO-ThO2-K. G. when over 380℃. In the case of this catalyst, But the conversion of propylene to the total it is characteristic that over 380℃, the content nitriles and the yield of the total nitriles based of i-and n-butyronitrile was very low. on the consumed propylene with Ni-MgO-K. G. (c) Effects of reaction temperature. was higher than those with Ni-MgO-ThO2-K. G. The composition of nitriles in the products With Ni-silicate, the content of acetonitrile was affected considerably by the reaction was more than that with Ni-MgO-K. G., but temperature. the conversion of propylene to the total nitriles

79 Takeo Yamauchi etc. Vol. 2 (1960)

Table 2 Reactions of Propylene with Ammonia in the presence of Nickel Catalysts

and the yield of the total nitriles based on the city. consumed propylene were a little inferior to The conversion of propylene to the total with Ni-MgO-K. G. nitriles shows the maximum value at the total (b) Investigations on the reaction conditions. space velocity of 250l/hr./l, but the yield of The main factors of the reaction are the the total nitriles based on the consumed pro- reaction temperature, the molar ratio of the pylene does not show a great difference within reactants, and the total space velocity. By the range of the total space velocity investi- treating propylene with ammonia over Ni- gated in this study. MgO-K. G., these factors were investigated. (iii) Effect of molar ratio of the reactants. (i) Effects of the reaction temperature. The contents of n-butyronitrile and acetoni- As the temperature rises, the content of trile show the maximum value at the molar acetonitrile in the products also increases ratio of propylene to ammonia , 1 to 7 and 1 to while that of i-and n-butyronitrile decreases. 5. The contents of propionitrile and i-butyro- It is assumed that it is owing to the hydro- nitrile are not affected by the molar ratio of the reactants . genolysis of produced i-and n-butyronitrile by hydrogen which is formed by the decompo- The conversion of propylene is not affected sition of ammonia or propylene, or to passing by the molar ratio of the reactants, but the the course which yield acetonitrile via i-propyl- conversion of propylene to the total nitriles amine as A. F. Plate described in his paper10). and the yield of the total nitriles based on the Propionitrile contained in the total nitriles consumed propylene are good at the molar ratio of propylene to ammonia produced is only 4.0～7.0wt. %, and not greatly , 1 to 5 or 7. affected by reaction temperature. According to the results of the study on the The conversion of propylene to the total reaction conditions, it is assumed that the nitriles shows the maximum value at 350℃, composition of the produced nitriles is affected and as the temperaure rises, the rate of the by the reaction temperature critically, and also conversion shows the tendency to decrease. by the total space velocity, but it is not so At 400℃, nitriles is not obtained. It is as- critically as the temperature. sumed that it is owing to the decomposition These three variables also have effects on of propylene or the produced nitriles. the conversion of propylene to the total nitri- ii) Effects of total space velocity. ( tes and the yield of the total nitriles based on As the total space velocity increases, the the consumed propylene. But the reaction content of acetonitrile decreases and that of temperature is the most critical in all . i-and n-butyronitrile increases. But, propio- (c) Effects of the mixing ratio of propane nitrile is not changed by the total space velo- in propylene.

80 used.

Vol. 2 (1960) Vapor Phase Reactions of Alkenes with Ammonia under Atmospheric Pressure

Table 3. Reactions of Propane-Propylene mixtures with Ammonia Catalyst: Ni-MgO-K. G.

Because pure propylene is considerably more pylene. expensive than propane-propylene mixtures (3) Reaction over molybdenum or wolfram which are widely available in oil refineries, it sulfide-alumina would be advantageous to use such a mixture When propylene is reacted with ammonia rather than pure propylene. in the existence of molybdenum or wolfram Therefore, a study was made on the effects sulfide-alumina, or molybdenum-cobalt sulfide- of changing the proportions of propane to alumina, the product is predominantly aceto- propylene, while keeping the mole ratio of pro- nitrile accompanied by small amounts of pro- pylene to ammonia constant. The results and pionitrile. the conditions are illustrated in Table 3. They are greatly different from the reaction This study indicates that diluting the pro- products when cobalt or nickel catalysts are pylene with propane, reduces the content of n-butyronitrile and increases that of aceto- The results are illustrated in Table 4. nitrile. With these catalysts, good results are ob- The content of i-butyronitrile has the tend- tained by passing the reactants, at the molar ency of a little decrease, but that of propio- ratio of propylene to ammonia of 1 to 5, at nitrile is not affected by a mixing ratio of 550～600℃ and at the total space velocity of propane. 500l/hr./l. Wm. I. Denton described that by the reaction With WS2-Al2O3, the conversion of propylene of propane and ammonia over molybdena- to nitriles is a little inferior to with MoS2- alumina, a small amount of acetonitrile was Al2O3, but the content of propionitrile is a little obtained2). So, in our study, it is assumed higher than that with MoS2-Al2O3. And a very that as a proportion of propane increases, a small amount of i-butyronitrile is also obtain- certain degree of acetonitrile is formed. ed. The proportions of diluting the propylene By adding cobalt sulfide to molybdenum with propane does not affect the conversion sulfide, the conversion of propylene to the of propylene, but reduces the conversion of total nitriles is improved, but the composition propylene to the total nitriles and the yield of of nitriles does not change greatly. the total nitriles based on the consumed pro- On the reactions of alkenes with these

Table 4. Reactions of Propylene with Ammonia in the presence of Metal Sulfides

81 Takeo Yamauchi etc Vol. 2 (1960)

Table 5. Reactions of Ethylene with Ammonia

metallic sulfide catalysts, we will report in with Ni-K. G. or Ni-MgO-K. G. And also the detail before long. conversion of ethylene to the total nitriles and the yield of the total nitriles based on the II. The reaction of ethylene with ammonia consumed ethylene are a little lower than with By reacting ethylene with ammonia in the Ni-MgO-K. G. existence of nickel catalyst, it is ascertained (b) Studies on the reaction factors. that propionitrile, which has one more carbon With nickel-magnesia-diatomaceous earth, the atom than that of ethylene used, is obtained reaction factors were studied. principally. That the carbon number of a (i) Effects of the reaction temperature. principal nitrile is one more than that of Within the range of the reaction temperature oleffin used, is as same as in the reaction of in this study, the composition of nitriles is not propylene with ammonia in the existence of affected by the reaction temperature, and pro- nickel catalyst. pionitrile is obtained in 88～95wt. %content in Besides propionitrile, ammonium cyanide and the produced nitriles. acetonitrile are obtained as by-products. The conversion of ethylene to the total nitriles The conditions and the results of the reac- shows the maximum value at 380℃, but when tion are illustrated in Table 5. over 380℃, the rate reduced and the amount of (a) Study on catalysts. ammonium cyanide increases. Therefore, it is The composition of nitriles in the product is assumed that, as the reaction temperature rises, not much greatly different between the cases the produced nitriles would be decomposed. with Ni-K. G. and Ni-MgO-K. G., but with Ni- Also, the rise of the reaction temperature MgO-K. G. the conversion of ethylene to the increases the rate of conversion of ethylene to total nitriles and the yield of the total nitriles the total nitriles, but the yield of the total based on the consumed ethylene are higher nitriles based on the consumed ethylene has than with Ni-K. G. the tendency to decrease within 350～390℃, and With Ni-Mg-Silicate, propionitrile is the prin- above 390℃, the decrease is critical. Therefore, cipal product as with Ni-K. G. or Ni-MgO-K. G. it is assumed that, at high temperature, the But with Ni-Mg-Silicate, the content of aceto- decomposition of the produced nitriles or nitrile is about 30.0wt. % and this is more than ethylene would happen. about 10% content of acetonitrile as in the cases (ii) Effects of total space velocity.

82 Vol. 2 (1960) Vapor Phase Reactions of Alkenes with Ammonia under Atmospheric Pressure

As the total space velocity increases, the content of propionitrile also increases, and that III. Reactions of butylene with ammonia of propionitrile decreases. (A) Reaction of butylene-1 and-2 mixtures But this tendency is not so clear, and so, with ammonia. within the range of these conditions tested in By treating butylene-1 and-2 mixtures with this study. the total space velocity has no effect ammonia in the existence of nickel or cobalt on the composition of nitriles. catalysts, acetonitrile, propionitrile, n-butyro- The conversion of ethylene to the total nit- nitrile, sec. -and n-valeronitrile are obtained. riles indicates the maximum value at the total Besides them, a very small amount of ammo- space velocity of 250l/hr./l, and the yield of nium cyanide and i-butyronitrile are also ob- the total nitriles based on the consumed ethy- tained. It is assumed that i-butyronitrile is lene is good at the total space velocity of 200 formed by the reaction of i-butylene, which is and 250l/hr./l. At the total space velocity of contained in raw butylene mixtures, with am- 180l/hr./l, the conversion of ethylene to the monia, or through the rearrangement of the total nitriles and the yield of the total nitriles produced n-butyronitrile. based on the consumed ethylene are low, but The conditions and the results are illustrated the amount of ammonium cyanide increases, in Table 6. and so it is assumed that owing to the long When propylene or ethylene is reacted with residence time, the produced nitriles would be ammonia in the existence of nickel catalysts, decomposed. the principal nitrile has one more carbon than (iii) Effect of molar ratio of the reactants. that of alkene used. Similarly, by reacting The molar ratio of ethylene to ammonia has butylene mixtures with ammonia over nickel no effect on the composition of nitriles. catalysts, valeronitrile, having one more carbon The conversion of ethylene to the total nit- than that of butylene, is obtained as in the riles and the yield of the total nitriles based case with the principal nitrile. on the consumed ethylene are affected by the And in the reaction of propylene or ethylene molar ratio of the reactants and they show the with ammonia in the existence of nickel cata- maximum value at the molar ratio of ethylene lyst, nitrile, having the same number of carbons to ammonia, 1 to 7. as used alkene, is hardly affected by all reaction According to the results of the reaction va- conditions. Similarly, with butylene, the con- riables, it is assumed that the composition of tents of butyronitrile in the products is 1.0～ the total nitriles is hardly affected by all these 4.0wt. % through all reaction conditions and factors, but the conversion of ethylene to the has no great change. total nitriles and the yield of the total nitriles With Co-MgO-ThO2-K. G. I catalyst, the con- based on the consumed ethylene are affected tent of valeronitrile is very low. Under suitable by all of these factors. conditions, the contents of acetonitrile, propio- nitrile and n-butyronitrile are nearly equal.

Table 6. Reactions of Butylene-1 and-2 mixtures with Ammonia

83 Takeo Yamauchi etc. Vol. 2 (1960)

Table 7. Reactions of i-Butylene with Ammonia

The conversion of butylene mixtures to the With Co-MgO-K. G. II, at low reaction tem- total nitriles with Co-MgO-Th2-K. G. I is greater erature, the total content of i-and n-valero- than with Ni-MgO-K. G. nitrile is 50.0wt. %, but without any regard to The role of butylene-1 or butylene-2 con- the reaction condition, the content of i-butyro- tained in butylene can not be clarified by the nitrile is about 20.0wt. %. On the reaction of reaction products. As mentioned above, it is butylene with ammonia, we will report in detail assumed that i-butylene which is contained to before long. a certain degree produces i-butyronitrile. But, Acknowledgement it is also assumed that i-butyronitrile is formed by the rearrangement of n-butyronitrile or by We are grateful to the Nippon Shokubai the reaction of butylene-2 with ammonia, and Kagaku Kogyo K. K. for the financial support therefore, the causes of the formation of i- of this work.

butyronitrile is not determined distinctly. Reference And also the causes of the formation of valeronitrile are not clear. 1) W. Teter U. S. 2,417,892 (1947) ibid. 2,417,893 (1947) (B) Reaction of i-butylene with ammonia. ibid. 2,419,479 (1947) By reacting i-butylene with ammonia in the ibid. 2,437,487 (1948) existence of cobalt or nickel catalysts, aceto- ibid. 2,468,522 (1949) nitrile, propionitrile, i-butyronitrile, n-butyro- ibid. 2,479,879 (1949) ibid. 2,520,181 (1950) nitrile, n-and i-valeronitrile and a very small ibid. 2,623,061 (1952) amount of ammonium cyanide are obtained. ibid. 2,658,041 (1953) It is assumed that n-butyronitrile in formed by ibid. 2.643,266 (1953) the reaction of butylene-1, which is contained 2) Wm. I. Denton and R. B. Bishop: Ind. Eng. Chem., in raw i-butylene, with ammonia. 45, 282 (1953). The conditions and the results are illustrated A. F. Plate and M. E. Volpin: Doklady Akad. Nauk., in Table 7. With Ni-MgO-K. G., valeronitrile 89, 317 (1953). 3) Wm. I. Denton and R. B. Bishop: U is obtained principally. With butylene-1 and . S. 2,496,659 (1950). -2 mixtures , the kinds of valeronitrile is princi- 4) Wm. I. Denton and R. B. Bishop: U. S. 2,561,787 pally n-valeronitrile accompanied by sec. -va- (1951). leronitrile. On the contrary, with i-butylene, 5) Kominami, Hori: J. Chem. Soc. Japan. Ind. Chem. valeronitrile is principally i-valeronitrile ac- Section, 61, 1312 (1958). companied by n-valeronitrile and under suita- 6) T. Hayashi: Graduation thesis in the Department ble conditions, the contents of i-valeronitrile of Applied Chemistry, Faculty of Engineering, is about 75.0wt. % in the products. Osaka University, (1957). With Co-MgO-ThO2-K. G. I, the both contents T. Tubakimoto: ibid. (1958) . of acetonitrile and i-butyronitrile are 30～40 T. Yamauchi, S. Matsuda and M. Kato: J. Japan wt. %, and that of i-butyronitrile is 46.0wt.% Petroleum Institute, 3, (1), 19 (1960.) T. Yamauchi and S. Matsuda: ibid., 3, (2) at 350℃. Same as with the case of butylene-1 , 101(1960). T. Yamauchi and S. Matsuda: ibid., 3, (2) and-2 mixtures, the content of valeronitrile is , 109(1960). 7) P. H. Emmett: Catalysis, 1, 345 (1954). very low, but at 350℃ it is obtained fairly 8) Fr. P. 1, 023, 462 (1953). much. Still, only with this catalyst, a very 9) T. Yamanaka: Chemistry of Catalysis, 212 (1956). small amount of sec. -valeronitrile is obtained, 10) A. F. Plate and M. E. Volpin: Doklady Akad. Nauk, but the reason is not clear. 89, 491 (1953).

84