Komatsu, Shigeru

Kusumoto, Suehiko

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RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:On the Composition of JapanesePetroleum, IKomatsu, Shigeru; Kusumoto, SuehikoKomatsu, Shigeru ...[et al]. On the Composition of Japanese Petroleum, I. Memoirs of theCollege of Science, Kyoto Imperial University. Series A 1924, 7(2): 77-841924-02-10http://hdl.handle.net/2433/256656On the Composition of Japanese Petroleum, I. By Shigern l{omatsn and Snebiko Kusumoto. (Received June 12, 1!)23) K. Kobayashi\ S. Shimidzu1 , C. F. Mabery and S. Takano3 and T. Katayama4 have already investigated the composition of Japanese petroleum. The results of their investigations show that Japanese petroleum is composed for the greater part of hydrocarbons of the polymethylene series or naphthene. In addition to this, the geological survey of the oil fields in Japan5, presented some evidence to support the above statement brought forward by the chemists. Although no doubts exist th::>t polymethylene hydrocarbons constitute the main part of our petroleum, the studies made by these investigators provided no further knowledge of the exact constitution of the hydrocarbons, and moreover, were concerned specially with the fractions boiling at a higher temperature than 98°. The authors, therefore, have undertaken the present study to isolate polymethylene hydrocarbons in pure condition and to ascertain their constitutions by chemical means. The specimen used in this investigation was Nishiyama oil, Echigo, obtained by the kindness of Dr. T. Fujii. It was a dark green oil, having the sp. gr. 0.8230, and was composed of the following three portions: Temp. Distillate % belO\:v 150° 23.2 1so-:rno0 47.3 1 Kogyo Kwagaku Zas~hi, S, 321; 13, 1277. 2 Ibid., 7, !115. s Am. Chem. J., 25,297 (1901). 4 Kogyo Kwagaku Zasshi. 16, 1341; 17, 273. above 300° 29.5 ° C. Engler u. H. v. Hofer: Das Erdi:il. II. 467 (]909); J. Takahashi: Scie. Reports Tohoku Imp. Univ. (III). I, 143 (1922). 78 Shigeru Komatsu and Suehiko Kusumoto. The first portion was distillated under ordinary pressure three times in six successive portions : TABLE I. Fraction. Yield.% d""' 4• 1 32-50° 3.4 0.652:3 2 50-70° 5.fl 0.11841 3 70-90° 8,8 0.7196 4 90-120° 42.5 0.7529 5 120--150° 26.7 0.777;{ 6 above 150° rn.o 0.8151 2,350 grm. of the third fraction boiling at 70-90°, were shaken first with fuming sulphuric acid containing 7°/4 SO3 , and afterwards with a mixture of sulphuric and nitric acids, being left in contact with the mixed acids for some hours, and then washed ,vith water. It was then treated with 1 % caustic potash solution, washed with water and dried over calcium chloride ; finally distilled on metallic sodium in a deph-legrnator. The oil freed from aromatic and unsaturated hydrocarbons by the treatments above rr,entioned, was fractiqnated three times at 10° inter-vals, and then twice at 5° intervals. The fractions boiling at 75-85° after five distillations, amounted to 757 grm. having sp.gr. 0.7340. This portion was carefully distilled following S. Young's des-criptions1. The oil to he distilled, was kept in a fhsk which connected with a six column dephlegrnator, and was slowly distilled so that the drops of distillate fell at the rate of about one per second. After the 15th. distillation, the operation was continued at the rate of one drop of distillate every two seconds, and the liquid was collected in a flask cooled by ice water. The correction of boiling point for the barometric pressure during the operation was made, (0.01! 0 per 1 m. m.) and the bulb of the thermometer was covered with a little cotton-wool to prevent super-heating. 1 Distillation principles and processes, 100 (1921). R:; 100 90 ~ 80 E ::s ~ 70 C ... -o.°:'. <u 60 "' 0) I:: E l::l .Q. "' ~ 1-, 50 01) '1s- .s I:: ..E 40 .s 01) - ·o:; ·-"' ~ C l 30 C u ... -i:::: 20 -I:: a 10 0 70 .,.Ar----- -----x Fig. 1. No. 21th distillation. No. 18th distillation. ,✓ ', I ', 71 72 73 74 ' ' ' 75 76 77 78 78 80 Temperature (C 0 ) I \ I 81 82 83 84 85 86 87 I I I I I 'f I I I I I I,' j 88 80 Shigeru Komatsu and Suehiko Kusumoto. The results of the 21st. fraction - the weight of each distillate, the ratio of weight to temperature range t:.w/c,.t, specific gravity, and index of refraction - are given in Table II. In Fig. I. the actual weight of distillate against the temperature of 18th. and 21st. distillations is plotted. The temperature - weight curve of the 21st. distillation (Fig. I.) shows two maxima, one at 80-81 °, and the other at 72°, and there appeared to be a maximum in the neighbourhood of 90°. As seen in Table I, the major portion of the oil boils at 70-90°, distills at 80-81 °, and this fraction shows the largest index of refraction 1•414, and the highest density 0.765; and the fraction B. p. 71-72°, corres-ponding to the other maximum in the curve, indicates =d!f0.7295, n~r = 1.3965. TABLE II. Fraction. Temp. Weight. % L,w/MI cl••· 4. . ..nn I M.R. 1 66-70° 66 9.4 14 - -2 70-71° 34 4.8 34 0,7213 1,3930 3 71-72° 54 7.7 54 0.7295 1.3965 4 72-73° 25 3.:, 25 0.7847 1,4000 5 73--74° 25 3.5 25 0.7432 1.4035 6 74-76° 27 3.8 13.,; 0.7446 1.4045 7 76-77° 5 0.7 5 0,7449 1.4050 8 77-78° 10 1.4 10 0.7480 1.4072 9 78-79° 21 3.0 21 0.7521 1,4090 27.54 10 79-79,5° 43 6.1 86 0,7567 1.4125 27,83 l] 79.5-soc 76 10.8 152 0,7595 1.4130 27,36 12 80-80,5C 94 13.3 188 0,7652 1.4145 27.43 13 80.5-81° 19 2.7 38 0,7615 1.4130 27.36 14 81-82° 11 1.6 11 0,7568 1.4080 15 82-83° 5 0.7 :j 0,7526 1.4075 16 83-84° 8 l.l 8 0.7437 1,4042 17 84-86° 21 3.0 10.5 0.7413 1.4020 18 86-88° 63 8.9 31.5 0,7201 1.3920 )!) over 88° 99 14.0 - - -On the Compostition of Japanese Petoleum, /. 81 Two portions correspond to methylcyclopentane and cyclohexane and they show a slight difference in density and index of refraction, compared with the same compounds obtained by other chemists, indi-cating the presence of some aliphatic hydrocarbons as an impurity. The purification of these fractions, however, was not continued as our apparatus was insufficient for the purpose. CYCLOHEXANE. The hydrocarbon B. p. 80--81 °, isolated from Japanese petroleum, was also compared with respect to its physical constants with hexahy-drobenzene prepared from pure benzene by the method of Prof. P. Sabatier, passing with pure hydrogen over reduced nickel heated at 180°, and purified by distillation1 . TABLE III. Observers. B. p. Density I Index of refraction. Authors from petroleum 80-81° d!l'' =0.765 nfi 5 ' =1•414 " benzene 80.3-81° d!f'=0.7788 nfi 5 " = 1•4195 Markownikoff 80,5-81°(760 m.m.) dP'' = o.7727 -Zelinsky 81-82° d:f' =0.7764 nJ5°~ = 1.4258 Baeyer 79-79.5° Fortey, from american petroleum 80.55-80•650 dO"· 4• =0•7722 galician ,, 80.8° dO'' 4:,, =U-790:I Rosenthal 80.85°(760 m.m.' d:f =0•7764 nb 8 " = l .4:Jl!J7 R. Kissling 80,8°(760 m.m.J d:f = 0°7788 .n/59'• -= 1.4266 It gave, on analysis, the results shown in Table IV. which agree fairly well those required for cyclohexane. 1 C.R., 132, 210, 566 (1901). ll Ber. D. Chem. Ges., 28, 577 (189.5); 30, 1225 (1897); Lieb. Ann., 302, 1 (1898 ). a Ber. D. Chem. Ges., 28, 1205 (1895); 30, 390 (1897) . .i, Ibid., 26, 229 (1893); Lieb. Ann., 278, 88 (1893). 5 J. Chem. Soc., 73, 932 (1898). 6 Organische Verbindungen. 17, (1914). 'l' Chemische Technologie des Erdols, 31. 82 Shigeru Komatsu and Suehilco Kusumoto. TABLE IV. Fraction. , Temp. I Substance. I CO2 I H20 I co1 0 I HO! /0 9 I 78-79° I o,1459grm, 1 0.454(Jgl'lll, I O.l!JlfiKl'lll, 1 84.8/i I 14,62 " " 0,1311 0.4082 o. 171 !) 8-i.!J2 14.60 mean I 84.8!) I 14.61 10 I 79-79.5° I 0,1029 I 0.8211 I 0,1360 I 85.11 I 14.72 " " 0,1148 0.3578 0.141'4 85.37 14.40 " " O,ll:l2 0.3537 0,1487 85.21 14.63 mean I 85.2:l I 14.58 11 I 79.5-80° I 0.1034 I 0.3234 I O,ta26 I 85.29 I 14.29 " " 0,1031 0.B223 0.1:141 8,i.27 14.49 " " 0,1042 0.32,;7 0,1374 8.3.25 I 14,69 mean I 8,i.27 I 14.49 12 I 80-80.5° I 0.1371 I 0.42!!7 I 0.17;;7 I 8,i.43 I 14.27 " " 0,114!) <Ul610 0,14!):l 8:;,!i!J 14.4!1 " " 0,1010 o.a161; 0,1:ll(l 85.49 14.51 mean I 85.54 I 14.42 18 1805.-81° I 0.1280 I 0,401)1) I 0,16H5 I 8,i.23 I 14.22 " " O.lall 0.4105 0.1700 8i,.H9 14.44 " " o.10a2 O,!-l231 O.Ia54 8,i.39 14,62 mean I 8;j,a4 I 14.43 ~ 14 I 81-82° I o.1:m2 I 0.4:J;;O I 0.181(i I 85.2a I 14.53 " " 0,1179 o.:rn8!J 0.Li45 8,i.Hl 14.5!) mean I 8,i.27 I 14.56 - I Cale. for C6H12 I 8.i.62 I 14.:38 According to Prof. P. Sahatier, reduced nickel heated at 300° serves as a catalyst for the dehydrogenation of cyclohexane which loses all the six hydrogen atoms of the ring and yields hydrogen and benzene. At a lower temparature, the reverse change occurs, the passage of hy-dorgen and benzene over reduced nickel heated at 180° resulting in the hydrogenation of henzene. The catalytic transformation of cyclohexane under the influence of reduced nickel into benzene, thus offers a convenient method for identification of the hydrocarbon as observed by N. Zelinsk_y 1 in russian petroleum using heated palladium hlaC"k as a catalyst. 1 Ber. D. Chem. Ges., 45, 3678 ( 1912). On the Composition of Japanese Petroleum, !. 83 40 grm. of the substance B. p. 80-81 °, were passed over reduced nickel at 300°, and the product possessing an aromatic odour and boiling at 77 -81 °, was fractionated into two portions. 'fhe yield was 24 gnn. I Fractions. I Yield I d""· 4• .. I fl"l5 .. D I. I 77-70° I 14 grm. I 0.8178 I 1.4544 2. 79-81° 9 " 0.8288 1 .4648 The second fraction showing the same specific gravity and index of refraction as pure benzene, was treated with a mixture of cone. nit1 ic and sulphuric acids, yielding a compound which was purified hy distilla-tion. It boils at 210-211 °, d~' = 1.207 4, and gave, on analysis, the following results: C=58.59: 58.52; 58.61; H=3.99; 4.18; 4.42; N=ll.26; 11.76; 11.95 (theory requirs C=58.51; H=4.1U; N=ll.39 for C6H5NO2). The physical constants and analytical results agree with those of nitrobenzene. It yields by reduction aniline which was confirmed by forming a double salt with platinum chloride and also other chemical reactions. METHYLCYCLOPENTANE. The substance isolated from the petroleum gave, on analysis, the elementary composition and showed the ph)sical constants mentioned on the table V, with those of methylcyclopentane obtained by Markowni-koffl, Zelinsky2, S. Young3 and Aschan4• TABLE V. Observers. I B. p. I Density. Authors 71-72° d!,"' = o. 7205 Markownikoff, 71.5-72°(742 m.m.) d8~= 0.70 synthesized Baku oil 71-72c(755 m.m.) <lg~ =0.7664 Zelinsky 71.5-72.5° dgr:.r = o. 7501 Zelinsky and 71°(743 m.111.) dlf••' =0.7488 Moser Young 69.98-70.15° dr·=0.7157 1 Ber. D. Chem. Ges., 30 1222 (1897). Z Ibid., 30, 38!1 (1897). 3 J. Chem. Soc., 73, 913 (1898J. 4 Ber. D. Chem. Ges., 41, 2431 (1908). I lndex ot refraction. n~•· =l.3905 -----84 On the Composition of Japanese Petroleum,/. S. Komatsu & S. Kusumoto. For identification\ 20 grm. of the oil B. p. 71- 72°, in a flask were subjected to oxidation with 80 grm. fuming nitric acid (sp. gr. 1.51) and the solid reaction product deposited at the bottom of the flask, after 12 hours of reaction, was separated from the mother liquor by filtration. The yield was 3 grm. It melted at 97-120°. By repeated fractional crystallisation from its aqueous solution, it ,vas separated into two com-pounds, one melting at 184-189° and the other at 98°-100° The former compound, less soluble in water, was identified to be succinic acid by elementary analyis. C=40.40; l-1=5.02, and also by molecular weight determination with f-u- NaOH solution, 1\1. W.= 117 (theory requires C=40.67; I-I=5•08; M. W.= 118 for C4Hp4), The latter compound, more soluble in water, was also confirmed to he a mixture of oxalic and glutaric acids, varying carbon and hydrogen con-tents from 28.5 to 47.7 and from 3 to 5•3 respectively. The volatile acid found in the mother liquor, was noticed. to be acetic acid. Methylcyclopentane was identified by oxidation with nitric acid, yielding acetic, oxalic and succinic ;,_cids with some glutaric acid as noticed N. Zelinsky and Gutt2 and also by 0. Aschan3• Thus, by repeated fractional distillation of petroleum, for about four months, we succeeded, as we had expected, in isolating these polymethylenes in fairly pure condition, and the examination of the other portion boiling about 90° will be reported in another article, with that of the fraction boiling below 70°. April 1923. Laboratory of Organic and Biochemistry. 1 S. Nametkin: Ber. D. Chem. Ges. 42, J:l7:l (l!lO!J).; C. Engler, H. v. Hofer; Das Erd,;J. 1. 2:1,3 (191:l); Markownikoff: Ber. D. Chem. Ges., 32, 1445 (18H!l); 35, 1.384 (Hl02). " Ber. D. Chen1. Ges., 41, 2-i:31 (1008). s Ibid., 31, 1801 (18!!8). 

On the Composition of Japanese Petroleum, I

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On the Composition of Japanese Petroleum, I

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