Funasaka, Wataru

Kajiyama, Shigeru

Suga, Sohei

Yokokawa, Chikao

Kyoto University Research Information Repository

Title Studies on the Softening and Swelling Properties of Coal inCarbonization ProcessAuthor(s)Funasaka, Wataru; Yokokawa, Chikao; Suga, Sohei; Kajiyama,ShigeruCitation京都大学化学研究所報告 (1951), 24: 83-84Issue Date1951-03-30URL http://hdl.handle.net/2433/74225RightType Departmental Bulletin PaperTextversionpublisherKyoto UniversityBulletin,  vol. 20 (1950) 64.)    In this paper, some results obtained from the examination of  some problems on the  semi-commercial,scale purification of rice oil, employing the method, above mentioned, are described. The main parts of the results are as follows.    1. If aqueous solution of sulphuric acid is used as one of the most effective washing agents against crude oil, the condition under which the decoloration effect and the yield of clear top oil are  max  imun, is that the concentration of the solu-tion is about 10  4/,. (wt.) and the rate of the solution added to the oil is about 18 ,;,<,  (vol.).    2. Concerning the mode of the emulsive washing, the agitation by air bubbles is more effective than that by a stirrer.    4. As one of the means in order to prevent the coloration of declored rice oil, caused by contacting the oil with iron material, the  "  passive  " treatment of the iron surface is somewhat effective for oil whose acid value is lower than fifty.     25. Studies on the Softening and  Swelling Properties               of  Coat in Carbonization Process Wataru  Funagaka, Chikao  Yokoka'wa,  SOhei Suga and Shigeru  Kajiyauta,  (Kodaraa Laboratory)    For the testing methods of the plastic state of coal, there are Shefield  Laboratory Test, K. B.  S.-method and  Tadokoro's method etc.    Authors modified the K. B. S.-apparatus to obtain softening-swelling curve and gas evolution curve simultaneously. The used samples were of various ranks of coals (fuel ratio 0.5-5.0) in Japan.    By obtained softening-swelling curves, all samples were classified in three types,  non-softening type, softening type and softening-swelling type. Lignite or low rank coal and anthracite belonged to non-softening type, and were not caking. Bituminous coal belonged to the second or third type,  and the fuel ratio range of softening type coals was between 1 and 3, and that of softening-swelling type coals was between 0.5 and 2.5    The critical points of  these curves, softening temperature, maximum swelling temperature and temperature of maximum gas evolution rate, etc., were closely referred to the fuel ratio of coal samples.    The effects of size of coal and load to coal charge were examined with typical samples of each type, but no distinct conclusion was obtained. About artificial coals (prepared from cellulose, lignin, protein and their mixture in the medium of  H2O or  N/10  NaOH) were also examined, but it was difficult to compare artificial  (  83  ) coals  with  natural  coals by  :softening  (:urvo,  owing  to  the  difference of  physical. conditions.     26. Studies on the Mechanism of Friedel-Crafts Type                      Reactions. (VIII)                   Alkylation of Benzene by Organic Esters  Yoshinobu Takegami and  Harno  Shingu  1Codarna  L  abol  atory)    Esters of carboxylic acids can alkylate benzene in the presence of more than 1 mol aluminium halide per mol esters at the temperature below  50°C without accompanying acylation. (Bowden: J. Am. Chem. Soc. 60 645 (1938)) Norris (J. Am. Chem. Soc. 62 874 (1940)) obtained ethyl chloride and  CH3C00A1C12 when equimolecular amount of ethyl acetate and  AlC13 was heated at 140-170°C and su-ggested the mechahism that the  alkylation by the ester proceeds  through an inter-mediate formation of alkyl halide  (RCI). According to  this mechanism the rate of formation of RCI and that of alkylation by the ester must be in the same order of magnitude, because the rate  of alkylation of benzene by RC1 is very  large.t':    The authors studied the reactions between ethylacetate and  A1Br3 at 20°C (at this temperature ethylation of benzene proceeds smoothly). Only 4-9 of ethyla-cetate was decomposed even in the presence of excess  AIBr3 without any formation of ethyl bromide. Kinetical studies showed that the rate of alkylation is first order in esters and its rate constant is proportional to the concentration of free  AIBr3 (i. e. total AlBr3 concentration minus ester concentration).  These  result may be explained by the following  mechanism  : (1) only free  A1Br3 has catalytic activity and the  AIBr3 combined with the ester  (1:  1 mol complex) is catalyticaly inactive, (2) probably alkyl cation, accepted active intermediate of Friedel-Crafts reactions, may be formed by the interaction of free AlBr3 and ester-AlBr3 complex, (3) the alkyl cation alkylates benzene and never produces alkyl halide.    The velocity of alkylation is affected by structural change of R in the esters  (R'COOR) in the  order  : ethyl acetate 0.41 <n-propyl acetate 0.82  <n-butyl acetate 0.85  (min-1 per  mol/1  A1Br3). This order of reaction rate agrees with that of  RC1 and indicates that the inductive effect of alkyl group  facilitate the attack of  AlBr3 on the oxygen atom of alkoxy group. The order of reaction rate caused by the structural change of R' is as  follows: ethyl formate 2.07  j>ethyl acetate  0.41_,> ethyl butyrate 0.084, which shows that the strengh of  0-R bond is increased by the inductive effect of alkyl group in the acid residue. •  (  84  )

Studies on the Softening and Swelling Properties of Coal in Carbonization Process

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Studies on the Softening and Swelling Properties of Coal in Carbonization Process

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