石油学会誌
Print ISSN : 0582-4664
16 巻, 6 号
選択された号の論文の5件中1~5を表示しています
  • 今野 忠男, 五十嵐 哲, 荻野 義定
    1973 年 16 巻 6 号 p. 468-473
    発行日: 1973/06/01
    公開日: 2009/01/30
    ジャーナル フリー
    Ni-MgO catalysts were prepared from nickel nitrate and several kinds of basic magnesium carbonate, and the catalytic activities for the dealkylation of m-xylene with steam were measured at 450°C and 1atm pressure.
    Necessary conditions to be satisfied to obtain active catalysts were as follows:
    (i) An ethanol solution of nickel nitrate must be used in mixing the raw material of the catalyst support and nickel nitrate. The use of an aqueous solution gives the catalyst of poor activity.
    (ii) The raw material of the catalyst support must be selected adequately. Among the raw materials used in this work, the group-1 basic magnesium carbonate (a mixture of MgCO3•3H2O and 4MgCO3•Mg (OH)2•4H2O) is preferable to the other type. The selection of the desirable raw material is easily achieved by D. T. A. experiments.
  • 堤 銀次郎
    1973 年 16 巻 6 号 p. 474-478
    発行日: 1973/06/01
    公開日: 2009/01/30
    ジャーナル フリー
    A vapor-liquid equilibrium calculation method fit for compositional reservoir models was presented. The compositional effects on the equilibrium ratios were taken into account by employing Rowe's definition of convergence pressure14). The difficulty of insuring the smooth calculation when the fluid composition is close to a bubble point curve, a dew point curve, or a critical point, which is often the case when the convergence pressure is calculated iteratively, was resolved by defining the mole fraction of vapor phase V extendedly in (-∞, +∞) and equilibrium ratios in the pressure range greater or less than convergence pressure.
    The method was tested in the reservoir simulation of pressure maintenance processes using three and seven component fluid systems, and smooth calculation was observed. In addition, the method was compared with one employing a fixed convergence pressure, and it was found that the former could predict reliable phase diagrams of the three component system but the latter could not, and that the recovery curves in the pressure maintenance process predicted by the both methods were unlike. These two facts indicate the preferability of employing varying convergence pressure in compositional models. An additional computer time to recalculate convergence pressure was observed to have been small compared with the total computer time required for the reservoir simulation.
  • シクロヘキサン改質反応の動力学的検討
    長田 武雄
    1973 年 16 巻 6 号 p. 479-483
    発行日: 1973/06/01
    公開日: 2009/01/30
    ジャーナル フリー
    Reforming reaction of cyclohexane (CH) over stabilized Pt/Al2O3/Cl type catalyst was investigated under the conditions of industrial use such as reaction temperature; 400-470°C, liquid hourly space velocity; 3-30vol/vol•hr, initial hydrogen pressure; 17.8-35.0atm and H2/CH ratio; 5-15mol/mol. The following conclusions were obtained.
    (1) The conventional rate equations of initial overall reaction [υ0(T)], initial dehydrogenation [υ0(Bz)] and initial ring-isomerization [υ0(MCP)] are indicated as follows,
    υ0(T)=kTpCH-0.94pH20.66, υ0(Bz)=kBzpCH-0.94pH20.65 and υ0(MCP)=kMCPpCH-0.85pH20.49
    (2) Initial rate equations for individual reaction are indicated as follows,
    υ0(T)=kTK(CH•)pCH/pH21/2/[1+K(CH•)pCH/pH21/2]2, υ0(Bz)=kBzK(CH•)pCH/pH21/2/[1+K(CH•)pCH/pH21/2]2 and υ0(MCP)=kMCPK(CH•)pCH/pH21/2/[1+K(CH•)pCH/pH21/2]2
    These are derived from the rate controlling step; [(CH•)ads. on Pt-site_??_(CH:)ads. on Pt-site+(H•)ads. on Pt-site]. And these Langmuir-Hinshelwood type-initial rate equations satisfied the experimental data.
    (3) Activation energies (Ekcal/mol) and heat of adsorption [Q(CH•)kcal/mol] of cyclohexyl radical on Pt-site from the examination of initial rate equations are obtained.
    E(T)=18.2, E(Bz)=17.9, E(MCP)=19.6 and Q(CH•)=2.5-2.8
    (4) Reaction mechanism of reforming reaction of cyclohexane over Pt/Al2O3/Cl type petroleum reforming catalyst is assumed to be as follows.
  • 1,2,4-トリメチルベンゼンとフォルムアルデヒドとの縮合反応
    河合 是, 山崎 康男
    1973 年 16 巻 6 号 p. 484-489
    発行日: 1973/06/01
    公開日: 2009/01/30
    ジャーナル フリー
    By the condensation of 1, 2, 4-trimethylbenzene (1, 2, 4-TMB) with formaldehyde bis (trimethylphenyl) methanes (BTMPM) are obtained. The condensation reaction in liquid phase was studied with various catalysts.
    Results were summarized as follows.
    1) p-Toluene sulfonic acid catalyst was more active than formic acid catalyst. But p-toluene sulfonic acid acted also as reactant, and formed a sulfonic acid ester. The molecular weight of condensate obtained by p-toluene sulfonic acid catalyst was somewhat higher than the molecular weight of BTMPM. On the other hand, formic acid catalyst didn't accompany such an undesirable side reaction, and the molecular weight of condensate corresponded to that of BTMPM. So formic acid was more suitable catalyst than p-toluene sulfonic acid. The optimum conditions using formic acid catalyst were; molar ratio (HCOOH: 1, 2, 4-TMB: HCHO)=6-8:4-6:1, reaction temp. 100°C, and reaction time 1-2hr. Results obtained under the above conditions were 95-100% conversion (based on formaldehyde used) and 95% selectivity.
    2) Among solid catalysts studied phosphotungstic acid-silica gel, silicotungstic acid-silica gel and Amberlyst 15 were active for the condensation reaction.
    3) Gas chromatogram of the condensate comprised mainly two isomeric fractions, and the ratio of these fractions didn't vary so much by reaction conditions.
    4) The order of reactivity of C9 aromatics with formaldehyde was 1, 3, 5-TMB»1, 2, 3-TMB>1, 2, 4-TMB»m-ethyltoluene (m-ET)>o-ET>p-ET. Therefore, for the production of high purity 1, 2, 4, 5-tetramethylbenzene the presence of 1, 3, 5-TMB and 1, 2, 3-TMB is unfavourable.
  • 1,2,4-トリメチルベンゼンとフォルムアルデヒドとの縮合反応生成物の接触水素化分解
    河合 是, 山崎 康男, 佐野 章
    1973 年 16 巻 6 号 p. 490-494
    発行日: 1973/06/01
    公開日: 2009/01/30
    ジャーナル フリー
    The catalytic hydrocracking of bis (trimethylphenyl)-methane (BTMPM), condensation products of 1, 2, 4-trimethylbenzene (1, 2, 4-TMB) with formaldehyde, was studied with a fixed bed type reactor under atmospheric pressure. The CoO-MoO3-Al2O3 catalyst pretreated with hydrogen or hydrogen and hydrogen sulfide mixture was used. Benzene solution of recrystallized BTMPM was used as the feed. Reaction conditions covered the ranges of temperature from 340 to 500°C, molar ratio (H2/H. C.) from 1.5 to 8.5 and LHSV from 2 to 5hr-1. Results were summarised as follows.
    1) The hydrocracking of BTMPM occurred at a relatively low temperature such as 340°C, and the conversion was 100% under the above operating variables. The selectivity of tetramethylbenzenes (TeMB) was 92-95%, and the purity of 1, 2, 4, 5-TeMB in TeMB was 98%, while the selectivity of TMB was 105%. This fact suggested that hydrodemethylation of BTMPM and/or TeMB occurred slightly. The isomerization of 1, 2, 4, 5-TeMB was negligible under the above conditions.
    2) The activity change with the reaction time of the catalyst pretreated with hydrogen was relatively small. The deactivated catalyst was regenerated by calcination at 430-550°C in the presence of air, and following treatment with hydrogen.
    3) It was estimated that the crude condensation products of 1, 2, 4-TMB with formaldehyde are composed of 2, 4, 5, 2', 4', 5'-, 2, 3, 6, 2', 4', 5'- and 2, 3, 5, 2', 4', 5'-hexamethyldiphenylmethane.
    In the catalytic hydrocracking of unsymmetrical diarylmethane, two different sites of carbon-carbon cleavage are possible. It was estimated that these two cleavage don't proceed with equal probability, but one cleavage occurs in preference to another.
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