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Volume 41, Issue 6
Displaying 1-14 of 14 articles from this issue
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Jun KATO1983 Volume 41 Issue 6 Pages 479-484
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSIn Japan, the petrochemical industry has grown up and enlarged its production capacity by using mostly naphtha. Petroleum, however, has been tight in supply in quantity, so the petrochemical industry has the necessity of promptly developing other feed stock than oil.
The japanese government adopted the research and development of C1 Chemical Technology as one of the National Research and Development Program (commonly known as the Large-scale Project System).
The development of C1 Chemical Technology requires research over long period of time and large amount of money with high risks, so it is necessary for the government to take the initiative because japanese chemical companies are much smaller compared to the leading chemical companies in Europe and the U.S.A..
Under the circumstances, 14 major chemical companies and a research center organized the Research Association for C1 Chemical Technology to proceed the project systematically and effectively.
The project consists of the following three themes, 1. A new technology for synthesis of the basic chemical such as ethylene glycol, ethanol, acetic acid and olefins from the synthesis gas. 2. Technology of gas-separation and purification based on membrane method. 3. Survey and selection of gasification technologies.View full abstractDownload PDF (889K) -
Ryohei ODA1983 Volume 41 Issue 6 Pages 485-491
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSIn this article the author emphasizes the importance of the C1-chemistry, especially of the carbonmonoxide chemistry. Recently many kinds of substituted benzene derivatives and also N-containing heterocyclic compounds have been successfully synthesized starting from carbonmonoxide instead from petroleum benzene. Several fundamental examples in relation to the above mentioned description are explained in the article.View full abstractDownload PDF (628K) -
Makoto KOMIYAMA, Hidefumi HIRAI1983 Volume 41 Issue 6 Pages 492-497
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSRecent progresses in the methods of the separation of carbon monoxide from gas mixtures and those in the methods of purification of carbon monoxide are reviewed. Almost all of the methods take advantage of liquid absorbents or solid adsorbents, which absorb or adsorb carbon monoxide at ambient temperature, 1 atm (or higher), and release carbon monoxide at elevated temperatures or at reduced pressures. Important progresses are divided mainly into two categories :
1) preparations of liquid absorbents, which show highly selective separations and purifications under mild conditions, and in addition are stable against reactive components in gas mixtures such as hydrogen sulfide and water, and 2) preparations of solid adsorbents, which separate and purify carbon monoxide without contamination of any solvent vapors and furthermore are easily applicable to practical purposes.
Advantages and disadvantages of these absorbents or adsorbents As well as their preparations are described.View full abstractDownload PDF (965K) -
Shuichi NAITO1983 Volume 41 Issue 6 Pages 498-506
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe hydrogenation of carbon monoxide has been studied by many workers and various kinds of mechanisms and intermediates have been proposed. The characteristic feature of this reaction is that it produces various products such as methane, hydrocarbons, methanol, and various oxygen containing compounds. In this review, the mechanism of this complicated reaction and the nature of the active sites, which control the selectivity of this reaction will be discussed in depth.View full abstractDownload PDF (1107K) -
Noboru SONODA, Shinji MURAI1983 Volume 41 Issue 6 Pages 507-514
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe reactions of carbon monoxide are classified on the basis of its reaction types which include i) reduction ii) carbonylation, a) reaction with anions b) reaction with free radicals c) reaction with cations or. Lewis acids, and d) transition metal catalyzed reaction. For each class of reactions, recent advances in the use of carbon monoxide in organic synthesis have been reviewed.View full abstractDownload PDF (740K) -
Takeru ONODA, Keisuke WADA1983 Volume 41 Issue 6 Pages 515-523
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe growing scope of homogeneous metal catalyst in C1 chemistry is briefly reviewed. The matal catalyzed C1 reactions, important from industrical point of views, are classified, first, into several groups, in words of the starting material or the reaction pattern. Then, the relationships, between the elemental reaction path and the characteristic feature of the metal center, are discussed. Finally, some comments are added for application of the homogeneous catalyst to the actual commercial plant.View full abstractDownload PDF (1119K) -
Yoshio ONO1983 Volume 41 Issue 6 Pages 524-531
Published: June 01, 1983
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSSince discovery of MTG process (methanol to gasoline process) by Mobil, the conversion of methanol into hydrocarbons received great attention. The features of the process is briefly described. The catalyst which made this process possible is a new class of zeolites, ZSM-5. The acidic property and the unique pore structure of ZSM-5 is described in connection with the conversion of methanol. The prevailing mechanisms of hydrocarbon formation, especially the mechanism of the first carbon-carbon bond are discussed. The lower-olefins instead of gasolines can be main products over ZSM-5 modified with some additives or smaller pore zeolites like erionite. The recent efforts to produce hydrocarbons directly from syn-gas are described. The catalytic reactions involving other C1 molecules like HCHO over zeolites are also mentioned.View full abstractDownload PDF (1025K) -
Kaoru FUJIMOTO1983 Volume 41 Issue 6 Pages 532-544
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSSynthesis of Liquid Hydrocarbons from Synthesis gas which has been largely commerciallized for producing morter fuels from coal are described on their present status and future prospect. Carbon number distribution of product hydrocarbon from Fischer-Tropsch (F-T) synthesis on iron, cobalt and ruthenium catalysts have been shown to follow well the Schulz-Flory law which is derived from the assumption that the chain propagation probability is independent of carbon number. The probability of chain propagation is well controlled by regulating potassium content in the catalyst (for iron) or by regulating the size of metal particles (for ruthenium). Hydrocarbons from F-T synthesis are rich in normal paraffins and olefins while those from methanol conversion on zeolite are composed of iso-paraffins and aromatics. Slurry phase F-T process is suggested to be the most promising as the indirect coal liquefaction process for next generation. It is pointed out from the chemical structure of product hydrocarbon that F-T process is suitable for producing kerosene and diesel fuel whereas the direct coal hydrogenation is favored for producing gasoline base oil.View full abstractDownload PDF (1556K) -
Goshichi NAWATA, Haruhiko MIYAZAKI1983 Volume 41 Issue 6 Pages 545-552
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSVarious routes of ethylene glycol synthesis from one-carbon raw materials are reviewed. Recent advances and interesting developments in the direct synthesis from synthesis gas, the two-step process comprising oxidative coupling of CO to oxalates followed by hydrogenation, formaldehydebased routes via glycolic acid esters, hydroformylation of formaldehyde, reaction of methanol with formaldehyde and methanol coupling reactions are summarized.View full abstractDownload PDF (1039K) -
Akisuke SHIGAKI1983 Volume 41 Issue 6 Pages 553-560
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSAcetic acid, an important chemical intermediate, is produced commercially by one of three routes, acetaldehyde oxidation, liquid-phase hydrocarbon oxidation, and methanol carbonylation. Among them, the low pressure carbonylation of methanol, developed by Monsanto Co., has been highly appreciated in view of bright success of C1 chemistry. The history of acetic acid industry is reviewed, and the progress of acetic acid manufacturing technology is discussed.View full abstractDownload PDF (950K) -
Yoshie SOUMA1983 Volume 41 Issue 6 Pages 561-569
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSRhodium compounds are an excellent catalyst in the synthesis of acetic acid, ethanol and ethyleneglycol from synthesis gas. As the amount of rhodium is not enough, research of other catalysts is necessary.
The synthesis of ethylene glycol via glycolic acid was studied. The synthesis of glycolic acid was improved by using copper or silver carbonyl co-catalyst. Carbonylation of formaldehyde proceeded at atmospheric pressure of CO at 20 °C without side reactions by using copper or silver catalyst in H2SO4, BF3-H2O, and HF. Rate constants of carbonylation increased 30 times in the presence of co-catalyst. The rate decreased with the decrease of acid concentration. Ethyleneglycol was obtained by a hydrogenation of glycolic acid using Co-Cu, Co-Cr, Co-Zn-Cu, or RuO2 catalyst.
Copper and silver carbonyl catalysts were applied to the carbonylation of olefins, alcohols, and saturated hydrocarbons at atmospheric pressure of CO and room temperature. Tertiary-carboxylic acids were obtained in high yields.View full abstractDownload PDF (940K) -
Tamechika YAMAMOTO1983 Volume 41 Issue 6 Pages 570-576
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSFuel methanol made of natural gas or coal in large scale under adequate conditions can be substitute of petroleum products. In Japan now the fuel methanol is mainly considered as the fuel of internal combustion engines, however, the most profitable use of fuel methanol is the raw materials of petrochemicals industry. Ethylene and propylene can be made from by far higher yield than that from naphtha under mild conditions. Gasoline from methanol by MTB process contains about 30% of aromatic hydrocarbons. Against hydrocarbon steam reforming to make hydrogen carried out at 800-900°C, methanol can be steam reformed at 250300°C with more simple installation.
If the cost of calorific value of fuel methanol and petroleum products are same, the use of methanol as raw material is profitable far away than use of petroleum naphtha in Japan.View full abstractDownload PDF (903K) -
Yoshihiro SUGI1983 Volume 41 Issue 6 Pages 577-587
Published: June 01, 1983
Released on J-STAGE: November 13, 2009
JOURNAL FREE ACCESSThe recent advances in the homologation of methanol have been reviewed. The effects of iodine, phosphines, and co-catalysts on the cobalt catalyzed reaction are discussed. Methanol activation is enhanced by the addition of iodine through the formation of methyl iodide. Phosphine modification improves the selectivity of ethanol. The synergy is observed between cobalt and co-catalysts, such as ruthenium and iron. The addition of these co-catalysts improves the rate and the selectivity of ethanol. Transition metal complexes of iron, rhodium, ruthenium, and manganese catalyze the homologation of methanol in methanol amine solution. Carbon dioxide is produced as the oxygenated by-product in the place of water. The synergy between iron and manganese carbonyls enhances the rate and the selectivity of ethanol. The mechanistic aspects are also discussed.View full abstractDownload PDF (1463K) -
Masafumi GOTO, Tomoya SAKAI1983 Volume 41 Issue 6 Pages 588-594
Published: June 01, 1983
Released on J-STAGE: January 22, 2010
JOURNAL FREE ACCESSA brief review was given for mechanisms of the formose formation, followed by a survey for industrial utilization of formose. Recent progresses in improvement of selectivity of the reaction toward the production of branched-chain sugars and sugar alcohols, glucose, and C2 to C3 compounds were described.View full abstractDownload PDF (943K)
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