PL20137B1 - A method of reducing phenols. - Google Patents

A method of reducing phenols. Download PDF

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Publication number
PL20137B1
PL20137B1 PL20137A PL2013730A PL20137B1 PL 20137 B1 PL20137 B1 PL 20137B1 PL 20137 A PL20137 A PL 20137A PL 2013730 A PL2013730 A PL 2013730A PL 20137 B1 PL20137 B1 PL 20137B1
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PL
Poland
Prior art keywords
phenols
pressure
hydrogenation
products
reducing phenols
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Application number
PL20137A
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Polish (pl)
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Publication date
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Publication of PL20137B1 publication Critical patent/PL20137B1/en

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W znanych dotychczas sposobach roz¬ szczepiajacego uwodorniania zwiazków or¬ ganicznych pod cisnieniem, np. w sposobie Bergius'a, fenole nie ulegaja naruszeniu, podczas gdy przy katalitycznem uwodornia¬ niu zapomoca katalizatorów, np. miklu lub tlenku niklowego, bez cisnienia (wedlug Sabatier'a) lub pod cisnieniem podwyzszo- nem (wedlug Ipatiewa) powstaja zwiazki cyklohelksanolu, uwodornione w rdzeniu, lecz zawierajace jeszcze tlem.Stwierdzono obecnie, iz czysty fenol, jak równiez wyzsze homologi z frakcyj smolowych uwodorniaja sie latwo zarówno w rdzeniu, jak i w grupie hydroksylowej, tworzac zwiazki typu cykloparafin, które w przypadku fenoli homologicznych stoja bli¬ sko weglowodorów terpenowych, o ile cia¬ la te traktowac wodorem in statti nascen- di, powstajacym z wody przy dzialaniu drobnosproszkowanych metali podczas roz¬ szczepiania pod cisnieniem.Wedlug niniejszego wynalazku ogrzewa sie fenole wzglednie ciala, zawierajace fe¬ nol, razem z drobnosproszkowanym meta¬ lem i woda w naczyniu, wytrzymujacem ci¬ snienie, do temperatury 350° do 500°C, przyczem zaleznie od stopnia napelnienia wytwarza sie cisnienie, które winno wyno¬ sic co najmniej 150 atm.Zwlaszcza przy uzyciu czystego fenolu wystepuja reakcje poboczne, prowadzacedo produktów kondensacji. Produkty kon¬ densacji, wrzace powyzej 360°, posiadaja duza lepkosc i daja cenine smary. Powsta¬ ja przytem znaczne ilosci weglowodorów gazowych. Stwierdzono, ze tych reakcyj pobocznych mozna uniknac, mieszajac fe¬ nol z innemi olejami, najkorzystniej takie- mi, jakie same daja sie uwodorniac albo powstaja przy uwodornianiu, np. z olejami smolowemi albo produktami ich uwodor¬ niania. W ten sposób produkty kreozotowe, które powstaja w sposób, opisany w pa¬ tencie Nr 18176, np. z wegla brunatnego lub smoly generatorowej wegla brunatnego, mozna przetworzyc calkowicie w zabiegu nastepnym w nierozpuszczalne w alkaljach oleje obojetne, przyczem powstaja pro- cfukty uwodornienia w ilosci, odpowiadaja¬ cej zwiazkom, zawierajacym tlen.Otrzymane produkty, uwodornione w rdzeniu, mozna przetworzyc w drodze od- wodorniania zapomoca katalizatorów, np. niklu, w weglowodory aromatyczne.Ponizszy przyklad wykonania wyjasnia blizej wynalazek.Do autoklawu o pojemnosci 5 1, zaopa¬ trzonego w mieszadlo, wprowadza sie mie¬ szanine 1,5 kg krezolu, 900 g drobnospro- szkowanego zelaza i okolo 300 g wody i przez pewien czas ogrzewa w temperaturze 450° -=- 470°. Po ochlodzeniu naczynia 30 -z- 4o% jego zawartosci stanowia we¬ glowodory, wrzace do 180°, posiadajace w przyblizeniu ciezar wlasciwy 0,8, spólczyn- nik zalamania n^ ca. 1,45.Frakcje, wrzace powyzej 180°, zawie¬ raja oprócz niezmienionych krezolów 10 -~- 20% weglowodorów obojetnych, wrzacych ponizej 360°. PL PL PL PL PL PL PL PL PL PLIn the previously known methods of splitting hydrogenation of organic compounds under pressure, e.g. in the Bergius method, phenols are not damaged, whereas in catalytic hydrogenation with catalysts, e.g. nickel or nickel oxide, without pressure (according to Sabatier) or at increased pressure (according to Ipatiev), cyclohexanol compounds are formed, hydrogenated in the core, but still containing oxygen. It has now been found that pure phenol, as well as higher homologues from tar fractions, are easily hydrogenated both in the core and in the hydroxyl group, forming cycloparaffin-type compounds, which in the case of homologues phenols are close to terpene hydrocarbons, provided that the body These can be treated with nascent hydrogen, which is formed from water by the action of finely powdered metals during pressure cleavage. According to the present invention, phenols or phenol-containing bodies are heated together with finely powdered metal and water in a pressure-resistant vessel to a temperature of 350° to 500°C, whereby, depending on the filling level, a pressure of at least 150 atm is generated. Especially when pure phenol is used, side reactions occur, leading to condensation products. Condensation products boiling above 360°C are highly viscous and provide valuable lubricants. This produces significant amounts of gaseous hydrocarbons. It has been found that these side reactions can be avoided by mixing phenol with other oils, preferably those that are themselves hydrogenable or are formed during hydrogenation, e.g. tar oils or their hydrogenation products. In this way, creosote products, which are produced in the manner described in patent No. 18176, e.g. from brown coal or brown coal generator tar, can be completely converted in a subsequent step into alkali-insoluble neutral oils, whereby hydrogenation products are produced in an amount corresponding to oxygen-containing compounds. The obtained products, hydrogenated in the core, can be converted into aromatic hydrocarbons by dehydrogenation using catalysts, e.g. nickel. The following example of implementation explains the invention in more detail. A mixture of 1.5 kg of cresol, 900 g of finely powdered iron and approx. 300 g of water and heated for some time at 450° -=- 470°. After cooling the vessel, 30 -z- 40% of its contents consist of hydrocarbons boiling up to 180°, having approximately a specific gravity of 0.8, and a refractive index of approximately 1.45. The fractions boiling above 180° contain, in addition to unchanged cresols, 10 -~- 20% of neutral hydrocarbons boiling below 360°. PL PL PL PL PL PL PL PL PL PL PL

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PL20137A 1930-02-13 A method of reducing phenols. PL20137B1 (en)

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Publication Number Publication Date
PL20137B1 true PL20137B1 (en) 1934-06-30

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