DE2161847A1 - Process for hydrogenating polycyclic aromatic hydrocarbons - Google Patents

Description

DR. Γ: <Case F.-4515

DIPL-Γ. . ..... -iULLER

I MijNf.nl.;, 80
Gi-aiiii-S'ra.-e 38

TJniroyal, Inc., 123C Avenue of the Americas, New York,

New York 1OC2C (V.St.A.)

Process for hydrogenating polycyclic aromatic hydrocarbons

The invention "is based on the finding that sulfides the platinum group metals excellent catalysts for the hydrogenation of polycyclic aromatic hydrocarbons represent. Any platinum group metal sulfide can be used in accordance with the invention; i.e., the sulfides of palladium, osmium, iridium, rhodium and ruthenium as well as platinum sulfide. The preferred catalyst is Platinum sulfide, PtS ^, for its activity, selectivity, and stability. The inventive method is on polycyclic ^ aromatic hydrocarbons in general, whether linear or non-linear, including not limiting examples of such polycyclic aromatic hydrocarbons as e.g. B. naphthalene, anthracene, Indene, acenaphthylene, coumarin, phenanthrene, pyrene, Chrysene, perylene, fluoranthene, etc. applicable. Included in the aforementioned compounds as equivalents are the substituted forms, e.g. B. substituted

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Naphthalenes, for example 1-methylnaphthalene, 2-methylnaphthalene, other 1- or 2-alkyl-substituted naphthalenes, where the alkyl group is ethyl, propyl, butyl, pentyl, hexyl, Can be cyclohexyl, etc., dialkyl-substituted naphthalenes, for example 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, etc. and higher substituted alkylnaphthalenes with up to 8 alkyl groups equally substituted naphthalenes, in which the substituent is halogen, alkoxy, aryloxy, carboxy, May be carbalkoxy or a similar group that is non-reactive under the reaction conditions, including Combinations of such groups. Likewise, any of the other polynuclear hydrocarbons listed can be variously substituted by one or more and by any combination of inactive groups be.

The invention is made practical by contacting carried out of the polycyclic aromatic hydrocarbon with hydrogen and the catalyst. I'm best To achieve results, the catalyst is conventionally supported on a solid support or deposited, such as carbon, alumina, silica, clay or other common carriers or i & uerfeste _ substances (such as after American patent specification 3,285,984-, column 2, Lines 23-42).

The process can be carried out in batches, for example in one Autoclaves, or in a continuous system using either container or tubular

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Reactors are carried out. The hydrogenation can be carried out in the liquid phase using a catalyst slurry or a fixed bed of catalyst. On the other hand, the invention in the Vapor phase can be practiced with either fluidized or fixed bed catalysts.

In liquid phase hydrogenation it is usually convenient to have a suitable inert solvent present, such as a hydrocarbon, whether aliphatic such as alkanes,. For example, η-hexane, n-octane, etc., cycloaliphatic such as cycloalkanes, such as cyclohexane, etc., or aromatic, such as j benzene, toluene, etc., or other

such as halogenated hydrocarbons such as dichlorobenzene, etc., or an alcohol such as Alkanols (e.g. methanol, ethanol, 2-propanol, etc.), ethers such as diethyl ether, dibutyl ether, Dioxane, glycol diether, etc .; Esters such as ethyl acetate, butyl acetate, 2-ethylhexyl acetate, etc. or any other suitable conventional solvent.

Stirring, elevated temperatures and pressure increase the rate of hydrogenation. Varies in each particular case the economic optimization of the temperature, the pressure, the catalyst content, the feed concentration and the time for one cycle and can be determined in a conventional manner. Compared to the state of the art, as for example the American patent specification 3,285,984- it represents a remarkable advance of the invention that extremely high operating temperatures are not usually required. Temperatures

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are in the range of 80 to 300 ° C and hydrogen pressures are in the range of 35 to 350 at (500 to 5000 psig) usually satisfactory, but other temperatures and pressures can be used.

The process according to the invention has the great advantage that no sulfur or no sulfur-containing compound must be added to the hydrocarbon feed. The catalysts of the invention are noteworthy resistant to poisons and allow the effective use of sulfur and other poisons containing Feeds that make the use of conventional metal and metal oxide hydrogenation catalysts impossible do.

It is an important advantage of the invention that the platinum group metal sulfides used as catalysts often the completely or almost completely selective formation of a single desired product, even if completely Effect implementation of the starting material.

The following examples serve to further illustrate the invention.

example 1

Reduction of naphthalene to tetralin

A mixture of 125 6 (0.975 mol) naphthalene, 200 ml toluene and 6.0 g of 5% platinum sulfide on carbon was poured into a 600 ml Magne-Dash autoclave. The autoclave was sealed, with nitrogen and then with hydrogen flushed, then hydrogen up to a pressure of 70 at (1000 psig). The container was stirring

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Heated for 17.5 hours at 275 Ms, 280 ⁰ O and 98 to 120 atm (1400-1700 psig). The autoclave was cooled and the pressure released and the reaction product discharged. The reaction mixture was filtered through diatomaceous earth to remove the catalyst. After the solvent had been distilled off from the piltrate, a liquid residue of 126 g remained. This residue was found to be 80% tetralin by infrared analysis and, according to analysis by gas chromatography, contained 81-6 tetralin and 19% naphthalene; decalin was not detectable.

Example 2

Reduction of anthracene to 9,1O-dihydroanthracene

A mixture of 35.6 g (0.20 mol) of anthracene, 220 ml of 2-propanol and 2.5 g of 5% platinum sulfide on carbon iS ^em was placed in a 600 ml Magne Dash autoclave. The autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen was introduced to a pressure of 91 atm (1300 psig). The container was heated with stirring at 165 ° G and 109-112 atm (1550 to 1600 psig) for 4 hours. The autoclave was cooled, the pressure released and the reaction product discharged. The reaction mixture was filtered through diatomaceous earth to remove the catalyst. The catalyst was washed with hot 2-propanol and the solvent was removed from the combined filtrate and washings by concentration on a steam bath. The residue consisted of 34 g of a solid from which dihydroanthracene with a melting point of 1 (W- to 108 ⁰ G (literature value 108.5 ° C.) was obtained by recrystallization from 2-propanol.

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Example 5

Reduction -fron indene to indan

A mixture of 65.1 g (0.56 mol) indene, 225 ml toluene and 6.0 g 5% platinum sulfide on carbon was placed in a 600 ml Magne-Dash autoclave. The autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen was introduced to a pressure of 84 atm (1200 psig). The container was heated with stirring at 120 ⁰ C and 84-98 at Temperature (1200 to 1400 psig) for one hour, whereupon the reaction after hydrogen absorption of about 0.55 moles (98% of theory) abruptly ceased. The autoclave was cooled, the pressure released and the reaction product discharged. The reaction mixture was filtered through diatomaceous earth to remove the catalyst. The solvent was concentrated from the filtrate on a rotary evaporator under reduced pressure. The liquid residue was found to be identical to an authentic sample of indan by gas chromatography and infrared spectroscopy.

Example 4

Reduction of acenaphthylene to acenaphthene

A mixture of 85.2 g (0.56 mol) of acenaphthylene, 200 ml of toluene and 6.0 g ^>% ± gem platinum sulfide on carbon was placed in a 600 ml Magne-Dash autoclave. The autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen was introduced to a pressure of 84 atm (1200 psig). The container was heated with stirring at 100 to 140 ° C and? 0 to 91 atm (1000 to 1300 psig) for 20 minutes, after which gas uptake ceased abruptly. The autoclave was cooled, the

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ORIGINAL INSPECTED

Released pressure and discharged the reaction product. The reaction mixture was used to remove the catalyst filtered through diatomaceous earth. The solvent was removed from the filtrate on a rotary evaporator evaporated under reduced pressure. The residue consisted of 82 g (95% yield) of a solid, which, according to gas chromatography, consisted of a single component, acenaphthene with an authentic sample was identical.

Example 5

Reduction of coumarin to dihydro coumarin

A mixture of 43.8 g (0.30 mole) of coumarin, 115 ml of benzene, and 3.3 g of 5% platinum sulfide on carbon was placed in a 265 Eil Magne-Dash autoclave. The autoclave was sealed, purged with nitrogen, then hydrogen, and hydrogen was introduced to a pressure of 49 atm (700 psig). The container was 5.5 hours with stirring at 190 ⁰ C and 42 to 63 at heated (600 to 900 psig). The hydrogen uptake was about 0.3 mol (100% of theory). The autoclave was cooled and the pressure was released, and the reaction product was discharged. The reaction mixture was filtered through diatomaceous earth to remove the catalyst. The solvent was evaporated from the filtrate on a steam bath. The residue was found to be identical to an authentic sample of dihydrocoumarin by gas chromatography.

8th -

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BATH ORIGINAL

Claims (1)

P at 6 η ⁴ :;.:. n s ρ ri; e. Ii s Procedure sum Hyäris :: '62i εΐ; ΐ ££ pclysyoiisciie ::! ax ^ matiaeiies. Hydrocarbons, characterized gekenas ei t Ii a s ΐ that the polycyclic "aromatic Hsliiiiiifasae ^ s ^ off with hydrogen in the presence sir.sF 3'la Fe3 Grupp ^ ^: ii"-; £ ^ ll ^: l... fid catalyst in contact ge1: rft ^ iit; "titr-l * Proceed according to Ansp ^ icii Λ-. -Iz ^ z-Qk. ^: - £ 3 κ :: ■ - ζ e lehnet, dr.S as Satal ^ atcr i ^ Ls.tia.suIl, i; ii · is used. 3, The method of claim 1, characterized geke ζ η η ~ eic it η et in that the polycyclic aromatic F.chlenwftsserstoff naphthalene, anthracene ₅ indene, acenaphthylene, Ciiaiarin, phenanthrene, pyrene, chrysene, perylene or Pluorantlien. % ^r is used. 4 ·, Yerfahren na el ·. Claim Ί, thereby g e k e η η - ■ records that a hydrogen pressure of 35 his 5§0 at (500 to 5000 psig) is used. 5. The method according to claim 1, characterized in that it is carried out at a temperature of 8C "to? 00 ⁰ G. 6 «The method according to claim 1, characterized geke η η 2 eic h η et that the polycyclic ^ aromatic dissolved in an inert solvent 2 0 9827/109 7. The method according to claim 1, characterized in that one on a solid support deposited catalyst is used. S. The method according to claim 7 »thereby draw g e k e η η t that coal is used as a carrier. 9. The method according to claim 1, characterized in that as a polycyclic aromatic Hydrocarbon naphthalene is used and this is hydrogenated to tetralin. 10. The method according to claim 1, characterized in that as a polycyclic aromatic Hydrocarbon anthracene is used and this is hydrogenated to 9j10-dihydroanthracene. 11. The method according to claim 1, characterized in that as a polycyclic aromatic Hydrocarbon indene is used and this is hydrogenated to indane. 12. The method according to claim 1, characterized in that as a polycyclic aromatic Hydrocarbon acenaphthylene is used and this is hydrogenated to acenaphthene. 13 · The method according to claim 1, characterized in that the polycyclic aromatic Hydrocarbon coumarin is used and this:, li I) ili7 / drocuiiiarin is hydrogenated. '«. fr: 'ahren for the selective hydrogenation of a polycyclic 209827/1093 BATH ORIGINAL - ίο - see aromatic hydrocarbon, characterized in that the hydrocarbon in an inert solvent in the presence of hydrogen under pressure and one platinum metal sulfide deposited on a support is stirred as a catalyst. 15. Method according to claim 14, characterized in that g e k e η η draws that as a polycyclic aromatic hydrocarbon naphthalene in the presence of platinum sulfide is hydrogenated as a catalyst to tetralin. 209827/1093