US3719719A - Selective hydrogenation of polycyclic aromatic hydrocarbons using as catalyst a sulfide of a platinum group metal - Google Patents

Selective hydrogenation of polycyclic aromatic hydrocarbons using as catalyst a sulfide of a platinum group metal Download PDF

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Publication number
US3719719A
US3719719A US00098165A US3719719DA US3719719A US 3719719 A US3719719 A US 3719719A US 00098165 A US00098165 A US 00098165A US 3719719D A US3719719D A US 3719719DA US 3719719 A US3719719 A US 3719719A
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United States
Prior art keywords
polycyclic aromatic
aromatic hydrocarbon
catalyst
sulfide
hydrogen
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Expired - Lifetime
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US00098165A
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English (en)
Inventor
R Amidon
H Greenfield
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Uniroyal Chemical Co Inc
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Uniroyal Inc
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Assigned to UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY reassignment UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTERS, MIDDLEBURY, CT. 06749, A CORP. OF NEW JERSEY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NEW YORK CORP.
Assigned to UNIROYAL CHEMICAL COMPANY, INC. reassignment UNIROYAL CHEMICAL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNIROYAL, INC., A NJ CORP.
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/20—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 hydrogenated in the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/04—Sulfides
    • C07C2527/043—Sulfides with iron group metals or platinum group metals
    • C07C2527/045—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/20—Acenaphthenes; Hydrogenated acenaphthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes

Definitions

  • ABSTRACT PP -I 8,165 Polycyclic aromatic hydrocarbons are selectively hydrogenated using a sulfide of a platinum group 521 U.S. c1 ..260/667, 208/143 metal as a cawlyst- For p naphthalene is p 51 Int. Cl ..C07c 5/10 tially reduced to tetralin y hydrogenation in the [53] presence of platinum sulfide.
  • the present invention is based on the discovery that the sulfides of the platinum group metals are excellent catalysts for hydrogenation of polycyclic aromatic hydrocarbons.
  • Any platinum group metal sulfides may be employed in the invention, i.e., the sulfides of palladium, osmium, iridium, rhodium and ruthenium, as well as the sulfide of platinum.
  • the preferred catalyst is platinum sulfide, PtS,, on the basis of activity, selectivity and stability.
  • the method of the invention is applicable to polycyclic aromatic hydrocarbons in general, whether linear or non-linear, includingby way of nonlimiting example such polycyclic aromatic hydrocarbons as naphthalene, anthracene, indene, acenaphthylene, coumarin, phenanthrene, pyrene, chrysene, perylene, fluoranthene, etc.
  • polycyclic aromatic hydrocarbons as naphthalene, anthracene, indene, acenaphthylene, coumarin, phenanthrene, pyrene, chrysene, perylene, fluoranthene, etc.
  • substituted forms such as substituted naphthalenes, e.g., l-methylnaphthalene, 2-methylnaphthalene, other lor 2- alkyl substituted naphthalenes where the alkyl group may be ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, etc., dialkyl substituted naphthalenes, e.g., 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,S-dimethylnaphthalene, etc., and higher substituted alkyl naphthalenes containing up to 8 alkyl groups; similarly substituted naphthalenes where the substituent may be a halogen, alkoxy, aryloxy, carboxy, carboalkoxy, or similar grouping that is unreactive under the
  • the invention is practiced by contacting the poly A cyclic aromatic hydrocarbon with hydrogen and the catalyst.
  • the catalyst is supported or deposited in conventional manner on a solid carrier substance, such as carbon, alumina, silica, clay,-or other usual supports or refractory substances (see, for example, U.S. Pat. No. 3,285,984, col. 2, lines 23-42).
  • the process may be carried out batchwise, for example in an autoclave, or in a continuous-system using either tank or pipe-line reactors.
  • the hydrogenation may be effected in the liquid phase using a slurry of catalyst or a fixed catalyst bed.
  • the invention may be practiced in the vapor phase with either fluidized or fixed bed catalysts.
  • an appropriate inert solvent such as for example a hydrocarbon, whether aliphatic as in such alkanes as n-hexane, n-octane, etc., cycloalipatic as in such cycloalkanes as cyclohexane, etc., or aromatic as in benzene, toluene, etc.
  • an appropriate inert solvent such as for example a hydrocarbon, whether aliphatic as in such alkanes as n-hexane, n-octane, etc., cycloalipatic as in such cycloalkanes as cyclohexane, etc., or aromatic as in benzene, toluene, etc.
  • halogenated hydrocarbons as dichlorobenzene, etc.
  • an alcohol such as the alkanols (e.g., methanol, ethanol, 2-propanol, etc.), ethers, such as diethyether, dibutyl ether, dioxane, glycol diethers, etc; esters, such as ethyl acetate, butyl acetate, l-ethylhexyl acetate", etc, or any other suitable conventional solvent.
  • the process of this invention has the great advantage that no sulfur or sulfur-containing compound need be added to the hydrocarbon feed.
  • the present catalysts are remarkably poison resistant and make possible the efficient use of feeds containing sulfur and other poisons that render impractical the use of conventional metal and metallic oxide hydrogenation catalysts.
  • platinum group metal sulfides employed as catalysts often effect completeor almost complete selective formation of a single desired product even at complete conversion of the starting-material.
  • the autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen added to a pressure of 1300 psig.
  • the vessel was heated with agitation for 4 hours at 165C. and 1550-1600 psig.
  • the autoclave was cooled and depressurized, and the reaction produce removed.
  • 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 evaporation on a steam bath.
  • the residue consisted of 34 grams of a solid from which dihydroanthracene melting at l04-l08C. (lit. value, 108.5C.) was obtained by recrystallization from 2- propanol.
  • Example 4 Reduction of acenaphthylene acenaphthene A mixture of 85.2 grams (0.56 mole) of acenaphthylene, 200 ml. of toluene, and 6.0 grams of 5 percent platinum sulfide on carbon was added to a 600- ml. Magne Dash autoclave. The autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen added to a pressure of 1200 psig. The vessel was heated with agitation at l00l40C.
  • Example 5 Reduction of coumarin to dihydrocoumarin A mixture of 43.8 grams (0.30 mole) of coumarin, ml. of benzene, and 3.3 grams of 5 percent platinum sulfide on carbon was added to a 265-ml. Magne Dash autoclave. The autoclave was sealed, purged with nitrogen and then hydrogen, and hydrogen added to a pressure of 700 psig. The vessel was heated with agitation for 5.5 hours at C. and 600-900 psig. The hydrogen absorption was about 0.3 mole (100 percent of theory). The autoclave was cooled and depressurized, and the reaction product removed. 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 shown by glpc to be identical with an authentic sample of dihydrocoumarin.
  • a method of selectively hydrogenating a polycyclic aromatic hydrocarbon comprising contacting said polycyclic hydrocarbon with hydrogen in the presence of a catalyst consisting of platinum sulfide.
  • a method of selectively partially hydrogenating a polycyclic aromatic hydrocarbon comprising contacting said polycyclic aromatic hydrocarbon with hydrogen in the presence of a catalyst consisting of platinum sulfide, the said polycyclic aromatic hydrocarbon being selected from the group consisting of naphthalene, anthracene, indene, acenaphthalene, and coumarin, to produce a partially hydrogenated product selected from the group consisting of,'respectively, tetralin, 9,10-dihyroanthracene, indane, acenaphthene and dihydrocoumarin.
  • a method as in claim 2 carried out at a hydrogen pressure of 500 to 5000 psig.
  • a method as in claim 2 carried out at a temperature of 80 to 300C.
  • a method as in claim 2 in which said polycyclic aromatic hydrocarbon is agitated in an inert solvent in the presence of hydrogen under pressure and the said catalyst is deposited on a carrier.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00098165A 1970-12-14 1970-12-14 Selective hydrogenation of polycyclic aromatic hydrocarbons using as catalyst a sulfide of a platinum group metal Expired - Lifetime US3719719A (en)

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US9816570A 1970-12-14 1970-12-14

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US (1) US3719719A (enExample)
BE (1) BE775795A (enExample)
CA (1) CA956328A (enExample)
DE (1) DE2161847A1 (enExample)
FR (1) FR2118468A5 (enExample)
GB (1) GB1374433A (enExample)
IT (1) IT942946B (enExample)
NL (1) NL7115238A (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640764A (en) * 1986-02-24 1987-02-03 Shell Oil Company Selective tricyclic hydrogenation and cracking process and catalyst suitable for such hydroconversion
US4950386A (en) * 1988-08-15 1990-08-21 Exxon Research And Engineering Company Acidic promotion of transition metal sulfide catalysts for selective hydrogenation
US20050234275A1 (en) * 2004-04-16 2005-10-20 Shifang Luo Reduction of naphthalene concentration in aromatic fluids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125817B (en) * 1982-08-23 1987-04-29 British Gas Corp Production of partially saturated polycyclic hydrocarbons and methane rich gas

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640764A (en) * 1986-02-24 1987-02-03 Shell Oil Company Selective tricyclic hydrogenation and cracking process and catalyst suitable for such hydroconversion
US4950386A (en) * 1988-08-15 1990-08-21 Exxon Research And Engineering Company Acidic promotion of transition metal sulfide catalysts for selective hydrogenation
US20050234275A1 (en) * 2004-04-16 2005-10-20 Shifang Luo Reduction of naphthalene concentration in aromatic fluids

Also Published As

Publication number Publication date
BE775795A (fr) 1972-05-25
FR2118468A5 (enExample) 1972-07-28
NL7115238A (enExample) 1972-06-16
GB1374433A (en) 1974-11-20
DE2161847A1 (de) 1972-06-29
CA956328A (en) 1974-10-15
IT942946B (it) 1973-04-02

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Owner name: UNIROYAL CHEMICAL COMPANY, INC., WORLD HEADQUARTER

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNIROYAL, INC., A NEW YORK CORP.;REEL/FRAME:004488/0204

Effective date: 19851027

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE DATE OCTOBER 27, 1985.;ASSIGNOR:UNIROYAL, INC., A NJ CORP.;REEL/FRAME:004754/0186

Effective date: 19870130