EP0000617B1 - Herstellung von substituiertem oder unsubstituiertem Inden. - Google Patents

Herstellung von substituiertem oder unsubstituiertem Inden. Download PDF

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Publication number
EP0000617B1
EP0000617B1 EP78300066A EP78300066A EP0000617B1 EP 0000617 B1 EP0000617 B1 EP 0000617B1 EP 78300066 A EP78300066 A EP 78300066A EP 78300066 A EP78300066 A EP 78300066A EP 0000617 B1 EP0000617 B1 EP 0000617B1
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Prior art keywords
indene
precursor
catalyst
alkyl
oxygen
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EP78300066A
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French (fr)
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EP0000617A1 (de
Inventor
Robert Karl Grasselli
Joseph Peter Bartek
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Standard Oil Co
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Standard Oil Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor

Definitions

  • the present invention relates to a novel catalytic technique for making unsubstituted and substituted indene.
  • the invention is concerned with the problem of making unsubstituted or substituted indene in a simple economic and straightforward manner.
  • suitable indene precursors may be converted to unsubstituted and substituted indene by a dehydrogenation process which involves contacting the indene precursors with a phosphate catalyst at elevated temperature in the presence of an oxygen donor.
  • the invention therefore provides a process for producing unsubstituted or substituted indene by the oxydehydrogenation of an unsubstituted bicyclic indene precursor or a bicyclic indene precursor substituted with C 1 to C4 alkyl, C 1 to C 4 alkenyl or phenyl group, said precursor being more saturated than indene, characterised in that the indene precursor is contacted with a phosphate catalyst in the presence of an oxygen donor at a temperature of at least 100°C.
  • the present invention is based on the observation that a wide variety of phosphate-containing inorganic compounds will catalyse the catalytic removal of hydrogen from indene precursors more saturated than indene in the presence of an oxygen donor so as to yield indene and substituted indene as a product.
  • unsubstituted indene and substituted indenes are produced from bicyclic and substituted bicyclic indene precursors more saturated than indene.
  • the substituted bicyclic compounds contain one or more alkyl or alkenyl groups having from 1 to 4 carbon atoms or phenyl groups attached to one or both rings.
  • the substituted indenes produced from these precursors normally have the corresponding alkyl, alkenyl or phenyl groups attached, although thay may have fewer groups, or may have groups with fewer carbon atoms attached.
  • precursors which may be converted into indene or substituted indenes in accordance with this invention include indane, alkyl indanes in which the alkyl groups have from 1 to 4 carbon atoms especially methyl indanes, tetrahydroindene (especially the bicyclo ⁇ 4.3.0 ⁇ nona-3,7-diene isomer), alkyl tetrahydroindenes in which the alkyl groups have from 1 to 4 carbon atoms, hexahydroindene, hexahydroindane and vinyl norbornene (5-vinyl bicyclo ⁇ 2.2.1 ⁇ -2-heptene).
  • the indene precursor which is discussed above is contacted in the presence of an oxygen donor with a catalyst comprising a phosphate, i.e. a salt of one of the phosphoric acids.
  • a catalyst comprising a phosphate, i.e. a salt of one of the phosphoric acids.
  • a phosphate i.e. a salt of one of the phosphoric acids.
  • Any type of phosphoric acid salt can be employed be it an orthophosphate, a hypophosphate, a metaphosphate, a pyrophosphate, or other polyphosphate.
  • any cation can be employed, and in addition different types of cations can be employed in a single phosphate.
  • an orthophosphate catalyst which can be used in accordance with the present invention can contain one, two or three different metals depending, of course, upon valence requirements, as well as hydrogen.
  • the other types of phosphates can contain one or more different metal cations as well as hydrogen.
  • Preferred catalysts for use in the process of the invention are those of the following formula: wherein M is one of more elements selected from Mg, Sr, Ca, Ba, La, Ce, other rare earths, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, Bi, Te, B, Al, Rh, Sb, As, U, Th, Ge and Ru; and
  • the catalysts employed in the inventive process are characterized by the following formula: wherein M is at least one of Bi, Fe, Ni, Co, Cr, La, Sn, Mg, Ca, Ce, U, Sb;
  • M' is at least one element selected from Ge, Pb, Mo, W, Sr, Ba, Re, Th, As, Te, and elements selected from groups IA, IB, IIB, IIIA and VB of the Periodic Table;
  • 0.1 ⁇ a ⁇ _ 16, 0 ⁇ b ⁇ 16, 0.5 ⁇ x ⁇ 16 and y is a number such that the valence requirements of the remaining elements for oxygen are satisfied.
  • particularly preferred cations are Bi, Fe, Co, Cr, La, Sn, Mg, U, Sb, Mo, W and Te when used in combinations of two or more.
  • Still another class of catalysts which has been found especially useful in accordance with the invention is characterized by the formula: wherein M is at least one element selected from Mg, Ca, Co, Ba, Sr, Fe(II), Mn(II); Ni, Cu, Zn and Pb;
  • X is at least one of Fe(III), La, Cr, Ce, other rare earths, B, Al, Ru, and Rh;
  • the catalysts used in the process of the present invention can be used either as on their own or the catalysts can be supported on suitable inert supports such as alpha alumina, Alundum (Registered Trade Mark), silica, silicon carbide, titania, zirconia and the like.
  • suitable inert supports such as alpha alumina, Alundum (Registered Trade Mark), silica, silicon carbide, titania, zirconia and the like.
  • phosphate support materials such as BP0 4 , TiP 2 O 7 , ZrP 2 0 7 , SbP ⁇ 4 and AIP0 4 can also be employed, wherein the catalyst support will exhibit some catalytic action of its own.
  • the active catalytic component can be incorporated with the support by any known technique such as coprecipitation, impregnation or coating with a wet slurry, a partially dry powder or pelleting.
  • the size of the catalyst particles is not critical and can vary between wide limits.
  • the catalyst particle size may be extremely small (e.g. microspheroidal) so that the catalyst can be employed in a fluid-bed reactor or the catalyst can be significantly larger in particle size so that the catalyst can be employed in a fixed-bed reactor.
  • the dehydrogenation reaction according to the invention is carried out in the presence of an oxygen donor.
  • an oxygen donor elemental oxygen, O2 is normally employed.
  • air is normally employed as a feed since it is cheapest and most convenient.
  • Other compounds which will serve as oxygen donors in a dehydrogenation reaction can also be employed.
  • SO 2 , COS and HOCI can also be employed.
  • the amount of oxygen donor fed to the reaction vessel should at least be the stoichiometric amount necessary to react with all of the hydrogen to be withdrawn from the indene precursor feed. Of course, less than the stoichiometric amount can be fed to the reactor, but this will simply decrease the efficiency of the process.
  • the amount of oxygen donor fed to the reaction vessel is at least twice, preferably 2 to 5 times, the stoichiometric amount necessary to react all of the hydrogen withdrawn from the indene precursor.
  • a gaseous promoter known to increase oxidation rates can also be fed to the reaction vessel for improving the efficiency of the dehydrogenation reaction according to the invention.
  • certain compounds such as halides (gaseous HCI, HBr, C1 2 , Br 2 , alkyl halides of the formula C x H Y X Z wherein X is halide and x is 1-5, y is 0-16, and z is 1-16 and so forth) serve to promote various types of dehydrogenation reactions.
  • such gaseous promoters can also be fed to the reaction vessel normally together with the oxygen donor (which is normally in a gaseous state) for increasing the efficiency of the reaction according to the invention.
  • the amount of gaseous promoter is less than 10%, in particular preferably less than 5%, of the oxygen donor fed to the reaction vessel in order that the hydrocarbon feed is not halogenated.
  • the gaseous materials fed to the reaction vessel can also contain a gaseous diluent.
  • a gaseous diluent Any gas inert to the reaction and catalyst can be employed as the gaseous diluent.
  • Preferred gaseous diluents include N 2 , CO 2 , H 2 0, combustion gases and light hydrocarbon gases (e.g. methane). Methane is an especially preferred gaseous diluent since it suppresses explosions and hence allows more oxygen donor to be tolerated by the system without fear of explosion.
  • the oxygen donor- is O2
  • the amount of inert diluent should be in the range of 0 to 20 times the amount of O2 fed to the reaction vessel.
  • a stoichiometrically corresponding amount of inert diluent can be employed.
  • the reaction according to the invention can be carried out either in fixed-bed mode or fluid-bed mode.
  • the liquid hourly space velocity of the indene precursor feed is from 0.01 to 10, preferably 0.05 to 1, optimally 0.25 hours-1.
  • the contact time for the reactants in the inventive process is normally from 0.1 to 20 seconds, preferably 2 to 10 seconds.
  • the reaction pressure is normally maintained at approximately atmospheric pressure, although a lower or higher pressure can be employed if desired. Indeed, any practicable pressure can be utilized.
  • the reaction temperature must be at least 100°C and is normally maintained between 100°C and 650°C, preferably 250°C to 550°C.
  • the preferred reaction temperature varies depending upon the indene precursor to be processed with a temperature range of 350°C to 600°C being preferred for indane dehydrogenation and 200° to 550°C being preferred for dehydrogenation of a more saturated precursor.
  • each of these catalysts was prepared by mixing an appropriate amount of each of the metals in question in the form of an aqueous nitrate solution with an aqueous solution of NH 4 H 2 PO 4 to form a precipitate, drying the precipitate and calcining the dried precipitate at a temperature of from 500 to 600°C in air for a period of 120 to 1200 minutes.
  • the particle size of each of the catalysts was between 0.833 mm and 0.417 mm mesh.
  • Tetrahydroindene (bicyclo ⁇ 4.3.0 ⁇ nona-3,7 diene) was oxydehydrogenated to indene by the same procedure and under the same conditions as in Examples 1 to 11 except that the reaction temperature was 470°C and the catalysts used are those specified in Table II below. These catalysts were also prepared in the same way as the catalysts used in Examples 1 to 1 1. The results of Examples 12 to 17 are set forth in the following Table II.
  • Examples 12 to 17 The procedure of Examples 12 to 17 was repeated using vinyl norbornene (5-vinyl-bicyclo ⁇ 2.2.1 - 2-heptene) as the feed and a catalyst comprising CO 7 La 1.5 Bi 2 P 12 0y as a catalyst.
  • the per pass conversion to indene was 18% while the per pass conversion to indane was 5%.
  • Isomerization also occurred to tetrahydroindene in an amount of 14% per pass conversion. 50% of the product was cracked predominantly to butadiene and cyclopentadiene, while approximately 10% of the reactant was combusted.
  • Indene is produced with high yields in substantially all of the foregoing examples.
  • substituted indene precursors especially alkyl substituted indene precursors of the foregoing type in which the alkyl groups have from 1 to 4 carbon atoms can also be employed.
  • the hydrocarbon starting material can comprise a mixture of different indene precursors as well as a single indene precursor.
  • the reaction product obtained by carrying out a Diels-Alder reaction on cyclopentadiene and butadiene, which normally contains both tetrahydroindene and vinyl norbornene could be directly processed in accordance with the present invention to form indene.
  • indene precursor byproduct of the process of the invention it is also possible and may be preferable in accordance with the present invention to recycle indene precursor byproduct of the process of the invention in order to treat further these indene precursors to form indene.
  • cyclopentadiene and butadiene are the predominant cracking products of the inventive reaction, it is also possible to subject these byproducts to a Diels-Alder reaction to form tetrahydroindene and vinyl norbornene which in turn can be used as a starting material in the process of the invention.
  • the phosphate catalysts employed on the inventive process can be prepared in any conventional manner, such as by using a nitrate solution as discussed above or any other convenient technique.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Claims (9)

1. Verfahren zur Herstellung eines unsubstituierten oder substituierten Indens durch Oxydehydrierung eines unsubstituierten bicyclischen Indenvorläufers oder eines bicyclischen Indenvorläufers, der mit C,- bis C4-Alkyl-, C1- bis C4-Alkenyl- oder Phenylgruppen substituiert ist, wobei der Vorläufer stärker gesättigt ist als das Inden, dadurch gekennzeichnet, daß man den Indenvorläufer mit einem Phosphatkatalysator in Gegenwart eines Sauerstoffdonators bei einer Temperatur von mindestens 100°C kontaktiert.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Reaktionstemperatur 100 bis 650°C beträgt.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Reaktionstemperatur 250 bis 550°C beträgt.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Indenvorläufer eine Substanz oder mehrere Substanzen aus der folgenden Gruppe ist bzw. sind: Indan, ein Alkylindan, bei dem die Alkylgruppe 1 bis 4 Kohlenstoffatome aufweist, Tetrahydroinden, ein Alkyltetrahydroinden, bei dem die Alkylgruppe 1 bis 4 Kohlenstoffatome aufweist, Hexahydroinden, Hexahydroindan und Vinylnorbornen.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Phosphatkatalysator durch die Formel:
Figure imgb0029
angegeben wird, wobei M ein oder mehrere Elemente, ausgewählt aus Mg, Sr, Ca, Ba, La, Ce, andere Seltene Erden, Cr, Mn, Fe, C, Ni, Cu, Zn, Sn, Pb, Bi, Te, B, Al, Rh, Sb, As, Ge, U, Th und Ru, ist bzw. sind und wobei 0,1 x ≤ ∑a ≤ 10x, wobei Σa die Summe der Indizes a aller Metallionen ist und y eine solche Zahl 'ist, daß den Wertigkeitserfordernissen der Metallionen für Sauerstoff genügt wird.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Phosphatkatalysator die Formel:
Figure imgb0030
aufweist, worin M mindestens eines von Bi, Fe, Ni, Co, Cr, La, Sn, Mg, Ca, Ce, U, Sb ist, wobei M' mindestens ein Element, ausgewählt aus Ge, Pb, Mo, W, Sr, Ba, Re, Th, As, Te, und Elementen der Gruppen IA, IB, IIB, IIIA und VB des Periodensystems ist und wobei 0,1 ≤ a ≤ 16, 0 ≤ b ≤ 16, 0,5 ≤ x ≤ 16, wobei y eine solche Zahl ist, daß den Wertigkeitserfordernissen der restlichen Elemente für Sauerstoff genügt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß der Phosphatkatalysator mindestens eines von Bi, Fe, Co, Cr, La, Sn, Mg, U und Sb enthält und weiter dadurch gekennzeichnet, daß der Katalysator mindestens eines von Mo, W und Te enthält.
8. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Phosphatkatalysator durch die Formel:
Figure imgb0031
angegeben wird, wobei M ein oder mehrere Elemente, ausgewählt aus Mg, Ca, Co, Ba, Sr, Fe(II), Mn(II), Ni, Cu, Zn und Pb ist bzw. sind, wobei X mindestens eines von Fe(III), La, Cr, Ce, andere Seltene Erden, B, Al, Ru und Rh ist und wobei 0 ≤ Σa + Σb ≤ 10x und 0,5 x ≤ 100, wobei ∑a + Σb die Summe der Indizes a + b ist und y eine solche Zahl ist, daß den Wertigkeitserfordernissen der anderen Elemente für Sauerstoff genügt wird.
9. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Katalysator einer der folgenden Substanzen ist:
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
EP78300066A 1977-07-18 1978-06-22 Herstellung von substituiertem oder unsubstituiertem Inden. Expired EP0000617B1 (de)

Applications Claiming Priority (2)

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US05/816,638 US4143082A (en) 1977-07-18 1977-07-18 Method for making indene
US816638 1977-07-18

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EP0000617B1 true EP0000617B1 (de) 1981-08-12

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US (1) US4143082A (de)
EP (1) EP0000617B1 (de)
JP (1) JPS5439060A (de)
AT (1) AT362779B (de)
AU (1) AU519566B2 (de)
CA (1) CA1092163A (de)
DE (1) DE2860929D1 (de)
DK (1) DK320978A (de)
IT (1) IT1195255B (de)
ZA (1) ZA783692B (de)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292455A (en) * 1979-12-28 1981-09-29 The Standard Oil Co. Multi-stage dehydrogenation process for preparing indene
US4291180A (en) * 1979-12-28 1981-09-22 Standard Oil Company Co-production of indene and styrene
US4291181A (en) * 1979-12-28 1981-09-22 Standard Oil Company Indenes from tetrahydroindenes
US4292456A (en) * 1979-12-28 1981-09-29 The Standard Oil Co. Oxydehydrogenation process for preparing indenes
CA1182803A (en) * 1980-12-31 1985-02-19 Svend E. Pedersen Mixed metal phosphorus oxide catalyst for the oxidative dehydrogenation of carboxylic acids
US4366088A (en) * 1981-01-26 1982-12-28 Ashland Oil, Inc. Support for a phosphate-containing catalyst
JPS6360840A (ja) * 1986-08-29 1988-03-16 Canon Inc シ−ト取扱装置
US5001102A (en) * 1989-01-11 1991-03-19 Pq Corporation Heterogeneous catalysts
WO2000010949A1 (fr) * 1998-08-18 2000-03-02 Nippon Petrochemicals Company, Limited Production d'indne
JP2003081889A (ja) * 2001-09-11 2003-03-19 Nippon Petrochemicals Co Ltd １，４−メタノ−１，４，４ａ，９ａ−テトラヒドロフルオレンの製造方法
CN102089690A (zh) 2008-05-09 2011-06-08 惠普开发有限公司 接近自由空间光学互连
DE102010032206A1 (de) * 2010-07-26 2012-04-05 Süd-Chemie AG Gasphasenbeschichtetes Lithium-Übergangsmetallphosphat und Verfahren zu dessen Herstellung
JP2013133293A (ja) * 2011-12-26 2013-07-08 Waseda Univ インダンおよび／またはインデンの製造方法
JP2019156758A (ja) 2018-03-13 2019-09-19 Ｊｘｔｇエネルギー株式会社 インデンの製造方法
JP7029346B2 (ja) * 2018-04-27 2022-03-03 Ｅｎｅｏｓ株式会社 インデンの製造方法

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
US3320329A (en) * 1965-04-23 1967-05-16 Phillips Petroleum Co Oxidative dehydrogenation over stannic phosphate catalyst
DE1816697A1 (de) * 1967-12-26 1969-08-28 Phillips Petroleum Co Oxydative Umwandlung,die eine Dehydrierung einschliesst
US3716545A (en) * 1970-01-16 1973-02-13 Phillips Petroleum Co Oxidative conversion including dehydrogenation
US4044066A (en) * 1971-05-06 1977-08-23 Phillips Petroleum Company Nickel-phosphorus oxidative dehydrogenation catalyst
US3824195A (en) * 1971-11-01 1974-07-16 Phillips Petroleum Co Oxidative dehydrogenation catalyst
US3845156A (en) * 1972-04-05 1974-10-29 Phillips Petroleum Co Processes for dehydrogenation of organic compounds
US3975301A (en) * 1973-10-26 1976-08-17 Eastman Kodak Company Dehydrogenation catalyst consisting of the calcined residue of ferric phosphate and lead phosphate
US4010114A (en) * 1975-04-30 1977-03-01 Phillips Petroleum Company Oxidative dehydrogenation catalyst

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US4143082A (en) 1979-03-06
IT7825217A0 (it) 1978-06-30
JPS6138176B2 (de) 1986-08-28
IT1195255B (it) 1988-10-12
ZA783692B (en) 1980-01-30
JPS5439060A (en) 1979-03-24
DE2860929D1 (en) 1981-11-12
AU3727878A (en) 1980-01-03
AT362779B (de) 1981-06-10
CA1092163A (en) 1980-12-23
AU519566B2 (en) 1981-12-10
EP0000617A1 (de) 1979-02-07
DK320978A (da) 1979-01-19
ATA512178A (de) 1980-11-15

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