EP0907696A1 - Catalyseur et son utilisation pour la deshydrogenation d'hydrocarbures paraffiniques/naphteniques - Google Patents

Catalyseur et son utilisation pour la deshydrogenation d'hydrocarbures paraffiniques/naphteniques

Info

Publication number
EP0907696A1
EP0907696A1 EP97920738A EP97920738A EP0907696A1 EP 0907696 A1 EP0907696 A1 EP 0907696A1 EP 97920738 A EP97920738 A EP 97920738A EP 97920738 A EP97920738 A EP 97920738A EP 0907696 A1 EP0907696 A1 EP 0907696A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
catalyst according
compound
carbon atoms
branched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97920738A
Other languages
German (de)
English (en)
Inventor
Daniel Heineke
Alfred Hagemeyer
Joachim Wulff-Döring
Christopher William Rieker
Werner Schnurr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0907696A1 publication Critical patent/EP0907696A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C07C5/412—Catalytic processes with metal oxides or metal sulfides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths

Definitions

  • the invention relates to a catalyst and its use for the dehydrogenation of paraffinic / naphthenic hydrocarbons which have straight-chain, branched or cyclic alkyl or alkylene radicals having 6 to 8 carbon atoms.
  • the invention relates in particular to the production of aromatic compounds having 6 to 8 carbon atoms.
  • the most important source of technically important C ⁇ to Ca aromatics such as benzene, xylenes or ethylbenzene is large-scale reforming.
  • straight-chain paraffin hydrocarbons are converted into branched paraffin hydrocarbons and aliphatic-aromatic and aromatic hydrocarbons.
  • This process is used on the one hand to increase the knock resistance of petrol fuels, i.e. the reaction mixtures obtained remain essentially unchanged; on the other hand, the aromatic compounds formed are e.g. separated by distillation and found as intermediates and synthesis building blocks e.g. for the production of synthetic rubbers and synthetic fibers.
  • the ethylbenzene formed from components of the Cs fraction is used, for example, to obtain styrene, the starting material for polystyrene.
  • Catalytic reforming finds a variety of
  • Catalysts which contain other metals besides platinum, such as Pt-Re / Al 2 ⁇ 3 .Si0 2 or Pt / Sn / Al 2 0 3 .Si0 2 are also known; for example, a catalyst based on Pt / Sn / Al 2 0 3 in J. Mol. Catal. .88. (1994) 359-376.
  • the carrier materials are mostly aluminosilicates or zeolites.
  • Pt catalysts on L-zeolites (cf. Energy Progress 1, (1987), 215-222) achieve a high aromatic selectivity, which is attributed to the shape selectivity of the support, but with a low space-time yield.
  • multi-stage catalysts such as Pt / Co / Nd (US Pat. No. 4,136,130) or Pt / Co / Re / Ge (US Pat. No. 4,136,017) on non-zeolitic chlorinated Al 2 O 3 supports develop higher activity, but tend to do so to Formation of crack products and thus less aromatic selectivity, especially with regard to the formation of C ⁇ aromatics (ethyl- 'benzene;styrene; xylenes).
  • the aforementioned catalysts have the disadvantage of being precious metal catalysts, i.e. they are expensive, especially if they have to contain other, also rare, components such as rhenium or palladium. It is also disadvantageous that catalysts containing noble metals do not achieve a long service life because the active constituent, which is in elemental form, tends to agglomerate at a process temperature of 450 to 550 ° C. and possibly subsequently to sintering, that is to say to the loss of an effective surface, and is therefore rapid loses activity. Finally, it is disadvantageous that platinum catalysts promote coking and therefore from time to time - usually in a reductive atmosphere, i.e. using hydrogen - must be regenerated to remove the deposited carbon.
  • the object of the invention is to create a catalyst which does not have the disadvantages mentioned and can convert C 6 to Cs hydrocarbon streams to aromatics in high yield.
  • This object was achieved by using a noble metal-free catalyst based on an oxide of a metal from group IV B of the periodic table, in particular Zr0 2 and Ti0 2 .
  • the oxide according to the invention also acts as a catalyst and as a carrier, so that ideally no other carrier auxiliary has to be used.
  • a particularly favorable result is achieved if the metal oxide from group IV B together with one or more compounds from the third main or subgroup of the periodic Stems or combined with basic additives such as alkali or alkaline earth metal compounds, rare earth or zinc "compounds which are converted into the corresponding oxides by calcining at a higher temperature.
  • basic additives such as alkali or alkaline earth metal compounds, rare earth or zinc "compounds which are converted into the corresponding oxides by calcining at a higher temperature.
  • the catalysts according to the invention are considerably cheaper than the known noble metal catalysts and their selectivity, i.e. the preference for the conversion of aliphatic to aromatic hydrocarbons is very good. In particular, however, they are very insensitive to coking and, if necessary, can be regenerated either reductively, for example with hydrogen, or oxidatively, for example with air. Regeneration with air in particular is cheaper than conventional regeneration, e.g. with hydrogen. It also proves to be an advantage that the processes can be operated using the catalysts according to the invention without adding hydrogen to the reaction mixture. Other advantages are high mechanical strength, long service life and easy shaping.
  • amphoteric oxides of the IV-B metals in question or mixtures thereof or suitable precursors which can be converted into the oxides by calcining can be used.
  • Known elements such as the sol-gel process, precipitation of the salts, dewatering of the corresponding acids, dry mixing, slurrying and spray drying can be used to carry out the individual steps of the production process.
  • the doping can be carried out during production, for example by co-precipitation or subsequently, for example by impregnating the catalyst oxide with a dissolved alkali metal or alkaline earth metal compound or a compound of the 3rd subgroup or a rare earth metal compound and, if appropriate, re-calcining happen.
  • the catalyst can be in the form of shaped articles such as grit, tablets or spheres or as an extrudate with a suitable cross section, e.g. in the form of wagon wheels, stars, monoliths or rings.
  • the content of additives can be up to 20% by weight, preferably between 1 and 15% by weight, particularly preferably between 1 and 10% by weight. -% lie.
  • alkali and alkaline earth metal supplier use is generally made of compounds which can be converted into the corresponding oxides by calcining. For example, hydroxides, carbonates, oxalates, Acetates, nitrates or mixed hydroxycarbonates of the alkali and alkaline earth metals.
  • group IV-B support is additionally or exclusively doped with a metal from the third main or subgroup, then one should also start from compounds which can be converted into the corresponding oxides by calcining.
  • lanthanum for example lanthanum oxide carbonate, La (OH) 3 , La 3 (C0 3 ) 2 , La (N0 3 ) 3 or lanthanum compounds containing organic anions, such as La acetate, La formate or Suitable for la-oxalate.
  • the catalysts of the invention have a high BET surface area. Depending on the production, a BET surface area of up to 500 m 2 / g, usually up to 300 m 2 / g, is observed. Are suitable
  • the pore volume is generally between 0.1 and 1 ml / g, mostly between 0.1 to 0.6 ml / g, pore volumes of 0.15 to 0.5 ml / g are particularly preferred.
  • the average pore diameter which can be determined by mercury penetration analysis, is between 0.008 and 0.06 ⁇ m, mostly between 0.01 and 0.04 ⁇ m.
  • reaction temperatures of 300 to 800 ° C, preferably 400 to 600 ° C at pressures from 100 mbar to 100 bar, preferably 1 bar to 40 bar with an LHSV (Liquid Hourly Space Velocity) of 0.01 to 100 h 1, preferably 0.1 to 20 h " 1.
  • LHSV Liquid Hourly Space Velocity
  • hydrogen can be added, the molar ratio of hydrogen to hydrocarbons being 0.1 to 100, but usually less than 20.
  • a particular advantage of the catalyst according to the invention is that the regeneration of the catalyst can be carried out in one step, both reductively and oxidatively. Regardless of the process chosen, the regeneration takes place in the range from 300 to 900, preferably 400 to 800 ° C. and can take place at reduced, atmospheric or elevated pressure. Pressures in the range of 500 mbar to 100 bar are suitable. Examples
  • Strands with a diameter of 3 mm were produced from commercial Zr0 2 (commercial product XZ 16075 from Norton; largely monoclinic), which had a BET surface area of 46 m 2 / g, a pore volume of 0.23 ml / g (Hg porosimetry ) and had a proportion of pores with more than 20 nm of about 15%.
  • the reactions were carried out in a microfixed bed pulse reactor through which helium as the carrier gas flowed at 450 (example 2) or 500 ° C. (remaining examples).
  • helium as the carrier gas flowed at 450 (example 2) or 500 ° C. (remaining examples).
  • about 0.6 g of catalyst was weighed into a fixed micro-bed and the carrier gas was pulsed with pure n-octane at atmospheric pressure and a flow rate of approx. 21.5 ml / min.
  • a single pulse contains approx. 100 ⁇ g n-octane.
  • the reaction products were quantified for each pulse on-line by gas spectrometry (GC-MS) evaluated by mass spectrometry.
  • GC-MS gas spectrometry
  • Table 1 relate to the point in time when the maximum turnover was reached.
  • the noble metal-free catalyst according to the invention achieves a significantly better overall selectivity (proportion of aromatics formed) than the commercially available comparative catalyst. Particularly noteworthy is the high proportion of C 8 aromatics, which indicates that side reactions which lead to crack products are suppressed.

Landscapes

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

Abstract

L'invention concerne un catalyseur, notamment pour la production de composés aromatiques comportant 6 à 8 atomes de carbone à partir d'hydrocarbures non aromatiques à chaînes alkyle ou alkylène linéaires, ramifiées et/ou cycliques, avec 6 à 8 atomes de carbone, contenant essentiellement au moins un oxyde d'un métal de transition du groupe IVB de la classification périodique et le cas échéant un composé de métaux alcalins ou alcalinoterreux et/ou un composé du troisième groupe principal ou secondaire de la classification périodique et/ou un composé de zinc ou de métaux des terres rares ou leurs mélanges, à condition que les composés se transforment en oxydes correspondants lors de la calcination.
EP97920738A 1996-04-26 1997-04-23 Catalyseur et son utilisation pour la deshydrogenation d'hydrocarbures paraffiniques/naphteniques Withdrawn EP0907696A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19616738 1996-04-26
DE19616738A DE19616738A1 (de) 1996-04-26 1996-04-26 Katalysator und seine Verwendung zur Dehydrierung von paraffinischen/naphthenischen Kohlenwasserstoffen
PCT/EP1997/002040 WO1997041192A1 (fr) 1996-04-26 1997-04-23 Catalyseur et son utilisation pour la deshydrogenation d'hydrocarbures paraffiniques/naphteniques

Publications (1)

Publication Number Publication Date
EP0907696A1 true EP0907696A1 (fr) 1999-04-14

Family

ID=7792548

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97920738A Withdrawn EP0907696A1 (fr) 1996-04-26 1997-04-23 Catalyseur et son utilisation pour la deshydrogenation d'hydrocarbures paraffiniques/naphteniques

Country Status (3)

Country Link
EP (1) EP0907696A1 (fr)
DE (1) DE19616738A1 (fr)
WO (1) WO1997041192A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11859136B2 (en) 2020-03-06 2024-01-02 Exxonmobil Chemical Patents Inc. Processes for upgrading alkanes and alkyl aromatic hydrocarbons
EP4114812A1 (fr) 2020-03-06 2023-01-11 ExxonMobil Chemical Patents Inc. Procédés de valorisation d'alcanes et d'hydrocarbures aromatiques alkyliques

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2279198A (en) * 1938-01-18 1942-04-07 Union Oil Co Catalytic conversion of hydrocarbons
US3884834A (en) * 1971-09-24 1975-05-20 Exxon Research Engineering Co Process catalyst
US4263133A (en) * 1980-02-28 1981-04-21 Phillips Petroleum Company Catalytic reforming and hydrocracking of organic compounds employing zinc titanate as the catalytic agent
FR2621577B1 (fr) * 1987-10-09 1990-01-12 Rhone Poulenc Chimie Oxyde de titane a proprietes stabilisees
DE19516318A1 (de) * 1995-04-28 1996-10-31 Inst Angewandte Chemie Berlin Selektiver Aromatisierungskatalysator, Verfahren zur Herstellung und Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9741192A1 *

Also Published As

Publication number Publication date
DE19616738A1 (de) 1997-10-30
WO1997041192A1 (fr) 1997-11-06

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