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WO2009063178A1 - Procédé de production de triptane - Google Patents

Procédé de production de triptane Download PDF

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Publication number
WO2009063178A1
WO2009063178A1 PCT/GB2008/003777 GB2008003777W WO2009063178A1 WO 2009063178 A1 WO2009063178 A1 WO 2009063178A1 GB 2008003777 W GB2008003777 W GB 2008003777W WO 2009063178 A1 WO2009063178 A1 WO 2009063178A1
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Prior art keywords
zeolite
framework
methanol
atoms
catalyst
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PCT/GB2008/003777
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Inventor
Berian John Daniel
Benjamin Patrick Gracey
David John Law
Barry Martin Maunders
John Glenn Sunley
Jan Cornelis Van Der Waal
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BP PLC
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BP PLC
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Priority claimed from EP07254491A external-priority patent/EP2060551A1/fr
Priority claimed from GB0803209A external-priority patent/GB0803209D0/en
Application filed by BP PLC filed Critical BP PLC
Publication of WO2009063178A1 publication Critical patent/WO2009063178A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C07C2529/12—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C07C2529/14—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/76—Iron group metals or copper

Definitions

  • This invention relates to the production of triptane, more specifically to the production of triptane from methanol and/or one or more derivatives thereof and one or more olefins.
  • branched hydrocarbons are generally favoured over linear . hydrocarbons as they result in a fuel with a higher octane number.
  • An example of a branched chain hydrocarbon desirable in gasoline formulations due to its high octane number is triptane (2,2,3 -trimethylbutane), which can be used in unleaded aviation gasoline and unleaded motor gasoline, as described for example in WO 98/22556 and WO 99/49003.
  • Branched chain hydrocarbons may be synthesised by a number of routes, for example by homologation of methanol and/or dimethyl ether in the presence of a zinc halide catalyst, as described, for example in GB 1,547,955, US 2,492,984, US 3,969,427, US 4,059,646, US 4,059,647, US 4,249,031 and WO 02/70440.
  • Olefins can also be reacted with alcohols, in particular methanol, to produce hydrocarbons.
  • alcohols in particular methanol
  • US 4,151,214 describes the use of zinc bromide or iodide catalysts in the production of triptane from methanol or dimethyl ether with an olefin.
  • US 2,417,119 describes the reaction of methyl chloride with trimethylethylene (2,3-dimethylbut-2-ene) in the presence of quicklime or calcium oxide to produce a composition comprising 2,2,3-trimethyl-butene, which can be separated and hydrogenated to form triptane. This process does not appear to be catalytic in nature, as the calcium-reagent is converted to calcium chloride and calcium hydroxide.
  • halide-containing catalysts or reagents A common problem associated with the use of halide-containing catalysts or reagents is that the halides can contribute to corrosion problems in plant equipment. Additionally, halides can contaminate the triptane product and needs to be removed before the triptane can be used as a fuel. Zeolites have been reported as being able to produce alkanes from methanol or ethers, as described for example in US 3,894,106 and US 3,894,107. However, the products have high aromatic content, and nothing is taught about whether triptane is or could be created.
  • a process for the production of triptane and/or triptene from methanol and/or one or more derivatives thereof and one or more olefins, optionally in the presence of one or more further alcohols and/or derivatives thereof comprises contacting a reaction composition comprising the methanol and/or one or more derivatives thereof, the one or more olefins, and optionally one or more further alcohols and/or derivatives thereof with a zeolite catalyst at a temperature in the range of from 150 to 400 0 C to produce triptane and/or triptene, characterised by the catalyst having Br ⁇ nsted acidity and being selected from one or more of the following: i.
  • Zeolites having frameworks comprising silicon and aluminium atoms and having a channel structure comprising a ring size of 12 or more non-oxygen framework atoms in 2 or 3 dimensions; ii. Alkali metal-containing zeolites having frameworks comprising silicon and aluminium atoms and which have a framework ring comprising 12 or more non- oxygen atoms accessible on the external surface of the zeolite, and a channel structure in which all of the channels have a ring-size of less than 12 non-oxygen framework atoms;
  • crystalline zeolites in particular aluminosilicate zeolites, can act as catalysts for the conversion of methanol and/or one or more derivatives thereof to triptane (2,2,3-trimethylbutane) and/or triptene (2,3,3-trimethylbut-l -ene) in the presence of one or more olefins.
  • Triptane and triptene are herein collectively referred to as triptyl compounds.
  • the zeolite catalysts have at least some Br ⁇ nsted acid character, and provide a combination of high triptyl yields and high fractions of triptyl compounds as a percentage of all C 7 hydrocarbons produced in the reaction.
  • Crystalline zeolites typically comprise an ordered inorganic oxide framework structure having a regular array of pores, often with enlarged cages where two or more pores intersect. Most commonly, the framework is principally aluminosilicate, comprising silicon and aluminium atoms. However, often zeolites can comprise other framework heteroatoms, for example phosphorus, gallium, titanium, germanium, iron and cobalt. Where present, these other framework heteroatoms are typically present at a level of up to 10 mole%, based on the total number of (non-oxygen) framework atoms.
  • the overall charge on the framework must be negative, such that positive ions, in particular protons, are required to balance the charge.
  • the framework of aluminosilicate zeolites and silicoaluminophosphate zeolites is negatively charged, which negative charge can be balanced by protons to produce Br ⁇ nsted acid sites. This type of Br ⁇ nsted acidity is represented below in equation I.
  • the framework negative charge can also be balanced by another cation, for example a transition metal or lanthanide ion, which itself can possess Br ⁇ nsted acid character, for example by deprotonation of coordinated water molecules.
  • Br ⁇ nsted acidity is represented below in equation II.
  • the negative charges of the framework are counter-balanced by protons.
  • the zeolite should have a sufficient number of acid sites to enable the acid-catalysed reaction of the methanol and/or derivatives thereof and one or more olefins to triptyl compounds to proceed. This can be conveniently expressed in terms of the framework silicon to aluminium mole ratio, which is typically 100 or less, for example 80 or less, such as 50 or less.
  • part of the negative charge of the zeolite framework can be counterbalanced by cations other than protons, for example ammonium ions or one or more alkali- metal ions, for example one or more of sodium, potassium, rubidium and caesium.
  • one or more alkaline-earth ions can be present, for example one or more of magnesium, calcium, strontium and barium.
  • one or more p-block metal metals, transition metals and lanthanides can be present, for example one or more of lanthanum, cerium, silver, bismuth, copper, cobalt, indium, zinc, rhodium, platinum and palladium.
  • the number of acid sites in a zeolite can also be modified by treating the zeolite with organic silicon compounds or silicon compounds comprising halides, for example alkoxy silanes, alkyl silanes, silicon halides, or alkyl silicon halides. Specific examples include tetraethoxysilane, tetramethylsilane, silicon tetrachloride, and dimethyl dichloro silane. These react at proton sites, and hence by controlling the level of treatment a controlled quantity of acid sites can be blocked.
  • Treated zeolites are typically treated by calcination in air at a temperature in the range of 400 to 600 0 C after treatment with the silicon compound.
  • the loading of the non-framework metals can be conveniently expressed in terms of a molar ratio compared to the element or elements of the zeolite responsible for imparting negative change to the zeolite framework.
  • Such elements are herein referred to as T- elements.
  • T- elements For example, in aluminosilicate zeolites, aluminium is the T-element. In gallo- aluminosilicate zeolites, both gallium and aluminium are T-elements.
  • the loading can be expressed in terms of the total quantity of non-framework metal compared to the total quantity of T-element(s) in the zeolite.
  • the loadings of non-framework metal, where present, are typically lmol% or more relative to the total T-element content of the zeolite. More preferably, the loadings are in the range of from 1 to 10mol% relative to the total T-element content of the zeolite.
  • zeolites of structure type (i) result in a combination of higher triptyl yields and higher triptyl fractions in the C 7 hydrocarbons compared to zeolites that do not adopt either the type (i) or type (ii) structures.
  • zeolites of structure type (ii) zeolites comprising one or more alkali-metals show the improved combination of higher triptyl yields and fractions compared to those that do not adopt either the type (i) or (ii) structures.
  • the non-framework metal where present is preferably selected from one or more of copper, silver, and caesium.
  • the alkali-metal is preferably caesium.
  • the zeolite catalyst can be mixed with a binder.
  • a binder is often used to provide robustness to a catalyst and/or to disperse crystals of the zeolite catalyst particles through a porous matrix to improve diffusion of reactants and products to and from the zeolite catalyst particles.
  • Typical binders are selected from clays or refractory oxides, and in one embodiment the binder is alumina.
  • the binder is present typically in an amount of up to 50% of the total weight of the catalyst.
  • the reaction that is catalysed is the production of triptyl compounds, i.e. triptane, triptene or mixtures thereof, from a reaction composition comprising methanol and/or one or more derivatives thereof, and one or more olefins.
  • a derivative of methanol is a compound that can release methanol through a hydrolysis reaction. Examples of methanol derivatives include methyl esters, methyl ethers and methyl carbonates, specific examples being dimethyl ether and dimethyl carbonate.
  • the reaction composition comprises methanol and/or dimethyl ether.
  • the reaction composition can comprise one or more further alcohols and/or derivatives thereof, an alcohol derivative being a compound that releases the corresponding alcohol through a hydrolysis reaction.
  • the one or more further alcohols and/or derivatives thereof are selected from one or more C 2 to C 6 alcohols and/or derivatives thereof, for example C 2 to C 4 alcohols and/or derivatives thereof, examples being ethanol, iso-propanol, n-propanol, iso-butanol, sec-butanol and n- butanol.
  • the alcohol and/or derivative thereof can optionally be biologically derived.
  • ethanol and butanol can be produced from the fermentation of biomass. This is advantageous, as the use of biologically-derived feedstocks can result in the triptane having a lower impact on atmospheric CO 2 -emissions when combusted, because biomass ultimately derives from atmospheric CO 2 .
  • the olefin is typically a C 2 to C 6 olefin, i.e. an olefin comprising 2 to 6 carbon atoms, such as ethene, propene, 1-butene, cis and trans 2-butene, isobutene, 2-methyl-2-butene and 2,3-dimethyl-2-butene.
  • 2,3-dimethyl-2-butene is a particularly suitable olefin as triptyl compounds can be formed by the addition of a just single carbon atom at the olefin double bond.
  • Pentenes or butenes can be a desirable constituent of the reaction composition, as they are potentially available in large quantities from refinery and petrochemical processes, being constituents of light hydrocarbon products from steam cracking or fluid catalytic cracking processes for example.
  • a reaction composition comprising methanol and/or one or more derivatives thereof, and the one or more olefins, optionally with one or more alcohols and/or derivatives thereof, are fed to a reactor in which the catalyst resides.
  • a product stream is produced, comprising unconverted reactants, triptyl compounds and other by- products such as linear and branched alkanes and alkenes, cyclic hydrocarbons and aromatic compounds.
  • the ratio is in the range of from 5 : 1 to 30 : 1.
  • methanol relates to methanol present in the reaction composition c and/or to methanol derivable from the one or more derivatives thereof present in the reaction composition.
  • methanol derivable from a methanol derivative is meant the number of methanol molecules that would be produced in the event of hydrolysis of the methanol derivative.
  • DME dimethyl ether
  • two methanol molecules would result from hydrolysis.
  • a molecule of dimethyl carbonate (DMC) for example would also produce two molecules of methanol on hydrolysis.
  • a DME or DMC olefin mole ratio of 5 : 1 provides a methanol : olefin mole ratio of 10 : 1.
  • the reactions are conducted so that all reactants are in the gas-phase.
  • the temperature is in the range of from 150 to 400 0 C, and preferably in the range of from 200 to 35O 0 C, and even more preferably in the range of from 21O 0 C to 300 0 C.
  • the total gas hourly space velocity (GHSV) of the reactants over the catalyst is suitably up to 5000 h "1 , preferably 500 h "1 or above, and more preferably 3000 h "1 or less.
  • the GHSV is in the range of from 1000 to 3000 h "1 .
  • the GHSV is given in units of mL gas, corrected to O 0 C and 1 atm pressure, per mL catalyst per hour.
  • the reaction pressure is typically in the range of from 1 bara (0.1 MPa) to 100 bara (1 OMPa).
  • the catalyst is suitably layered, such that the carbon monoxide and hydrogen-containing feedstock contacts the alcohols synthesis catalyst first, the so- formed methanol and/or one or more derivatives thereof and optionally further alcohols and/or derivatives thereof subsequently contact a layer of the zeolite catalyst of the present invention to form triptyl compounds.
  • the catalyst is suitable for the production of mixed alcohols, such as a mixture of C 1 to C 4 alcohols and/or derivatives thereof, for example a cobalt- molydenum-sulphide catalyst (CoMoS).
  • mixed alcohols such as a mixture of C 1 to C 4 alcohols and/or derivatives thereof, for example a cobalt- molydenum-sulphide catalyst (CoMoS).
  • CoMoS cobalt- molydenum-sulphide catalyst
  • the ring comprises a total of 12 silicon and aluminium atoms.
  • the zeolite is a silico-alurninophosphate, for example, then the ring comprises a total of 12 silicon, aluminium and phosphorus atoms.
  • Non-framework atoms for example charge balancing ions such as protons, alkali-metal ions or other positively charged cations which are not incorporated into the zeolite framework, are not considered to be part of the 12-membered ring.
  • 12-membered rings are large enough to accommodate the reactant molecules and the necessary intermediates involved in triptyl formation. Although larger ring sizes would also be sufficiently large, for example having 14- or 16-membered rings, such zeolites are generally more unstable than those having 12-membered rings.
  • zeolite types There are two types of zeolite structure that are able to provide a combination of high triptyl yields and also high triptyl fractions in the C 7 hydrocarbons, which are referred to herein as zeolite types (i) and (ii).
  • Type (i) zeolites comprise a 2 or 3-dimensional network of pores, the ring size of the pores being 12 or more non-oxygen framework atoms in at least 2 dimensions.
  • Zeolites in this category include zeolites of the FAU, BEA or EMT structures. Full details of zeolite structures can be found in the Atlas of Zeolite Structure Types, available from the International Zeolite Association.
  • MWW structure which has a two-dimensional pore structure, in which all the pores in the network have a 10-membered ring at their narrowest portion.
  • the channels intersect at cylindrical cages formed of 12- membered rings, the cage dimensions being about 7.1 A diameter across the short axis and about 18.2A in length.
  • the external surfaces of the crystals comprise opened cages, thus making the 12-membered rings accessible to reactants.
  • MCM-22 described in US 4,992,615, is an example of an aluminosilicate zeolite with this structure, typically having a Si/Al ratio of 5 or more.
  • the cages appear as cups or pockets on the crystal surface, having a diameter of about 7.1 A and a depth of about 7.0A.
  • ITQ-2 is an example of a delaminated zeolite.
  • the ITQ-2 framework is based on that of the layered MCM-22 (MWW) structure, of the structure type (ii), except that condensation of the MCM-22 layers at the framework cages is disrupted during the synthesis, resulting in a disordered layered structure and an increased proportion of 12- membered ring cages open and accessible to reactants at the external crystal surface.
  • MWW layered MCM-22
  • ii structure type
  • Metal cations where present are preferably selected from one or more of silver and copper (in addition to alkali metals such as caesium), with loadings of lmol% or more, preferably in the range of from 1 to 10 mol%, based on the T-element content of the zeolite.
  • Figure 3 is a GC trace of the gaseous portion of a product stream resulting from a feedstock of nitrogen-diluted methanol and 2,3-dimethyl-2-butene being fed over zeolite Y.
  • Figure 4 is a GC trace of the gaseous portion of a product stream resulting from a feedstock of nitrogen-diluted methanol and 2,3-dimethyl-2-butene being fed over zeolite MCM-22.
  • Metal-loaded zeolites were prepared by incipient wetness impregnation, by evaporation a suspension of the zeolite in an aqueous solution of relevant soluble metal salts to dryness at a temperature of 50-60 0 C. The material was then dried at 110 0 C for 1 hour, and calcined in air overnight at 500 0 C.
  • the following zeolite catalysts were obtained commercially, and comprised 20% by weight of alumina binder: Beta, Y and ZSM-5.
  • Si/Al molar ratios of the zeolites are as follows (in brackets): Beta (13), Y (2.5), ZSM-5 (15), ZSM-12 (45), X (1.2) and MCM-22 (25).
  • the feedstock was a mixture of methanol and 2,3-dimethyl-2-butene (2,3-DMB) in a 20:1 molar ratio, diluted in nitrogen at a nitrogen : (methanol + 2,3-DMB) molar ratio of 4:1.
  • the feedstock was fed over the catalyst at a pressure of 1 bara (0.1 MPa), a temperature of 275 0 C, and a total GHSV of 2000 h "1 .
  • the following aluminosilicate zeolites in their protonated form were tested: Beta, ZSM-5, MCM-22, X, Y and ZSM-12.
  • Table 2 Triptyl Fractions for zeolite catalysts using methanol/2,3 -DMB Feedstock.
  • Table 4 Triptyl Fractions for zeolite catalysts using Dimethyl Ether/2,3-DMB Feedstock.

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Abstract

L'invention concerne un procédé de production de triptane et/ou de triptène à partir de méthanol et/ou d'un ou de plusieurs dérivés de celui-ci, et d'une ou plusieurs oléfines en présence d'un catalyseur possédant une acidité de Brønsted et une structure sélectionnée dans le groupe constitué par : i) des zéolites présentant des squelettes d'atomes de silicium et d'aluminium et une structure canalaire composée d'un noyau d'atomes de squelettes autres qu'oxygène égal ou supérieur à 12 en 2 ou 3 dimensions; et ii) des zéolites présentant des squelettes d'atomes de silicium et d'aluminium, et ayant un noyau de squelette qui comprend 12 atomes ou plus autres qu'oxygène accessibles sur la surface extérieure de la zéolite et une structure canalaire dans laquelle tous les canaux présentent un noyau inférieur à 12 atomes de squelette autres qu'oxygène, les zéolites de type (ii) comprenant un métal alcalin dans lequel le méthanol n'est pas un réactif.
PCT/GB2008/003777 2007-11-16 2008-11-07 Procédé de production de triptane Ceased WO2009063178A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07254491.9 2007-11-16
EP07254491A EP2060551A1 (fr) 2007-11-16 2007-11-16 Procédé de production de triptane
GB0803209.6 2008-02-21
GB0803209A GB0803209D0 (en) 2008-02-21 2008-02-21 Process for producing triptane

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US4151214A (en) * 1977-11-14 1979-04-24 Shell Oil Company Process for methylation of olefins
JPS62121787A (ja) * 1985-09-23 1987-06-03 モ−ビル　オイル　コ−ポレ−ション 酸素含有化合物のアルキル化した液体炭化水素類への転化方法
EP0485145A1 (fr) * 1990-11-08 1992-05-13 The British Petroleum Company P.L.C. Procédé pour la préparation d'oléfines ramifiées
EP1900714A1 (fr) * 2006-09-12 2008-03-19 Bp Oil International Limited Procédé pour la production d'hydrocarbures

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Publication number Priority date Publication date Assignee Title
WO2021102541A1 (fr) 2019-11-26 2021-06-03 Petróleo Brasileiro S.A. - Petrobras Procédé d'obtention de composés, parmi lesquels le triptane, par réaction de couplage d'alcools

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