WO2011077242A1 - Procédé pour la production de composants de carburant pour véhicules à moteur - Google Patents

Procédé pour la production de composants de carburant pour véhicules à moteur Download PDF

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WO2011077242A1
WO2011077242A1 PCT/IB2010/003379 IB2010003379W WO2011077242A1 WO 2011077242 A1 WO2011077242 A1 WO 2011077242A1 IB 2010003379 W IB2010003379 W IB 2010003379W WO 2011077242 A1 WO2011077242 A1 WO 2011077242A1
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benzene
process according
alkylation
mixture
alcohols
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PCT/IB2010/003379
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English (en)
Inventor
Franco Rivetti
Maria Angela Mantegazza
Daniele Bianchi
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Eni S.P.A.
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Publication of WO2011077242A1 publication Critical patent/WO2011077242A1/fr

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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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • 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

Definitions

  • the present invention relates to a process for the production of fuel components for motor vehicles of the gasoline type, by the alkylation, with one or more alcohols, of a mixture containing benzene, and the separation of a product which boils within gasoline boiling range, wherein the alkylation and separation take place in two different steps.
  • the process is carried out in the presence of a zeolite belonging to the BEA family.
  • a substantial amount of benzene is no longer present in the final mixture, i.e. the mixture obtained at the end of the alkylation step, due to the alkylation of said substrate with the alcohol or alcohols used.
  • the process also allows a fraction which boils within the diesel boiling range to be obtained.
  • a particularly preferred aspect is to use alcohols deriving from raw materials of an agricultural or vegetable origin.
  • the invention also relates to the gasolines obtainable with the process of the present invention, having a high octane number and improved characteristics from the point of view of environmental impact.
  • the invention also relates to the diesel cuts obtainable with the process of the present invention, which can be used as components of diesel compositions.
  • a gasoline from catalytic reforming typically contains about 25% in moles of benzene and about 50% in moles of other aromatic components .
  • Benzene cyclohexane, , methylcyclopentane, hexane
  • the precursors of benzene can be removed at the beginning from the feedstock fed to the catalytic reforming, or the benzene contained in the reformate stream to be sent to the gasoline pool can be saturated by hydrogenation to cyclohexane .
  • the benzene can be extracted (UDEX and Sulfolan processes) by extraction with a solvent .
  • Hydrogen is a valuable by-product which is increasingly used in refineries, for example, in hydrocracking and hydrodesulfurization operations. Extraction with a solvent requires storage facilities and sales structures of the benzene on the market or its captive use for petrochemical plants which are not always available.
  • alkylation of benzene, contained in the reformate, to alkylbenzenes has been proposed, using olefins available in refineries, for example the ethylene and propylene present in the FCC gases .
  • olefins available in refineries, for example the ethylene and propylene present in the FCC gases .
  • the reduction of the benzene content by means of alkylation has definite advantages such as an increase in the volume of gasoline produced and an increase in the octane number.
  • This method however also has its problems, it requires, for example, the pretreatment of the FCC gases for the removal of the sulfur and nitrogen contaminants and the separation and concentration of olefins, and is still in the development phase as it has not been affirmed in consolidated commercial applications.
  • Patent EP 796234 describes a process for the alkylation of a reformate stream containing benzene and alkyl-aromatics with a hydrocarbon stream containing C2-C5 olefins in the presence of a zeolitic catalyst MCM-49.
  • Patent 375547 describes the production of a fuel with a reduced benzene content and a high octane number starting from a light reformate distillation cut rich in benzene which is reacted with a cracking gas containing C2-C5 olefins on a zeolitic catalyst containing mordenite.
  • EP 414590 describes an analogous process in which the light reformate cut, rich in benzene, is preliminarily put in contact at room temperature with the gas containing olefins, separating them from the cracking gas and concentrating them, before proceeding with the alkylation step.
  • US 5,082,990 describes the reduction of the benzene content of a refinery stream by reaction with an olefinic stream in a reactive distillation column on fixed beds of zeolitic alkylation catalyst, for example a beta or Y zeolite.
  • Patent US 5,336,820 describes a process for the alkylation of gasoline cuts rich in benzene with C2-C5 olefins in which the aromatic cut is put in contact in a first step with the more reactive C3-C5 olefins and in a second step with ethylene, using an alumino-silicate catalyst.
  • the patent WO 200694008 describes an analogous process carried out in vapour phase on a series of two catalytic beds containing ZSM- 5 and MCM-22 zeolites.
  • Another very important aspect relates to the regulations adopted in recent years by the governments of the main industrialized countries and European Community aimed at promoting the production and use of biofuels .
  • This term refers to hydrocarbon compounds produced starting from renewable raw materials of an animal or, more frequently, an agricultural and vegetable origin, suitable for use as fuels for motor vehicles.
  • biofuels There are various reasons for sustaining the diffusion of biofuels, ranging from the widely-shared request for a reduction in greenhouse gas emissions into the atmosphere, and in particular carbon dioxide, in accordance with the Kyoto protocol, the desire for reducing the energy dependence on producer countries of crude oil, improving supply security through diversification of the sources, to predictions of a future exhaustion of the availability of fossil fuels.
  • Biofuels also guarantee various technical advantages such as the absence of sulfur and in general a cleaner combustion, with a reduction in polluting emissions in the combustion phase.
  • the biofuels which are currently most widely-used are bioethanol in the gasoline field and biodiesel.
  • Bioethanol for example, has a lower calorific value with respect to gasoline (-37%) and increases its volatility, at the same time it can create problems of cold ignition and induces a lower tolerance to the presence of water (demixing) , so that the maximum amount of ethanol tolerated in gasoline can reach 10% for use in current engines. Higher quantities are tolerated only after more or less significant modifications to the engines or can even require vehicles constructed ad hoc .
  • EN 228 envisages the use of ethanol in gasoline in an amount not higher than 5% by volume.
  • An alternative to the use of bioethanol as such in gasoline consists in the production of ethyl-t-butylether (ETBE) .
  • ETBE is not miscible with water, it does not have logistic problems and does not increase the volatility of gasoline.
  • the use of ETBE however also has its drawbacks, as its production is limited by the relative availability of the olefins (isobutene) used. It is consequently strategically and also economically important to find new upgradings of bioethanol in the field of the production of intermediates of industrial interest .
  • EP 1069099 describes an alkylation process of benzene with isopropanol under complete gas phase conditions, in the presence of beta zeolite as catalyst.
  • EP 1069100 describes an alkylation process of benzene with isopropanol under liquid or mixed phase conditions, in the presence of beta zeolite as catalyst .
  • the benzene at least partly reacts with an alcohol or an ester in the presence of an alkylation catalyst
  • An object of the present invention therefore relates to a process for the alkylation of a mixture containing benzene which comprises reacting said mixture with one or more alcohols having the formula ROH, wherein R is an alkyl group, in the presence of a catalytic composition containing a zeolite belonging to the BEA family, and separating a product which boils within the boiling range of gasoline, wherein the alkylation and separation take place in two different steps .
  • the product which boils within the range of gasoline contains alkylbenzenes deriving from the alkylation, with one or more alcohols, of the benzene contained in the starting mixture .
  • the alkylation reaction and separation of the products obtained from the reaction mixture do not take place simultaneously, and therefore the alkylation reaction takes place without the removal of the products, i.e. without the removal of the reaction products as they are formed contemporaneously with the reaction.
  • the separation of the products obtained from the reaction environment takes place in a step subsequent to that of the reaction and consequently the alkylation reaction and the separation are effected in two different areas.
  • the sequence used allows a product to be obtained, which is not only impoverished in benzene, but enriched in alkylbenzenes, and possibly dialkyl-benzenes , useful as gasoline components.
  • Poly-alkylbenzenes which can be used as components for diesel blends, are also obtained.
  • the alcohol or alcohols which can be used in the process of the present invention have the formula ROH, wherein R is an alkyl group, preferably containing from 2 to 5 carbon atoms.
  • Alcohols which can be conveniently used are therefore ethanol, isopropanol, n-propanol, n- butanol, iso-butanol, sec-butanol, ter-butanol, pentanol, and ethanol, iso-propanol and n-butanol are preferably used.
  • all mixtures containing benzene, and possibly containing one or more alkyl-aromatic compounds with seven or more carbon atoms, such as, for example, toluene, ethylbenzene , xylenes and cumene, can be used.
  • the mixtures used can contain, in addition to benzene and C7+ alkyl-aromatic compounds, saturated compounds containing from 5 to 8 carbon atoms, such as, for example, isomers of pentane, hexane and heptane, and naphthenes, such as, for example, cyclopentanes and cyclohexanes.
  • Mixtures containing benzene and possibly alkylbenzenes which can be conveniently used in the process of the present invention can, for example, be mixtures from reforming, FCC cuts, light FCC naphtha, coker naphtha, pyrolysis cuts, straight run gasoline cuts, and mixtures thereof. Mixtures concentrated in benzene, deriving from these by distillation, can also be used.
  • reformate mixtures which are suitable for being treated in the process of the present invention are mixtures deriving from reforming processes, containing benzene, typically in a quantity of at least 5% by volume, normally at least 12% by volume, preferably from 20 to 60% by volume.
  • the following fractions deriving from reforming can be distinguished: full range reformates, light cut reformates, heavy reformates and heart cut reformates. These fractions typically contain n-paraffins, isoparaffins , naphthenes and aromatic compounds.
  • other aromatic compounds which can be present in the reforming mixtures are toluene, xylenes, ethylbenzene and cumene .
  • Mixtures deriving from these by distillation which can enrich the benzene content can also contain 80% of benzene and can be conveniently used in the process of the present invention .
  • Mixtures containing benzene which can be used in the process of the present invention typically have an end boiling point of about 260°C, preferably 120°C, even more preferably ranging from 40 to 120 °C.
  • the light reformate has a boiling range varying from C5 to 121°C
  • the full range reformate has a boiling range varying from C5 to 232 °C.
  • the mixture resulting from the alkylation step contains a larger quantity of alkylbenzenes with respect to the starting mixture, substantially deriving from the alkylation of benzene, and in a smaller quantity from the alkylation of the possible alkylbenzenes already present in the mixture before the treatment .
  • the quantity of benzene in the mixture leaving the reactor is at least 30% moles, preferably 40%, lower with respect to that of the starting mixture.
  • the mixture obtained from the alkylation step in particular proves to contain alkyl-aromatic compounds and polyalkyl-aromatic compounds deriving from the alkylation of benzene, and from the alkylation of the C7+ alkyl aromatic compounds possibly already present in the starting cut, for example a reformate cut, such as for example toluene, xylenes and ethylbenzene .
  • the compounds obtained, with reference to benzene are mainly mono-alkylation and di-alkylation products of benzene, but the formation of tri- alkylation and tetra-alkylation products is also observed.
  • ethylbenzene and diethylbenzene deriving from the reaction of benzene with ethanol, cumene and di-isopropylbenzene deriving from the reaction of benzene with isopropanol, butyl- benzene and di-butyl-benzene deriving from the reaction of benzene with butanol may be present for example in the final mixture, depending on the alcohol or alcohols used; ethyl toluene deriving from the reaction of toluene with ethanol, and cymene deriving from the reaction of toluene with isopropanol, may also be present .
  • the mixture deriving from the alkylation reaction is subjected to a separation treatment which can be effected with any of the known techniques, preferably by distillation.
  • a separation treatment which can be effected with any of the known techniques, preferably by distillation.
  • At least one product which boils within the gasoline boiling range i.e. a fraction which has a boiling range within the range of gasoline, wherein said gasoline range varies from C5 to 210 °C, is isolated from the separation.
  • the highest boiling fraction i.e. the fraction which boils at a temperature higher than 210 °C, preferably higher than 210°C and lower than 350°C, can be used as diesel component.
  • the fraction which boils within the gasoline range preferably contains alkylation products of benzene having a number of carbon atoms not higher than 12 and more preferably not higher than 10.
  • the fraction which boils within the gasoline range is selected from the range varying from C5 to 190 °C.
  • the gasoline fraction can contain the corresponding mono-alkylation product of benzene, and, in the case of the use of ethanol, also the di-alkylation product.
  • the gasoline fraction is selected from the boiling range of C7 to 190°C.
  • the octane number (RON) of the fraction which boils within the gasoline range is at least equal to that of the mixture used as starting feed, preferably at least
  • the highest boiling fraction i.e. the fraction which boils at a temperature higher than 210 °C, comprises alkyl-aromatics containing more than 12 carbon atoms, deriving from the polyalkylation of benzene, and possibly from the alkylation of alkylbenzenes with at least seven carbon atoms present in the mixture containing benzene subjected to alkylation.
  • the fraction which boils at a temperature higher than 210°C will contain, in the case of the use of ethanol, as aromatic products, at least tri- ethylbenzene compounds; in the case of the use of alcohol having three or more carbon atoms, the di- alkylation products may also be contained in this fraction.
  • a phase containing water and unconverted alcohol is isolated by demixing. Cooling can be effected before the demixing.
  • the benzene content can be further reduced by cutting the lighter products during the separation, by distillation.
  • the fraction which boils within the gasoline range can be used as gasoline component, blended for example with a non-reformate gasoline to obtain gasoline containing less than 1% of benzene. Due to the content of alkyl-aromatics having a high octane number, the product thus obtained will have a high octane number.
  • the alkylation process of the present invention is carried out under alkylation conditions of benzene, preferably at a temperature ranging from 150 to 300°C, even more preferably ranging from 180 to 280°C.
  • the operating pressure varies from atmospheric pressure to 30 atm, preferably higher than atmospheric pressure, i.e. higher than 1 atm, even more preferably ranging from 2 to 20 atm.
  • the WHSV preferably ranges from 1 to 10 hours "1 .
  • a preferred aspect of the present invention is to operate at a benzene/alcohol molar ratio lower than 4, preferably higher than 0.4 and lower than 3 , even more preferably ranging from 0.5 to 2.
  • the molar ratios indicated above refer to the ratio between benzene and the sum of the moles of alcohols used.
  • An unexpected aspect of the present invention is in fact the possibility of operating at very low benzene/alcohol (s) ratios: a high activity is unexpectedly obtained, whereas the catalyst does not suffer from the presence of water, whether it be formed during the process or fed together with the alkylating agent, if said alkylating agent is used in aqueous form.
  • the process of the present invention can be effected in gas phase, in liquid phase or in mixed phase. It is preferable to operate in gas phase or mixed phase .
  • catalysts containing a zeolite belonging to the BEA family are used, preferably beta zeolite.
  • the beta zeolite used as component of the catalytic composition of the process according to the present invention corresponds to that described in US 3,308,069, and is a porous crystalline material having the composition
  • n is the oxidation state of , x is less than 1, y ranges from 5 to 100, w from 0 to 4, M is a metal selected from those of groups IA, IIA, IIIA of the Periodic System, i.e. from transition metals and TEA is tetra-ethylammonium hydroxide.
  • Beta zeolite is also described for example in US 4,642,226 and EP159846.
  • a preferred aspect of the present invention is for the beta zeolite to be in acid form, i.e. in the form in which the H + ion has partially or totally substituted the metallic cations initially present. This substitution is effected in accordance with the known methods by means of an exchange with ammonium ions, washing and subsequent calcination.
  • the catalytic system used in the present invention can comprise suitable ligands, for example oxides of groups IIIA, IVA and IVB. More preferably, the catalytic system can contain an oxide of Si or Al as a binding carrier. Even more preferably, the catalytic system can contain ⁇ -alumina as binding carrier, ⁇ -alumina is a known material and commercially available in the form, preferred for the purposes of the present invention, of bohemite or pseudobohemite precursors, subsequently transformed into ⁇ -alumina during the preparation of the catalytic system, in the final calcination phase.
  • the ligand is preferably used in a relative weight amount with respect to the catalytic system ranging from 5:95 to 95:5.
  • a particularly preferable aspect of the present invention is to use the catalytic compositions containing beta zeolite described in EP 687500 and EP 847802.
  • EP 687500 describes a catalytic composition containing beta zeolite, as such or modified by the isomorphic substitution of the aluminium with boron, iron or gallium or by the introduction of alkaline or alkaline earth metals according to ion exchange procedures, and an inorganic ligand, in which the extrazeolite porosity is such as to be composed for a fraction of at least 25% of pores with a radius higher than 100 A.
  • EP 847802 describes a catalytic composition containing beta zeolite, as such or modified by the isomorphic substitution of the aluminium with boron, iron or gallium or by the introduction of alkaline or alkaline earth metals according to ion exchange procedures, and an inorganic ligand, in which the extrazeolite porosity is such as to be composed for a fraction of at least 25% of pores with a radius higher than 100 A, and characterized by a total volume of extrazeolite pores higher than or equal to 0.80 ml/g.
  • the reaction can be carried out in continuous, in semi-continuous or batchwise, in a fixed bed, fluid bed, circulating bed catalytic reactor, and is preferably effected in a fixed bed reactor.
  • a preferred aspect of the present invention is to use, as alcohol, a bioalcohol or a mixture of bioalcohols, i.e. alcohols of a biological origin, preferably obtained by the fermentation of sugars deriving from biomasses. These alcohols do not contain either sulfur or other contaminants typical of products of a petroleum origin.
  • a preferred aspect of the present invention therefore relates to a process for the alkylation of a mixture containing benzene which comprises putting said mixture in contact with one or more alcohols ROH, wherein R is an alkyl group, in the presence of a catalyst containing a zeolite belonging to the BEA family, and separating a product which boils within the boiling range of gasolines, wherein the alkylation and separation take place in two different steps, and wherein the alcohol or alcohols ROH are obtained from biomasses, preferably lignocellulosic biomasses.
  • an object of the present invention relates to a process for the alkylation of a mixture containing benzene and alkyl-aromatics containing at least seven carbon atoms, which comprises :
  • step (3) alkylating a mixture comprising benzene with the alcohol or mixture of alcohols obtained in step (2) , in the presence of a catalyst containing a zeolite belonging to the BEA family, and separating a product which boils within the boiling range of gasolines, wherein the alkylation and separation take place in two different steps.
  • a preferred aspect of the present invention is to use ethanol as alkylating agent.
  • bioethanol i.e. ethanol of a biological origin, preferably obtained by the fermentation of sugars deriving from biomasses .
  • ethanol obtained from the fermentation of sugars deriving from biomasses, preferably lignocellulosic biomasses, according to any of the methods known to experts in the field. Even more in particular, ethanol is used, obtained by means of a process in which the biomass, preferably lignocellulosic, is transformed into a feedstock which can be used for fermentation, preferably in the form of sugars, and then subjected to fermentation.
  • Biomass is defined as being any substance having an organic, vegetable or animal matrix, which can be destined for energy purposes, for example, as raw material for the production of biofuels, or components which can be added to fuels.
  • lignocellulosic biomass is a complex structure comprising three main components: cellulose, hemicellulose, and lignin. Their relative quantities vary according to the type of lignocellulosic biomass used.
  • Cellulose is the greatest constituent of lignocellulosic biomass and consists of glucose molecules (from about 500 to 10,000 units) bound to each other through a ⁇ -l, 4-glucoside bond.
  • Hemicellulose which is generally present in a quantity ranging from 10% by weight to 40% by weight with respect to the total weight of the lignocellulosic biomass appears as a mixed polymer, relatively short and branched, made up of both sugars with six carbon atoms and also sugars with five carbon atoms.
  • Lignin is generally present in a quantity ranging from 10% by weight to 30% by weight with respect to the total weight of the lignocellulosic biomass.
  • the synthesis of ethanol from biomass is divided into various steps and comprises the conversion of the biomass into a feedstock which can be used for the fermentation (normally in the form of sugars) by applying one of the many technological processes available: said conversion forms the step which differentiates the various technological solutions in the synthesis of bioethanol .
  • This step is followed by the fermentation of the intermediates of the biomass using bio-catalysts (micro-organisms such as yeast and bacteria) to obtain ethanol in a low-concentration solution.
  • bio-catalysts micro-organisms such as yeast and bacteria
  • the first step in order to optimize the transformation of the lignocellulosic biomass into products for energy use, subjecting said biomass to a treatment which separates the lignin and hydrolyzes the cellulose and hemicellulose to simple sugars such as, for example, glucose and xylose, which can then be subjected to fermentation processes to produce alcohols, is known.
  • hydrolysis preferably acid
  • strong mineral acids generally H 2 S0 4 , HC1 or HN0 3
  • SHF process enzymatic hydrolysis
  • the first and second step can be effected simultaneously, for example in the presence of the fungus T. reesei and yeast S. cerevisiae (SSF process) .
  • the ethanol obtained from step (2) is separated, for example, by means of distillation.
  • propanol preferably isopropanol
  • alkylating agent preferably isopropanol
  • propanol of a biological origin is used, preferably obtained by the fermentation of biomasses, as described for example in US2009/0246842.
  • a further aspect of the present invention is to use butanol, preferably n-butanol, as alkylating agent, according to what is specified above in general for bioalcohols.
  • biobutanol is used, i.e. butanol of a biological origin, preferably prepared by the fermentation of biomasses, according to the A.B.E.
  • Another aspect of this invention is the use, as alkylating agent, of mixtures of alcohols, in particular mixtures containing at least two alcohols selected from ethanol, propanol, butanol.
  • Mixtures of alcohols which can be conveniently used are those deriving from conversion processes of biomasses, such as, for example, the MixAlco process or the ABE process described above, or Fusel alcohol mixtures, obtained as by-product of the fermentation to ethyl alcohol, can be used.
  • the MixAlco process comprises both biological and chemical steps, and converts biodegradable material to carboxylic acids, then to ketones, and subsequently to mixtures of primary alcohols (ethanol, propanol, butanol) , and secondary alcohols (isopropanol, 2- butanol, 3-pentanol) .
  • a method which allows these mixtures of alcohols to be obtained is for example that described in US 2008/0176301 which comprises subjecting a biomass to fermentation to obtain carboxylic acids or carboxylates , and hydrogen, separating the hydrogen and using it in a subsequent step for converting the carboxylates or carboxylic acids into alcohols.
  • Another process which can be adopted for obtaining mixtures of alcohols which can be used directly in the process of the present invention is the A.B.E. process, described above with respect to the production of biobutanol. If this mixture of alcohols is to be used, there is no need to isolate the single alcohol components .
  • Another mixture of alcohols which can be used in the process of the present invention is Fusel alcohol, a by-product of the fermentation of ethanol, containing 60-70% of amyl alcohol and smaller quantities of n- propyl and iso-butyl alcohol.
  • an extruded catalyst based on beta zeolite are charged into a tubular reactor (diameter of about 1.5 cm).
  • the catalyst is prepared as described in Example 4 of EP 847 802, using the beta zeolite prepared as described in Example 3 of EP 847 802 and alumina in the form of bohemite .
  • the catalyst has a porosity fraction with a radius higher than 100 A of over 35% and the extrazeolite pore volume is equal to 0.81 ml/g.
  • the characteristics correspond to those indicated in Table I of EP 847 802.
  • the catalyst is granulated and sieved into the fraction 0.8-1 mm.
  • the temperature of the reactor is brought to 250°C and the pressure to 10 atm, in a flow of N 2 (5 Nl/hour) .
  • the nitrogen flow is interrupted and 8.2 g/hour of a C6/C7 "heart cut" reformate mixture, having a boiling point within the range of 40-100 °C, containing 38.9% by weight of benzene, the remaining percentage consisting of C6 and C7 paraffins, are then fed to the reactor together with 1.9 g/hour of anhydrous ethanol, with a benzene/alcohol molar ratio of 1.0 and a total WHSV of 2.0 hours "1 .
  • the organic reaction effluent collected from the beginning to the 71 st operating hour i.e. the effluent obtained after separation of the water formed during the reaction by demixing, is sent to a gaschromatograph to be analyzed.
  • the quantity of water separated from the effluent mixture of the reaction proves to be equal to 7.3% by weight with respect to the weight of the total effluent mixture.
  • the data obtained from the gaschromatographic analysis show a conversion of benzene of 43.0% moles and a conversion of ethanol of 98.8% moles.
  • the selectivity to alkyl-aromatics with respect to the ethanol is 93.3% moles and with respect to the benzene >99.6% moles, wherein alkyl-aromatics refer to ethyl- benzene, diethylbenzene and polyethyl-benzenes .
  • the selectivity to ethyl-benzene and diethyl-benzene with respect to the benzene proves to be 64.0% moles.
  • a fraction boiling within the range of 100 a 210 °C is separated, which can be used as component of gasolines, and a fraction which boils from a temperature higher than 210°C to 320°C which can be used as diesel component .
  • a test is carried out under the same conditions and with the same catalyst as Example 1, feeding to the reactor, 7.0 g/hour of a C6/C7 "heart cut" reformate mixture, having a boiling point within the range of 40- 100 °C, containing 39.1% by weight of benzene, the remaining percentage consisting of C6 and C7 paraffins, and 2.0 g/hour of aqueous ethanol at 95% by weight, with a benzene/alcohol molar ratio of 0.8 and a total WHSV of 1.8 hours "1 .
  • the organic effluents of the reaction are collected periodically over 175 operating hours and, after separation of the reaction water by demixing, are sent to a gaschromatograph to be analyzed.
  • the average quantity of water separated from the effluent mixture of the reaction proves to be equal to 9.2% by weight with respect to the weight of the total effluent mixture.
  • the data obtained from the gaschromatographic analysis show an average conversion of benzene of 40.0% moles and a conversion of ethanol of 95.6% moles.
  • the average selectivity to alkyl-aromatics with respect to the ethanol is 87.8% moles and with respect to the benzene >99.6% moles, wherein alkyl-aromatics refer to ethyl-benzene , diethylbenzene and polyethyl-benzenes .
  • the average selectivity to ethyl-benzene and diethyl-benzene with respect to the benzene proves to be 62.9% moles.
  • a fraction boiling within the range of 100 a 210 °C is separated, which can be used as component of gasolines, and a fraction which boils from a temperature higher than 210°C to 320°C which can be used as diesel component .
  • Example 2 The test of Example 2 is continued, feeding, at 383 operating hours, all the operative conditions remaining unvaried, 7.2 g/hour of the same C6/C7 "heart cut" reformate mixture as Example 2, containing 39.1% by weight of benzene, the remaining percentage consisting of C6 and C7 paraffins, and 1.7 g/hour of aqueous ethanol at 90% by weight, with a benzene/alcohol molar ratio of 1.1 and a total WHSV of 1.8 hours "1 .
  • the organic effluents of the reaction are collected periodically up to 580 operating hours and, after separation of the reaction water by demixing, subjected to gaschromatographic analysis.
  • the average quantity of water separated from the effluent mixture of the reaction proves to be equal to 6.7% by weight with respect to the weight of the total effluent mixture.
  • the data obtained from the gaschromatographic analysis show an average conversion of benzene of 28.9% moles and a conversion of ethanol of 81.9% moles.
  • the average selectivity to alkyl-aromatics with respect to the ethanol is 86.1% moles and with respect to the benzene >99.5% moles, wherein alkyl-aromatics refer to ethyl-benzene, diethylbenzene and polyethyl-benzenes .
  • the average selectivity to ethyl-benzene and diethyl-benzene with respect to the benzene proves to be 70.8% moles.
  • a fraction boiling within the range of 100 a 210 °C is separated, which can be used as component of gasolines, and a fraction which boils from a temperature higher than 210°C to 320°C which can be used as diesel component .
  • Example 3 The test of Example 3 is continued, feeding, at 581 operating hours, all the operative conditions remaining unvaried, 7.6 g/hour of the same C6/C7 "heart cut" reformate mixture as Example 2, containing 39.1% by weight of benzene, the remaining percentage consisting of C6 and C7 paraffins, and 1.7 g/hour of aqueous ethanol at 80% by weight, with a benzene/alcohol molar ratio of 1.25 and a total HSV of 1.9 hours "1 .
  • the average selectivity to alkyl-aromatics with respect to the ethanol is 76.6% moles and with respect to the benzene >99.5% moles, wherein alkyl-aromatics refer to ethyl-benzene, diethylbenzene and polyethyl- benzenes.
  • the average selectivity to ethyl-benzene and diethyl-benzene with respect to the benzene proves to be 73.4% moles.
  • the average quantity of water separated from the effluent mixture of the reaction proves to be equal to 7.7% by weight with respect to the weight of the total effluent mixture.
  • a fraction boiling within the range of 100 a 210 °C is separated, which can be used as component of gasolines, and a fraction which boils from a temperature higher than 210°C to 320°C which can be used as diesel component .
  • a test is carried out in the same reactor and with the same catalyst as Example 1, at a temperature of 190°C and a pressure of 10 atm, feeding to the reactor 6.8 g/hour of a C6/C7 "heart cut” reformate mixture and 1.2 g/hour of isopropanol, with a benzene/alcohol molar ratio of 1.67 and a total WHSV of 1.6 hours "1 .
  • the C6/C7 mixture contains 37.6% by weight of benzene and 5.2% of toluene, the remaining percentage consisting of C6 and C7 paraffins.
  • the quantity of water separated from the effluent mixture of the reaction proves to be equal to 4.5 % by weight with respect to the weight of the total effluent mixture .
  • the data show a conversion of benzene of 43.7% moles, a conversion of toluene of 31.8% moles and isopropanol of 98.5% moles.
  • the selectivity to alkyl- aromatics with respect to the isopropanol is 83.6% moles, with respect to the benzene and toluene >99.5% moles, wherein alkyl-aromatics refer to the products isopropyl -benzene, di-isopropyl-benzene, poly- isopropyl-benzene, iso-propyl-toluene, di-isopropyl- toluene .

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Abstract

L'invention porte sur un procédé pour la production de composants de carburant pour véhicules à moteur par l'alkylation, avec un ou plusieurs alcools, d'un mélange contenant du benzène et la séparation d'un produit qui a un point d'ébullition dans le domaine d'ébullition de l'essence, l'alkylation et la séparation ayant lieu dans deux étapes différentes. Le procédé est effectué en présence d'une zéolite appartenant à la famille BEA. À la fin du procédé, une quantité importante de benzène n'est plus présente dans le mélange final, à cause de l'alkylation dudit substrat avec l'alcool ou les alcools utilisés. Le procédé permet également d'obtenir un produit qui a un point d'ébullition dans le domaine d'ébullition du diesel. Un aspect particulièrement préféré de l'invention consiste à utiliser des alcools issus de matières premières d'origine agricole ou végétale.
PCT/IB2010/003379 2009-12-23 2010-12-23 Procédé pour la production de composants de carburant pour véhicules à moteur WO2011077242A1 (fr)

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ITMI2009A002290 2009-12-23

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WO2014109766A1 (fr) * 2013-01-14 2014-07-17 Badger Licensing Llc Procédé d'équilibrage entre la production d'essence et de distillat dans une raffinerie
EP2631282B1 (fr) * 2012-02-24 2015-04-08 Repsol, S.A. Procédé de production de distillats moyens
US9790444B2 (en) 2013-04-26 2017-10-17 The Regents Of The University Of California Methods to produce fuels
US9856427B2 (en) 2011-05-27 2018-01-02 The Regents Of The University Of California Method to convert fermentation mixture into fuels
US10106480B2 (en) 2014-10-29 2018-10-23 The Regents Of The University Of California Methods for producing fuels, gasoline additives, and lubricants using amine catalysts
US10138193B2 (en) 2014-10-29 2018-11-27 The Regents Of The University Of California Methods for producing fuels, gasoline additives, and lubricants using amine catalysts
US10207961B2 (en) 2014-03-24 2019-02-19 The Regents Of The University Of California Methods for producing cyclic and acyclic ketones

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9856427B2 (en) 2011-05-27 2018-01-02 The Regents Of The University Of California Method to convert fermentation mixture into fuels
EP2631282B1 (fr) * 2012-02-24 2015-04-08 Repsol, S.A. Procédé de production de distillats moyens
WO2014109766A1 (fr) * 2013-01-14 2014-07-17 Badger Licensing Llc Procédé d'équilibrage entre la production d'essence et de distillat dans une raffinerie
US9790444B2 (en) 2013-04-26 2017-10-17 The Regents Of The University Of California Methods to produce fuels
US10207961B2 (en) 2014-03-24 2019-02-19 The Regents Of The University Of California Methods for producing cyclic and acyclic ketones
US10618856B2 (en) 2014-03-24 2020-04-14 The Regents Of The University Of California Methods for producing cyclic and acyclic ketones
US10106480B2 (en) 2014-10-29 2018-10-23 The Regents Of The University Of California Methods for producing fuels, gasoline additives, and lubricants using amine catalysts
US10138193B2 (en) 2014-10-29 2018-11-27 The Regents Of The University Of California Methods for producing fuels, gasoline additives, and lubricants using amine catalysts

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