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EP2631282B1 - Procédé de production de distillats moyens - Google Patents

Procédé de production de distillats moyens Download PDF

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Publication number
EP2631282B1
EP2631282B1 EP12382067.2A EP12382067A EP2631282B1 EP 2631282 B1 EP2631282 B1 EP 2631282B1 EP 12382067 A EP12382067 A EP 12382067A EP 2631282 B1 EP2631282 B1 EP 2631282B1
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EP
European Patent Office
Prior art keywords
naphtha
stream
process according
catalyst
alkylation
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.)
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EP12382067.2A
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German (de)
English (en)
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EP2631282A1 (fr
Inventor
Iñigo Ribas Sanguesa
Rafael Roldán Mesa
Juan Pedro GÓMEZ MARTÍN
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Repsol SA
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Repsol SA
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Priority to ES12382067.2T priority patent/ES2541052T3/es
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • 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
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a process for producing middle distillates.
  • the process produces hydrogen, gasoline and middle distillate from a heavy naphtha and an olefinic stream.
  • Catalytic reforming units are catalytic units with several reactors in series, where a straight run naphtha or a conversion naphtha, such as, for example, an FCC (Fluid Catalytic Cracking) naphtha, undergoes naphthene dehydrogenation, paraffin isomerisation and paraffin dehydrocyclisation reactions, in order to improve the properties of said naphthas as fuels and, more specifically, increase their octane number for gasolines.
  • a straight run naphtha or a conversion naphtha such as, for example, an FCC (Fluid Catalytic Cracking) naphtha
  • FCC Fluid Catalytic Cracking
  • patent WO 00/39253 discloses the improvement of the cetane number of FCC heavy naphthas or FCC light gas oil, by directly alkylating them with olefinic streams, in the presence of a solid acid catalyst.
  • Patent US 4594143 discloses the alkylation of Jet-fuel (150°C-260°C) with an olefinic stream, to produce a diesel fuel fraction, using a solid acid catalyst.
  • Patent US 290460 discloses the production of alkyl aromatics with a high octane number in the gasoline distillation range, starting from aromatic and olefinic streams.
  • diesel fuel is produced from the alkylation of a direct distillation naphtha with a high aromatic content and FCC naphthas with an acid catalyst such as aluminum chloride.
  • Patent WO 00/39253 discloses a process for obtaining diesel fuel by the alkylation of a heavy naphtha stream or a distillate containing more than 40% by weight of aromatics with a second stream that contains olefins, in the presence of a solid acid catalyst. Said patent does not mention that the aromatic-rich stream may be obtained by reforming the heavy naphtha nor the naphthene content of said stream.
  • Patent WO 2008/043066 discloses a process for the production of middle distillates, such as kerosene and diesel fuel.
  • the process includes a step where the paraffinic naphtha is converted into benzene and olefins, and the benzene and the olefins are made react, in order to obtain alkylbenzenes.
  • the process described uses a Sn/Pt catalyst to perform the first step. In said step, the production of aromatics is practically limited to benzene, since the rest of the C7+ paraffins are basically converted into olefins.
  • Patents US 5380425 and US 5273644 disclose processes comprising reforming and alkylation. Both processes introduce a benzene-containing effluent to the alkylation step.
  • Patent US 4594144 discloses a process for reforming and alkylation, with intermediate extraction of aromatic compounds
  • the present invention relates to a process to produce hydrogen, gasoline and a middle distillate which can be used for the blending of middle distillates dedicated to fuels.
  • the process can be implemented from scratch, it can be also implemented by modifying an existing catalytic reforming plant, by using one of the multiple reforming reactors for the dehydrogenation of naphthenes and the remaining reactors to carry out an alkylation process.
  • the process as herein disclosed produces hydrogen, gasoline and a middle distillate.
  • the process can also produce a LPG fraction.
  • Another advantage of the process is that it can be used as raw material olefinic streams and straight run naphthas, whose current destination is the production of gasoline or the chemical industry.
  • hydrogen is obtained, which is currently a necessary and expensive chemical and refineries may present a deficit of it.
  • the possibility of adapting a catalytic reforming plant for the production of a middle distillate from an aromatic and/or a naphthenic stream and an olefinic stream entails a reduction of the costs.
  • the catalyst of the process can be regenerated in situ by burning the coke formed during the process with air.
  • a process for producing hydrogen, gasoline and a middle distillate is provided according to claim 1.
  • Preferred heavy naphtha to be used in step (i) is an hydrocarbon stream with a content of at least 20% w/w of naphthenes plus aromatics, and with a distillation range between 75°C to 200°C, preferably between 90°C to 140 °C.
  • suitable naphtha for the process as herein disclosed are straight-run naphtha, heart cut FCC naphtha, aromatic concentrates, coker naphtha, visbreaker naphtha, steam cracker naphta or mixtures thereof.
  • the naphtha is straight-run.
  • C6+ heavy naphtha is also preferred.
  • a C6+ heavy naphtha is a heavy naphtha that consists essentially of molecules with 6 or more carbon atoms.
  • the dehydrogenation of the heavy naphtha of step (i) is carried out at typical temperature higher than 250°C, preferably between 250°C and 650°C, more preferably between 350°C and 650°C and more preferably between 480°C and 530 °C.
  • the pressure of the system in this step is typically between 1 and 80 bar, and preferably between 3 and 30 bar.
  • the aromatic compounds are typically produced in the dehydrogenation of heavy naphtha in the presence of at least one reforming catalyst of step (i).
  • the content of naphthenes is typically reduced after the dehydrogenation of heavy naphtha in the presence of at least one reforming catalyst of step (i).
  • excellent results are obtained when the amount of naphthenes is as low as possible and the amount of aromatic compounds is as high as possible.
  • at least a 20% by weight of the stream of naphtha used in step (ii) are aromatics and less than a 1 % by weight of the stream of naphtha used in step (ii) are naphthenes.
  • a reforming catalyst is used in step (i). It will be understood by those having skill in the art that there may be more than one reforming catalyst in step (i). Examples of useful reforming catalysts used in step (i) as herein disclosed include Pt, Re, Ir, Ge, Sn or mixtures thereof supported over alumina.
  • the reforming catalyst could be preferably selected from RG-582 and RG-682 of Axens or R62, R86, R56 and R98 of UOP or mixtures thereof.
  • At least 90% of the hydrogen produced at the stage of dehydrogenation is separated between steps (i) and (ii) or between steps (ii) and (iii).
  • essentially all the hydrogen produced at the stage of dehydrogenation is separated between steps (i) and (ii) or between steps (ii) and (iii). Even more preferably, more than 99 % of the hydrogen produced is separated.
  • an alkylation step (ii) is carried out.
  • the olefins are alkylated with the aromatic compounds produced in step (i) or oligomerised by reacting among them, giving rise to a new hydrocarbon stream, which is rich in compounds with a distillation range of 150+ (products that distillate at temperature above 150°C according to standard ASTM D86).
  • the alkylation of aromatic compounds with olefinic streams, using a solid acid catalyst such as zeolites, acidic resins or supported phosphoric acid, to produce alkylaromatics and oligomers, is studied in the literature.
  • the solid acid catalyst is a zeolite.
  • Preferred zeolites are beta, mordenite, ferrierite, ZSM-5, faujasite (type Y or X) or mixtures thereof. More preferably the zeolite is a beta zeolite. And more preferably, the zeolite is beta zeolite with a SiO 2 /Al 2 O 3 ratio of 25, which will be called hereafter "Beta 25".
  • the solid acid catalyst is an ITQ catalyst, synthesized at Instituto Tecnologico Quimico (ITQ) at Valencia (Spain).
  • ITQ Instituto Tecnologico Quimico
  • the preferred ITQ catalysts are ITQ-39, ITQ-30, ITQ-2 or mixtures thereof.
  • the solid acid catalyst is a MCM catalyst.
  • the preferred MCM catalysts are MCM-5, MCM-22, MCM-36, MCM-49, MCM-56 or mixtures thereof. More preferably, the MCM catalyst is MCM-5 catalyst.
  • the solid acid catalyst is an acid resin.
  • the preferred acid resins are selected from Acid Resins manufactured by Purolite, or the AMBERLYSTTM manufactured by Rohm and Haas and supported Nafion resin manufactured by Dupont and mixtures thereof.
  • Nafion refers to a sulfonated tetrafluoroethylene based fluoropolymercopolymer.
  • Preferred Nafion for the present invention are Nafion NR50, NR40, R1000 and R1100.
  • the acid resin is Purolite CT-275, Amberlyst A-15, A-35, A-36, A-46 or mixtures thereof. More preferably the acid resin is Purolite CT-275.
  • the deactivation of the catalyst is due to the formation of coke or coke precursors on the surface thereof, it may be required to periodically regenerate the catalyst.
  • the three typical processes to regenerate the alkylation catalyst are: hydrogen stripping, gasoline/naphtha washing and combustion with air.
  • the catalyst regeneration is normally held at intervals of at least six months after stopping the unit, and air is introduced to burn the coke.
  • the process contemplates having two (even three) reactors in parallel or in series with a facility such that while one is in normal operation, the other is regenerating the catalyst.
  • the zeolite catalyst regeneration may be performed by washing with a stream of hydrocarbon as disclosed in the patent WO 01/83408 or by a stripping with hydrogen as disclosed in the patent EP 0679437 or by burning the coke with air.
  • the adequate temperature to carry out step (ii) depend on the solid acid catalyst used, preferably the temperature is between 80°C and 350°C, more preferably between 200 and 300°C.
  • the pressure of the system is normally between 2 and 120 bars, and preferably between 30 and 60 bars.
  • the olefinic stream is selected from ethylene; propylene; butene, preferably FCC butene; pentene, preferably FCC or Cracker pentene; olefinic LPG; heart cut FCC naphtha; coker naphtha; FCC light naphtha and mixtures thereof. More preferably the olefinic stream of step (ii) is selected from the group consisting of propylene, butene, pentene, FCC light naphtha, and mixtures thereof.
  • the fraction obtained in step (iii) also comprises LPG.
  • LPG are mixtures of C3 and C4 hydrocarbons which are predominantly propane, propylene, n-butane, butylenes, iso-butane and isobutylene.
  • the production of the middle distillate fraction is typically between 10 and 70% weight/weight of the initial mixture of compounds obtained in step (ii).
  • the fraction rich in gasoline is typically between 30 and 90% weight/weight of the initial mixture of compounds obtained in step (ii).
  • the fraction rich in LPG is typically less than 45% of the mixture of compounds obtained in step (ii).
  • the separation of the middle distillate and other fraction rich in gasoline may be carried out by distillation.
  • the heavy naphtha of step (i) comprises less than 0.5 ppm of sulphur and less than 0.5 ppm of nitrogen.
  • the olefinic stream which feeds step (ii) comprises less than 1 ppm of nitrogen.
  • the elimination of nitrogen can be carried out by treatment with acid resins for example.
  • contents of nitrogen higher than 1 ppm in the olefinic stream of step (ii) may inhibit the formation of middle distillates by alkylation reactions.
  • the obtained product may need to be fractionated into gasoline (150-, which are products that distillate at temperature below 150°C according to standard ASTM D86) and middle distillate (150+), preferably by distillation.
  • gasoline 150-, which are products that distillate at temperature below 150°C according to standard ASTM D86
  • middle distillate 150+
  • LHSV Liquid Hourly Space Velocity (units: h -1 ). It is calculated as volumetric flowrate divided by the volumen of the catalyst in the reactors, and it is equivalent to the inverse of the residence time.
  • WHSV Weight hourly space velocity (units: h -1 ). It is calculated as mass flowrate divided by mass of catalyst in the reactors.
  • ASTM D86 This test method covers the atmospheric distillation of petroleum products using a laboratory batch distillation unit to determine quantitatively the boiling range characteristics of such products.
  • PIONA Method of analysing chemical components by means of chromatography.
  • the compounds are grouped into families (Paraffins, Isoparaffins, Olefins, Naphthenes and Aromatics).
  • octane number sometimes called “octane rating” is a scale that measures the anti-knock capacity of the fuel (such as gasoline) when it is compressed inside an engine cylinder.
  • octane rating is a scale that measures the anti-knock capacity of the fuel (such as gasoline) when it is compressed inside an engine cylinder.
  • cetane number or rating is related to the time that elapses between the injection of fuel and the beginning of the combustion thereof, called “Ignition interval”. High-quality combustion takes place when there is a fast ignition, followed by total, uniform burning of the fuel. In sum, it is an indicator of the efficiency of the reaction that takes place in internal combustion engines.
  • This number is calculated from the density and the boiling point of the hydrocarbons that make up the basis of the fuel.
  • the calculation method has always been strictly standardised, and for quite a long time a two-variable equation was used to determine it (ASTM D976); currently, a more precise correlation (ASTM D4737) is applied, which operates with four variables.
  • FCC Fluid Catalytic Cracking
  • the catalyst is separated from the reaction products by means of cyclones, and the coke that is generated and adhered thereto due to the high reaction temperatures is burnt in a special equipment prior to being re-circulated into the reactor; the energy released during the burning is used to provide part of the heating to the load stream.
  • Coker this process consists of heating a residual oil feed to its thermal cracking temperature in a furnace with multiple parallel passes. This cracks the heavy, long chain hydrocarbon molecules of the residual oil into coker gas oil and petroleum coke.
  • Heart cut FCC naphtha Naphtha produced in an FCC process with a distillation range of between 80°C-150°C.
  • Reformate Naphtha produced in a catalytic reforming process. Its boiling range is between 75°C-170°C and it is basically composed of aromatics and isoparaffins.
  • Hydrogenation Process whereby a hydrocarbon molecule loses one or more Hydrogen molecules. When it is applied to the production of aromatic compounds, each hydrocarbon molecule loses 3 hydrogen molecules.
  • Alkylation Chemical process whereby an aromatic compound and an olefin react to form an alkyl aromatic compound.
  • LPG Liquefied petroleum gas is a flammable mixture of hydrocarbon gases used as a fuel in heating appliances and vehicles. It consists of hydrocarbon molecules of 3 and 4 carbon atoms.
  • full range naphtha is defined as the fraction of hydrocarbons in petroleum boiling between 30 °C and 200 °C. It consists of a complex mixture of hydrocarbon molecules generally having between 5 and 12 carbon atoms. It typically constitutes 15-30% of crude oil, by weight.
  • Light naphtha is the fraction boiling between 30 °C and 90 °C and consists of molecules with 5-6 carbon atoms.
  • Heavy naphtha boils between 90 °C and 200 °C and consists of molecules with C6+, preferably 6-12 carbons.
  • gasoline refers to any liquid fuel that can be used to operate a spark ignition internal combustion engine.
  • Gasoline typically contains a mixture of C5 to C10 hydrocarbons having a boiling range of about 70 °C to 160 °C (ASTM D86).
  • step (ii) The term “partially recycled” refers to a stream of at least 90%(v) with respect to the fraction rich in gasoline obtained in step (ii).
  • middle distillate refers to a hydrocarbon fraction, wherein the hydrocarbons consist essentially of hydrocarbons typically having a carbon chain length of 10 to 25 (designated C 10 -C 25 ).
  • the middle distillate fraction typically has a boiling point in the range of 150 °C to 430 °C (ASTM D86) and preferably 175 °C to 350 °C (ASTM D86).
  • the middle distillate hydrocarbons are those typically used as kerosene and/or diesel fuels. It should be noted that since distillation does not provide an absolute cut off at a specific chain length, the various distillate fractions may contain insignificant amounts of hydrocarbons having a slightly lower or slightly higher carbon chain lengths.
  • a distillate fraction comprising a wider range of hydrocarbons such as C 9 to C 26 or a narrower range of hydrocarbons such as C 14 to C 18 should also be understood as a middle distillate fraction.
  • Light fraction refers to a hydrocarbon fraction, wherein the hydrocarbon chain length is 1 to 4 (designated C 1 -C 4 ).
  • the light fraction also includes other gaseous components such as hydrogen, depending on the process from which the light fraction derives.
  • kerosene refers to a hydrocarbon fraction with a boiling point of 150°C to 220°C. It is part of the called Middle distillate.
  • diesel refers to a hydrocarbon fraction with a boiling point of 220°C to 380°C. It is part of the called Middle distillate.
  • reforming catalyst refers to a dehydrogenation catalyst and requires a metal to provide the dehydrogenating activity, preferably dispersed on a support material.
  • metals include platinum and palladium, although several metals may be present at the same time, such as, for example, platinum-rhenium, platinum-germanium or platinum-tin. If cyclisation and/or isomerisation activity are required in the catalyst, as in the case of the catalytic reforming process catalyst, it is preferred that the metal or metals be dispersed on an acid support, such as, for example, alumina, chlorided alumina or a zeolite.
  • the reforming catalysts may be prepared by using any suitable techniques. Example of those catalysts are well known in the art, as for example in the patents US 4124491 and CA 1080689 .
  • acid catalyst is meant a substance which has the ability to donate protons as defined by Bronsted, or a substance which can form a covalent bond with an atom, molecule or ion that has an unshared electron pair as defined by Lewis, or a substance which presents both Bronsted and Lewis acid sites. Any known acid catalyst can be used for the process as herein disclosed.
  • a zeolitic catalyst or zeolite refers to a microporous aluminosilicate with a three-dimensional channel system. It is generally acidic and may present numerous different structures, known as topologies. Their small pore size, of molecular dimensions, gives zeolites the property of being molecular sieves, i.e. useful in the separation of molecules with different sizes. Moreover, these acidity and morphological properties provide catalytic activity in numerous reactions, such as cracking, isomerisation, dewaxing or NO x decomposition. They present shape selectivity, which means that the dimension of their channels allows for certain chemical reactions to take place in the interior thereof and prevents others from taking place. Examples of zeolites are faujasite (X and Y), beta, mordenite, ferrierite, ZSM-5 and MCM-22. Example of zeolite applications may be found in patents EP 0550120 and US 4740292 .
  • the "ITQ catalysts” are zeolitic catalysts that have been developed by the Instituto Tecnológico Quimico at Valencia (Spain).
  • MCM catalysts are known in the art, and can be obtained from, for example, ExxonMobil Catalyst Technologies LLC (Baytown, TX). MCM type catalysts, including synthesis details, are described in, for example, the patents U.S. 7198711 , US 5639931 , US 5296428 , US 5146029 and U.S. Application 2006/0194998 .
  • Acid resin is understood to mean a matrix made of an organic polymer.
  • the structure presents pores wherein ions may be exchanged, which makes them capable of being used in purification and separation.
  • the most typical resins are based on a cross-linked polystyrene matrix, which is obtained by adding another compound, such as, for example, divinylbenzene, to styrene during the polymerisation process.
  • Another compound such as, for example, divinylbenzene
  • protons from the surface thereof By substituting protons from the surface thereof with other organic groups, it is possible to functionalise the resins, such that they may be acidic or basic.
  • acid resins have sulfonic acid groups inside them.
  • resins are CT-275, manufactured by Purolite, or A-15, A-35 and A-36, manufactured by Rohm and Haas. As an application example, they are used industrially for the production of ethers, as described in patents US 4423251 and US 4540831 .
  • Tables 1 and 2 list the typical compositions of the major streams that are obtained throughout the typical process described in Figure 1 .
  • stream (A), rich in naphthenes and aromatics feeds section (B) (dehydrogenation section), to obtain a hydrogen-rich gaseous stream (D).
  • the naphtha produced in the dehydrogenation section may be fractionated in order to reduce its benzene content. Jointly with an olefin-rich stream (H), hhe naphtha stream without benzene (G) feeds the alkylation section (I).
  • the product of the alkylation section (K) is fractionated, to obtain two differentiated streams, a gasoline stream (M), which may be partially recycled (P) as a feed for the naphthene alkylation section (I) , and a middle distillate stream (kerosene + diesel fuel) (N).
  • M gasoline stream
  • P partially recycled
  • N middle distillate stream
  • Table 1 Stream see Fig.
  • F1 corresponds to the heavy naphtha stream and F2 corresponds to the olefinic stream.
  • Tables 6 and 7 attempt to illustrate the effect of the % of aromatics and the % of naphthenes in the feed that is supplied to the alkylation section on the middle distillate yield of the product.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (14)

  1. Un procédé pour produire de l'hydrogène, de l'essence et du distillat moyen, comprenant au moins les étapes suivantes :
    (i) déshydrogénation d'un naphta lourd en présence d'au moins un catalyseur de reformage, pour obtenir un flux de naphta déshydrogéné ;
    (ii) alkylation du flux de naphta déshydrogéné riche en composés aromatiques plus lourds que le benzène obtenu au cours de l'étape (i) avec un flux oléfinique en présence d'un catalyseur acide solide ; et
    (iii) séparation du mélange de composés obtenu au cours de l'étape (ii) dans au moins une fraction de distillat moyen et une fraction riche en essence ;
    (iv) la fraction riche en essence obtenue au cours de l'étape (iii) est partiellement recyclée vers le flux oléfinique à l'entrée d'alkylation de l'étape (ii) ;
    et dans lequel une séparation totale ou partielle de l'hydrogène produit au cours de l'étape (i) est réalisée entre les étapes (i) et (ii) ou entre les étapes (ii) et (iii) afin d'obtenir un flux d'hydrogène, et qui comprend la séparation du naphta léger riche en benzène et du naphta lourd riche en composés aromatiques plus lourds que le benzène entre les étapes (i) et (ii).
  2. Le procédé selon la revendication précédente, dans lequel le naphta lourd utilisé au cours de l'étape (i) est un flux d'hydrocarbure avec une teneur d'au moins 20% p/p en naphtènes plus aromatiques, et avec une gamme de distillation comprise entre 75°C et 200°C, de préférence entre 90°C et 140°C.
  3. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel le naphta lourd utilisé au cours de l'étape (i) est sélectionné dans le groupe composé de : naphta de distillation directe, naphta fraction de coeur par craquage catalytique fluide, concentrés d'aromatiques, naphta de cokéfaction ou leurs mélanges, le naphta est de préférence du naphta de distillation directe.
  4. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel la déshydrogénation du naphta lourd de l'étape (i) est réalisée à une température comprise entre 250°C et 650°C, de préférence entre 350°C et 650°C et de préférence encore entre 480 et 530°C.
  5. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel la déshydrogénation du naphta lourd de l'étape (i) est réalisée à une pression comprise entre 1 et 80 bar, de préférence entre 3 et 30 bar.
  6. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel au moins 90% de l'hydrogène produit au cours de l'étape de déshydrogénation est séparé entre les étapes (i) et (ii) ou entre les étapes (ii) et (iii).
  7. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel l'alkylation du flux de naphta déshydrogéné obtenue au cours de l'étape (ii) avec un flux oléfinique est réalisée en présence d'un catalyseur acide solide sélectionné dans le groupe composé de zéolithes, résines acides, acide phosphorique supporté, aluminosilicates, Nafion ou leurs mélanges, le catalyseur acide solide est de préférence un catalyseur ITQ, un catalyseur MCM, un catalyseur bêta 25, une résine A-35 ou Purolite CT-275.
  8. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel l'alkylation du flux de naphta obtenue au cours de l'étape (ii) est réalisée à une température comprise entre 80°C et 350°C, de préférence entre 200°C et 300°C.
  9. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel l'alkylation du flux de naphta obtenue au cours de l'étape (ii) est réalisée à une pression comprise entre 2 et 120 bar, de préférence entre 30 et 60 bar.
  10. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel le flux oléfinique de l'étape (ii) est sélectionné dans le groupe composé d'éthylène, propylène, butène, pentène, GPL oléfiniques, naphta fraction de coeur par craquage catalytique fluide, naphta de cokéfaction, naphta léger par craquage catalytique fluide, ou leurs mélanges.
  11. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel la fraction de distillat moyen obtenue est comprise en 10 et 70% poids/poids du mélange initial de composés obtenu au cours de l'étape (ii).
  12. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel la fraction riche en essence est comprise en 30 et 90% poids/poids du mélange initial de composés obtenu au cours de l'étape (ii).
  13. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel le flux oléfinique qui alimente l'étape (ii) comprend moins de 1 ppm d'azote.
  14. Le procédé selon n'importe laquelle des revendications précédentes, dans lequel la teneur en naphtènes est réduite après la déshydrogénation d'un naphta lourd en présence d'au moins un catalyseur de reformage de l'étape (i), de préférence la teneur en naphtènes est inférieure à 1 % en poids.
EP12382067.2A 2012-02-24 2012-02-24 Procédé de production de distillats moyens Not-in-force EP2631282B1 (fr)

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ES12382067.2T ES2541052T3 (es) 2012-02-24 2012-02-24 Proceso para la producción de destilados medios

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