EP3717596A1 - Procede d'amelioration de production de benzene et toluene - Google Patents
Procede d'amelioration de production de benzene et tolueneInfo
- Publication number
- EP3717596A1 EP3717596A1 EP18800661.3A EP18800661A EP3717596A1 EP 3717596 A1 EP3717596 A1 EP 3717596A1 EP 18800661 A EP18800661 A EP 18800661A EP 3717596 A1 EP3717596 A1 EP 3717596A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- effluent
- stream
- hydrocarbon
- liquid
- gaseous
- 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.)
- Pending
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Classifications
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- 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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
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- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
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- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/06—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural parallel 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- 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
- C10G2400/30—Aromatics
Definitions
- the present invention relates to the field of processes for the production of aromatic compounds, and more particularly to aromatic compounds of the benzene, toluene and xylene type by catalytic reforming of a hydrocarbon feedstock of the naphtha type.
- a catalytic reforming unit Generally, the objective of a catalytic reforming unit is to convert naphthenic and paraffinic compounds (n-paraffins and iso-paraffins) into aromatic compounds.
- the main reactions involved are dehydrogenation of naphthenes and dehydrocyclization of paraffins to aromatics, isomerization of paraffins and naphthenes.
- Other so-called "parasite” reactions can also occur such as the hydrocracking and hydrogenolysis of paraffins and naphthenes, the hydro-dealkylation of the alkyl-aromatics giving rise to lighter compounds and lighter aromatics, as well as the formation of coke on the surface of the catalysts.
- Charges typically sent to a catalytic reforming unit are rich in paraffinic and naphthenic compounds and relatively low in aromatic compounds. These are generally naphthas from the distillation of crude oil or condensates of natural gas. Other fillers may also be available, containing varying amounts of aromatics, namely heavy naphthas catalytic cracking, coking, hydrocracking, or steam crackers.
- Aromatic compounds are generally treated in an aromatic complex to maximize the production of one or more products, most often xylenes and benzene. Toluene and heavier aromatics can be valorized for the constitution of gasoline bases or by the production of xylenes mixture.
- the production of C6-C7 aromatic compounds makes it possible, in particular, to improve the octane number of the gasoline, and / or to increase the supply of benzene, toluene and xylenes.
- a specific catalyst system generally comprising a catalytically active metal (generally platinum) and a nonacidic zeolite is used.
- a naphtha stream is sent to a fractionation unit, generating a first stream comprising C7 and lighter hydrocarbons, and a second stream comprising heavier hydrocarbons;
- the first stream is sent to a first reforming unit generating a first effluent
- the second stream is sent to a second reforming unit at a temperature higher than the temperature applied in the first reforming unit, generating a second effluent
- the first effluent and the second effluent are sent to a reformate separation column, thus creating a head flow and a bottom flow;
- the head stream is sent to a purification unit for aromatic compounds, thus creating a purified aromatic stream comprising aromatic compounds C6 and C7, and a raffinate stream,
- the raffinate stream is recycled to the first reforming unit.
- Such a process allows increased production of aromatic hydrocarbons, and in particular benzene and toluene, from a naphtha feed stream. More particularly, the raffinate recycling step and the repositioning of the aromatics extraction unit with respect to the two catalytic reforming units in parallel results in a 25% increase in benzene yields and an increase in benzene yields. about 10% of the toluene yields.
- US Pat. No. 6,051,128 discloses a process for the catalytic reforming of a hydrocarbon feedstock of the naphtha type whose objective is to increase the production of xylene and benzene.
- An object of the invention is to provide a catalytic reforming process for improving the recovery of benzene and toluene, while maximizing the recovery of hydrogen and C3 and C4 hydrocarbons which can be better valued compared to a simple consumption as fuel in the refinery and which is more economical from the energy point of view.
- the subject of the present invention is a process for producing C6-C7 aromatic compounds, especially benzene, toluene, (and even optionally C8 xylene), from a naphtha-type hydrocarbon feedstock comprising the following steps:
- the hydrocarbon effluent is sent to a stabilization section to recover a second gaseous effluent enriched in C 1 and C 2 hydrocarbon compounds, a liquid phase containing predominantly C 3 and C 4 hydrocarbons and a liquid fraction mainly comprising hydrocarbon compounds; having at least four carbon atoms;
- said liquid fraction is fed into a reformate separation column to obtain a head stream comprising C6 and C7 hydrocarbon compounds and a bottom stream comprising hydrocarbon compounds having at least eight carbon atoms.
- the process also comprises a step g) in which the overhead stream obtained in step f) is sent to an aromatics extraction unit to form a stream comprising mainly compounds C6-C7 aromatics and a raffinate stream.
- said raffinate stream is recycled to step b) upstream of said first catalytic reforming unit.
- step d) of the method comprises the following substeps:
- step i) separating the reformate combined stream into a gaseous phase and a hydrocarbon-containing liquid phase; ii) the liquid phase resulting from step i) is cooled to a temperature of less than or equal to 45 ° C by means of a cooling device;
- a first recontacting of the cooled liquid phase with the gaseous phase is carried out in a separation means so as to recover a first gaseous effluent rich in hydrogen and a first liquid effluent of hydrocarbons;
- a second recontacting of the first hydrocarbon liquid effluent with a recycle gas is carried out and a second hydrocarbon enriched effluent C1 and C2 and a second hydrocarbon liquid effluent are separated;
- step v) condensing the gaseous overhead fraction from step v) and separating a liquid phase containing predominantly C3 and C4 hydrocarbons and a gaseous phase which is recycled in step iv).
- the flow in question comprises, by weight, at least 50% of the components in question, especially at least 80%, especially at least 90 or 95% by weight of said components. It can also be all the components considered, with the usual impurities.
- the separation means is a recontacting column operating against the current or a separating flask.
- the liquid phase resulting from step i) is pre-cooled by heat exchange in an exchanger fed with the first gaseous effluent and / or the first liquid hydrocarbon effluent from the step iii).
- the liquid phase resulting from step i) undergoes heat exchange in an exchanger fed with the first gaseous effluent and in which the gaseous phase resulting from step i) undergoes an exchange. in a heat exchanger fed with the first hydrocarbon liquid effluent.
- the liquid phase resulting from step i) undergoes heat exchange in an exchanger fed with the first liquid hydrocarbon effluent and in which the gaseous phase resulting from step i) undergoes heat exchange in an exchanger fed with the first gaseous effluent.
- part or all of the second hydrocarbon enriched effluent C1 and C2 is recycled before the first recontacting step.
- the second gaseous effluent is recycled as a mixture with the gaseous phase from step i).
- a hydrodesulfurization step is carried out in the upper flow and / or the lower flow in a hydrotreatment unit.
- step b) or step c) of catalytic reforming is carried out at a temperature of between 400 and 600 ° C., a pressure of between 0.1 and 3 MPa, a molar ratio of hydrogen and the compounds.
- hydrocarbon compounds of the upper stream or the hydrocarbon compounds of the lower stream of between 0.8 and 8 mole / mole, and a mass flow rate of treated flux per unit mass of catalyst and per hour is between 1 and 10 h 1 .
- the catalyst used in step b) comprises an active phase comprising at least one metal chosen from platinum, zinc or molybdenum, and a support comprising a zeolite chosen from zeolite L, zeolite X and zeolite Y. or a zeolite ZSM-5, and optionally a binder selected from aluminosilicate, alumina, silica, clays, silicon carbides, alone or in combination.
- the zeolite is a zeolite L and the binder is silica.
- the catalyst used in stage c) comprises an active phase comprising at least one metal chosen from nickel, ruthenium, rhodium, palladium, iridium or platinum, at least one promoter chosen from rhenium, tin, germanium, cobalt, nickel, iridium, rhodium or ruthenium, and a support based on alumina, silica-alumina or silica.
- Figure 1 is a simplified schematic representation of the method according to the invention.
- Figure 2 is a schematic representation of the recontacting and stabilizing sections shown in Figure 1 according to a first embodiment of the invention.
- Figure 3 is a schematic representation of the recontacting and stabilizing sections shown in Figure 1 according to a second embodiment of the invention.
- Figure 4 is a schematic representation of the method according to the prior art.
- group IB according to the CAS classification corresponds to the metals of column 1 1 according to the new IUPAC classification.
- recontacting section is meant a section comprising an operation for extracting compounds contained in a gaseous phase by means of a liquid phase which has an absorbency by contacting the two phases.
- a recontacting can be provided by making direct contact by in-line mixing of the liquid and gaseous phases or in a recontacting device dedicated to the unit operation.
- stabilized for a reformate refers to a reformate having been distilled to remove most, and generally substantially all of the 4 or less (C 4 ) carbon compounds.
- hydrocarbon fraction C n is meant a section comprising hydrocarbons with n carbon atoms.
- C n + cut means a cut comprising hydrocarbons having at least n carbon atoms.
- C n- By cutting C n- is meant a cut comprising hydrocarbons having at most n carbon atoms.
- the present invention relates to a process for producing aromatic compounds, preferably C6-C7, and especially benzene and toluene (and optionally xylene in
- the method comprises the following steps:
- the hydrocarbon effluent is sent to a stabilization section to recover a second gaseous effluent enriched in C 1 and C 2 hydrocarbon compounds, a liquefied petroleum gas stream and a liquid fraction comprising predominantly hydrocarbon compounds having at least 4 atoms; carbon (C4 +);
- the process according to the invention advantageously uses the frigories contained in the gaseous or liquid effluents generated in the recontacting stage carried out in a recontacting (or absorption) column to pre-cool the hydrocarbon liquid phase before the latter does not undergo cooling which makes it possible to reach the desired temperature for the recontacting step.
- the thermal integration thus makes it possible to significantly reduce the consumption of cold utility and therefore the overall energy consumption of the process.
- This thermal integration is all the more advantageous as the hydrocarbon liquid phase must be cooled to a temperature of less than or equal to 10 ° C., this cooling then necessitating the use of a refrigerating unit which is an energy-consuming equipment.
- the two catalytic reforming stages are carried out under controlled operating conditions to promote dehydrocyclization reactions and to limit parasitic reactions.
- the pressure used is generally between 0.1 and 3 MPa
- the molar ratio hydrogen / H 2 / HC hydrocarbons is generally between 0.8 and 8 mole / mole.
- the temperature is generally between 400 and 600 ° C, preferably between 470 and 570 ° C.
- the mass flow rate of flow to be treated per unit mass of catalyst and per hour is generally between 0.1 and 10 h 1 , preferably between 0.5 and 6 h 1 .
- the first catalytic reforming unit into which is sent a stream comprising predominantly C 6 and C 7 hydrocarbon compounds, preferably comprises a catalyst comprising an active phase comprising at least one metal selected from the group consisting of platinum, zinc or molybdenum, taken alone or in admixture, and a support comprising a zeolite and optionally a binder. More preferably, the metal is platinum.
- the catalyst contains a quantity of metal of between 0.02 and 2% by weight, preferably between 0.05 and 1.5% by weight, even more preferably between 0.1 and 0.8% by weight relative to to the total weight of the catalyst.
- the zeolite is chosen from a zeolite L, a zeolite X, a zeolite Y, a zeolite ZSM-5. More preferentially, the zeolite is an L zeolite.
- the binder is chosen from aluminosilicate, alumina, silica, clays, silicon carbides, taken alone or in combination. More preferably, the binder is selected from silica.
- the catalyst may also comprise at least one doping metal selected from the group consisting of gallium, gold, nickel, rhenium, barium, silver, iron, bismuth, indium, yttrium, lanthanides (cerium, dysprosium, ytterbium), taken alone or as a mixture.
- the content of each doping metal is in relation to the total weight of the catalyst between 0 and 2% by weight, preferably from 0.01 to 1% by weight, preferably from 0.01 to 0.7% by weight. relative to the total weight of the catalyst.
- the catalyst may also comprise at least one halogen used to acidify the alumina support.
- the halogen content may represent between 0.1 and 15% by weight relative to the total weight of the catalyst, preferably 0.2 and 5% relative to the total weight of the catalyst.
- the chlorine content is between 0.5 and 2% by weight relative to the total weight of the catalyst.
- the catalyst may also comprise an alkali metal in proportions of the order of 0.1 to 3% by weight relative to the total weight of the catalyst.
- the alkali metal is potassium.
- the second catalytic reforming unit into which is sent a stream comprising predominantly C8 to C10 hydrocarbon compounds, preferably comprises a catalyst with an active phase comprising at least one metal selected from the group consisting of nickel, ruthenium, rhodium, palladium, iridium or platinum, and at least one promoter selected from rhenium, tin, germanium, cobalt, nickel, iridium, rhodium or ruthenium .
- the catalyst comprises an active phase comprising platinum and tin.
- the amount of metal is between 0.02 and 2% by weight, preferably between 0.05 and 1.5% by weight, more preferably between 0.1 and 0.8% by weight relative to the total weight of the product. catalyst.
- the catalyst comprises a support selected from alumina, silica-alumina or silica.
- the support is based on alumina.
- the alumina (s) of the porous support used in the catalyst are of type c, h, g or d.
- they are of type g or d. Even more preferably, they are of type y.
- FIGS. 1 to 3 The invention will now be illustrated based on FIGS. 1 to 3 with particularly advantageous embodiments.
- a naphtha-type feedstock 1 comprising C 6 to C 10 hydrocarbons is sent into a separation column 2 to obtain a higher flow 3 comprising mainly hydrocarbon compounds C6 and C7 and a lower stream 9 comprising predominantly C8 to C10 compounds.
- the lower stream 9 comprises less than 10% by volume of C7- compounds.
- the upper stream 3 is sent to a hydrodesulfurization unit (hydrotreatment) 4 and the upper hydrodesulphurized stream 5 is sent to a first catalytic reforming unit 6, comprising a catalyst comprising a platinum-based active phase and a zeolite-type support.
- the operating conditions in the first reforming unit 6 are as follows: the temperature is between 400 and 600 ° C., the pressure is between 0.3 and 2.5 MPa, the molar ratio between hydrogen and the upper stream hydrotreated 5 is between 0.8 and 8 mole / mole, the mass flow rate of flux to be treated per unit mass of catalyst per hour is between 1 and 10 h 1 .
- the lower stream 9 is sent to a hydrodesulfurization unit (hydrotreatment) 10 and then the hydrodesulphurized lower stream 11 is sent to a second catalytic reforming unit 12, comprising a bifunctional catalyst comprising a platinum-based active phase and tin (Pt-Sn) supported on alumina.
- the operating conditions in the second reforming unit 12 are as follows: the temperature is between 400 and 600 ° C., the pressure is between 0.3 and 2.5 MPa, the molar ratio between hydrogen and the bottom stream hydrotreated 11 is between 0.8 and 8 mole / mole, the mass flow rate of flux to be treated per unit mass of catalyst per hour is between 1 and 10 h 1 .
- the first reformate 8 from the first reforming unit 6 and the second reformate 14 from the second reforming unit 12 are then combined with each other to form a reformate stream 15 which is then fed into a recontacting section 16 (described in FIG. detail below) in order to form a first gaseous effluent 45 rich in hydrogen, and a hydrocarbon liquid effluent 55.
- the liquid hydrocarbon effluent 55 is sent to a stabilization section 19 (described in detail below) in order to recover a second gaseous effluent 52 enriched in C1 and C2 hydrocarbons, a stream of liquefied petroleum gas (LPG) and a liquid fraction 21 predominantly containing hydrocarbons containing at least 4 carbon atoms.
- LPG liquefied petroleum gas
- the liquid fraction 21 is then sent to a reformate separation column 22 to obtain a top stream 23 comprising C6 to C7 compounds and a bottom stream 24 comprising C8 + aromatic compounds.
- the top stream 23 is sent to an aromatics extraction unit 25 to form a stream of purified aromatic compounds 26 and a raffinate stream 27 comprising aliphatic compounds some of which can be recycled upstream of the first reforming unit 6 via line 7.
- Streams 24 and 26 can then be recombined to form a stream 28 of aromatic compounds.
- the reformate stream 15 is sent to a gas-liquid separation device 30 which can be a separator gas-liquid balloon known to those skilled in the art.
- the separation device 30 makes it possible to recover a gaseous phase 31 and a hydrocarbon liquid phase 32, respectively at the top and at the bottom of said device 30.
- the gaseous fraction 31 of the head which mainly contains hydrogen and light hydrocarbons C1, C2, C3 and C4 can be divided into two streams 33 and 34.
- the stream 33 is recycled as a recycle gas in an upstream reaction unit, such as the catalytic reforming unit 6.
- the gas stream 34 it is compressed by means of the compressor 35 and then sent into a cooling system 36.
- the gas 34 is typically compressed to a pressure of between 0.6 and 1.0 MPa.
- the compressed gas 34 is optionally mixed with a recycle gas, fed via line 53, the origin of which is detailed below.
- the gas or gas mixture is cooled, for example, to a temperature below 55 ° C.
- the gas or mixture of gases from the cooling system 36 (for example an air or water cooler) is transferred to a separator tank 37 to recover a purified gas 38 of liquid hydrocarbons which have condensed by cooling.
- the cooled gas 38 is compressed by means of the compressor 35 at a pressure generally between 1.6 and 4.0 MPa.
- the compressed gas 38 is subjected to a low temperature recontacting step in the presence of the liquid hydrocarbon phase 32 from the gas-liquid separation device 30.
- the compressed gas is firstly cooled by means of a cooler (air or water) 40, then undergoes an indirect heat exchanger by means of an exchanger 41 which is fed with a cold flow described below.
- the gas can then be advantageously cooled by means of a cooling device (not shown), for example a refrigeration unit ("chiller" according to English terminology) in order to bring the gas to a temperature less than or equal to 0 ° C.
- the hydrocarbon liquid phase 32 is used as the absorbing liquid in the recontacting step.
- the hydrocarbon liquid phase 32 is first pre-cooled by indirect heat exchange, via an exchanger 39 which is fed with a cold flow described below.
- the pre-cooled hydrocarbon liquid phase 32 is then cooled to a temperature of less than or equal to 45 ° C by means of a cooling device 43.
- Different types of cooling means can be used depending on the desired temperature. For example, an air or water cooler is used when the target temperature is between 20 and 45 ° C.
- a refrigeration unit "chiller" in the English terminology) when we try to cool the hydrocarbon liquid phase at a temperature of less than or equal to 20 ° C, preferably at a temperature between -10 and 20 ° C.
- the gas 38 and the cooled liquid hydrocarbon phase 32 are brought into counter-current contact in a recontacting (or absorption) column 44 which may comprise perforated or cap-shaped trays, or any other contact plate or else be lined with structured packing elements or not (pall, raschig or other rings).
- the column may for example have a number of theoretical separation plates of between 5 and 15, preferably between 7 and 10.
- the recontacting consists in carrying out an absorption of the C1 to C4 hydrocarbons present in the gas by means of the liquid phase. of cooled hydrocarbons.
- the recontacting step is carried out at a temperature between -20 and 55 ° C., preferably between -10 and 10 ° C. ° C.
- a hydrogen-rich gaseous effluent is withdrawn via line 45.
- the cold gaseous effluent is used as a thermal fluid for the exchanger 39 which carries out an indirect heat exchange with the hydrocarbon liquid phase 32, as described above.
- the cold liquid effluent discharged through the bottom of the column 44 via the line 46 is also used as a thermal fluid to supply the exchanger 41 to pre-cool the gas phase 38.
- the use of cold fluids from the recontacting step significantly reduces the energy consumption of the cooling devices 43 (see Figure 2) and 42 (see Figure 3) which are necessary to achieve cooling of the liquid phase. of hydrocarbons to increase its absorption capacity for use as a liquid recontacting fluid.
- the hydrogen-rich gas 45 is discharged from the treatment unit via line 17 after possibly passing through a guard bed 48 ("guard bed” according to the English terminology) in order to adsorb the chlorine present in the gas.
- the liquid effluent 46 coming from the recontacting column 44 is used as a recontacting fluid in a second recontacting step which consists in bringing the said liquid effluent into contact with a recycle gaseous fluid brought by the line 49, so as to to improve the recovery of C3 and C4 (LPG) compounds and to remove methane and ethane from the process.
- a second recontacting step which consists in bringing the said liquid effluent into contact with a recycle gaseous fluid brought by the line 49, so as to improve the recovery of C3 and C4 (LPG) compounds and to remove methane and ethane from the process.
- the second recontacting is carried out by direct contact in line mixing of the liquid effluent 46 with the recycle gas 49.
- the second step of recontacting is performed at a temperature higher than that of the first recontacting step, which is generally between 10 and 55 ° C. This temperature results from the thermodynamic equilibrium of the absorption of the liquid 46 and the vapor 49.
- no means of controlling the temperature for example of the heat exchanger type is used.
- the gas / liquid mixture is transferred via line 18 to a separator tank 51 which is operated so as to maximize the recovery in the overhead gas of hydrogen and C 1 and C 2 hydrocarbons.
- the gaseous effluent containing hydrogen and C1 and C2 hydrocarbons is withdrawn via line 52 to be recycled in whole or in part in the process via line 53.
- the part of the gaseous effluent containing hydrogen and C1 and C2 hydrocarbons which is not recycled, is removed from the process by line 29.
- This gaseous effluent can be used in particular as a fuel gas in the refinery.
- the recycling, in whole or in part, of the gaseous effluent containing hydrogen and C1 and C2 hydrocarbons upstream of the first recontacting step, for example as indicated in FIG. 2 mixed with the compressed gas 33 from the separator tank 30 has the advantageous effect of improving the recovery efficiency of the hydrogen during the first recontacting step.
- the bottom of the separation tank 51 is recovered a liquid effluent 55 containing mainly hydrocarbons having three and more than three carbon atoms (C3 +) and also minor hydrocarbons C1 and C2.
- the liquid effluent 55 is heated before being sent to a stabilization unit which is operated so as to recover a stabilized hydrocarbon liquid effluent and a distillate comprising mainly C 3 and C 4 hydrocarbons.
- the stabilization unit comprises a distillation column 63 whose bottom is provided with a circulation pipe equipped with a recirculation circuit comprising a reboiler (not shown) and a discharge pipe 21 of the liquid effluent. stabilized.
- the overhead gas of the column 63 flows in a duct 58 connected to a condensing system comprising a cooling device 59 of the overhead gas and a reflux tank 60.
- the condensed liquid separated at the reflux tank 60 is discharged via the line 61 and is divided into two streams, a stream being recycled in column 63 by line 62 while the non-recycled complementary stream is discharged through line 20 out of the process as LPG stream.
- the residual gas withdrawn at the top of the uncondensed reflux flask 60 and potentially comprising significant quantities of C3 and C4 hydrocarbons is discharged via line 49 and recycled to the process to undergo a recontacting step with the liquid effluent. from the recontacting column 44, as mentioned above.
- the stabilized liquid effluent 21 recovered at the bottom of the distillation column 63 advantageously serves to feed a heat exchanger system.
- indirect heat 64, 65 to preheat the liquid effluent 55 before entering the distillation column 63. This thermal integration thus reduces the heating power required for the reboiler to operate the distillation column 63.
- a guard bed 66 configured to capture the chlorine possibly present in the liquid effluent 55.
- FIG. 3 represents a schematic diagram of the method according to the invention according to a second embodiment.
- the second embodiment differs from that of FIG. 2 in that on the one hand the hydrocarbon liquid phase 32 is pre-cooled by heat exchange in an exchanger 39 fed with a cold fluid which is the liquid effluent 46 from of the recontacting column 44 and, secondly, in that the compressed gas 38 is pre-cooled by indirect heat exchanger by means of an exchanger 41 which is fed by the gaseous effluent 45 rich in hydrogen withdrawn at the top of the recontacting column 44.
- This configuration makes it easier to balance the flow rates of the gaseous and liquid effluents that feed the exchangers 39 and 41 according to the needs and / or the availability of the frigories to pre-cool the gaseous and liquid phases which are brought into contact in the column.
- a scheme not in accordance with the invention does not include mutualized recontacting and stabilization section for the two catalytic reforming reactors (see FIG. 4) and two schemes in accordance with FIG. invention, including a scheme not comprising a step of recycling the gaseous effluent containing hydrogen and C1 and C2 hydrocarbons (the entire gaseous effluent from the bottom of the separation tank 51 is removed from the process via line 29, see Figures 2 or 3), and a diagram comprising said recycling step (via line 53, see Figures 2 or 3).
- a naphtha-type filler 101 comprising C 6 -C 10 hydrocarbons is sent into a separation column 102 to obtain an upper stream 103 comprising mainly C 6 and C 7 hydrocarbon compounds and a lower stream 112. comprising predominantly C8 to C10 compounds.
- the lower stream 112 comprises less than 10% by volume of C7- compounds.
- the upper stream 103 is sent to a hydrodesulfurization unit 104 and the upper hydrodesulfurized stream 105 is sent to a first catalytic reforming unit 106, comprising a catalyst comprising a platinum-based active phase and a zeolite-type support.
- the operating conditions in the first reforming unit 106 are as follows: the temperature is between 400 and 600 ° C., the pressure is between 0.3 and 2 MPa, the molar ratio between hydrogen and the hydrotreated upper stream is 1: 1 and 10: 1, the mass flow of treated feedstock per unit mass of catalyst per hour is between 0.1 and 10 h 1 .
- the lower stream 112 is sent to a hydrodesulphurization unit 113 and the hydrodesulphurized lower stream 114 is sent to a second catalytic reforming unit 115 comprising a bifunctional catalyst comprising an active phase based on platinum and tin (Pt -Sn) supported on alumina.
- the operating conditions in the second reforming unit 115 are as follows: the temperature is between 400 and 600 ° C., the pressure is between 0.3 and 2.5 MPa, the molar ratio between hydrogen and the lower flow hydrotreated 114 is 1: 1 and 10: 1, the mass flow rate treated per unit mass of catalyst per hour is between 0.1 and 10 h 1 .
- the first reformate 107 from the first reforming unit 106 and the second reformate 116 from the second reforming unit 115 are then respectively respectively sent to a recontacting section 108 and 117 and the liquid effluents 109 and 118 obtained are then sent to a stabilization column 110 and 119.
- the streams 125 and 126 comprising predominantly C5- hydrocarbon compounds are removed from the process.
- the stabilized effluents 111 and 120 comprising predominantly C6 + hydrocarbon compounds are then combined together to form a reformate stream 121 which is then fed into a reformate separation column 122 to obtain a top stream 123 comprising predominantly hydrocarbon compounds at C6 and C7 and a bottom stream 124 comprising predominantly C8 + hydrocarbon compounds.
- the head stream 123 is then sent to an aromatics extraction unit similar to that used in the process according to the invention to obtain a flow of aromatic compounds.
- Example 2 Reformaae Process According to the Invention (Without Recycling) corresponds to the process corresponding to FIGS. 1 and 2 in which all of the gaseous effluent from separation tank 51 is removed from the process via line 29.
- the reforming process according to Example 3 corresponds to the process corresponding to FIGS. 1 and 2 in which all of the gaseous effluent from separation tank 51 is recycled upstream of the recontacting section via line 53.
- the operating procedures of the reforming reactors and the aromatics extraction unit are identical to those of the prior art.
- Table 1 shows that the process according to the invention (Examples 2 and 3) in which a step of recontacting the recombined reformate effluents is carried out makes it possible to increase recovering C 6 and C 7 hydrocarbon compounds (1976 and 1977 tonnes / day respectively) while improving the recovery of C 3 and C 4 hydrocarbon compounds (153 and 165 tons / day respectively compared with 55 tons / day in Example 1 according to US Pat. prior art) compared to a non-conforming method not comprising mutualized recontacting and stabilizing section for the two catalytic reforming reactors. Furthermore, the process according to the invention makes it possible to recover hydrogen at a purity level (95.9% and 95.13% by mol respectively for Examples 2 and 3) higher than in the prior art ( 92.5 mol%).
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1761373A FR3074175B1 (fr) | 2017-11-29 | 2017-11-29 | Procede d'amelioration de production de benzene et toluene |
PCT/EP2018/081582 WO2019105767A1 (fr) | 2017-11-29 | 2018-11-16 | Procede d'amelioration de production de benzene et toluene |
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EP3717596A1 true EP3717596A1 (fr) | 2020-10-07 |
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EP18800661.3A Pending EP3717596A1 (fr) | 2017-11-29 | 2018-11-16 | Procede d'amelioration de production de benzene et toluene |
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Country | Link |
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US (1) | US11453829B2 (fr) |
EP (1) | EP3717596A1 (fr) |
JP (1) | JP2021504383A (fr) |
KR (1) | KR20200092969A (fr) |
CN (1) | CN111630138A (fr) |
FR (1) | FR3074175B1 (fr) |
WO (1) | WO2019105767A1 (fr) |
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KR102464478B1 (ko) * | 2020-06-16 | 2022-11-07 | 주식회사 엘지화학 | 방향족 탄화수소 제조장치 |
KR102464480B1 (ko) | 2020-06-16 | 2022-11-07 | 주식회사 엘지화학 | 방향족 탄화수소의 제조방법 |
Family Cites Families (6)
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US6051128A (en) | 1995-06-06 | 2000-04-18 | Chevron Chemical Company | Split-feed two-stage parallel aromatization for maximum para-xylene yield |
EP0993500B1 (fr) * | 1997-06-16 | 2002-09-18 | Chevron Phillips Chemical Company Lp | Aromatisation a charge partagee, en deux etapes pour rendement maximal en paraxylene |
FR2873710B1 (fr) * | 2004-08-02 | 2006-12-01 | Inst Francais Du Petrole | Procede pour le traitement d'une charge hydrocarbonee |
US8926829B2 (en) * | 2011-04-29 | 2015-01-06 | Uop Llc | Process for increasing benzene and toluene production |
FR3038906B1 (fr) * | 2015-07-15 | 2019-06-21 | IFP Energies Nouvelles | Procede de traitement d'une charge hydrocarbonee contenant de l'hydrogene et des hydrocarbures |
FR3038907B1 (fr) * | 2015-07-15 | 2017-07-28 | Ifp Energies Now | Procede de traitement d'une charge hydrocarbonee comprenant de l'hydrogene et des hydrocarbures en c1 a c4. |
-
2017
- 2017-11-29 FR FR1761373A patent/FR3074175B1/fr active Active
-
2018
- 2018-11-16 US US16/767,939 patent/US11453829B2/en active Active
- 2018-11-16 EP EP18800661.3A patent/EP3717596A1/fr active Pending
- 2018-11-16 CN CN201880077407.0A patent/CN111630138A/zh active Pending
- 2018-11-16 JP JP2020529151A patent/JP2021504383A/ja active Pending
- 2018-11-16 WO PCT/EP2018/081582 patent/WO2019105767A1/fr active Application Filing
- 2018-11-16 KR KR1020207015280A patent/KR20200092969A/ko not_active Application Discontinuation
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US20200369970A1 (en) | 2020-11-26 |
FR3074175B1 (fr) | 2019-11-01 |
CN111630138A (zh) | 2020-09-04 |
FR3074175A1 (fr) | 2019-05-31 |
KR20200092969A (ko) | 2020-08-04 |
WO2019105767A1 (fr) | 2019-06-06 |
JP2021504383A (ja) | 2021-02-15 |
US11453829B2 (en) | 2022-09-27 |
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