EP1132453A1 - Selektives Hydrierungsverfahren mit Membrantrennung von Wasserstoff stromaufwärts einer Reaktionskolonne - Google Patents

Selektives Hydrierungsverfahren mit Membrantrennung von Wasserstoff stromaufwärts einer Reaktionskolonne Download PDF

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EP1132453A1
EP1132453A1 EP01400357A EP01400357A EP1132453A1 EP 1132453 A1 EP1132453 A1 EP 1132453A1 EP 01400357 A EP01400357 A EP 01400357A EP 01400357 A EP01400357 A EP 01400357A EP 1132453 A1 EP1132453 A1 EP 1132453A1
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Prior art keywords
hydrogen
membrane
hydrocarbons
selective hydrogenation
membranes
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EP01400357A
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English (en)
French (fr)
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EP1132453B1 (de
Inventor
Christophe Chau
Michel Derrien
Alain Methivier
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G49/007—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 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only 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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00

Definitions

  • the present invention relates to a process for the selective hydrogenation of a hydrocarbon fraction in a reactive column.
  • the charge of the process according to the invention essentially comprises hydrocarbons having from 1 to 6 carbon atoms, as well as hydrogen and optionally C 6 + hydrocarbons, comprising 6 or more carbon atoms.
  • Said method makes it possible to hydrogenate the acetylenic compounds, the di- and polyolefins, without significantly affecting the monoolefins present in the feed.
  • the selective hydrogenation stage is generally carried out after splitting said effluents into several sections. Each of the separate sections is then hydrogenated separately in a specific reactor.
  • patent application WO96 / 06900 describes a process for the selective hydrogenation of cracked gas, in which the gas from a steam cracker is fractionated in order to remove the methane (C 1 ), then the compounds in C 2 and in C 3 (i.e. compounds containing 2 or 3 carbon atoms per molecule). The fraction containing the compounds C 4 (compounds comprising 4 carbon atoms) and the C 5 + (compounds comprising 5 or more carbon atoms) is then hydrogenated, and a fraction of the hydrogenated effluent recycled to the fractionation section.
  • patent application WO 95/15934 describes a process in which a stream of hydrogen, on the one hand, and a stream of hydrocarbons, on the other hand, are brought separately to a hydrogenation reactor. These two separate streams can optionally be mixed just before entering the reactor.
  • the prior art therefore describes processes in which all of the hydrogen is separated from a gas flow, either upstream or downstream of a hydrogenation unit.
  • Complete separation upstream requires cryogenic units, which are very disadvantageous in terms of investment.
  • the downstream separation implies that excess hydrogen flows through the hydrogenation reactor. This excess of hydrogen generates risks of runaway and makes the control of the reaction more complex.
  • the present invention relates to a process for the selective hydrogenation of a hydrocarbon fraction in a reactive column (also called a catalytic column).
  • a reactive column also called a catalytic column.
  • the charge of the process according to the invention essentially comprises hydrocarbons having from 1 to 6 carbon atoms and optionally C 6 + hydrocarbons.
  • Said process makes it possible to hydrogenate acetylenic compounds, di- and polyolefins, without significantly affecting the monoolefins present in the feed.
  • Said feed also includes hydrogen in variable quantity, depending on the upstream process from which it is derived (for example a steam cracking process, or thermal cracking, or catalytic cracking, or even pyrolysis).
  • a partial separation of the hydrogen is carried out before selective hydrogenation.
  • This partial separation is carried out from preferably by means of a membrane, rather than by cryogenics. Indeed, the cryogenic separation is better suited to substantially complete separation of charge hydrogen and requires much more investment important.
  • the object of the present invention is the selective hydrogenation of a charge composed of C 2 + hydrocarbons (hydrocarbons containing at least 2 carbon atoms per molecule), that is to say the hydrogenation of acetylenic compounds, or di- or poly-olefins, contained in said charge.
  • the process according to the invention is a process for the selective hydrogenation of a hydrocarbon feed containing hydrogen and C 2 + hydrocarbons, characterized in that it comprises at least one step of separation of a fraction of the hydrogen contained in the feed by means of a membrane (step a) and a step of selective hydrogenation of the effluent from step a in a reactive column (step b).
  • the feedstock of the process according to the invention is a hydrocarbon feedstock containing also hydrogen and preferably from a production process steam cracking, or thermal cracking, or catalytic cracking, or pyrolysis.
  • C n hydrocarbons or “C n cut” will be called a mixture of hydrocarbons having n carbon atoms per molecule, and “C n -C m cut” a mixture of hydrocarbons having n to m atoms of carbon per molecule.
  • a C 1 -C 6 cut contains hydrocarbons having a number of carbon atoms per molecule between 1 and 6.
  • the charge of the process according to the invention is for example a C 1 -C 6 cut (that is to say a cut containing hydrocarbons having 1 to 6 carbon atoms per molecule).
  • Said filler can also be chosen from cuts C 1 -C 2 , C 1 -C 3 , C 1 -C 4 , C 1 -C 5 , C 1 -C 6 , C 2 -C 3 , C 2 -C 4 , C 2 -C 5 , C 2 -C 6 , C 3 -C 4 , C 3 -C 5 , C 3 -C 6 , C 4 -C 5 , C 4 -C 6 , C 5 -C 6 , or a mixture of said cuts, when said cuts or said mixture also contain hydrogen, optionally added or already present in said cut or said mixture. It is also possible to treat, in the process according to the invention, any charge containing hydrogen and at least 2 cuts chosen from the group consisting of cuts C 2 , C 3 , C 4 ,
  • said charge may optionally contain C 6 + hydrocarbons, preferably at a content of less than 20% by weight, as well as methane (C 1 ).
  • the feedstock of the process according to the invention contains hydrogen, methane, C 2 -C 6 hydrocarbons and C 6 + hydrocarbons.
  • said charge comes from a process of steam cracking (steam-cracking according to English terminology) or thermal cracking (thermal cracking) or even pyrolysis (pyrolysis).
  • membranes allow to perform a partial separation of the hydrogen contained in a charge hydrocarbon derived, for example, from a steam cracking or cracking process thermal, or catalytic cracking, or pyrolysis.
  • step a makes it possible to obtain an effluent having the adequate composition in terms of hydrogen molar ratio on hydrocarbons to be hydrogenated (R ratio defined below).
  • Said effluent can thus feed, preferably directly, a reactive column in which is placed a selective hydrogenation catalyst based on at least one metal chosen from preference among the metals of groups 8, 9 or 10 of the new classification periodic (group VIII of the old periodic classification).
  • step b it may however be useful or even necessary to compress and / or reheat the effluent from step a, before operating the hydrogenation step (step b).
  • the molar ratio: R hydrogen: (diolefins + polyolefins + acetylenics) the effluent which contains most of the hydrocarbons at the end of step a of the process according to the invention (retentate from the membrane separation process) is preferably between 0.5: 1 and 4: 1, more preferably between 0.8: 1 and 3: 1, even more preferably between 1: 1 and 3: 1 and very preferably between 1.1: 1 and 2.5: 1, or even possibly between 1 , 2: 1 and 1.8: 1.
  • Gas permeation membranes allow separation of mixtures gaseous by selective transfer, under the effect of pressure differences, through a thin, continuous layer of a polymer, composite material (e.g. a polymer loaded with mineral crystallites), or through a ceramic or inorganic material.
  • This gas permeation separation process can in particular be applied to separation of hydrogen.
  • a retentate is obtained, which in this case is depleted in hydrogen, and contains most of the hydrocarbons initially present in the feed.
  • the amount of hydrogen that can be collected in the permeate and its purity depend on several factors, including the composition of the gas to be separated, temperature, gas pressure feeding the membrane separation unit (permeation unit), the pressure at which the permeate is recovered, from the surface membrane used, as well as the permeability and selectivity of the membrane.
  • Membrane separation techniques are generally easy to implement work, because the permeation units are most often modular, operated in continuous, consuming little energy. However, the investments they require are related to the cost of the membrane and modules. The units to membrane therefore have a scale factor unfavorable to the realization large units. However, in the case of the method according to the invention, the fluxes of loads to be treated are usually very important.
  • a load from a steam cracking process it is common to treat loads whose flow rate is between several tens and several hundred tonnes per hour.
  • a C 1 -C 6 steam cracking cut will be available at the outlet of the steam cracking unit at a flow rate of between a few tens of tonnes per hour and a few hundred tonnes per hour.
  • the membranes which can be used in the process according to the invention must therefore be capable of treating such flows, while having a sufficient selectivity for the separation of hydrogen.
  • any type of membrane can a priori be used in the process according to the invention.
  • an organic membrane should preferably be used, since it has been found by the plaintiff that this type of membrane already makes it possible to treat high charge rates, with selectivity for hydrogen separation large and membrane surfaces compatible with use industrial.
  • the usable mineral membranes in the process according to the invention will therefore preferably be chosen from the group consisting of: zeolites, membranes based on carbon fibers, membranes based on microporous silica deposited on a porous support, ceramic membranes and membranes comprising an alloy based on palladium.
  • Organic membranes which can preferably be used in the process according to the invention preferably comprise a polymer such as for example at least one polymer chosen from the group consisting of: polyimides, polyaramides, polycarbonates, polysulfones, cellulose derivatives or fluorides of polyvinyl. It is in particular advantageous to preferably use membranes with based on polymers, in particular polyaramides, sold by the company MEDAL.
  • organic membranes make it possible to treat very large charge flows, for example 90,000 m 3 per hour, and to obtain variable permeate flows depending on the operating pressures and the temperature used, for example 15,000 m 3 per hour. .
  • Such separation can be carried out in compact modules having a floor area of the order of 7 m 2 .
  • a permeate is therefore obtained containing the species having crossed the membrane, i.e. essentially hydrogen and small amounts of hydrocarbons, and a retentate depleted in hydrogen, but containing most of the hydrocarbons initially present in load.
  • Step b of selective hydrogenation of diolefinic hydrocarbons, polyolefins and acetylenics is operated in a reactive column comprising at least one, preferably several fixed catalyst beds.
  • any reactive column known to those skilled in the art can be used in the method according to the invention.
  • a reactive column containing one or more beds of catalysts which are integrated into the structure of the distillation column. He is in particular possible to use the catalytic columns described in the patents US 5,368,691, US 5,523,062, FR 2,737,131, FR 2,737,132, EP-A-0 461 855
  • step b according to the invention it is also possible to use for carrying out step b according to the invention at minus one reactor coupled with a distillation column (side reactor according to the Anglo-Saxon terminology).
  • the catalytic zone can be partly internal and partly external to the column, or completely external to said column.
  • a distillation column not comprising reaction zone that is to say comprising no catalyst, but in which takes part of the liquid from the column on a distillation tray to send it to a selective hydrogenation reactor comprising a catalyst in a fixed bed.
  • the effluent from said reactor is then returned to the column distillation at the same or a neighboring tray, so as to ensure continuity in the distillation.
  • said reactor external to a reactive column comprising at least one catalyst bed.
  • Devices comprising at least one external reactor and usable in the process according to the invention are in particular described in US Patents 5,177,283, US 5,817,227 and US 5,888,355.
  • the effluent obtained at the end of the process according to the invention essentially contains saturated hydrocarbons and mono-olefins. Any scheme known to those skilled in the art can be used for the separation of olefins contained in this effluent. Usable fractionation schemes with the method according to the invention are for example described in Ullman's Encyclopedia of Industrial Chemistry, 5 th edition, Volume A10, pages 77 and 80.
  • Said effluent can thus for example be fractionated in order to recover the mono-olefins contained in each of the cuts C n , by means of a demethanizer, followed by a de-ethanizer of the cut C2 + which makes it possible to separate a cut C 2 , then a depropanizer of the C 3 + cut, and possibly a debutanizer of the C 4 + cut and / or a depentanizer of the C 5 + cut. It is also possible to place the de-ethanizer upstream of the demethanizer or the depropanizer upstream of the de-ethanizer.
  • the process according to the invention is therefore a process for the selective hydrogenation of a hydrocarbon feedstock containing hydrogen and C2 + hydrocarbons characterized in that it comprises at least one step of separation of a fraction of the hydrogen contained in said charge by means of a membrane (step a) and a selective hydrogenation step of the effluent from step a in a column reactive (step b).
  • the method according to the invention comprises in in addition to a step c of hydrogenation of the effluent from step b.
  • a very variant preferred method of the invention is detailed in Figure 1.
  • the charge 1, which essentially comprises hydrogen, hydrocarbons having from 1 to 6 carbon atoms, and possibly C 6 + hydrocarbons, is admitted into the unit 3 for hydrogen separation by membrane (step a). It is preferable to use a charge from a steam cracking unit, for example and preferably a charge taken after the washing with soda, compression and drying steps. Such a charge is available at a temperature close to 40 ° C and a pressure of the order of 3 to 3.5 MPa.
  • the load by means of the heater 2, which may preferably be a exchanger working with the steam used in the steam cracking unit. So for example, in the case of an organic membrane it is preferred to heat the charging at a temperature above 40 ° C, more preferably included between about 40 ° C and about 100 ° C, for example at a temperature between about 70 ° C and about 85 ° C.
  • a permeate (effluent 4) enriched in hydrogen is recovered, and a retentate (effluent 5) depleted in hydrogen, which contains most of the hydrocarbons C 1 to C 6 and is sent to the reactive column. 8 via line 5.
  • effluent 4 a permeate
  • effluent 5 a retentate
  • These effluents are obtained at a pressure generally between 0.1 and 1.0 MPa.
  • step b of hydrogenation it is optionally possible to insert a compressor 6 in line 5, in order to to obtain an effluent compressed via line 7 and to carry out step b of hydrogenation at a higher pressure, for example between 1.0 and 3.5 MPa. It is also possible to reheat said charge before step b, for example at by means of an exchanger (not shown).
  • the reactive column 8 comprises either at least one fixed bed of catalyst selective hydrogenation, and preferably several beds of catalysts distributed in the column, i.e. at least one external reactor associated with the distillation of a simple distillation column or a reactive column, depending on the mode described above (side reactors according to Anglo-Saxon terminology).
  • a catalyst based on at least one metal is preferably used noble, preferably a palladium-based catalyst, such as for example a catalyst comprising palladium or palladium and silver deposited on alumina or on silica, or on titanium oxide.
  • FIG. 1 an exemplary embodiment is presented in which three beds catalysts 29, 30 and 31 are arranged in the reactive column.
  • a more or less catalytic beds can be used in depends in particular on the composition of stream 7 to be hydrogenated.
  • the reactive column 8 used in step b of the process according to the invention thus makes it possible to simultaneously carry out the fractionation of the stream 7 comprising hydrocarbons having between 1 and 6 carbon atoms per molecule, and the hydrogenation of the unsaturated hydrocarbons contained in this stream 7, using the hydrogen present in this stream.
  • the molar ratio R in streams 5 and 7 is between 0.5: 1 and 4: 1, which makes it possible to selectively hydrogenate the diolefins, polyolefins and acetylenes to C 2 , C 3 , C 4 , C 5 or C 6 , and even C 6 + possibly contained in stream 7, without hydrogenating the mono-olefins.
  • a heavy effluent 9 is recovered at least partially hydrogen.
  • This effluent can be partly recycled at the bottom of the catalytic column via line 10, then after reheating by means of reheater 11 (reboiler), via the line 12.
  • reheater 11 refrigerator
  • the non-recycled fraction is recovered via line 13.
  • a light effluent 14 is recovered, which is preferably condensed in condenser 15, then introduced via line 16 into a separator 17.
  • the liquid fraction 18 (reflux) is recycled to the reactive column 8, and the fraction gas recovered via line 19.
  • the reactive column preferably operates so as to carry out a fractionation at the level of the C 4 or C 5 hydrocarbons.
  • the light effluent 14 then essentially contains C 4 - or C 5 - hydrocarbons, that is to say hydrocarbons containing respectively at most 4 or 5 carbon atoms per molecule.
  • a fraction of C 4 , and / or C 5 , and / or C 6 hydrocarbons can be present simultaneously in the two effluents 9 and 14.
  • the hydrogenation reaction is generally carried out essentially in phase liquid at a temperature between 15 ° C and 300 ° C, more preferably between 20 ° C and 250 ° C and very preferably between 25 ° C and 200 ° C, or even 30 ° C and 150 ° C, a pressure between 0.5 and 5MPa, preferably between 0.7 and 4 MPa, and more preferably between 0.8 and 3 MPa.
  • the column head temperature is preferably between 30 ° C and 200 ° C, preferably between 35 ° C and 150 ° C, and the bottom temperature of the column is generally between 40 ° C and 350 ° C, more preferably between 70 ° C and 300 ° C, and very preferably between 100 ° C and 200 ° C.
  • a second reactor selective hydrogenation 26 is added, which allows if necessary to complete the selective hydrogenation reaction.
  • This reactor can be a conventional reactor operating with a fixed catalyst bed, for example a trickle bed reactor (trickle bed reactor according to Anglo-Saxon terminology).
  • Said reactor can also be a reactive column identical or different from column 8.
  • Said the reactive column is then preferably equipped with a reflux zone with condenser and a reboiler, as already described for the reactive column 8.
  • the reactor or reactive column 26 is preferably supplied with hydrogen via line 25, by means of a fraction hydrogen collected in step a.
  • a light hydrogenated effluent is collected at the head of the reactor 26, which can optionally be recycled in step a (separator 3) or in step b (reactive column 8) and at the bottom of said reactor a hydrogenated effluent 27 is that is to say no longer containing di- or polyolefins, or acetylenics.
  • the charge 1 is a C 1 -C 6 cut of steam cracking, a gasoline containing paraffins and mono-olefins is recovered.
  • the process according to the invention is therefore a process for the selective hydrogenation of a hydrocarbon feedstock containing hydrogen and C 2 + hydrocarbons, characterized in that it comprises at least one step of separation of a fraction of the hydrogen contained in the feedstock by means of a membrane (step a) and a step of selective hydrogenation of the effluent from step a in a reactive column (step b).
  • all or part of the hydrogen separated in step a is possibly sent to a selective hydrogenation unit.
  • the process according to the invention may also include a step c of hydrogenation of the effluent from of step b, and all or part of the hydrogen separated in step a can optionally be sent to step c.
  • the effluent from step a can optionally be compressed before being hydrogenated in step b.
  • at least part of the fraction collected at the head of said reactive column can optionally be recycled in step a, or in step b, or even in step c.
  • At least part of the fraction collected at the head of said reactive column is optionally recycled in step a or in step b, or optionally in step c.
  • the charge of the method according to the invention preferably comes from a method of steam cracking, thermal cracking or pyrolysis. More preferably, said charge comprises hydrogen and hydrocarbons having a number carbon atoms between 1 and 6.
  • the membrane used in step a of the process according to the invention can optionally be an organic membrane, preferably comprising at least one polymer chosen from the group consisting of: polyimides, polyaramides, polycarbonates, polysulfones, cellulose derivatives or fluorides of polyvinyl.
  • the membrane used in step a of the process according to the invention can also optionally be a mineral membrane, preferably chosen from the group consisting of: zeolites, membranes based on carbon fibers, membranes based on microporous silica deposited on a porous support, ceramic membranes and membranes comprising a palladium alloy.
  • the operating conditions and the membrane are preferably chosen so that the retentate obtained in step a generally has a hydrogen molar ratio: (diolefins + polyolefins + acetylenics) between 0.5: 1 and 4: 1.
  • the catalyst used in step b of the process according to the invention comprises preferably palladium, or palladium and silver.
  • step a of the process according to the invention illustrates the separation carried out in step a of the process according to the invention.
  • Such a separation can in particular be carried out in the separator 3 of figure 1.
  • Example 1 (according to the invention):
  • the feed to be separated has a typical composition of a C 1 -C 6 feed containing hydrogen and coming from a steam cracker. This charge is collected after the washing with soda, compression and drying stages with a flow rate of 150 tonnes per hour (t / h).
  • the flow rates and flow compositions are listed in Table 1.
  • An organic membrane comprising a polymer with a high specific surface and of the polyimide type is used to separate approximately 50% of the hydrogen contained in the feed (step a), before the selective hydrogenation (step b).
  • the separation is operated at a temperature of 80 ° C and an upstream pressure of 3.5 MPa. Pressure downstream of the membrane is 0.1 MPa.
  • the membrane used has a hydrogen / hydrocarbon and hydrogen / monoxide separation selectivity carbon of 250 for the selective extraction of 50% of the hydrogen present in the charge.
  • Table 1 summarizes the compositions and flow rates of the permeate and the retentate after separation by means of the membrane.
  • the retentate obtained can be used in step b of selective hydrogenation, without additional addition or separation of hydrogen.
  • the charge to be separated in step a of the process is a C 1 -C 6 charge identical to that of Example 1, but the operating conditions for the separation are modified.
  • the membrane used is a polyaramid membrane, the separation temperature is 60 ° C., the pressure upstream of the membrane of 6 MPa, and the pressure downstream of the membrane of 0.2 MPa.
  • Table 2 summarizes the compositions and flow rates of the permeate and retentate after separation by means of the membrane.
  • the retentate obtained can be used in step b selective hydrogenation, without additional addition or separation of hydrogen.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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EP01400357A 2000-03-08 2001-02-12 Selektives Hydrierungsverfahren mit Membrantrennung von Wasserstoff stromaufwärts einer Reaktionskolonne Expired - Lifetime EP1132453B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0003066 2000-03-08
FR0003066A FR2806093B1 (fr) 2000-03-08 2000-03-08 Procede d'hydrogenation selective comprenant une separation partielle d'hydrogene par membrane en amont d'une colonne reactive

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EP1132453A1 true EP1132453A1 (de) 2001-09-12
EP1132453B1 EP1132453B1 (de) 2004-12-15

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EP01400357A Expired - Lifetime EP1132453B1 (de) 2000-03-08 2001-02-12 Selektives Hydrierungsverfahren mit Membrantrennung von Wasserstoff stromaufwärts einer Reaktionskolonne

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US (1) US6410811B2 (de)
EP (1) EP1132453B1 (de)
JP (1) JP4780539B2 (de)
KR (1) KR100752994B1 (de)
DE (1) DE60107737T2 (de)
ES (1) ES2234785T3 (de)
FR (1) FR2806093B1 (de)

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US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
US9745191B2 (en) 2011-04-11 2017-08-29 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures

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FR2828187B1 (fr) * 2001-08-03 2003-12-05 Inst Francais Du Petrole Procede de recuperation d'hydrogene dans un effluent hydrocarbone gazeux, avec mise en oeuvre d'un reacteur membranaire
FR2850588B1 (fr) * 2003-01-31 2007-08-03 Inst Francais Du Petrole Membrane inorganique poreuse contenant du carbone, son procede de preparation et son utilisation
FR2850664B1 (fr) * 2003-01-31 2006-06-30 Inst Francais Du Petrole Procede d'hydrogenation selective mettant en oeuvre un reacteur catalytique a membrane selective a l'hydrogene
US7115789B2 (en) * 2003-03-28 2006-10-03 Exxon Mobil Chemical Patents Inc. Process for removal of alkynes and/or dienes from an olefin stream
JP2012246207A (ja) * 2011-05-31 2012-12-13 Ngk Insulators Ltd 水素分離方法及び水素分離装置
KR101298659B1 (ko) 2011-06-03 2013-08-21 한국에너지기술연구원 수소분리막을 이용한 탄화수소 고급화방법
KR101331785B1 (ko) 2011-07-22 2013-11-21 한국에너지기술연구원 프로톤 전도성물질을 이용한 탄화수소 고급화방법
US20140100397A1 (en) * 2011-06-03 2014-04-10 Korea Institute Of Energy Research Hydrocarbon Advancement Method
US9114352B2 (en) * 2012-12-18 2015-08-25 L'Air Liquide Société Anonyme Pour LÉtude Et L'Exploitation Des Procedes Georges Claude Staged membrane process for high pressure hydrogen production
EA034710B1 (ru) * 2015-01-29 2020-03-10 Ламмус Текнолоджи Инк. Производство олефинов c5 из потока углеводородов c5 установки парового крекинга
CN112705118B (zh) * 2019-10-25 2022-07-12 中国石油化工股份有限公司 重油加氢反应器及加氢工艺

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US5679241A (en) * 1995-05-17 1997-10-21 Abb Lummus Global Inc. Olefin plant recovery system employing catalytic distillation

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US5368691A (en) * 1991-12-16 1994-11-29 Institut Francais Du Petrole Reactive distillation process and apparatus for carrying it out
WO1995015934A1 (en) * 1993-12-08 1995-06-15 Chemical Research & Licensing Company Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams
US5679241A (en) * 1995-05-17 1997-10-21 Abb Lummus Global Inc. Olefin plant recovery system employing catalytic distillation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8597383B2 (en) 2011-04-11 2013-12-03 Saudi Arabian Oil Company Metal supported silica based catalytic membrane reactor assembly
US9745191B2 (en) 2011-04-11 2017-08-29 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10071909B2 (en) 2011-04-11 2018-09-11 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10093542B2 (en) 2011-04-11 2018-10-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures
US10252911B2 (en) 2011-04-11 2019-04-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic systems
US10252910B2 (en) 2011-04-11 2019-04-09 Saudi Arabian Oil Company Auto thermal reforming (ATR) catalytic structures

Also Published As

Publication number Publication date
EP1132453B1 (de) 2004-12-15
US20010031902A1 (en) 2001-10-18
DE60107737T2 (de) 2005-05-12
KR20010088378A (ko) 2001-09-26
JP2001342468A (ja) 2001-12-14
ES2234785T3 (es) 2005-07-01
FR2806093A1 (fr) 2001-09-14
JP4780539B2 (ja) 2011-09-28
DE60107737D1 (de) 2005-01-20
US6410811B2 (en) 2002-06-25
KR100752994B1 (ko) 2007-08-30
FR2806093B1 (fr) 2002-05-03

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