Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
  • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
  • C01B3/0015—Organic compounds; Solutions thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/06—Integration with other chemical processes
  • C01B2203/063—Refinery processes
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1252—Cyclic or aromatic hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/32—Hydrogen storage

Definitions

• the present invention relates to the field of storage and transport of energy sources and more particularly that of the storage and transport of hydrogen as an energy source, and in particular that of organic compounds capable of storing and transporting hydrogen. 'hydrogen.
• This hydrogen fixation is generally carried out in a stage of hydrogenation of the support molecule.
• the hydrogenated support molecule “stores” the fixed hydrogen and this so-called “hydrogenated” molecule can be stored and/or transported.
• the fixed hydrogen can then be released, most often near the place of consumption, in a stage of dehydrogenation of the hydrogenated support molecule.
• Carrier molecules are now the subject of numerous studies and are now better known by the acronym LOHC for "Liquid Organic Hydrogen Carrier" in English, that is to say "Organic Liquid Carrier of Hydrogen”.
• the traces of organic compounds can thus come both from toluene (molecule in hydrogenated form) and from methylcyclohexane (molecule in dehydrogenated form), but also from all their partially hydrogenated or dehydrogenated intermediates.
• LOHCs known today are aromatic fluids with two or three rings, represented in particular by benzyltoluene (BT) and/or dibenzyltoluene (DBT) and which have already been the subject of numerous studies and patent applications, such as patent EP2925669, for example, which describes the technology and operations for the hydrogenation and dehydrogenation of these fluids for the storage and release of hydrogen.
• Still other LOHC compounds are being studied and examples are presented in the article by Pàivi et al. (Journal of Power Sources, 396, (2016), 803-823). Such molecules are still today for the most part not commercially available or at prohibitive prices.
• the hydrogen resulting from this LOHC technology finds uses in very many fields, such as for example in fuel cells, in industrial processes, or even as fuel for means of transport (train, boats , trucks, motor cars).
• the LOHC technology today seems the most promising, but there remains a need for LOHC molecules that are easily available, inexpensive, or at least with very good yields in terms of hydrogenation/dehydrogenation cycles, with supply costs and operation as low as possible.
• One of the objectives of the present invention therefore consists in developing LOHC molecules allowing the transport and storage of the greatest possible quantity of hydrogen with the lowest possible operating cost, in other words a molecule Most cost effective LOHC possible for transporting and storing hydrogen.
• a first object of the present invention is the use of a liquid formulation at ambient temperature comprising a mixture of benzene, toluene and xylene for the fixation and release of hydrogen in at least one hydrogenation/dehydrogenation cycle of said wording.
• BTX mixtures can be obtained from petroleum products, and in particular by extraction of the aromatic compounds from a crude oil, in particular using an aprotic polar solvent, using a liquid extraction -liquid. The solvent is then eliminated and the BTX mixture is separated by distillation in order to recover the benzene, toluene and xylene.
• the xylene fraction includes the three isomers of xylene (ortho-, meta- and para-xylene), but may also include a more or less important fraction of ethylbenzene.
• the BTX mixture used in the formulation of the present invention is free of compounds containing more than 8 carbon atoms.
• the term "free from compounds with more than 8 carbon atoms" indicates that compounds with more than 8 carbon atoms may possibly be present, but in this case only in trace amounts, this is that is to say present in an amount which is not greater than 1000 ppm by weight, relative to the total weight of the formulation, and preferably not greater than 100 ppm by weight, relative to the total weight of the formulation.
• BTX mixtures are mixtures of benzene, toluene and xylene (ortho- and/or meta- and/or para-xylene), and optionally of ethylbenzene, in all proportions.
• the ratio of the benzene/toluene/xylene mixture can vary in any proportion ranging from 0% to 100%, limits excluded, by weight of each constituent, relative to the total weight of the BTX mixture.
• the BTX mixture consists of at least 2 products: toluene+benzene or toluene+xylene or xylene+benzene.
• the BTX mixture comprises the three components benzene, toluene and xylene, and most particularly preferably, in the proportions indicated above.
• the BTX mixture comprises, and preferably consists of:
• the BTX mixture comprises, and preferably consists of:
• the BTX mixture comprises, and preferably consists of:
• the mixture of benzene, toluene and xylene which can be used in the context of the present invention contains a benzene content greater than 1%, better still greater than 2%, preferably greater than 5% , more preferably still greater than 10%, and most preferably greater than 15% by weight, relative to the total weight of the BTX mixture.
• a BTX mixture which can advantageously be used in the context of the present invention contains 40% benzene, 30% toluene and 30% xylene, by weight relative to the total weight of the BTX mix.
• the BTX mixture contains 48% benzene, 33% toluene and 19% xylene, by weight relative to the total weight of the BTX mixture.
• the BTX mixtures may also comprise one or more other compounds, for example isomers of xylenes, such as ethylbenzene, or even one or more other hydrocarbons containing more than 8 atoms, preferably in an amount which is not greater than 1000 ppm by weight, relative to the total weight of the formulation, and preferably not greater than 100 ppm by weight, relative to the total weight of the formulation.
• xylenes such as ethylbenzene
• hydrocarbons containing more than 8 atoms preferably in an amount which is not greater than 1000 ppm by weight, relative to the total weight of the formulation, and preferably not greater than 100 ppm by weight, relative to the total weight of the formulation.
• composition of the BTX mixture can result directly from the preparation process, but can also be modified directly during the synthesis of said according to procedures well known to those skilled in the art, depending on the mixture that he wishes to obtain. .
• BTX mixtures can be used as an organic liquid hydrogen carrier (LOHC) in the same way as each of the constituents of said mixtures, namely benzene, toluene and xylene. , that is to say that the mixtures can be subjected to hydrogenation/dehydrogenation cycles in the same way as the components of said BTX mixtures taken in isolation and independently. It follows that it is useless to carry out the separation of the said components of the BTX mixtures, to use only one or the other of them and thereby save costs and make the use of the present invention quite competitive and more generally more economical than the LOHCs known from the prior art. For the purposes of the present invention, it is of course possible to use a single BTX mixture or even mixtures of several BTX mixtures as they have just been defined, in all proportions.
• LOHC organic liquid hydrogen carrier
• LOHC molecules are generally and most often characterized by their Theoretical Gravimetric Storage Capacity (CSGT).
• CSGT Theoretical Gravimetric Storage Capacity
• methylcyclohexane can theoretically be dehydrogenated into toluene (one of the components of BTX) by releasing 6 hydrogen atoms, as illustrated below:
• toluene when it is completely hydrogenated to methylcyclohexane and then theoretically completely dehydrogenated, can thus release 6 hydrogen atoms. It will therefore be indicated in the context of the present invention that toluene has a CSGT of 6.12%.
• the mixtures of benzene, toluene and xylene that can be used in the context of the present invention have a CSGT strictly greater than 0, preferably greater than or equal to 1%, better even greater than or equal to 2%, more preferably greater than or equal to 3%, most preferably greater than or equal to 4%, advantageously greater than or equal to 5%, typically greater than or equal to 6%, and even better still greater than or equal to 6.5%.
• the CSGT of the LOHCs it may be advantageous to modify, for example further increase, the CSGT of the LOHCs. It is therefore possible to envisage subjecting the mixture of benzene, toluene and xylene to various chemical reactions with other molecules, for example molecules derived from petrochemicals, in particular aromatic compounds derived from petrochemicals, such as benzene, toluene, xylenes, polyethylbenzene residues better known under the name PEBR, as well as mixtures thereof in all proportions, to cite only the most common.
• molecules derived from petrochemicals in particular aromatic compounds derived from petrochemicals, such as benzene, toluene, xylenes, polyethylbenzene residues better known under the name PEBR, as well as mixtures thereof in all proportions, to cite only the most common.
• PEBR polyethylbenzene residues
• BTX mixtures mixtures of benzene, toluene and xylene
• BTX mixtures mixtures of benzene, toluene and xylene
• reduction in LOHC access costs it may be useful, or even necessary in some cases, to carry out one or more purification operations on the BTX mixture, according to techniques well known to those skilled in the art, in order in particular to optimize the yields of the hydrogenation/dehydrogenation cycles during the use of LOHC formulations containing said BTX mixtures.
• the invention thus relates to the use of a liquid formulation at room temperature, in its partially or totally dehydrogenated form, as well as in its partially or totally hydrogenated form, comprising one or more BTX mixtures as they come from be defined for the transport, fixation and release of hydrogen in at least one hydrogenation/dehydrogenation cycle, partial or total, of said formulation.
• the formulation usable in the context of the present invention may also comprise one or more other LOHCs known to those skilled in the art, such as for example benzyltoluene (BT), dibenzyltoluene (DBT) and their mixtures in all proportions.
• the formulation usable in the present invention may also comprise one or more additive(s) and/or filler(s) also well known to those skilled in the art, and for example, and in a non-limiting manner, chosen from antioxidants, passivators, pour point depressants, decomposition inhibitors, colorants, flavors, and the like, as well as mixtures of one or more of them in any proportions.
• the formulation only comprises hydrogenatable/dehydrogenatable compounds (partially or totally), in particular the formulation consists of LOHC molecules , without other added products of additive or filler types.
• the formulation may however contain impurities, preferably in trace form, in particular inherent in the origin of the LOHC molecule used and/or its preparation process.
• the formulation has a boiling point above 80° C. at atmospheric pressure, preferably above 120° C., more preferably still above 150° C., advantageously greater than 180°C, and a melting point less than 40°C, preferably less than 30°C, more preferably less than 20°C, better still less than 15°C, and most preferably, a melting point below 10°C, and advantageously strictly below 0°C.
• the formulation used in the present invention has a kinematic viscosity at 20° C. (measured according to standard DIN 51562) of between 0.1 mm 2 s′ 1 and 500 mm 2 s′ 1 , preferably between 0.5 mm 2 s′ 1 and 300 mm 2 s′ 1 and preferably between 1 mm 2 s′ 1 and 200 mm 2 s′ 1 .
• the hydrogenation/dehydrogenation cycles are most often carried out according to methods that are now well known.
• the dehydrogenation reaction can be carried out according to any known method, the operating conditions of which can include, by way of non-limiting examples:
• reaction temperature generally between 200°C and 400°C, preferably between 250°C and 360°C, more preferably between 280°C and 340°C, more preferably between 280°C and 330°C and totally preferably between 280°C and 320°C,
• reaction pressure generally between 0.01 MPa and 1.00 MPa, and preferably between 0.01 MPa and 0.50 MPa
• the reaction is usually and advantageously carried out in the presence of at least one dehydrogenation catalyst well known to those skilled in the art.
• dehydrogenation catalyst well known to those skilled in the art.
• the catalysts that can be used for said partial dehydrogenation reaction mention may be made, by way of non-limiting examples, of heterogeneous catalysts containing at least one metal on a support.
• Said metal is chosen from among the metals of columns 3 to 12 of the periodic table of the elements of ULCPA, that is to say from among the transition metals of said periodic table.
• the metal is chosen from the metals from columns 5 to 11, more preferably from columns 5 to 10 of the periodic table of the elements of UlCPA.
• the metals of these catalysts are most often chosen from iron, cobalt, copper, titanium, molybdenum, manganese, nickel, platinum, palladium, rhodium, iridium, and ruthenium and their mixtures.
• the metals are chosen from nickel, copper, molybdenum, platinum, palladium, and mixtures of two or more of them in all proportions.
• the catalyst support can be of any type well known to those skilled in the art and is advantageously chosen from porous supports, more advantageously from porous refractory supports.
• supports include alumina, silica, zirconia, magnesia, beryllium oxide, chromium oxide, titanium oxide, thorium oxide, ceramic, carbon such as carbon black, graphite and activated carbon, and combinations thereof.
• specific and preferred examples of support which can be used in the process of the present invention, mention may be made of amorphous silico-aluminates, crystalline silico-aluminates (zeolites) and supports based on silica-titanium oxide.
• the hydrogenation reaction can also be carried out according to any method well known to those skilled in the art on a formulation comprising at least one BTX mixture, as defined above.
• the hydrogenation reaction is generally carried out at a temperature between 100° C. and 300° C., and preferably between 120° C. and 280° C. and even more preferably from 140° C. to 250° C.
• the pressure used for this reaction is generally between 0.1 MPa and 5 MPa, preferably between 0.5 MPa and 4 MPa, and even more preferably between 1 MPa and 3 MPa.
• the hydrogenation reaction is carried out in the presence of a catalyst, and more particularly of a hydrogenation catalyst well known to those skilled in the art, and advantageously chosen from, by way of examples non-limiting, heterogeneous catalysts containing supported metals.
• Said metal is chosen from the metals of columns 3 to 12 of the periodic table of the elements of UlCPA, that is to say among the transition metals of said periodic table.
• the metal is chosen from the metals from columns 5 to 11, more preferably from columns 5 to 10 of the periodic table of the elements of UlCPA.
• the metals of these hydrogenation catalysts are most often chosen from iron, cobalt, copper, titanium, molybdenum, manganese, nickel, platinum, palladium, rhodium, iridium, and ruthenium and their mixtures.
• the metals are chosen from nickel, copper, molybdenum, platinum, palladium, and mixtures of two or more of them in all proportions.
• the catalyst support can be of any type well known to those skilled in the art and is advantageously chosen from porous supports, more advantageously from porous refractory supports.
• supports include alumina, silica, zirconia, magnesia, beryllium oxide, chromium oxide, titanium oxide, thorium oxide, ceramic, carbon such as carbon black, graphite and activated carbon, and combinations thereof.
• specific and preferred examples of support which can be used in the process of the present invention, mention may be made of amorphous silico-aluminates, crystalline silico-aluminates (zeolites) and supports based on silica-titanium oxide.
• the hydrogenation reaction is carried out on a totally or partially dehydrogenated formulation, for example at least partially dehydrogenated, in one or more hydrogenation/dehydrogenation cycles.
• the hydrogenation reaction can be partial or total, and preferably the hydrogenation reaction is total in one or more hydrogenation/dehydrogenation cycles, that is to say that all of the double bonds present in the LOHC formulation capable of being hydrogenated are fully hydrogenated.
• the invention relates to a process for upgrading BTX.
• BTX are products considered toxic and eco-toxic and are very difficult to recover, even today little or not recovered, and simply destroyed, most often by combustion, thus generating, in addition to air pollution, significant emissions of carbon dioxide, which is known to be one of the causes of climate change and global warming.
• the upgrading process of the invention comprises supplying a so-called BTX mixture, as defined more high in a system where it is hydrogenated, in whole or at least in part, optionally stored, and/or optionally transported, then subjected to a stage of total or at least partial dehydrogenation, so as to release the hydrogen bound on the BTX totally or at least partially hydrogenated.
• the upgrading process of the invention can also comprise, and advantageously comprises, several hydrogenation/dehydrogenation cycles, for example from 2 to 200 cycles, preferably from 5 to 100 cycles.
• the BTX thus upgraded is used in a cycle comprising several hydrogenation/dehydrogenation operations, and is not, or only in very small proportions, in contact with the air or the people who have to handle it.
• the storage and/or transport of hydrogen in no way requires access to BTX itself, whether in dehydrogenated or totally or at least partially hydrogenated form.
• the so-called BTX mixtures are valued as energy storage products, this energy being hydrogen.
• the present invention relates to a hydrogenation/dehydrogenation cycle comprising a partial or total dehydrogenation reaction of an LOHC formulation as it has just been defined and at least one partial or total reaction of hydrogenating said organic liquid.
• the formulations for transporting hydrogen are particularly well suited because of their stability, which allows reuse in a large number of hydrogenation cycles. / dehydrogenation for transport, but also the storage and handling of hydrogen from the steam cracking of petroleum products, fatal hydrogen from chemical reactions such as the electrolysis of salt or hydrogen from the electrolysis of water.

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• 2020
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