EP4259572A1 - Liquid formulation for hydrogen storage - Google Patents
Liquid formulation for hydrogen storageInfo
- Publication number
- EP4259572A1 EP4259572A1 EP21840653.6A EP21840653A EP4259572A1 EP 4259572 A1 EP4259572 A1 EP 4259572A1 EP 21840653 A EP21840653 A EP 21840653A EP 4259572 A1 EP4259572 A1 EP 4259572A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- equal
- less
- ppm
- benzyltoluene
- 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
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000012669 liquid formulation Substances 0.000 title claims abstract description 8
- 238000003860 storage Methods 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 238000009472 formulation Methods 0.000 claims abstract description 49
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 40
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 19
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 claims description 27
- 239000012530 fluid Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003209 petroleum derivative Substances 0.000 claims description 4
- GNPWYHFXSMINJQ-UHFFFAOYSA-N 1,2-dimethyl-3-(1-phenylethyl)benzene Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CC=CC=C1 GNPWYHFXSMINJQ-UHFFFAOYSA-N 0.000 claims description 3
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical group CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 claims description 2
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 claims description 2
- HQCUSXPGMKCZGE-UHFFFAOYSA-N 1-(1-phenylethyl)-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCC2=CC=CC=C2C1C(C)C1=CC=CC=C1 HQCUSXPGMKCZGE-UHFFFAOYSA-N 0.000 claims description 2
- WKAXDAMWMOBXMP-UHFFFAOYSA-N 2,3-diphenylpyridine Chemical class C1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=C1 WKAXDAMWMOBXMP-UHFFFAOYSA-N 0.000 claims description 2
- PDINXYLAVFUHSA-UHFFFAOYSA-N 4-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)CCC1=CC=CC=C1 PDINXYLAVFUHSA-UHFFFAOYSA-N 0.000 claims description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000005359 phenylpyridines Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 22
- 239000010457 zeolite Substances 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- -1 aluminum silicates Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000020688 green tea extract Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- 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 liquid formulations capable of transporting hydrogen, and more particularly the field of formulations based on benzyltoluene capable of transporting hydrogen.
- Hydrogen today represents an alternative to fossil, natural or electrical energy sources.
- the storage and transport of this energy source, hydrogen remains a major challenge for the rapid and accessible development of this energy source.
- the principle of this LOHC technology consists in fixing hydrogen on a support molecule, which is preferably and most often liquid at room temperature, in a hydrogenation step, then in releasing the fixed hydrogen, at near the place of consumption, in a dehydrogenation step.
- Patent EP2925669 thus shows the use of BT and/or DBT in LOHC technology, and describes the hydrogenation and dehydrogenation operations of these fluids for the storage and release of hydrogen.
- the sequence of cycles and the maintenance of performance are key points for the economic aspect of this technology.
- the hydrogen resulting from this LOHC technology finds uses in very many fields, such as for example in fuel cells, as well as in various industrial processes, or even as fuel for all means of transport, such as trains, ships, trucks, motor cars, planes, and others. Any impurity present in the hydrogen, even in trace amounts, could have a negative impact, both on the hydrogenation/dehydrogenation process in terms of yield, and on the quality of the products manufactured or even on the yields in end uses. hydrogen produced by this technique.
- the present invention relates to a liquid formulation, based on benzyltoluene and containing very low levels of light hydrocarbons.
- This type of formulation makes it possible in particular to overcome all or part of the drawbacks noted in the prior art for LOHC fluids, by meeting in particular the requirements for storage, transport and removal of hydrogen, under optimal industrial and economic conditions, and in allowing the release, during the dehydrogenation step of said formulation, of hydrogen having a high purity, and in particular of hydrogen having a very low content of light hydrocarbons, these being particularly detrimental for the uses of hydrogen in a large number of applications, such as fuel cells for example.
- the present invention relates to a liquid formulation comprising: - an amount equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than 80% and most preferably equal to or greater than 90% by weight of benzyltoluene (BT), relative to the total weight of the formulation, and
- BT benzyltoluene
- the formulation according to the present invention is a liquid formulation at ambient temperature and pressure, that is to say at 25° C. and 1 atmosphere (1013 mbar or 1013 hPA).
- the formulation according to the present invention comprises an amount equal to or greater than 50% by weight of BT, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than greater than 80% and quite preferably equal to or greater than 90% by weight of BT.
- the formulation according to the present invention comprises an amount equal to or greater than 98% by weight of benzyltoluene (BT).
- the formulation according to the present invention preferably comprises benzyltoluene alone, or optionally with one or more other LOHC fluids as indicated below, that is to say without component other than impurities in the form of traces and in particular at least one light hydrocarbon (molar mass equal to or less than 100 g mol -1 ), present but in an amount equal to or less than 10 ppm by weight.
- the formulation according to the invention comprises an amount at most equal to 99.99% by weight of BT, preferably at most equal to 99.95% by weight of BT, more preferably at most equal to 99.9% by weight of BT.
- the formulation may also comprise one or more other LOHC fluids well known to those skilled in the art, such as those derived from petroleum products and/or products synthesized from petroleum products, or even derived from renewables and/or products synthesized from renewable products.
- Such other LOHC fluids are, for example and without limitation, those chosen from dibenzyltoluene (DBT), diphenylethane (DPE), diphenylmethane (DPM), ditolylether (DT), phenylxylylethane (PXE), mono- and bi-xylylxylenes, 1,2,3,4-tetrahydro-(1-phenylethyl)naphthalene, di-isopropylnaphthalene, mono-isopropylbiphenyl, phenylethylphenylethane (PEPE), N-ethylcarbazole, phenylpyridines, tolylpyridines, diphenylpyridines, dipyridylbenzenes, dipyridinetoluenes, as well as mixtures of two or more of them, in all proportions, to cite only the main organic fluids known and usable in the context of the present invention.
- DBT
- the formulation comprises at least 50% by weight of benzyltoluene (BT), and dibenzyltoluene (DBT).
- BT benzyltoluene
- DBT dibenzyltoluene
- the formulation comprises from 70% to 80% by weight of BT and from 20% to 30% by weight of DBT (relative to the total weight of BT + DBT).
- the formulation comprises from 80% to 99.9% by weight of BT and from 0.1% to 20% by weight of DBT (relative to the total weight of BT + DBT), preferably the formulation comprises from 90% to 99.9% by weight of BT and from 0.1% to 10% by weight of DBT (based on the total weight of BT + DBT), and more preferably the formulation comprises from 90% to 99.5% by weight of BT and 0.5% to 10% by weight of DBT (based on the total weight of BT + DBT).
- the formulation according to the present invention comprises an amount equal to or less than 10 ppm, preferably equal to or less than 5 ppm, more preferably equal to or less than 2 ppm by weight of at least one hydrocarbon of mass molar equal to or less than 100 g mol -1 . It has in fact been observed that hydrocarbons, and in particular so-called "light" hydrocarbons, and more precisely hydrocarbons with a molar mass equal to or less than 100 g mol -1 , very often lead to numerous disadvantages, whether during hydrogenation/dehydrogenation operations to which the LOHC formulations are subjected, but also in the hydrogen released during the dehydrogenation operations, hydrogen which may then not have the degree of purity required for the applications for which it is intended.
- Light hydrocarbons can in fact disrupt the hydrogenation/dehydrogenation reactions, and typically by degradation and/or total or partial deactivation of at least some of the catalysts used, lower yields of the hydrogenation/dehydrogenation cycles, or any other effect disturbing the operating conditions of said hydrogenation/dehydrogenation cycles.
- the light hydrocarbons are present in the formulation at a content of between 0.01 ppm by weight and 10 ppm by weight, preferably between 0.01 ppm by weight and 5 ppm by weight. , more preferably between 0.01 ppm by weight and 2 ppm by weight.
- the light hydrocarbons are present in the formulation at a content of between 0.05 ppm by weight and 10 ppm by weight, preferably between 0.05 ppm by weight and 5 ppm by weight, more preferably still between 0.05 wppm and 2 wppm.
- the light hydrocarbons are present in the formulation at a content of between 0.1 ppm by weight and 10 ppm by weight, preferably between 0.1 ppm by weight and 5 ppm by weight, more preferably between between 0.1 ppm by weight and 2 ppm by weight.
- light hydrocarbons within the meaning of the present invention, is meant hydrocarbons with a molar mass equal to or less than 100 g mol -1 .
- hydrocarbons is meant, in general, hydrocarbon compounds in the broad sense and well known to those skilled in the art.
- Light hydrocarbons means hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising carbon, hydrogen and optionally one or more heteroatoms chosen from oxygen, sulfur and nitrogen.
- the light hydrocarbons are hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising 6, 7 or 8 carbon atoms, and more preferably the light hydrocarbons are those chosen from, without be limited to, benzene and toluene.
- the formulation according to the invention may further, although this does not form a preferred embodiment, comprise one or more additives and/or fillers well known to those skilled in the art, and for example, and in such a way non-limiting, selected from antioxidants, pigments, colorants, flavors, odor masking agents, viscosity modifiers, passivators, pour point depressants, decomposition inhibitors and mixtures thereof.
- additives and/or fillers well known to those skilled in the art, and for example, and in such a way non-limiting, selected from antioxidants, pigments, colorants, flavors, odor masking agents, viscosity modifiers, passivators, pour point depressants, decomposition inhibitors and mixtures thereof.
- antioxidants which can be advantageously used in the formulation of the invention, mention may be made, by way of non-limiting examples, of phenolic antioxidants, such as for example dibutylhydroxytoluene, butylhydroxyanisole, tocopherols, as well as the acetates of these phenolic antioxidants.
- antioxidants of the amine type such as for example phenyl-a-naphthylamine, of the diamine type, for example N,N'-di-(2-naphthyl)-para-phenylenediamine, but also ascorbic acid and its salts, esters of ascorbic acid, alone or in mixtures of two or more of them or with other components, such as for example green tea extracts, coffee extracts.
- the present invention relates to a formulation comprising:
- BT benzyltoluene
- DBT dibenzyltoluene
- the present invention relates to a formulation comprising:
- BT benzyltoluene
- DBT dibenzyltoluene
- Benzyltoluene is a well-known compound, commercially available and the method of preparation of which is also well known to those skilled in the art.
- BT can easily be prepared by catalytic reaction of toluene with chlorotoluene, according to techniques now well known to those skilled in the art and in particular as described in patent EP0435737.
- BT synthetic crudes, but also BT-based LOHC liquids that have been engaged in hydrogenation/dehydrogenation cycles can thus contain variable amounts of at least one light hydrocarbon, as described above.
- the formulation according to the present invention can therefore be prepared, for example and typically, from these synthetic raw materials or liquid LOHCs based on BT, according to any method well known to those skilled in the art.
- the formulation according to the present invention can advantageously be prepared by treating a formulation comprising at least 50% of BT and at least one light hydrocarbon, in an amount greater than 10 ppm weight, by distillation, recrystallization, thin layer evaporation, and other methods or combinations of one or more of these methods.
- the filtering agents which can be used in the context of the present invention can be of all types and are well known to those skilled in the art.
- the filtering agents which have proved to be the most suitable are the adsorbent filtering agents, and more particularly the filtering agents comprising one or more compounds chosen from minerals based on silicates, carbonates, carbon, as well as mixtures of two or more of these minerals in all proportions.
- inorganic or organic filtering agents and in particular those chosen from clays, zeolites, diatomaceous earth, ceramics, carbonates, and carbon derivatives, as well as mixtures of two or more of them, in any proportion.
- filtering agents adsorbents and filter-adsorbents
- clays including silicates, and for example magnesium silicates, such as and without limitation, attapulgites, montmorillonites, selenites, bentonites, talcs, and others,
- Silicates in particular clays and zeolites, have proved to be very particularly effective for the preparation of the formulation of the present invention. Silicates have in fact shown themselves to be very particularly suitable for the elimination, or at least for the significant reduction, of one or more light hydrocarbon(s) present in a formulation comprising an equal or greater than 50% by weight of benzyltoluene (BT).
- BT benzyltoluene
- filtering agents advantageously usable for the preparation of the formulation of the present invention
- attapulgite Microsorb® 16/30 LVM from BASF (example of alumino-magnesian clay with the chemical formula (Mg, Al) 5 Si8O22(OH) 4 , SiC>2)
- Amcol Rafinol 900 FF from Minerals Technologies
- Amcol Rafinol 920 FF from Minerals Technologies
- Amcol Mineral Bent aluminum hydrosilicate
- Siliporite® in particular MK30B0 and MK30B2
- ARKEMA preparations based on zeolite of the alumino silicate type
- the filtering agent used for the preparation of the formulation comprising a content of at least one light hydrocarbon equal to or less than 10 ppm by weight is chosen from molecular sieves (also called “zeolitic adsorbents”), in particular molecular sieves allowing the adsorption, as selectively as possible, of light hydrocarbons, in particular hydrocarbons with a molar mass equal to or less than 100 g mol -1 .
- molecular sieves also called “zeolitic adsorbents”
- zeolite adsorbent materials that is to say materials comprising one or more zeolites
- zeolite adsorbent materials are advantageously chosen from molecular sieves based on synthetic zeolites which, by virtue of their wide variety of preparation methods, offer , a wide variety of parameters which can be finely adjusted, such as for example the thermal stability, the mechanical resistance or even the facilitation of regeneration, and this in order to meet the specific criteria required for the use of interest.
- zeolite adsorbent materials for use in the context of the present invention, mention may be made of natural or synthetic zeolites, and more particularly zeolite adsorbent materials chosen from natural zeolites, such as for example chabazite, and among synthetic zeolites, in particular LTA-type zeolites, FAU-type zeolites, EMT-type zeolites, MFI-type zeolites, and BEA-type zeolites.
- the present invention relates to the use of a formulation as defined above as LOHC fluid for the production of hydrogen comprising a low level of impurities and in particular for the production of hydrogen comprising a quantity equal to or less than 10 ppm by weight of at least one light hydrocarbon, and in particular of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 .
- the performance of the hydrogenation/dehydrogenation cycles are facilitated/improved, thanks to less degradation of the catalyst during successive cycles, in particular due to the fact that the LOHC formulation of the invention includes only traces of light hydrocarbons, as discussed above, hydrocarbons which are known to be catalyst poisons commonly used in hydrogenation/dehydrogenation reactions.
- the hydrogen stored and then released during the dehydrogenation step is high purity hydrogen, which can thus find uses in a very large number of applications, in particular for fuel cells, and all other industrial applications requiring the use of high purity hydrogen, such as the electronics sector for the production of microprocessors, semiconductors, and others.
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Abstract
The present invention relates to a liquid formulation comprising an amount greater than or equal to 50% by weight of benzyl toluene and an amount less than or equal to 10 ppm by weight of at least one hydrocarbon having a molar mass less than or equal to 100 g mol-1. The invention also relates to the use of said formulation, comprising an amount less than or equal to 10 ppm by weight of light hydrocarbon, as LOHC for producing hydrogen.
Description
FORMULATION LIQUIDE POUR STOCKAGE D’HYDROGÈNE LIQUID FORMULATION FOR HYDROGEN STORAGE
[0001] La présente invention concerne le domaine des formulations liquides aptes à transporter de l’hydrogène, et plus particulièrement le domaine des formulations à base de benzyltoluène aptes à transporter de l’hydrogène. The present invention relates to the field of liquid formulations capable of transporting hydrogen, and more particularly the field of formulations based on benzyltoluene capable of transporting hydrogen.
[0002] L’hydrogène représente aujourd’hui une alternative aux sources d’énergie fossiles, naturelles ou électriques. Le stockage et le transport de cette source d’énergie qu’est l’hydrogène reste cependant un enjeu majeur pour le développement rapide et accessible de cette source d’énergie. [0002] Hydrogen today represents an alternative to fossil, natural or electrical energy sources. However, the storage and transport of this energy source, hydrogen, remains a major challenge for the rapid and accessible development of this energy source.
[0003] Diverses approches ont été étudiées pour stocker et transporter plus facilement ce gaz très volatil et hautement explosif, et, parmi celles-ci, on peut citer le stockage sous pression, le stockage cryogénique, le stockage sur support. Parmi les types de support envisageables, la technologie basée sur les liquides organiques porteurs d’hydrogène (technologie dite LOHC pour « Liquid Organic Hydrogen Carrier » en langue anglaise) est une technologie prometteuse et particulièrement intéressante pour le transport longue distance, à des coûts tout à fait compatibles avec un développement à grande échelle. [0003] Various approaches have been studied to store and transport this very volatile and highly explosive gas more easily, and, among these, mention may be made of storage under pressure, cryogenic storage, storage on a support. Among the types of support that can be envisaged, the technology based on organic liquid hydrogen carriers (technology known as LOHC for "Liquid Organic Hydrogen Carrier" in English) is a promising and particularly interesting technology for long-distance transport, at very low costs. fully compatible with large-scale development.
[0004] Le principe de cette technologie LOHC consiste à fixer de l'hydrogène sur une molécule support, laquelle est de préférence et le plus souvent liquide à température ambiante, dans une étape d'hydrogénation, puis à libérer l’hydrogène fixé, à proximité du lieu de consommation, dans une étape de déshydrogénation. The principle of this LOHC technology consists in fixing hydrogen on a support molecule, which is preferably and most often liquid at room temperature, in a hydrogenation step, then in releasing the fixed hydrogen, at near the place of consumption, in a dehydrogenation step.
[0005] Parmi les molécules LOHC étudiées aujourd’hui, les liquides aromatiques à deux ou trois noyaux, telles que par exemple le benzyltoluène (BT) et/ou le dibenzyltoluène (DBT) qui ont déjà fait l'objet de nombreuses études et de demandes de brevets, représentent des molécules particulièrement bien adaptées à cette utilisation. Le brevet EP2925669 montre ainsi l’utilisation de BT et/ou de DBT dans la technologie LOHC, et décrit les opérations d’hydrogénation et de déshydrogénation de ces fluides pour le stockage et la libération d’hydrogène. [0005] Among the LOHC molecules studied today, aromatic liquids with two or three rings, such as for example benzyltoluene (BT) and/or dibenzyltoluene (DBT) which have already been the subject of numerous studies and patent applications, represent molecules particularly well suited to this use. Patent EP2925669 thus shows the use of BT and/or DBT in LOHC technology, and describes the hydrogenation and dehydrogenation operations of these fluids for the storage and release of hydrogen.
[0006] Au-delà de la performance instantanée des étapes d'hydrogénation et de déshydrogénation, l'enchaînement des cycles et le maintien des performances (rendement de fixation/libération d'hydrogène) ainsi que la pureté de l’hydrogène déstocké (ou libéré) lors de l’étape de déshydrogénation, sont des points clés pour l'aspect économique de cette technologie.
[0007] En effet, l’hydrogène issu de cette technologie LOHC trouve des utilisations dans de très nombreux domaines, comme par exemple dans les piles à combustibles, ainsi que dans divers procédés industriels, ou encore comme carburant pour tous les moyens de transport, tels que trains, bateaux, camions, voitures automobiles, avions, et autres. Toute impureté présente dans l’hydrogène, même à l’état de traces, pourrait avoir un impact négatif, tant sur le procédé hydrogénation/déshydrogénation en termes de rendement, que sur la qualité des produits fabriqués ou encore sur les rendements dans les utilisations finales de l’hydrogène produit par cette technique. [0006] Beyond the instantaneous performance of the hydrogenation and dehydrogenation steps, the sequence of cycles and the maintenance of performance (yield of hydrogen fixation/release) as well as the purity of the destocked hydrogen (or released) during the dehydrogenation step, are key points for the economic aspect of this technology. [0007] Indeed, the hydrogen resulting from this LOHC technology finds uses in very many fields, such as for example in fuel cells, as well as in various industrial processes, or even as fuel for all means of transport, such as trains, ships, trucks, motor cars, planes, and others. Any impurity present in the hydrogen, even in trace amounts, could have a negative impact, both on the hydrogenation/dehydrogenation process in terms of yield, and on the quality of the products manufactured or even on the yields in end uses. hydrogen produced by this technique.
[0008] Afin de pallier ces éventuels problèmes, une des solutions est que l’hydrogène libéré lors de l’étape de déshydrogénation soit le plus pur possible. Or l’hydrogène libéré lors de l’étape de déshydrogénation entraîne inévitablement avec lui des impuretés issues de composés organiques souvent présentes dans le liquide organique à déshydrogéner. [0008] In order to overcome these possible problems, one of the solutions is for the hydrogen released during the dehydrogenation step to be as pure as possible. However, the hydrogen released during the dehydrogenation step inevitably brings with it impurities from organic compounds often present in the organic liquid to be dehydrogenated.
[0009] Ces impuretés sont de natures diverses, et peuvent être présentes en quantités plus ou moins importantes, d’une part dans le fluide LOHC de départ, mais aussi dans le fluide LOHC après qu’il a subi de nombreux cycles hydrogénation/déshydrogénation (dit « fluide LOHC » dans la suite du présent exposé). Il reste donc un besoin pour des fluides LOHC performants, tant du point de vue de rendement en termes de stockage (cycles hydrogénation/déshydrogénation) que du point de vue de la pureté de l’hydrogène libéré lors de l’étape de déshydrogénation. D’autres objectifs encore apparaîtront dans la suite de la description de l’invention qui est exposée plus en détail ci-dessous. These impurities are of various natures, and can be present in greater or lesser quantities, on the one hand in the starting LOHC fluid, but also in the LOHC fluid after it has undergone numerous hydrogenation/dehydrogenation cycles. (called "LOHC fluid" in the remainder of this presentation). There is therefore still a need for high-performance LOHC fluids, both from the point of view of yield in terms of storage (hydrogenation/dehydrogenation cycles) and from the point of view of the purity of the hydrogen released during the dehydrogenation step. Still other objectives will appear in the remainder of the description of the invention which is set out in more detail below.
[0010] La Demanderesse a maintenant découvert une formulation de fluide LOHC tout à fait adaptée pour le stockage et le transport de l’hydrogène apte à libérer, lors de l’étape de déshydrogénation, de l’hydrogène de grande pureté. [0010] The Applicant has now discovered a formulation of LOHC fluid that is entirely suitable for the storage and transport of hydrogen capable of releasing, during the dehydrogenation step, hydrogen of high purity.
[0011] Ainsi, et selon un premier aspect, la présente invention concerne une formulation liquide, à base de benzyltoluène et contenant de très faibles teneurs en hydrocarbures légers. Ce type de formulation permet notamment de pallier tout ou partie des inconvénients relevés dans l’art antérieur pour les fluides LOHC, en répondant en particulier aux exigences de stockage, transport et déstockage d’hydrogène, dans des conditions industrielles et économiques optimales, et en permettant la libération, lors de l’étape de déshydrogénation de ladite formulation, de l’hydrogène présentant une grande pureté, et notamment de l’hydrogène présentant de très faibles teneurs en hydrocarbures légers, ceux-ci étant particulièrement préjudiciables pour les utilisations d’hydrogène dans un grand nombre d’applications, comme les piles à combustible par exemple. Thus, and according to a first aspect, the present invention relates to a liquid formulation, based on benzyltoluene and containing very low levels of light hydrocarbons. This type of formulation makes it possible in particular to overcome all or part of the drawbacks noted in the prior art for LOHC fluids, by meeting in particular the requirements for storage, transport and removal of hydrogen, under optimal industrial and economic conditions, and in allowing the release, during the dehydrogenation step of said formulation, of hydrogen having a high purity, and in particular of hydrogen having a very low content of light hydrocarbons, these being particularly detrimental for the uses of hydrogen in a large number of applications, such as fuel cells for example.
[0012] Plus spécifiquement, la présente invention concerne une formulation liquide comprenant :
- une quantité égale ou supérieure à 50%, de préférence égale ou supérieure à 60%, de préférence encore égale ou supérieure à 70%, mieux encore égale ou supérieure à 80% et de manière tout à fait préférée égale ou supérieure à 90% en poids de benzyltoluène (BT), par rapport au poids total de la formulation, et More specifically, the present invention relates to a liquid formulation comprising: - an amount equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than 80% and most preferably equal to or greater than 90% by weight of benzyltoluene (BT), relative to the total weight of the formulation, and
- une quantité égale ou inférieure à 10 ppm poids d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1. - an amount equal to or less than 10 ppm by weight of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 .
[0013] La formulation selon la présente invention est une formulation liquide à température et à pression ambiantes, c’est-à-dire à 25 °C et 1 atmosphère (1013 mbar ou 1013 hPA). The formulation according to the present invention is a liquid formulation at ambient temperature and pressure, that is to say at 25° C. and 1 atmosphere (1013 mbar or 1013 hPA).
[0014] Comme indiqué précédemment, la formulation selon la présente invention comprend une quantité égale ou supérieure à 50% en poids de BT, de préférence égale ou supérieure à 60%, de préférence encore égale ou supérieure à 70%, mieux encore égale ou supérieure à 80% et de manière tout à fait préférée égale ou supérieure à 90% en poids de BT. Dans un mode de réalisation tout particulièrement préféré, la formulation selon la présente invention comprend une quantité égale ou supérieure à 98% en poids de benzyltoluène (BT). As indicated above, the formulation according to the present invention comprises an amount equal to or greater than 50% by weight of BT, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than greater than 80% and quite preferably equal to or greater than 90% by weight of BT. In a very particularly preferred embodiment, the formulation according to the present invention comprises an amount equal to or greater than 98% by weight of benzyltoluene (BT).
[0015] La formulation selon la présente invention comprend de préférence du benzyltoluène seul, ou éventuellement avec un ou plusieurs autres fluide LOHC comme indiqué plus loin, c’est-à-dire sans composant autre que des impuretés sous forme de traces et en particulier au moins un hydrocarbure léger (masse molaire égale ou inférieure à 100 g mol-1), présent mais en quantité égale ou inférieure à 10 ppm poids. Ainsi, et dans un mode de réalisation préféré, la formulation selon l’invention comprend une quantité au plus égale à 99,99% en poids de BT, de préférence au plus égale à 99,95% en poids de BT, de préférence encore au plus égale à 99,9% en poids de BT. The formulation according to the present invention preferably comprises benzyltoluene alone, or optionally with one or more other LOHC fluids as indicated below, that is to say without component other than impurities in the form of traces and in particular at least one light hydrocarbon (molar mass equal to or less than 100 g mol -1 ), present but in an amount equal to or less than 10 ppm by weight. Thus, and in a preferred embodiment, the formulation according to the invention comprises an amount at most equal to 99.99% by weight of BT, preferably at most equal to 99.95% by weight of BT, more preferably at most equal to 99.9% by weight of BT.
[0016] Comme indiqué précédemment, la formulation peut également comprendre un ou plusieurs autres fluides LOHC bien connus de l’homme du métier tels que ceux issus de produits pétroliers et/ou de produits synthétisés à partir de produits pétroliers, ou encore issus de produits renouvelables et/ou de produits synthétisés à partir de produits renouvelables. [0016] As indicated above, the formulation may also comprise one or more other LOHC fluids well known to those skilled in the art, such as those derived from petroleum products and/or products synthesized from petroleum products, or even derived from renewables and/or products synthesized from renewable products.
[0017] De tels autres fluides LOHC sont par exemple et de manière non limitative ceux choisis parmi le dibenzyltoluène (DBT), le diphényléthane (DPE), le diphénylméthane (DPM), le ditolyléther (DT), le phénylxylyléthane (PXE), les mono- et bi-xylylxylènes, le 1 ,2,3,4-tétrahydro-(1 -phényléthyl)naphtalène, le di-isopropylnaphtalène, le mono- isopropylbiphényle, le phényléthylphényléthane (PEPE), le N-éthylcarbazole, les phénylpyridines, les tolylpyridines, les diphénylpyridines, les dipyridylbenzènes, les
dipyridinetoluènes, ainsi que les mélanges de deux ou plusieurs d’entre eux, en toutes proportions, pour ne citer que les principaux fluides organiques connus et utilisables dans le cadre de la présente invention. [0017] Such other LOHC fluids are, for example and without limitation, those chosen from dibenzyltoluene (DBT), diphenylethane (DPE), diphenylmethane (DPM), ditolylether (DT), phenylxylylethane (PXE), mono- and bi-xylylxylenes, 1,2,3,4-tetrahydro-(1-phenylethyl)naphthalene, di-isopropylnaphthalene, mono-isopropylbiphenyl, phenylethylphenylethane (PEPE), N-ethylcarbazole, phenylpyridines, tolylpyridines, diphenylpyridines, dipyridylbenzenes, dipyridinetoluenes, as well as mixtures of two or more of them, in all proportions, to cite only the main organic fluids known and usable in the context of the present invention.
[0018] Selon un mode de réalisation préféré de la présente invention, la formulation comprend au moins 50% en poids de benzyltoluène (BT), et du dibenzyltoluène (DBT). Selon un mode de réalisation de la présente invention, la formulation comprend de 70% à 80% en poids de BT et de 20% à 30% en poids de DBT (par rapport au poids total de BT + DBT). Selon un autre mode de réalisation, la formulation comprend de 80% à 99,9% en poids de BT et de 0,1% à 20% en poids de DBT (par rapport au poids total de BT + DBT), de préférence la formulation comprend de 90% à 99,9% en poids de BT et de 0,1% à 10% en poids de DBT (par rapport au poids total de BT + DBT), et de préférence encore la formulation comprend de 90% à 99,5% en poids de BT et de 0,5% à 10% en poids de DBT (par rapport au poids total de BT + DBT). According to a preferred embodiment of the present invention, the formulation comprises at least 50% by weight of benzyltoluene (BT), and dibenzyltoluene (DBT). According to an embodiment of the present invention, the formulation comprises from 70% to 80% by weight of BT and from 20% to 30% by weight of DBT (relative to the total weight of BT + DBT). According to another embodiment, the formulation comprises from 80% to 99.9% by weight of BT and from 0.1% to 20% by weight of DBT (relative to the total weight of BT + DBT), preferably the formulation comprises from 90% to 99.9% by weight of BT and from 0.1% to 10% by weight of DBT (based on the total weight of BT + DBT), and more preferably the formulation comprises from 90% to 99.5% by weight of BT and 0.5% to 10% by weight of DBT (based on the total weight of BT + DBT).
[0019] Comme indiqué précédemment, la formulation selon la présente invention comprend une quantité égale ou inférieure à 10 ppm, de préférence égale ou inférieure à 5 ppm, de préférence encore égale ou inférieure à 2 ppm poids d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1. Il a en effet été observé que les hydrocarbures, et notamment les hydrocarbures dits « légers », et plus précisément les hydrocarbures de masse molaire égale ou inférieure à 100 g mol-1 , conduisent très souvent à de nombreux inconvénients, que ce soit au cours des opérations d’hydrogénation/ déshydrogénation auxquelles sont soumises les formulations LOHC, mais aussi dans l’hydrogène libéré lors des opérations de déshydrogénation, hydrogène qui peut alors ne pas présenter le degré de pureté requis pour les applications auxquelles il est destiné. As indicated above, the formulation according to the present invention comprises an amount equal to or less than 10 ppm, preferably equal to or less than 5 ppm, more preferably equal to or less than 2 ppm by weight of at least one hydrocarbon of mass molar equal to or less than 100 g mol -1 . It has in fact been observed that hydrocarbons, and in particular so-called "light" hydrocarbons, and more precisely hydrocarbons with a molar mass equal to or less than 100 g mol -1 , very often lead to numerous disadvantages, whether during hydrogenation/dehydrogenation operations to which the LOHC formulations are subjected, but also in the hydrogen released during the dehydrogenation operations, hydrogen which may then not have the degree of purity required for the applications for which it is intended.
[0020] Les hydrocarbures légers peuvent en effet venir perturber les réactions d’hydrogénation/déshydrogénation, et typiquement par dégradation et/ou désactivation totale ou partielle d’au moins une partie des catalyseurs utilisés, baisse des rendements des cycles hydrogénation/déshydrogénation, ou tout autre effet perturbant les conditions opératoires desdits cycles hydrogénation/déshydrogénation. [0020] Light hydrocarbons can in fact disrupt the hydrogenation/dehydrogenation reactions, and typically by degradation and/or total or partial deactivation of at least some of the catalysts used, lower yields of the hydrogenation/dehydrogenation cycles, or any other effect disturbing the operating conditions of said hydrogenation/dehydrogenation cycles.
[0021] Par ailleurs, et plus spécifiquement en ce qui concerne la qualité de l’hydrogène libéré lors des opérations de déshydrogénation de la formulation selon la présente invention, il a été observé que la présence d’hydrocarbures légers dans une formulation destinée à stocker puis libérer de l’hydrogène entraîne la présence d’une quantité au moins aussi importante, dans l’hydrogène libéré, desdits hydrocarbures légers. Comme déjà indiqué précédemment la présence de telles impuretés dans l’hydrogène, en particulier en quantité supérieure à 10 ppm, peuvent s’avérer gênantes, voire rédhibitoires, dans
certaines utilisations, telles que par exemple pour les piles à combustible, et toutes les autres applications industrielles nécessitant l’utilisation d’hydrogène de haute pureté, telles que le secteur électronique pour la production de micro-processeurs, de semi-conducteurs, et autres. Furthermore, and more specifically as regards the quality of the hydrogen released during the dehydrogenation operations of the formulation according to the present invention, it has been observed that the presence of light hydrocarbons in a formulation intended to store then releasing hydrogen results in the presence of at least as large a quantity, in the released hydrogen, of said light hydrocarbons. As already indicated above, the presence of such impurities in hydrogen, in particular in a quantity greater than 10 ppm, can prove to be troublesome, even prohibitive, in certain uses, such as for example for fuel cells, and all other industrial applications requiring the use of high purity hydrogen, such as the electronics sector for the production of microprocessors, semiconductors, and others .
[0022] Dans un mode de réalisation préféré de la présente invention, les hydrocarbures légers sont présents dans la formulation à une teneur comprise entre 0,01 ppm poids et 10 ppm poids, de préférence comprise entre 0,01 ppm poids et 5 ppm poids, de préférence encore comprise entre 0,01 ppm poids et 2 ppm poids. Selon un autre mode de réalisation préféré, les hydrocarbures légers sont présents dans la formulation à une teneur comprise entre 0,05 ppm poids et 10 ppm poids, de préférence comprise entre 0,05 ppm poids et 5 ppm poids, de préférence encore comprise entre 0,05 ppm poids et 2 ppm poids. Selon encore un autre mode de réalisation préféré, les hydrocarbures légers sont présents dans la formulation à une teneur comprise entre 0,1 ppm poids et 10 ppm poids, de préférence comprise entre 0,1 ppm poids et 5 ppm poids, de préférence encore comprise entre 0,1 ppm poids et 2 ppm poids. In a preferred embodiment of the present invention, the light hydrocarbons are present in the formulation at a content of between 0.01 ppm by weight and 10 ppm by weight, preferably between 0.01 ppm by weight and 5 ppm by weight. , more preferably between 0.01 ppm by weight and 2 ppm by weight. According to another preferred embodiment, the light hydrocarbons are present in the formulation at a content of between 0.05 ppm by weight and 10 ppm by weight, preferably between 0.05 ppm by weight and 5 ppm by weight, more preferably still between 0.05 wppm and 2 wppm. According to yet another preferred embodiment, the light hydrocarbons are present in the formulation at a content of between 0.1 ppm by weight and 10 ppm by weight, preferably between 0.1 ppm by weight and 5 ppm by weight, more preferably between between 0.1 ppm by weight and 2 ppm by weight.
[0023] Par « hydrocarbures légers » au sens de la présente invention, on entend les hydrocarbures de masse molaire égale ou inférieure à 100 g mol-1. Par hydrocarbures, on entend, de manière générale, les composés hydrocarbonés au sens large et bien connus de l’homme du métier. Par « hydrocarbures légers » on entend les composés hydrocarbonés de masse molaire égale ou inférieure à 100 g mol-1 et comprenant du carbone, de l’hydrogène et éventuellement un ou plusieurs hétéroatomes choisi(s) parmi oxygène, soufre et azote. Selon un autre mode de réalisation préféré, les hydrocarbures légers sont les composés hydrocarbonés de masse molaire égale ou inférieure à 100 g mol-1 et comprenant 6, 7 ou 8 atomes de carbone, et plus préférentiellement les hydrocarbures légers sont ceux choisis parmi, sans être limités à, benzène et toluène. By "light hydrocarbons" within the meaning of the present invention, is meant hydrocarbons with a molar mass equal to or less than 100 g mol -1 . By hydrocarbons is meant, in general, hydrocarbon compounds in the broad sense and well known to those skilled in the art. “Light hydrocarbons” means hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising carbon, hydrogen and optionally one or more heteroatoms chosen from oxygen, sulfur and nitrogen. According to another preferred embodiment, the light hydrocarbons are hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising 6, 7 or 8 carbon atoms, and more preferably the light hydrocarbons are those chosen from, without be limited to, benzene and toluene.
[0024] La formulation selon l’invention peut en outre, bien que cela ne forme pas un mode de réalisation préféré, comprendre un ou plusieurs additifs et/ou charges bien connus de l’homme du métier, et par exemple, et de manière non limitative, choisis parmi les antioxydants, les pigments, colorants, arômes, agents masquants d’odeur, les modificateurs de viscosité, les passivateurs, les abaisseurs de point d’écoulement, les inhibiteurs de décomposition et leurs mélanges. [0024] The formulation according to the invention may further, although this does not form a preferred embodiment, comprise one or more additives and/or fillers well known to those skilled in the art, and for example, and in such a way non-limiting, selected from antioxidants, pigments, colorants, flavors, odor masking agents, viscosity modifiers, passivators, pour point depressants, decomposition inhibitors and mixtures thereof.
[0025] Parmi les antioxydants qui peuvent être avantageusement utilisés dans la formulation de l’invention, on peut citer, à titre d’exemples non limitatifs, les antioxydants phénoliques, tels que par exemple le dibutylhydroxytoluène, le butylhydroxyanisole, les tocophérols, ainsi que les acétates de ces anti-oxydants phénoliques. On peut également
citer les antioxydants de type amine, tels que par exemple la phényl-a-naphtylamine, de type diamine, par exemple la N,N’-di-(2-naphtyl)-para-phénylènediamine, mais aussi l’acide ascorbique et ses sels, les esters de l’acide ascorbique, seuls ou en mélanges de deux ou plusieurs d’entre eux ou avec d’autres composants, comme par exemple les extraits de thé vert, les extraits de café. Among the antioxidants which can be advantageously used in the formulation of the invention, mention may be made, by way of non-limiting examples, of phenolic antioxidants, such as for example dibutylhydroxytoluene, butylhydroxyanisole, tocopherols, as well as the acetates of these phenolic antioxidants. We can also mention antioxidants of the amine type, such as for example phenyl-a-naphthylamine, of the diamine type, for example N,N'-di-(2-naphthyl)-para-phenylenediamine, but also ascorbic acid and its salts, esters of ascorbic acid, alone or in mixtures of two or more of them or with other components, such as for example green tea extracts, coffee extracts.
[0026] Dans un mode de réalisation, la présente invention concerne une formulation comprenant : In one embodiment, the present invention relates to a formulation comprising:
- une quantité égale ou supérieure à 50%, de préférence égale ou supérieure à 60%, de préférence encore égale ou supérieure à 70%, mieux encore égale ou supérieure à 80% et de manière tout à fait préférée égale ou supérieure à 90% en poids de benzyltoluène (BT), et - an amount equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than 80% and most preferably equal to or greater than 90% by weight of benzyltoluene (BT), and
- éventuellement au moins un autre fluide LOHC, autre que le BT, de préférence éventuellement au moins un autre fluide LOHC qui est le dibenzyltoluène (DBT), - optionally at least one other LOHC fluid, other than BT, preferably optionally at least one other LOHC fluid which is dibenzyltoluene (DBT),
- une quantité égale ou inférieure à 10 ppm poids, de préférence comprise entre 0,01 ppm et 10 ppm poids, d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1 , - a quantity equal to or less than 10 ppm by weight, preferably between 0.01 ppm and 10 ppm by weight, of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 ,
- éventuellement au moins un additif, comme défini précédemment. - optionally at least one additive, as defined previously.
[0027] Dans un autre mode de réalisation, la présente invention concerne une formulation comprenant : In another embodiment, the present invention relates to a formulation comprising:
- une quantité égale ou supérieure à 50%, de préférence égale ou supérieure à 60%, de préférence encore égale ou supérieure à 70%, mieux encore égale ou supérieure à 80% et de manière tout à fait préférée égale ou supérieure à 90% en poids de benzyltoluène (BT), et - an amount equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than 80% and most preferably equal to or greater than 90% by weight of benzyltoluene (BT), and
- une quantité de dibenzyltoluène (DBT) comprise entre 0,1 % et 30% en poids, par rapport au poids total des fluides LOHC présent dans ladite formulation, - an amount of dibenzyltoluene (DBT) of between 0.1% and 30% by weight, relative to the total weight of the LOHC fluids present in said formulation,
- une quantité égale ou inférieure à 10 ppm, et de préférence comprise entre 0,01 ppm et 10 ppm d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1, et de préférence d’au moins un hydrocarbure choisi parmi ceux comportant 6, 7 ou 8 atomes de carbone, de préférence choisi parmi le benzène, et le toluène, ainsi que leurs mélanges en toutes proportions, - an amount equal to or less than 10 ppm, and preferably between 0.01 ppm and 10 ppm of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 , and preferably of at least one hydrocarbon chosen from those containing 6, 7 or 8 carbon atoms, preferably chosen from benzene and toluene, as well as mixtures thereof in all proportions,
- éventuellement au moins un additif et/ou charge, comme défini précédemment. - optionally at least one additive and/or filler, as defined above.
[0028] Le benzyltoluène (BT) est un composé bien connu, disponible dans le commerce et dont le mode de préparation est également bien connu de l’homme du métier. Par exemple le BT peut aisément être préparé par réaction catalytique de toluène avec du
chlorotoluène, selon des techniques maintenant bien connues de l’homme du métier et notamment comme décrit dans le brevet EP0435737. Benzyltoluene (BT) is a well-known compound, commercially available and the method of preparation of which is also well known to those skilled in the art. For example, BT can easily be prepared by catalytic reaction of toluene with chlorotoluene, according to techniques now well known to those skilled in the art and in particular as described in patent EP0435737.
[0029] Les bruts de synthèse de BT, mais aussi les liquides LOHC à base de BT ayant été engagés dans des cycles hydrogénation/déshydrogénation peuvent ainsi contenir des quantités variables d’au moins un hydrocarbure léger, comme décrit précédemment. La formulation selon la présente invention peut être par conséquent préparée par exemple et typiquement à partir de ces bruts de synthèse ou liquides LOHC à base de BT, selon toutes méthodes bien connues de l’homme du métier. [0029] BT synthetic crudes, but also BT-based LOHC liquids that have been engaged in hydrogenation/dehydrogenation cycles can thus contain variable amounts of at least one light hydrocarbon, as described above. The formulation according to the present invention can therefore be prepared, for example and typically, from these synthetic raw materials or liquid LOHCs based on BT, according to any method well known to those skilled in the art.
[0030] Ainsi, et à titre d’exemples non limitatifs, la formulation selon la présente invention peut avantageusement être préparée par traitement d’une formulation comprenant au moins 50% de BT et au moins un hydrocarbure léger, en quantité supérieure à 10 ppm poids, par distillation, recristallisation, évaporation sur couche mince, et autres méthodes ou encore les combinaisons de l’une ou plusieurs de ces méthodes. Thus, and by way of non-limiting examples, the formulation according to the present invention can advantageously be prepared by treating a formulation comprising at least 50% of BT and at least one light hydrocarbon, in an amount greater than 10 ppm weight, by distillation, recrystallization, thin layer evaporation, and other methods or combinations of one or more of these methods.
[0031 ] D’autres méthodes encore bien connues de l’homme du métier peuvent être mises en œuvre, en complément ou en remplacement des méthodes décrites ci-dessus pour préparer la formulation selon la présente invention, et parmi ces dernières, on peut citer à titre d’exemples non limitatifs les traitements sur agents filtrants et/ou adsorbants. [0031] Other methods still well known to those skilled in the art can be implemented, in addition to or replacing the methods described above to prepare the formulation according to the present invention, and among these, mention may be made by way of non-limiting examples, treatments with filtering agents and/or adsorbents.
[0032] Les agents filtrants qui peuvent être utilisés dans le cadre de la présente invention peuvent être de tous types et sont bien connus de l’homme du métier. Les agents filtrants qui se sont montrés les plus appropriés sont les agents filtrants adsorbants, et plus particulièrement les agents filtrants comprenant un ou plusieurs composés choisis parmi les minéraux à base de silicates, de carbonates, de charbon, ainsi que les mélanges de deux ou plusieurs de ces minéraux en toutes proportions. The filtering agents which can be used in the context of the present invention can be of all types and are well known to those skilled in the art. The filtering agents which have proved to be the most suitable are the adsorbent filtering agents, and more particularly the filtering agents comprising one or more compounds chosen from minerals based on silicates, carbonates, carbon, as well as mixtures of two or more of these minerals in all proportions.
[0033] À titre d’exemples non imitatifs, on peut citer les agents filtrants minéraux ou organiques, et en particulier ceux choisis parmi les argiles, les zéolithes, les terres de diatomée, les céramiques, les carbonates, et les dérivés de charbon, ainsi que les mélanges de deux ou plusieurs d’entre eux, en toutes proportions. By way of non-imitative examples, mention may be made of inorganic or organic filtering agents, and in particular those chosen from clays, zeolites, diatomaceous earth, ceramics, carbonates, and carbon derivatives, as well as mixtures of two or more of them, in any proportion.
[0034] On peut citer plus particulièrement comme agents filtrants, adsorbants et filtrants- adsorbants : The following can be mentioned more particularly as filtering agents, adsorbents and filter-adsorbents:
• les argiles, dont les silicates, et par exemple les silicates de magnésium, tels que et de manière non limitative, attapulgites, montmorillonites, sélénites, bentonites, talcs, et autres, • clays, including silicates, and for example magnesium silicates, such as and without limitation, attapulgites, montmorillonites, selenites, bentonites, talcs, and others,
• les silicates d’aluminium naturels ou synthétiques, en particulier kaolins, kaolinites, zéolithes,
• les carbonates, par exemple de calcium et/ou de magnésium, et plus particulièrement ceux connus sous les noms de calcaire ou craies, • natural or synthetic aluminum silicates, in particular kaolins, kaolinites, zeolites, • carbonates, for example of calcium and/or magnesium, and more particularly those known under the names of limestone or chalks,
• les dérivés de charbon, de bois, de coques par exemple de coques de noix de coco, noyaux ou grignons d’olives, et plus généralement ceux connus sous la dénomination de charbons actifs, • derivatives of charcoal, wood, shells, for example coconut shells, olive stones or pomace, and more generally those known under the name of activated carbon,
• et autres et leurs mélanges. • and others and mixtures thereof.
[0035] Les silicates, en particulier les argiles et les zéolithes, se sont montrés tout particulièrement efficaces pour la préparation de la formulation de la présente invention. Les silicates se sont en effet montrés tout particulièrement adaptés pour l’élimination, ou tout au moins pour la réduction importante, d’un ou de plusieurs hydrocarbure(s) léger(s) présent(s) dans une formulation comprenant une quantité égale ou supérieure à 50% en poids de benzyltoluène (BT). [0035] Silicates, in particular clays and zeolites, have proved to be very particularly effective for the preparation of the formulation of the present invention. Silicates have in fact shown themselves to be very particularly suitable for the elimination, or at least for the significant reduction, of one or more light hydrocarbon(s) present in a formulation comprising an equal or greater than 50% by weight of benzyltoluene (BT).
[0036] Selon un mode de réalisation tout particulièrement préféré de la présente invention, à titre d’exemples d’agents filtrants avantageusement utilisables pour la préparation de la formulation de la présente invention, on peut citer l’attapulgite Microsorb® 16/30 LVM de BASF (exemple d’argile alumino-magnésienne de formule chimique (Mg, AI)5Si8O22(OH)4, SiC>2), l’Amcol Rafinol 900 FF de Minerais Technologies, l’Amcol Rafinol 920 FF de Minerais Technologies, l’Amcol Mineral Bent (hydrosilicate d'aluminium) de Minerais Technologies), et les Siliporite®, notamment MK30B0 et MK30B2, de ARKEMA (préparations à base de zéolithe de type alumino silicate). According to a very particularly preferred embodiment of the present invention, as examples of filtering agents advantageously usable for the preparation of the formulation of the present invention, mention may be made of attapulgite Microsorb® 16/30 LVM from BASF (example of alumino-magnesian clay with the chemical formula (Mg, Al) 5 Si8O22(OH) 4 , SiC>2), Amcol Rafinol 900 FF from Minerals Technologies, Amcol Rafinol 920 FF from Minerals Technologies, Amcol Mineral Bent (aluminum hydrosilicate) from Minerals Technologies), and Siliporite®, in particular MK30B0 and MK30B2, from ARKEMA (preparations based on zeolite of the alumino silicate type).
[0037] Dans un mode de réalisation tout particulièrement préféré de la présente invention, l’agent filtrant utilisé pour la préparation de la formulation comprenant une teneur en au moins un hydrocarbure léger égale ou inférieure à 10 ppm poids, est choisi parmi les tamis moléculaires (également dénommés « adsorbants zéolitiques »), notamment les tamis moléculaires permettant l’adsorption, de manière aussi sélective que possible, des hydrocarbures légers, en particulier des hydrocarbures de masse molaire égale ou inférieure à 100 g mol-1. In a very particularly preferred embodiment of the present invention, the filtering agent used for the preparation of the formulation comprising a content of at least one light hydrocarbon equal to or less than 10 ppm by weight, is chosen from molecular sieves (also called “zeolitic adsorbents”), in particular molecular sieves allowing the adsorption, as selectively as possible, of light hydrocarbons, in particular hydrocarbons with a molar mass equal to or less than 100 g mol -1 .
[0038] Les matériaux adsorbants zéolithiques, c’est-à-dire les matériaux comprenant une ou plusieurs zéolithes, les plus appropriés sont avantageusement choisis parmi les tamis moléculaires à base de zéolithes synthétiques qui offrent, de par leur grande variété de procédés de préparation, une grande diversité de paramètres qui peuvent être finement ajustés, tels que par exemple la stabilité thermique, la résistance mécanique ou encore la facilitation de régénération, et ceci afin de répondre aux critères spécifiques requis pour l’utilisation d’intérêt.
[0039] Selon un mode de réalisation préféré, parmi les matériaux adsorbants zéolithiques les plus adaptés pour utilisation dans le cadre de la présente invention, on peut citer les zéolithes naturelles ou synthétiques, et plus particulièrement les matériaux adsorbants zéolithiques choisis parmi les zéolithes naturelles, comme par exemple la chabazite, et parmi les zéolithes synthétiques, notamment les zéolithes de type LTA, les zéolithes de type FAU, les zéolithes de type EMT, les zéolithes de type MFI, et les zéolithes de type BEA. The most suitable zeolite adsorbent materials, that is to say materials comprising one or more zeolites, are advantageously chosen from molecular sieves based on synthetic zeolites which, by virtue of their wide variety of preparation methods, offer , a wide variety of parameters which can be finely adjusted, such as for example the thermal stability, the mechanical resistance or even the facilitation of regeneration, and this in order to meet the specific criteria required for the use of interest. According to a preferred embodiment, among the most suitable zeolite adsorbent materials for use in the context of the present invention, mention may be made of natural or synthetic zeolites, and more particularly zeolite adsorbent materials chosen from natural zeolites, such as for example chabazite, and among synthetic zeolites, in particular LTA-type zeolites, FAU-type zeolites, EMT-type zeolites, MFI-type zeolites, and BEA-type zeolites.
[0040] Les différents types de zéolithes précités sont aisément accessibles à l’homme du métier dans le commerce ou facilement synthétisables à partir de modes opératoires connus et disponibles dans la littérature scientifique et la littérature brevet. En outre les différents types de zéolithe sont clairement définis et exposés par exemple dans « Atlas of Zeolite Framework Types », 5e édition, (2001 ), Elsevier. [0040] The different types of zeolites mentioned above are easily accessible to those skilled in the art in the trade or easily synthesized using known procedures and available in the scientific literature and the patent literature. In addition, the different types of zeolite are clearly defined and exposed, for example, in “Atlas of Zeolite Framework Types”, 5th edition, ( 2001), Elsevier.
[0041 ] Selon un autre aspect, la présente invention concerne l’utilisation d’une formulation telle que définie précédemment comme fluide LOHC pour la production d’hydrogène comprenant un faible taux d’impuretés et notamment pour la production d’hydrogène comprenant une quantité égale ou inférieure à 10 ppm poids d’au moins un hydrocarbure léger, et en particulier d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1. [0041] According to another aspect, the present invention relates to the use of a formulation as defined above as LOHC fluid for the production of hydrogen comprising a low level of impurities and in particular for the production of hydrogen comprising a quantity equal to or less than 10 ppm by weight of at least one light hydrocarbon, and in particular of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 .
[0042] Grâce à la formulation de la présente invention, les performances des cycles hydrogénation/déshydrogénation sont facilitées/améliorées, grâce à une moindre dégradation du catalyseur au cours de cycles successifs, notamment en raison du fait que la formulation LOHC de l’invention ne comprend que des traces d’hydrocarbures légers, comme exposé ci-dessus, hydrocarbures qui sont connus pour être des poisons des catalyseurs couramment utilisés dans les réactions d’hydrogénation/déshydrogénation. Thanks to the formulation of the present invention, the performance of the hydrogenation/dehydrogenation cycles are facilitated/improved, thanks to less degradation of the catalyst during successive cycles, in particular due to the fact that the LOHC formulation of the invention includes only traces of light hydrocarbons, as discussed above, hydrocarbons which are known to be catalyst poisons commonly used in hydrogenation/dehydrogenation reactions.
[0043] Par ailleurs, l’hydrogène stocké puis libéré lors de l’étape de déshydrogénation est un hydrogène de haute pureté, qui peut ainsi trouver des utilisations dans un très grand nombre d’applications, notamment pour les piles à combustible, et toutes les autres applications industrielles nécessitant l’utilisation d’hydrogène de haute pureté, telles que le secteur électronique pour la production de micro-processeurs, de semi-conducteurs, et autres.
Furthermore, the hydrogen stored and then released during the dehydrogenation step is high purity hydrogen, which can thus find uses in a very large number of applications, in particular for fuel cells, and all other industrial applications requiring the use of high purity hydrogen, such as the electronics sector for the production of microprocessors, semiconductors, and others.
Claims
1. Formulation liquide comprenant : 1. Liquid formulation comprising:
- une quantité égale ou supérieure à 50%, de préférence égale ou supérieure à 60%, de préférence encore égale ou supérieure à 70%, mieux encore égale ou supérieure à 80% et de manière tout à fait préférée égale ou supérieure à 90% en poids de benzyltoluène (BT), par rapport au poids total de la formulation, et - an amount equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, better still equal to or greater than 80% and most preferably equal to or greater than 90% by weight of benzyltoluene (BT), relative to the total weight of the formulation, and
- une quantité égale ou inférieure à 10 ppm poids d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1. - an amount equal to or less than 10 ppm by weight of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 .
2. Formulation selon la revendication 1 , comprenant une quantité égale ou supérieure à 98% en poids de benzyltoluène. 2. Formulation according to claim 1, comprising an amount equal to or greater than 98% by weight of benzyltoluene.
3. Formulation selon la revendication 1 ou la revendication 2, comprenant un ou plusieurs autres fluides LOHC issus de produits pétroliers et/ou de produits synthétisés à partir de produits pétroliers, ou encore issus de produits renouvelables et/ou de produits synthétisés à partir de produits renouvelables. 3. Formulation according to claim 1 or claim 2, comprising one or more other LOHC fluids derived from petroleum products and/or products synthesized from petroleum products, or also derived from renewable products and/or products synthesized from renewable products.
4. Formulation selon l’une quelconque des revendications précédentes, comprenant un ou plusieurs autres fluides LOHC choisis parmi dibenzyltoluène, diphényléthane, diphénylméthane, ditolyléther, phénylxylyléthane, mono- et bi-xylylxylènes, 1 ,2,3,4— tétra- hydro-(1 -phényléthyl)naphtalène, di-isopropylnaphtalène, mono-isopropylbiphényle, phényléthylphényléthane, N-éthylcarbazole, phénylpyridines, tolylpyridines, diphényl- pyridines, dipyridylbenzènes, dipyridinetoluènes, ainsi que les mélanges de deux ou plusieurs d’entre eux, en toutes proportions. 4. Formulation according to any one of the preceding claims, comprising one or more other LOHC fluids chosen from dibenzyltoluene, diphenylethane, diphenylmethane, ditolyl ether, phenylxylylethane, mono- and bi-xylylxylenes, 1,2,3,4-tetra-hydro- (1-phenylethyl)naphthalene, di-isopropylnaphthalene, mono-isopropylbiphenyl, phenylethylphenylethane, N-ethylcarbazole, phenylpyridines, tolylpyridines, diphenylpyridines, dipyridylbenzenes, dipyridinetoluenes, as well as mixtures of two or more of them, in all proportions.
5. Formulation selon l’une quelconque des revendications précédentes, comprenant au moins 50% en poids de benzyltoluène et du dibenzyltoluène, de préférence de 70% à 80% en poids de benzyltoluène et de 20% à 30% en poids de dibenzyltoluène, par rapport au poids total de benzyltoluène + dibenzyltoluène. 5. Formulation according to any one of the preceding claims, comprising at least 50% by weight of benzyltoluene and dibenzyltoluene, preferably from 70% to 80% by weight of benzyltoluene and from 20% to 30% by weight of dibenzyltoluene, by relative to the total weight of benzyltoluene + dibenzyltoluene.
6. Formulation selon l’une quelconque des revendications 1 à 4, comprenant de 80% à 99,9% en poids de benzyltoluène et de 0,1% à 20% en poids de dibenzyltoluène (par rapport au poids total de benzyltoluène + dibenzyltoluène), de préférence la formulation
comprend de 90% à 99,9% en poids de benzyltoluène et de 0,1% à 10% en poids de dibenzyltoluène, par rapport au poids total de benzyltoluène + dibenzyltoluène. 6. Formulation according to any one of claims 1 to 4, comprising from 80% to 99.9% by weight of benzyltoluene and from 0.1% to 20% by weight of dibenzyltoluene (relative to the total weight of benzyltoluene + dibenzyltoluene ), preferably the wording comprises from 90% to 99.9% by weight of benzyltoluene and from 0.1% to 10% by weight of dibenzyltoluene, based on the total weight of benzyltoluene + dibenzyltoluene.
7. Formulation selon l’une quelconque des revendications précédentes, dans laquelle la quantité d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1 , est égale ou inférieure à 10 ppm poids, de préférence égale ou inférieure à 5 ppm poids, de préférence encore égale ou inférieure à 2 ppm poids. 7. Formulation according to any one of the preceding claims, in which the quantity of at least one hydrocarbon with a molar mass equal to or less than 100 g mol -1 , is equal to or less than 10 ppm by weight, preferably equal to or less than 5 ppm by weight, more preferably equal to or less than 2 ppm by weight.
8. Formulation selon l’une quelconque des revendications précédentes, dans laquelle ledit au moins un hydrocarbure est choisi parmi les composés hydrocarbonés de masse molaire égale ou inférieure à 100 g mol-1 et comprenant du carbone, de l’hydrogène et éventuellement un ou plusieurs hétéroatomes choisi(s) parmi oxygène, soufre et azote, de préférence choisis parmi les composés hydrocarbonés de masse molaire égale ou inférieure à 100 g mol-1 et comprenant 6, 7 ou 8 atomes de carbone, et plus préférentiellement choisis parmi, sans être limités à, benzène et toluène. 8. Formulation according to any one of the preceding claims, in which the said at least one hydrocarbon is chosen from hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising carbon, hydrogen and optionally one or more several heteroatoms chosen from oxygen, sulfur and nitrogen, preferably chosen from hydrocarbon compounds with a molar mass equal to or less than 100 g mol -1 and comprising 6, 7 or 8 carbon atoms, and more preferably chosen from, without be limited to, benzene and toluene.
9. Utilisation d’une formulation selon l’une quelconque des revendications précédentes, comme fluide LOHC pour la production d’hydrogène comprenant un faible taux d’impuretés et notamment pour la production d’hydrogène comprenant une quantité égale ou inférieure à 10 ppm poids d’au moins un hydrocarbure léger, et en particulier une quantité égale ou inférieure à 10 ppm poids d’au moins un hydrocarbure de masse molaire égale ou inférieure à 100 g mol-1. 9. Use of a formulation according to any one of the preceding claims, as LOHC fluid for the production of hydrogen comprising a low level of impurities and in particular for the production of hydrogen comprising an amount equal to or less than 10 ppm by weight of at least one light hydrocarbon, and in particular a quantity equal to or less than 10 ppm by weight of at least one hydrocarbon with a molar mass equal to or less than 100 g mol −1 .
10. Utilisation selon la revendication précédente, pour la production d’hydrogène utilisable dans les piles à combustible, ou dans le secteur électronique pour la production de micro-processeurs, de semi-conducteurs, et autres.
10. Use according to the preceding claim, for the production of hydrogen usable in fuel cells, or in the electronics sector for the production of microprocessors, semiconductors, and others.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2012920A FR3117113B1 (en) | 2020-12-09 | 2020-12-09 | LIQUID FORMULATION FOR HYDROGEN STORAGE |
| PCT/FR2021/052221 WO2022123165A1 (en) | 2020-12-09 | 2021-12-07 | Liquid formulation for hydrogen storage |
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| Publication Number | Publication Date |
|---|---|
| EP4259572A1 true EP4259572A1 (en) | 2023-10-18 |
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| EP21840653.6A Pending EP4259572A1 (en) | 2020-12-09 | 2021-12-07 | Liquid formulation for hydrogen storage |
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| US (1) | US20240150167A1 (en) |
| EP (1) | EP4259572A1 (en) |
| JP (1) | JP2023553231A (en) |
| CN (1) | CN115715272A (en) |
| AU (1) | AU2021396717A1 (en) |
| CA (1) | CA3180258A1 (en) |
| FR (1) | FR3117113B1 (en) |
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| JP2514024B2 (en) * | 1987-03-11 | 1996-07-10 | 日本石油化学株式会社 | Method for producing novel electrical insulating oil composition |
| FR2656603B1 (en) * | 1989-12-28 | 1993-05-21 | Atochem | METHODS OF SYNTHESIS OF BENZYLTOLUENE AND LOW CHLORINE DIBENZYLTOLUENE. |
| NO177820C (en) * | 1991-11-26 | 1995-11-29 | Atochem Elf Sa | Mixture based on benzyltoluenes and benzylxylenes and their use as dielectrics |
| DE102012221809A1 (en) | 2012-11-28 | 2014-05-28 | Bayerische Motoren Werke Aktiengesellschaft | Liquid compounds and processes for their use as hydrogen storage |
| DE102013223589B4 (en) * | 2013-11-19 | 2016-11-17 | Hydrogenious Technologies Gmbh | Plant and method for storing energy |
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| FR3117113B1 (en) | 2024-04-12 |
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| FR3117113A1 (en) | 2022-06-10 |
| US20240150167A1 (en) | 2024-05-09 |
| CN115715272A (en) | 2023-02-24 |
| WO2022123165A1 (en) | 2022-06-16 |
| AU2021396717A1 (en) | 2022-12-22 |
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