Aromatic hydrocarbon compositions, hydrogen conjugates and uses thereof

Abstract

The invention belongs to the technical field of hydrogen storage, and relates to a synthesis method and a hydrogen supply method of an organic hydride hydrogen conjugate with high hydrogen content and good fluidity. The invention provides a novel organic hydride hydrogen conjugate synthesis method which comprises the following steps: preparing initial materials of three or more specified types of aromatic compounds, pretreating the materials, and carrying out hydrogenation reaction treatment on the materials to obtain the hydrogen conjugate. The hydrogen conjugate passes through a fixed bed reactor to obtain hydrogen and produce an aromatic hydrocarbon composition. The aromatic hydrocarbon composition, the hydrogen conjugate and a liquid-phase product after hydrogen supply of the hydrogen conjugate can be kept in a liquid state at the temperature not lower than 5 DEG C. The hydrogen supply mass ratio of the hydrogen conjugate is not less than 6.3 wt%, and the hydrogen purity is high. The invention provides a novel formula and process method for the technical field of hydrogen storage of organic hydrides.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen storage, and in particular relates to an aromatic hydrocarbon composition, a hydrogen bond and uses thereof. Background Art

[0002] The booming development of the hydrogen energy industry has given rise to the industry's demand for high-density and safe hydrogen storage materials. Hydrogen storage materials that achieve hydrogen storage by chemical methods are mainly divided into two categories: liquid organic hydrides and hydride metal compounds. When selecting hydrogen storage materials, the main factors to consider are their hydrogen storage capacity, reaction kinetics, thermodynamic stability and cost. For example, cyclohexane, toluene, etc., as liquid organic hydrides, have high hydrogen storage capacity and good stability; while hydride metal compounds such as aluminum hydride and magnesium hydride, although they have large hydrogen storage capacity, have slow reaction kinetics and relatively high costs. Organic liquid hydrogen storage technology is an efficient and safe way to store hydrogen. Its principle is to use specific organic compounds as hydrogen storage media, and to combine hydrogen in the form of chemical bonds in organic molecules through chemical reactions under mild conditions. This technology is characterized by high hydrogen storage density, low storage temperature, low pressure, and can be carried out through conventional liquid transportation and storage facilities, greatly improving the convenience of hydrogen storage and transportation. However, it is still difficult to obtain organic hydride carriers with good comprehensive performance in all aspects.

[0003] Dodecahydrobenzyltoluene and octahydrodibenzyltoluene are two organic hydride hydrogen compounds that have received much attention in the field. A journal article (Y.Suh et al., J.Catal.2022,413,127) reported a study on the catalytic dehydrogenation of these two materials as hydrogen carriers, using a S-modified Pt / Al2O3 catalyst. The modification of S promoted the catalytic dehydrogenation activity of the catalyst, achieving a dehydrogenation conversion rate of 86.6% for dodecahydrobenzyltoluene at 250°C, and a similar value for the dehydrogenation conversion rate of octahydrodibenzyltoluene at 270°C. However, since the theoretical upper limit of the hydrogen content of the two is only 6.18wt%, even if the conversion rate exceeds 80%, in fact only about 5.36wt% of hydrogen can be released.

[0004] Dodecahydro-N-ethylcarbazole is another hydrogen carrier that has attracted much attention. Its main advantage is that the dehydrogenation temperature is low, and a considerable amount of hydrogen can be released at a temperature not exceeding 200°C. The journal (J.Fu et al., Fuel.2020,275,117896) reported that the use of PdO / C catalyst can completely dehydrogenate hydrogen-containing materials based on this carrier at 140°C for 8h. However, the theoretical upper limit of hydrogen content of dodecahydro-N-ethylcarbazole is 5.79wt%, and it is difficult to completely dehydrogenate. At the same time, the hydrogen-poor product formed after dehydrogenation is solid at room temperature, and this property will make it inconvenient to store and transport in practical applications. Therefore, the further large-scale application of dodecahydro-N-ethylcarbazole is greatly restricted.

[0005] In summary, there is still a need in the art to develop new organic hydrogen carriers, especially organic hydrogen carriers that have the advantages of high actual dehydrogenation rate and / or low dehydrogenation energy consumption, and are liquid at room temperature and pressure and have good fluidity for easy storage and transportation. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention provides an aromatic hydrocarbon composition, wherein the aromatic hydrocarbon composition comprises at least one 1-6 Alkyl-substituted biphenyl and at least one C 1-6 Alkyl substituted benzene.

[0007] According to an embodiment of the present invention, the biphenyl is diphenyl, which is usually referred to as "biphenyl" by those skilled in the art.

[0008] According to an embodiment of the present invention, the C 1-6 The alkyl group is preferably C 1-4 Alkyl, more preferably C 1-3 Alkyl, for example methyl, ethyl, propyl or isopropyl.

[0009] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, the one or more C 1-6 The alkyl-substituted biphenyl may be present in one or more species, for example, 1, 2, 3, 4, 5 or 6 species.

[0010] According to an embodiment of the present invention, the one or more C 1-6 The alkyl-substituted biphenyls may be selected from the group consisting of 1, 2, 3, 4, 5, 6 or more C 1-6 For example, the one or more C 1-6 The alkyl-substituted biphenyl may be selected from one or more biphenyls substituted with one or more methyl groups, for example, one or more biphenyls substituted with 1, 2, 3, 4, 5, 6 or more methyl groups.

[0011] According to an embodiment of the present invention, the 1-6 In alkyl-substituted biphenyls, the C 1-6 The alkyl group may be optionally substituted at any position except the 1-position and the 1'-position in the biphenyl structure. It should be understood by those skilled in the art that the above "any position except the 1-position and the 1'-position" may be independently selected from the 2-position, 3-position, 4-position, 5-position, 6-position, 2'-position, 3'-position, 4'-position, 5'-position and 6'-position of the biphenyl. The above substitution positions are known to those skilled in the art and may be specifically shown in the following formula:

[0012]

[0013] According to an embodiment of the present invention, 1 C 1-6 The alkyl-substituted biphenyl may be selected from 2-C 1-6 Alkyl biphenyl, 3-C 1-6 Alkyl biphenyl, 4-C 1-6 Alkyl biphenyl, 5-C 1-6 Alkyl biphenyl or 6-C 1-6 One or more of alkylbiphenyls. Specifically, examples of biphenyls substituted with one methyl group include one or more of 2-methylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl, 5-methylbiphenyl or 6-methylbiphenyl.

[0014] According to an embodiment of the present invention, by 2 C 1-6 Examples of alkyl-substituted biphenyls include, but are not limited to: 2,2'-di(C 1-6 alkyl)biphenyl, 3,3'-di(C 1-6 alkyl)biphenyl, 4,4'-di(C 1-6 alkyl)biphenyl, 5,5'-di(C 1-6 alkyl)biphenyl, 6,6'-di(C 1-6 alkyl)biphenyl, 2,6'-di(C 1-6 alkyl)biphenyl, 3,5'-di(C 1-6 alkyl)biphenyl, 2,5'-di(C 1-6 alkyl)biphenyl, 2,4'-di(C 1-6 Alkyl) biphenyl, 2,3-di(C 1-6 Alkyl) biphenyl, 2,4-di(C 1-6 Alkyl) biphenyl, 2,5-di(C 1-6 Alkyl) biphenyl, 2,6-di(C 1-6 Specifically, examples of biphenyls substituted with two methyl groups include, but are not limited to, one or more of 2,2'-dimethylbiphenyl, 3,3'-dimethylbiphenyl, 4,4'-dimethylbiphenyl, 5,5'-dimethylbiphenyl, 6,6'-dimethylbiphenyl, 2,6'-dimethylbiphenyl, 3,5'-dimethylbiphenyl, 2,5'-dimethylbiphenyl, 2,4'-dimethylbiphenyl, 2,3-dimethylbiphenyl, 2,4-dimethylbiphenyl, 2,5-dimethylbiphenyl, and 2,6-dimethylbiphenyl.

[0015] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, the one or more C 1-6The total content of alkyl-substituted biphenyls may be 55 wt% or higher, for example, 55 wt% to 99 wt%. Alternatively, the total content of biphenyls substituted with one or more methyl groups is >55 wt% and ≤95 wt%. As an example, in the aromatic hydrocarbon composition, the total content of biphenyl substituted with one or more methyl groups can be 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, or 90wt%.

[0016] According to an embodiment of the present invention, the aromatic hydrocarbon composition may include 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 One of the alkyl biphenyls (such as 3-methyl biphenyl), or a mixture of the above two.

[0017] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The content of alkylbiphenyl (such as 3-methylbiphenyl) can be independently 0wt% or greater than 0wt%, provided that the 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The contents of the alkylbiphenyls (such as 3-methylbiphenyl) are not all 0 wt %.

[0018] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The total content of alkyl biphenyls (such as 3-methyl biphenyl) is 55wt% or higher, such as 55wt% to 99wt%, or such as 55wt% to 95wt%. As an example, in the aromatic hydrocarbon composition, 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6The sum of the contents of alkylbiphenyls (such as 3-methylbiphenyl) can be 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, or 90wt%.

[0019] It should be understood that when the aromatic hydrocarbon composition comprises only 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 When the alkyl biphenyl (such as 3-methyl biphenyl) is one of the 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The sum of the contents of alkylbiphenyls (such as 3-methylbiphenyl) is the sum of the contents of 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The content of one of the alkyl biphenyls (such as 3-methylbiphenyl).

[0020] Therefore, when the aromatic hydrocarbon composition contains only 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 When one of the alkyl biphenyls (such as 3-methyl biphenyl) is present in the aromatic hydrocarbon composition, 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The content of one of the alkylbiphenyls (such as 3-methylbiphenyl) can be 55wt% or more, for example 55wt% to 99wt%, or for example 55wt% to 95wt%, such as 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%.

[0021] When the aromatic hydrocarbon composition comprises 2-C 1-6Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 When two of the alkyl biphenyls (such as 3-methyl biphenyl) are present, the ratio between them is not particularly limited. 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The content ratio (wt / wt) of alkylbiphenyl (such as 3-methylbiphenyl) can be 1:99 to 99:1, for example, 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40 or 50:50.

[0022] According to an embodiment of the present invention, the aromatic hydrocarbon composition may further comprise di(C 1-6 alkyl)biphenyl.

[0023] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, the one or more C 1-6 The alkyl-substituted benzene may be present in one or more species, for example, 1, 2, 3, 4, 5 or 6 species.

[0024] According to an embodiment of the present invention, the one or more C 1-6 The alkyl-substituted benzene may be selected from the group consisting of 1, 2, 3, 4, 5 or 6 C 1-6 For example, the one or more C 1-6 The alkyl-substituted benzene may be selected from one or more benzenes substituted with one or more methyl groups, for example, one or more benzenes substituted with 1, 2, 3, 4, 5 or 6 methyl groups.

[0025] According to an embodiment of the present invention, the 1-6 In alkyl-substituted benzene, the C 1-6 The alkyl group may be optionally substituted at any position in the benzene structure. It should be understood by those skilled in the art that the above-mentioned "any position in the benzene structure" may be independently selected from the 1-position, 2-position, 3-position, 4-position, 5-position or 6-position of benzene. It should be understood by those skilled in the art that when benzene is replaced by 2 C 1-6 When alkyl is substituted, examples thereof include, but are not limited to: o-di(C 1-6 Alkyl)benzene (1,2-di(C 1-6 alkyl)benzene, such as o-xylene), m-xylene (C 1-6 Alkyl)benzene (1,3-di(C 1-6 alkyl)benzenes, such as m-xylene), p-xylene (C 1-6 Alkyl)benzene (1,4-di(C 1-6 alkyl)benzenes, such as p-xylene).

[0026] According to an embodiment of the present invention, the aromatic hydrocarbon composition may include di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 alkyl)benzenes (such as xylene), for example, 1, 2, 3, 4, 5 or 6. Preferably, the aromatic hydrocarbon composition comprises di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 Alkyl)benzenes (such as xylene).

[0027] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, di(C 1-6 Alkyl) biphenyl, C 1-6 Alkylbenzene and di(C 1-6 The content of alkyl)benzene is each independently greater than or equal to 0.

[0028] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 The sum of the contents of alkyl)benzenes (such as xylene) is 1wt% to 15wt%, for example 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%.

[0029] It should be understood that when the aromatic hydrocarbon composition comprises only di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 alkyl)benzene (such as xylene), the "di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 The sum of the contents of di(C alkyl)benzenes (such as xylene) present in the aromatic hydrocarbon composition refers to the 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 Alternatively, when the aromatic hydrocarbon composition contains only di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 alkyl)benzenes (such as xylene), the "di(C 1-6Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 The sum of the contents of di(C alkyl)benzenes (such as xylene) present in the aromatic hydrocarbon composition refers to the 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 The sum of the contents of two types of alkyl)benzenes (such as xylene).

[0030] According to an embodiment of the present invention, the aromatic hydrocarbon composition may further comprise biphenyl, 4-C 1-6 One or more of alkyl biphenyls (such as 4-methyl biphenyl), for example, 1, 2, 3, 4, 5 or 6. For example, the aromatic hydrocarbon composition comprises one of 4-methyl biphenyl and biphenyl, or a mixture of the two.

[0031] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, biphenyl and 4-C 1-6 The content of alkylbiphenyls (such as 4-methylbiphenyl) is independently greater than or equal to zero.

[0032] According to an embodiment of the present invention, in the aromatic hydrocarbon composition, biphenyl and 4-C 1-6 The sum of the contents of alkylbiphenyls (such as 4-methylbiphenyl) is 20wt% to 44wt%, for example, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 205wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, and 44wt%.

[0033] It should be understood that when the aromatic hydrocarbon composition contains only biphenyl and 4-C 1-6 When the alkyl biphenyl (such as 4-methyl biphenyl) is one of the 1-6 The sum of the contents of alkylbiphenyls (such as 4-methylbiphenyl) is the sum of the contents of biphenyl and 4-C 1-6 The content of one of the alkyl biphenyls (such as 4-methyl biphenyl).

[0034] According to an embodiment of the present invention, the aromatic hydrocarbon composition comprises:

[0035] 2-C 1-6 Alkyl biphenyl and / or 3-C 1-6 Alkyl biphenyls;

[0036] C 1-6 Alkylbenzene or di(C1-6 alkyl)benzene; and

[0037] 4-C 1-6 Alkylbiphenyls and / or biphenyls.

[0038] According to an exemplary embodiment of the present invention, the aromatic hydrocarbon composition comprises:

[0039] 2-methylbiphenyl and / or 3-methylbiphenyl;

[0040] Toluene or xylene; and

[0041] 4-Methylbiphenyl and / or biphenyl.

[0042] According to an exemplary embodiment of the present invention, the aromatic hydrocarbon composition comprises or consists of the following components: 2-methylbiphenyl, 4-methylbiphenyl, biphenyl and toluene.

[0043] Preferably, the aromatic hydrocarbon composition comprises or consists of the following components:

[0044] 2-Methylbiphenyl 40 wt% to 80 wt% (e.g., 50 wt% to 70 wt%, 55 wt% to 65 wt% or 60 wt%);

[0045] 4-Methylbiphenyl 15 wt% to 25 wt% (e.g., 17 wt% to 23 wt%, 18 wt% to 22 wt% or 20 wt% to 21 wt%);

[0046] Biphenyl 8 wt% to 16 wt% (e.g., 10 wt% to 14 wt%, 11 wt% to 13 wt% or 12 wt%); and

[0047] Toluene 4wt% to 10wt% (eg, 5wt% to 9wt%, 6wt% to 8wt% or 7.2wt%).

[0048] According to an exemplary embodiment of the present invention, the aromatic hydrocarbon composition comprises or consists of the following components: 2-methylbiphenyl, 3-methylbiphenyl, biphenyl and xylene.

[0049] Preferably, the aromatic hydrocarbon composition comprises or consists of the following components:

[0050] 2-methylbiphenyl 30 wt% to 60 wt% (e.g., 35 wt% to 55 wt%, 40 wt% to 50 wt% or 45 wt%);

[0051] 3-Methylbiphenyl 15 wt% to 30 wt% (e.g., 17 wt% to 27 wt%, 20 wt% to 24 wt% or 22 wt%);

[0052] Biphenyl 20 wt% to 35 wt% (e.g., 22 wt% to 30 wt%, 25 wt% to 27 wt% or 26 wt%); and

[0053] Xylene 4wt% to 10wt% (e.g., 5wt% to 9wt%, 6wt% to 8wt% or 7wt%).

[0054] According to an embodiment of the present invention, the sum of the contents of the components contained in the aromatic hydrocarbon composition is 100 wt%.

[0055] According to an embodiment of the present invention, the aromatic hydrocarbon composition is in a liquid state at a normal pressure of not less than 5°C.

[0056] The present invention also provides a method for preparing the aromatic hydrocarbon composition, wherein the preparation method comprises mixing the components of the aromatic hydrocarbon composition to obtain the aromatic hydrocarbon composition.

[0057] The present invention also provides application of the aromatic hydrocarbon composition in hydrogen storage.

[0058] The present invention also provides a hydrogen-containing mixture, wherein the hydrogen-containing mixture comprises the aromatic hydrocarbon composition and hydrogen.

[0059] According to an embodiment of the present invention, the hydrogen-containing mixture further comprises a hydrogenation catalyst.

[0060] According to an embodiment of the present invention, the hydrogenation catalyst is a catalyst suitable for hydrogenation of aromatic compounds known to those skilled in the art. The hydrogenation catalyst may contain an active metal, wherein the active metal may be selected from at least one metal in the VIII subgroup of the periodic table, or may further contain at least one metal in the I or VII subgroup of the periodic table. As an example, the active metal may be one or more of ruthenium, palladium, platinum, nickel, and rhodium.

[0061] According to an embodiment of the present invention, the hydrogenation catalyst may be supported on a carrier. The carrier may be inert, and specific examples of suitable carriers include, but are not limited to, one or more of aluminum oxide, activated carbon, pumice, magnesium oxide, zirconium oxide, diatomaceous earth, bleaching earth, silicon carbide, porous sintered materials containing silicon and / or silicon carbide, silicon oxide, selected clay, and artificial or natural ceramics.

[0062] According to an embodiment of the present invention, the hydrogenation catalyst includes but is not limited to one or more selected from the following: a nickel-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a ruthenium-based catalyst and a rhodium-based catalyst.

[0063] Alternatively, the hydrogenation catalyst may also be an unsupported hydrogenation catalyst, such as a nickel-molybdenum two-component oxide unsupported catalyst.

[0064] According to an embodiment of the present invention, there is no particular limitation on the content of the active ingredient in the hydrogenation catalyst, as long as it can reach the effective amount required for the catalytic hydrogenation reaction. As an example, in the hydrogenation catalyst, the content of the active ingredient can be 0.5wt% to 10wt% of the hydrogenation catalyst, such as 0.5wt%, 1wt%, 1.5wt%, 2%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%.

[0065] According to an embodiment of the present invention, the specific surface area of ​​the hydrogenation catalyst is not less than 50m 2 / g, for example, 80 to 200 m 2 / g, 85m 2 / g, 90m 2 / g, 95m 2 / g、100m 2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 170m 2 / g, 180m 2 / g, 190m 2 / g, 200m 2 / g or a number between any two of the above numbers;

[0066] According to an embodiment of the present invention, the particle diameter of the hydrogenation catalyst may be 40 to 80 meshes.

[0067] The present invention also provides a method for preparing the hydrogen-containing mixture, wherein the preparation method comprises mixing the components of the hydrogen-containing mixture to obtain the hydrogen-containing mixture.

[0068] The present invention also provides application of the hydrogen-containing mixture in hydrogen storage.

[0069] The present invention also provides a hydrogen bond, wherein the hydrogen bond comprises the aromatic hydrocarbon composition and hydrogen bonded to at least one component of the aromatic hydrocarbon composition through a chemical bond.

[0070] According to an embodiment of the present invention, the hydrocombinate comprises a product in which at least some of the components in the aromatic hydrocarbon composition are reduced.

[0071] According to an embodiment of the present invention, the hydrocombinate comprises a product in which at least part of the components of the aromatic hydrocarbon composition are reduced to a non-aromatic product.

[0072] According to an embodiment of the present invention, in the hydrogen bond, when the components in the aromatic hydrocarbon composition contain a benzene ring, the benzene ring is reduced to a cyclohexyl group; or, when the components in the aromatic hydrocarbon composition contain a biphenyl structure, at least one benzene ring in the biphenyl structure is reduced to a cyclohexyl group, preferably two benzene rings are reduced to a cyclohexyl group.

[0073] Preferably, in the combination, the content of the reduced component is more than 1wt%, more than 2wt%, more than 3wt%, more than 4wt%, more than 5wt%, more than 6wt%, more than 7wt%, more than 8wt%, more than 9wt%, more than 10wt%, more than 20wt%, more than 30wt%, more than 40wt%, more than 50wt%, more than 60wt%, more than 70wt%, more than 80wt%, more than 90wt%, more than 95wt% or more than 99wt% of the combination.

[0074] According to an embodiment of the present invention, the hydroconjugate comprises at least one 1-6 Alkyl-substituted cyclohexyl-cyclohexane (also known as "bicyclohexane") and at least one cyclohexyl group substituted with one or more C 1-6 Alkyl substituted cyclohexane.

[0075] According to an embodiment of the present invention, the C 1-6 The alkyl group is preferably C 1-4 Alkyl, more preferably C 1-3 Alkyl, for example methyl, ethyl, propyl or isopropyl.

[0076] According to an embodiment of the present invention, in the hydrogen bond, the one or more C 1-6 The alkyl-substituted bicyclohexyl groups may be present in one or more species, for example, 1, 2, 3, 4, 5 or 6 species.

[0077] According to an embodiment of the present invention, the one or more C 1-6 The alkyl-substituted bicyclohexyl may be selected from 1, 2, 3, 4, 5, 6 or more C 1-6 One or more of the bicyclohexyls substituted with alkyl. For example, the 1-6 The alkyl-substituted bicyclohexyl may be selected from one or more bicyclohexanes substituted with one or more methyl groups, for example, one or more bicyclohexanes substituted with 1, 2, 3, 4, 5, 6 or more methyl groups.

[0078] According to an embodiment of the present invention, the1-6 In alkyl-substituted bicyclohexane, the C 1-6 The alkyl group may be optionally substituted at any position except the 1-position and the 1'-position in the bicyclohexyl structure. It should be understood by those skilled in the art that the above-mentioned "any position except the 1-position and the 1'-position" may be independently selected from the 2-position, 3-position, 4-position, 5-position, 6-position, 2'-position, 3'-position, 4'-position, 5'-position and 6'-position of the bicyclohexyl. The above-mentioned substitution positions are known to those skilled in the art, and may be specifically shown in the following formula:

[0079]

[0080] According to an embodiment of the present invention, 1 C 1-6 The alkyl-substituted bicyclohexane may be selected from 2-C 1-6 Alkyl bicyclohexane, 3-C 1-6 Alkyl bicyclohexane, 4-C 1-6 Alkyl bicyclohexane, 5-C 1-6 Alkyl bicyclohexane or 6-C 1-6 One or more of alkyl bicyclohexanes. Specifically, examples of bicyclohexanes substituted with one methyl group include one or more of 2-methyl bicyclohexyl, 3-methyl bicyclohexyl, 4-methyl bicyclohexyl, 5-methyl bicyclohexyl or 6-methyl bicyclohexyl.

[0081] According to an embodiment of the present invention, by 2 C 1-6 Examples of alkyl-substituted bicyclohexanes include, but are not limited to: 2,2'-di(C 1-6 alkyl) bicyclohexane, 3,3'-di(C 1-6 alkyl) bicyclohexane, 4,4'-di(C 1-6 alkyl) bicyclohexane, 5,5'-di(C 1-6 alkyl) bicyclohexane, 6,6'-di(C 1-6 alkyl) bicyclohexane, 2,6'-di(C 1-6 alkyl) bicyclohexane, 3,5'-di(C 1-6 alkyl) bicyclohexane, 2,5'-di(C 1-6 alkyl) bicyclohexane, 2,4'-di(C 1-6 alkyl) bicyclohexane, 2,3-di(C 1-6 alkyl) bicyclohexane, 2,4-di(C 1-6 alkyl) bicyclohexane, 2,5-di(C 1-6 alkyl) bicyclohexane, 2,6-di(C 1-6Specifically, examples of bicyclohexanes substituted with two methyl groups include, but are not limited to, one or more of 2,2'-dimethyl bicyclohexane, 3,3'-dimethyl bicyclohexane, 4,4'-dimethyl bicyclohexane, 5,5'-dimethyl bicyclohexane, 6,6'-dimethyl bicyclohexane, 2,6'-dimethyl bicyclohexane, 3,5'-dimethyl bicyclohexane, 2,5'-dimethyl bicyclohexane, 2,4'-dimethyl bicyclohexane, 2,3-dimethyl bicyclohexane, 2,4-dimethyl bicyclohexane, 2,5-dimethyl bicyclohexane, and 2,6-dimethyl bicyclohexane.

[0082] According to an embodiment of the present invention, the hydroconjugate may comprise 2-C 1-6 Alkyl bicyclohexane (such as 2-methyl bicyclohexane) and 3-C 1-6 One of the alkyl bicyclohexanes (such as 3-methyl bicyclohexane), or a mixture of the above two.

[0083] According to an embodiment of the present invention, the hydroconjugate may also contain di(C 1-6 alkyl)bicyclohexane.

[0084] According to an embodiment of the present invention, in the hydrogen bond, the one or more C 1-6 The alkyl-substituted cyclohexanes may be present in one or more species, for example, 1, 2, 3, 4, 5 or 6 species.

[0085] According to an embodiment of the present invention, the one or more C 1-6 The alkyl-substituted cyclohexane may be selected from 1, 2, 3, 4, 5 or 6 C 1-6 One or more of the cyclohexane substituted with an alkyl group. For example, the 1-6 The alkyl-substituted cyclohexane may be selected from one or more cyclohexanes substituted with one or more methyl groups, for example, one or more cyclohexanes substituted with 1, 2, 3, 4, 5 or 6 methyl groups.

[0086] According to an embodiment of the present invention, the 1-6 In alkyl-substituted cyclohexane, the C 1-6 The alkyl group may be optionally substituted at any position in the cyclohexane structure. It should be understood by those skilled in the art that the above-mentioned "any position in the cyclohexane structure" may be independently selected from the 1-position, 2-position, 3-position, 4-position, 5-position or 6-position of cyclohexane. It should be understood by those skilled in the art that when cyclohexane is replaced by 2 C 1-6 When alkyl is substituted, examples thereof include, but are not limited to: o-di(C 1-6 Alkyl)cyclohexane (1,2-di(C 1-6alkyl) cyclohexane, such as o-dimethylcyclohexane), m-di(C 1-6 Alkyl)cyclohexane (1,3-di(C 1-6 alkyl) cyclohexane, such as m-dimethylcyclohexane), p-di(C 1-6 Alkyl)cyclohexane (1,4-di(C 1-6 alkyl)cyclohexane, such as p-dimethylcyclohexane).

[0087] According to an embodiment of the present invention, the hydroconjugate may comprise di(C 1-6 Alkyl) bicyclohexane (such as dimethyl bicyclohexane), C 1-6 Alkylcyclohexanes (such as methylcyclohexane) and di(C 1-6 One or more of the following: cyclohexanes (e.g., dimethylcyclohexane) and dimethylcyclohexane, for example, 1, 2, 3, 4, 5 or 6. Preferably, the hydrogen bond comprises di(C 1-6 Alkyl) bicyclohexane (such as dimethyl bicyclohexane), C 1-6 Alkylcyclohexanes (such as methylcyclohexane) and di(C 1-6 Alkyl) cyclohexane (such as dimethylcyclohexane).

[0088] According to an embodiment of the present invention, the hydrogen bond may also include a compound selected from bicyclohexyl, 4-C 1-6 One or more of alkyl bicyclohexanes (such as 4-methyl bicyclohexyl), for example 1, 2, 3, 4, 5 or 6. For example, the hydrogen conjugate comprises one of 4-methyl bicyclohexyl and bicyclohexyl, or a mixture of the two.

[0089] According to an embodiment of the present invention, the hydroconjugate comprises:

[0090] 2-C 1-6 Alkyl bicyclohexane and / or 3-C 1-6 Alkyl bicyclohexanes;

[0091] C 1-6 Alkylcyclohexane or di(C 1-6 alkyl)cyclohexane; and

[0092] 4-C 1-6 Alkyl bicyclohexyl and / or bicyclohexyl.

[0093] According to an exemplary embodiment of the present invention, the hydroconjugate comprises:

[0094] 2-methylbicyclohexyl and / or 3-methylbicyclohexyl;

[0095] Methylcyclohexane or dimethylcyclohexane; and

[0096] 4-Methylbicyclohexyl and / or bicyclohexyl.

[0097] According to an exemplary embodiment of the present invention, the hydrogen bond comprises or consists of the following components: 2-methylbicyclohexyl, 4-methylbicyclohexyl, bicyclohexyl and methylcyclohexyl.

[0098] According to an exemplary embodiment of the present invention, the hydrogen bond comprises or consists of the following components: 2-methylbicyclohexyl, 3-methylbicyclohexyl, bicyclohexyl and dimethylcyclohexyl.

[0099] According to an embodiment of the present invention, the sum of the contents of the components contained in the hydrocompound is 100 wt %.

[0100] According to an embodiment of the present invention, the hydrocompound further comprises a hydrogenation catalyst, wherein the hydrogenation catalyst has the definition as described above.

[0101] According to an embodiment of the present invention, the hydrogen combination is obtained by hydrogenating the aromatic hydrocarbon composition and hydrogen; wherein the hydrogenation reaction is achieved by using a fixed bed reactor in which a hydrogenation catalyst is loaded;

[0102] Preferably, the hydrogenation catalyst is an alumina-supported ruthenium catalyst, a nickel-molybdenum two-component oxide non-supported catalyst, or the like.

[0103] The present invention also provides application of the hydrogen combination in hydrogen storage or hydrogen supply.

[0104] The present invention also provides a method for preparing the hydrogen combination, wherein the method comprises reacting the aromatic hydrocarbon composition with hydrogen.

[0105] According to an embodiment of the present invention, the preparation method comprises subjecting the aromatic hydrocarbon composition to a hydrogenation reaction in the presence of hydrogen.

[0106] According to an embodiment of the present invention, the preparation method comprises subjecting the aromatic hydrocarbon composition to a hydrogenation reaction in the presence of hydrogen and a hydrogenation catalyst, wherein the hydrogenation catalyst has the definition as described above.

[0107] According to an embodiment of the present invention, the preparation method further comprises pretreating the aromatic hydrocarbon composition and then performing a hydrogenation reaction.

[0108] According to an embodiment of the present invention, the pretreatment is a heating treatment, such as heating under reflux. For example, the aromatic hydrocarbon composition may be cooled after the heating treatment.

[0109] According to an embodiment of the present invention, the temperature of the heat treatment may be 90 to 145° C. (eg, 100 to 120° C.).

[0110] According to an embodiment of the present invention, the heating treatment time may be 0.5 to 48 hours (eg, 3 to 12 hours).

[0111] According to an embodiment of the present invention, the operating conditions of the hydrogenation include:

[0112] Control the mass space velocity of the aromatic composition in the reactor to 0.1 to 6 h -1 ;

[0113] and / or, the mass flow rate ratio of hydrogen to the aromatic hydrocarbon composition is 0.05 to 1.2;

[0114] and / or, the reactor pressure is 2 to 9 MPa;

[0115] And / or, the reaction temperature is 80-250°C.

[0116] For example, the operating conditions of the hydrogenation include:

[0117] Control the mass space velocity of the aromatic composition in the reactor to 0.2-1h -1 ;

[0118] and / or, the mass flow rate ratio of hydrogen to the aromatic hydrocarbon composition is 0.07 to 1.1;

[0119] and / or, the reactor pressure is 3-8 MPa;

[0120] And / or, the reaction temperature is 100-200°C.

[0121] According to an embodiment of the present invention, the hydrogenation reaction may be performed in, for example, a fixed bed reactor.

[0122] The present invention also provides a hydrogen supply method, comprising dehydrogenating the hydrogen-combined product to provide free hydrogen (such as hydrogen gas).

[0123] According to an embodiment of the present invention, the dehydrogenation is performed in the presence of a dehydrogenation catalyst.

[0124] The dehydrogenation catalyst can be selected from catalysts known to those skilled in the art that are suitable for dehydrogenating cycloalkanes. As an example, the dehydrogenation catalyst can be selected from one or both of alumina-supported platinum catalysts and alumina-supported palladium catalysts.

[0125] According to an embodiment of the present invention, there is no particular limitation on the content of the active ingredient in the dehydrogenation catalyst, as long as it can reach the effective amount required for the catalytic dehydrogenation reaction. As an example, in the dehydrogenation catalyst, the content of the active ingredient can be 0.5wt% to 10wt% of the dehydrogenation catalyst, such as 0.5wt%, 1wt%, 1.5wt%, 2%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%.

[0126] According to an embodiment of the present invention, the specific surface area of ​​the dehydrogenation catalyst is not less than 120 m 2 / g, for example, 140 to 220 m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 170m 2 / g, 180m 2 / g, 190m 2 / g, 200m 2 / g, 210m 2 / g, 220m 2 / g or a number between any two of the above numbers.

[0127] According to an embodiment of the present invention, the particle diameter of the dehydrogenation catalyst is 60 to 100 meshes.

[0128] According to an embodiment of the present invention, the operating parameters of the hydrogen supply include:

[0129] Control the space velocity of the hydrogen bond in the reactor to be 0.03 to 10 h -1 ;

[0130] And / or, the reaction temperature is 100-400°C.

[0131] For example, the operating conditions of the hydrogen supply include:

[0132] Control the space velocity of the hydrogen bond in the reactor to be 0.3 to 2 h -1 ;

[0133] And / or, the reaction temperature is 240-380°C, for example, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 320°C, 340°C, 360°C.

[0134] According to an embodiment of the present invention, the reaction may be carried out in a fixed bed reactor.

[0135] According to an embodiment of the present invention, the hydrogen supply method comprises: the hydrogen combination is reacted through a dehydrogenation catalyst bed, and the reaction product is subjected to gas-liquid separation to obtain hydrogen and liquid products;

[0136] In some embodiments, the liquid phase product can be recycled to prepare the above aromatic hydrocarbon composition or hydrogen combination.

[0137] As an example, the present invention provides a method for preparing a hydrocompound, comprising the following steps:

[0138] S1: preparing the aromatic hydrocarbon composition: mixing materials including the methyl-substituted benzene, biphenyl and methyl-substituted biphenyl;

[0139] S2: pretreatment of the aromatic composition; after preliminary stirring the aromatic composition prepared in step S1, transfer it to a reflux condenser for heating and reflux condensation treatment; the heating temperature is 80 to 145° C., and the time is 0.5 to 48 hours; and then naturally cool it;

[0140] S3: Hydrogenation to synthesize hydrogen conjugates;

[0141] Using a fixed bed reactor with a combined feeding device, feeding the aromatic hydrocarbon composition pretreated in step S2, and then passing it through a hydrogenation catalyst bed in a reaction tube to perform a hydrogenation reaction to obtain a reaction product; wherein the bed is filled with a hydrogenation catalyst;

[0142] Specifically, the process conditions of the hydrogenation reaction are as follows:

[0143] The material obtained in S1 is placed in a storage tank and introduced into the reaction tube of the fixed bed reactor through a sampling pump to pass through the hydrogenation catalyst bed; the mass space velocity of the aromatic composition in the fixed bed reactor is controlled to be 0.1 to 6 h -1 , the mass flow rate ratio of hydrogen to aromatic hydrocarbon composition is between 0.05 and 1.2, the reactor pressure is between 2 and 9 MPa, the reaction temperature is between 80 and 250° C., and the reaction is carried out continuously;

[0144] After the synthesis of the hydroconjugate is completed, the hydroconjugate can be obtained from the gas-liquid separation tank downstream of the reactor and then obtained in the product collection tank after gas-liquid separation.

[0145] As an example, the present invention provides a hydrogen supply method, comprising the following steps:

[0146] In a fixed bed reactor, the hydrogen-combined material is injected into a reaction tube through an injection pump and passes through a bed layer filled with a dehydrogenation catalyst to react and obtain a reaction product.

[0147] Specifically, the hydrogen combination is placed in a material storage tank, introduced into a reaction tube of a fixed bed reactor through a sampling pump, and passed through a bed layer filled with a dehydrogenation catalyst;

[0148] Control the space velocity of hydrogen bond in fixed bed reactor to 0.03~10h -1 , the reaction temperature is between 100 and 400°C;

[0149] After the reaction products come out of the reaction tube, they are separated into gas and liquid, and the hydrogen-bound products begin to be fully or partially converted into aromatic products;

[0150] The aromatic products are collected in the liquid phase product tank, and the hydrogen produced is obtained from the gas phase product collection point;

[0151] Preferably, the hydrogen can be metered, analyzed and subsequently used.

[0152] The aromatic hydrocarbon composition, hydrogen combination product, and liquid phase product after hydrogenation of the hydrogen combination product of the present invention can all be kept in liquid state at a temperature not lower than 5° C. and normal pressure.

[0153] Preferably, the reaction temperature is 100-280°C.

[0154] According to an embodiment of the present invention, the aromatic hydrocarbon product can be recycled as an aromatic hydrocarbon composition for use in the above-mentioned steps S2 and / or S3.

[0155] According to an embodiment of the present invention, the hydrogen supply mass ratio of the hydrogen combiner of the present invention (i.e. the ratio of the mass of free hydrogen to the mass of hydrogen combiner) is not less than 6.3wt%; the purity of the provided (free) hydrogen is not less than 99.97v / v%, for example, not less than 99.99v / v%.

[0156] The liquid phase product after the hydrogenation of the hydrogen combination can be used as an aromatic hydrocarbon composition and subsequently used through the above step S3; the related technical solutions are also within the scope of protection.

[0157] Definition and explanation of terms

[0158] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-10" should be understood as recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the decimal value between two adjacent values, for example, at least recording the sum of the smaller value of two adjacent values ​​and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9 respectively. For another example, the numerical range of “55wt%-99wt%” should be understood as recording each integer value in the numerical range of “55wt%-99wt%”, namely 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt%, 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, %, 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, and decimal values ​​between two adjacent values, for example, at least the sum of the smaller of two adjacent values ​​and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9, respectively.

[0159] The unit "wt" or "w / w" used in percentage values ​​indicates that the percentage value is a weight ratio.

[0160] The unit "v / v" used in percentage values ​​indicates that the percentage value is a volume ratio.

[0161] It should be understood that in the “one or more” described herein, “plurality” should refer to an integer greater than or equal to 2, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0162] “C 1-6The term “alkyl” refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0163] "Fixed bed reactor" is a commonly used reaction device in the fields of energy, chemical industry, material research and production. The characteristics of fixed bed reactor are that the solid catalyst is filled at a certain position in the reaction tube to form a bed layer, and the reactants enter the reaction tube driven by a pump or pressure difference, flow through the bed layer and flow out of the reaction tube; the temperature, pressure in the reaction tube, and the flow rate of each component of the reactants can be controlled according to actual needs.

[0164] The product gas from the reactor outlet is generally processed including gas separation and purification, chromatography analysis, tail gas treatment, and further use. The gas from the reactor outlet can be used or processed in different ways.

[0165] "Space velocity" or "space speed" is a parameter of fixed bed reactor process, such as "volume space velocity" or "mass space velocity", which refers to the ratio of the volume or mass flow rate of the fluid to the volume or mass of the catalyst, and the unit is usually h -1 Or the reciprocal of some other time unit.

[0166] Beneficial Effects

[0167] The present invention provides an organic liquid hydrogen-carrying material with high hydrogen content, high actual dehydrogenation rate and good fluidity and a preparation method thereof. 1-6 The dehydrogenation enthalpy of the alkyl-substituted bicyclohexane or alkyl bicyclohexane is small, so that the dehydrogenation energy consumption is small in actual use, and a higher hydrogen equilibrium pressure can be obtained at low temperature than that of commonly used organic hydrogen carriers (such as octahydrodibenzyltoluene, methylcyclohexane), etc.; it can remain in liquid state under normal pressure conditions of not less than 5°C. In addition, the aromatic hydrocarbon composition and hydrogen conjugate of the present invention can achieve a higher actual hydrogen content than similar hydrogen conjugates (for example, methylcyclohexane can provide hydrogen up to 6.2wt%, and usually requires 320°C to achieve hydrogen supply), and can provide high-purity hydrogen, which has a more favorable application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0168] Figure 1 Schematic diagram of a synthesis device for the hydrogen-carrying material (hydrogen compound) of the present invention;

[0169] Among them, each figure mark has the following meaning: 1, storage tank; 2, filtering device; 3, sampling pump; 4, tee; 5, hydrogen source; 6, mass flow controller; 7, upstream pressure gauge; 8, fixed bed reactor; 9, catalyst bed; 10, downstream pressure gauge; 11, back pressure valve; 12, gas-liquid separation tank; 13, collection tank; 14, exhaust gas treatment unit or emission unit.

[0170] Figure 2 This is a schematic diagram of a hydrogen supply process device for the hydrogen-carrying material of the present invention;

[0171] Among them, each figure mark has the following meaning: 1', hydrogen-carrying material storage tank; 2', filtering device; 3', sampling pump; 4', fixed bed reactor; 5', catalyst bed; 6', downstream pressure gauge; 7', gas-liquid separation tank; 8', collecting tank; 9', drying unit; 10', mass flow meter; 11', downstream use unit. DETAILED DESCRIPTION

[0172] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0173] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0174] Example 1: Preparation of Hydrogen-Carrying Material and Hydrogen Supply Method

[0175] 1A. Preparation of Hydroconjugates

[0176] The method for preparing the hydroconjugate comprises the following steps:

[0177] S1: Based on the weight percentage content of the following compounds in the aromatic composition, the aromatic composition is obtained by mixing them:

[0178]

[0179] The total mass of the aromatic composition was 40.0 g.

[0180] S2: Pretreatment of aromatic hydrocarbon composition: After stirring the aromatic hydrocarbon composition prepared in step S1, transfer it to a reflux condenser for heating and reflux condensation treatment; the heating temperature is 105° C. for 6 hours, and then naturally cool it;

[0181] S3: hydrogenating the aromatic hydrocarbon composition pretreated in step S2 to prepare a hydrogenated product;

[0182] Among them, the synthesis of hydrogen conjugates uses Figure 1 The fixed bed reactor shown has a device for combining feeds. Among them, the material in the storage tank 1 is pre-treated in step S2 to obtain the material of the aromatic composition, which is filtered out by the filter device 2 to remove possible particulate matter and then pumped into the fixed bed reactor 8 by the sampling pump 3; the hydrogen is released from the hydrogen source 5 and the flow rate is controlled by the mass flow controller 6, and the pressure of the hydrogen is measured by the upstream pressure gauge 7; the hydrogen and the aromatic composition are combined and introduced into the fixed bed reactor 8 after passing through the tee 4, and pass through the catalyst bed 9 in the reaction tube to carry out hydrogenation reaction, the reaction product is pressure-measured by the downstream pressure gauge 10, and enters the gas-liquid separation tank 12 through the back pressure valve 11, and the liquid phase product obtained by separation enters the collection tank 13, and the gas enters the tail gas treatment unit or the emission unit 14;

[0183] The catalyst filled in the bed is alumina-supported ruthenium catalyst with a mass of 5.0 g. Other characteristics of the catalyst are as follows: particle size is 40 to 80 mesh; catalyst specific surface area is 137 m 2 / g; the ruthenium component content on the catalyst is 5.0wt%.

[0184] Based on the above reactor and catalyst, the process conditions for synthesis are as follows:

[0185] The space velocity of the aromatic composition in the fixed bed reactor was controlled to be 0.4 h -1 , the mass flow rate ratio of hydrogen to aromatic hydrocarbon composition is 0.094, the reactor pressure is 5 MPa, and the reaction temperature is 150°C; after the process parameters reach stability, the synthesis of the hydrogen conjugate is continued until all the initial raw materials are consumed to obtain the hydrogen conjugate;

[0186] The resulting hydrocompound is obtained in a collection tank 13 .

[0187] 1B. Hydrogen Donation of Hydrogen Conjugates

[0188] The hydrogen supply process of the hydroconjugate uses a fixed bed reactor, such as Figure 2 As shown, after the hydrogen combination is filtered out of possible particulate matter by the filter device 2' in the storage tank 1', it is injected into the reaction tube of the fixed bed reactor 4' by the sampling pump 3', and the reaction product is obtained by passing through the catalyst bed 5'; the reaction product is pressure-measured by the downstream pressure gauge 6', enters the gas-liquid separation tank 7', and the liquid phase product obtained by separation enters the collection tank 8', and the gas enters the drying unit 9', and the gas flow rate is controlled by the mass flow meter 10' and sent to the downstream use unit 11';

[0189] The catalyst filled in the bed is alumina-supported platinum catalyst with a mass of 5.0 g. Other characteristics of the catalyst are as follows: particle size is 60-100 mesh; catalyst specific surface area is 166 m 2 / g; the platinum content on the catalyst is 1.05wt%; the reaction pressure is the normal pressure connected to the outside;

[0190] Based on the above reactor and catalyst, the process conditions for hydrogen supply are as follows:

[0191] The space velocity of the hydrogen bond in the fixed bed reactor was controlled to be 0.3 h -1 , the reaction temperature is 276°C; after the process parameters reach stability, the reaction products come out of the reaction tube and undergo gas-liquid separation, the hydrogen-combined products begin to fully or partially convert into aromatic hydrocarbon compositions and are obtained in the collection tank, and at the same time, hydrogen is generated and sent to drying for downstream use; the hydrogen supply process ends here.

[0192] The aromatic hydrocarbon composition, hydrogen combination product, and liquid phase product after hydrogenation of the hydrogen combination product in this embodiment can all be kept in liquid state at a temperature not lower than 5°C.

[0193] In the hydrogen supply of the hydrogen combination in this embodiment, the hydrogen supply mass ratio is 6.36wt% through hydrogen flow measurement and mass conversion; and the purity of hydrogen is not less than 99.97% (volume content) through gas chromatography analysis.

[0194] Some notes on this implementation are as follows:

[0195] The above-mentioned hydrogen supply amount is calculated as follows: (mass of released hydrogen / mass of hydrogen-bound products)*100%.

[0196] The preparation method of the supported catalyst is the conventional equal volume impregnation method in the art; the method for determining the specific surface area of ​​the catalyst is also the conventional method for determining the surface area of ​​solid materials in the art; the mesh size range of the catalyst is a measure of the size of the catalyst particles.

[0197] Comparative Example 1

[0198] Example 1 was repeated, except that in step S1, all methylbiphenyls (i.e., 2-methylbiphenyl and 4-methylbiphenyl) were replaced with biphenyl, so that the content of biphenyl in the aromatic hydrocarbon composition was 92.8 wt % and the content of toluene was 7.2 wt %.

[0199] Results change: The aromatic composition exists in a viscous state close to solid at room temperature; it is difficult to inject samples through the injection pump at room temperature, and it is difficult to carry out the subsequent fixed bed reactor reaction; the raw material tank and the injection area of ​​the injection pump are properly heated to about 60°C, and the injection and subsequent reaction work can be carried out. This shows that methyl biphenyl is very important for maintaining the fluidity of the aromatic composition at room temperature.

[0200] In the hydrogen supply of the hydrogen conjugate of Comparative Example 1, the hydrogen supply mass ratio was 6.1 wt % by hydrogen flow metering and mass conversion. This indicates that the hydrogen conjugate generated by methylbiphenyl has a better kinetic hydrogen release advantage than the hydrogen conjugate generated by biphenyl, although the hydride of biphenyl theoretically has a better total hydrogen supply mass ratio.

[0201] Example 2

[0202] Example 1 was repeated, except that:

[0203] In step S1 of 1A, the composition of the aromatic hydrocarbon composition is as follows:

[0204] 2-Methylbiphenyl 45.0wt%;

[0205] 3-Methylbiphenyl 22.0wt%;

[0206] Biphenyl 26.0wt%;

[0207] Xylene 7.0 wt%.

[0208] In the hydrogen supply method 1B, the space velocity is 0.6h -1 , the reaction temperature is 325℃.

[0209] In the hydrogen supply of the hydrogen combination in this embodiment, the hydrogen supply mass ratio is 6.44wt% through hydrogen flow metering and mass conversion; the hydrogen purity is about 99.97% as measured by analysis.

[0210] Example 3

[0211] Example 1 was repeated, except that: in step S3 of 1A, an alumina-supported nickel catalyst was used, and the catalyst specific surface area was 95 m 2 / g, the nickel content on the catalyst is 20.5wt%; the reaction temperature is 180°C;

[0212] Results: When the hydrogen combination in this embodiment is used for hydrogen supply, the hydrogen supply mass ratio is 6.30wt% through hydrogen flow measurement and mass conversion, which is basically consistent with Example 1.

[0213] Comparative Example 2

[0214] Example 1 was repeated, except that in step S3 of 1A, an alumina-supported platinum catalyst was used, and the other parameters of the catalyst were the same as those in Example 1.

[0215] Results: In the hydrogen supply of the hydrogen conjugate in this comparative example, the hydrogen supply mass ratio was 2.9 wt % by hydrogen flow measurement and mass conversion. This indicates that the type of active metal component of the catalyst used in the synthesis process of the hydrogen conjugate is very important.

[0216] Example 5

[0217] The same method as in Example 2 was repeated, except that: in the hydrogen supply method of 1B, an alumina-supported palladium catalyst was used; other characteristics of the catalyst were as follows: the particle size was 60 to 100 mesh; the specific surface area of ​​the catalyst was 170 m 2 / g; the palladium content on the catalyst is 1.0wt%; and the reaction temperature is 340°C.

[0218] Results: In the use of the hydrogen combination in this embodiment for hydrogen supply, the hydrogen supply mass ratio was obtained by hydrogen flow measurement and mass conversion to be 6.38wt%.

[0219] The above is an exemplary description of the implementation of the technical solution of the present disclosure. It should be understood that the protection scope of the present disclosure is not limited to the above-mentioned implementation. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present disclosure shall be included in the protection scope of the claims of this application.

Claims

1. An aromatic hydrocarbon composition, wherein The aromatic hydrocarbon composition comprises at least one 1-6 Alkyl-substituted biphenyl and at least one C 1-6 Alkyl substituted benzene.

2. The aromatic hydrocarbon composition according to claim 1, wherein The C 1-6 The alkyl group is preferably C 1-4 alkyl; and / or, the one or more C 1-6 There are one or more alkyl-substituted biphenyls; Preferably, the one or more C 1-6 Alkyl-substituted biphenyls are selected from the group consisting of 1, 2, 3, 4, 5, 6 or more C 1-6 one or more of alkyl-substituted biphenyls; Preferably, 1 C 1-6 The alkyl-substituted biphenyl is selected from 2-C 1-6 Alkyl biphenyl, 3-C 1-6 Alkyl biphenyl, 4-C 1-6 Alkyl biphenyl, 5-C 1-6 Alkyl biphenyl or 6-C 1-6 One or more of alkyl biphenyls; Preferably, two C 1-6 Examples of alkyl-substituted biphenyls include, but are not limited to: 2,2'-di(C 1-6 alkyl)biphenyl, 3,3'-di(C 1-6 alkyl)biphenyl, 4,4'-di(C 1-6 alkyl)biphenyl, 5,5'-di(C 1-6 alkyl)biphenyl, 6,6'-di(C 1-6 alkyl)biphenyl, 2,6'-di(C 1-6 alkyl)biphenyl, 3,5'-di(C 1-6 alkyl)biphenyl, 2,5'-di(C 1-6 alkyl)biphenyl, 2,4'-di(C 1-6 alkyl)biphenyl, 2,3-di(C 1-6 Alkyl) biphenyl, 2,4-di(C 1-6 Alkyl) biphenyl, 2,5-di(C 1-6 Alkyl) biphenyl, 2,6-di(C 1-6 alkyl)biphenyl; Preferably, the biphenyl substituted with one methyl group includes one or more of 2-methylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl, 5-methylbiphenyl or 6-methylbiphenyl; Preferably, the biphenyl substituted with 2 methyl groups includes, but is not limited to, one or more of 2,2'-dimethylbiphenyl, 3,3'-dimethylbiphenyl, 4,4'-dimethylbiphenyl, 5,5'-dimethylbiphenyl, 6,6'-dimethylbiphenyl, 2,6'-dimethylbiphenyl, 3,5'-dimethylbiphenyl, 2,5'-dimethylbiphenyl, 2,4'-dimethylbiphenyl, 2,3-dimethylbiphenyl, 2,4-dimethylbiphenyl, 2,5-dimethylbiphenyl, and 2,6-dimethylbiphenyl; Preferably, the one or more C 1-6 There are one or more alkyl-substituted benzenes; Preferably, the one or more C 1-6 Alkyl-substituted benzene is selected from benzene substituted with 1, 2, 3, 4, 5 or 6 C 1-6 One or more of alkyl-substituted benzenes.

3. The aromatic hydrocarbon composition according to claim 1 or 2, wherein: The one or more C 1-6 The total content of alkyl-substituted biphenyls is 55 wt% or more, such as 55 wt% to 99 wt%; Preferably, the aromatic hydrocarbon composition comprises 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 One of the alkyl biphenyls (such as 3-methyl biphenyl) or a mixture of the two above; Preferably, 2-C 1-6 Alkyl biphenyls (such as 2-methyl biphenyl) and 3-C 1-6 The total content of alkylbiphenyls (such as 3-methylbiphenyl) is 55 wt% or higher, for example, 55 wt% to 99 wt%; Preferably, the aromatic hydrocarbon composition further comprises di(C 1-6 alkyl)biphenyl.

4. The aromatic hydrocarbon composition according to claim 1, wherein The aromatic hydrocarbon composition comprises di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 alkyl)benzene (such as xylene); preferably, the aromatic hydrocarbon composition comprises di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 Alkyl)benzenes (such as xylene); Preferably, two (C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 The sum of the contents of alkyl)benzenes (such as xylene) is 1wt% to 15wt%; Preferably, the aromatic hydrocarbon composition further comprises biphenyl, 4-C 1-6 One or more of alkylbiphenyls (such as 4-methylbiphenyl); Preferably, in the aromatic hydrocarbon composition, biphenyl and 4-C 1-6 The total content of alkylbiphenyls (such as 4-methylbiphenyl) is 20 wt % to 44 wt %.

5. The aromatic hydrocarbon composition according to any one of claims 1 to 4, wherein: The aromatic hydrocarbon composition comprises: 2-C 1-6 Alkyl biphenyl and / or 3-C 1-6 Alkyl biphenyls; C 1-6 Alkylbenzene or di(C 1-6 alkyl)benzene; and 4-C 1-6 Alkylbiphenyls and / or biphenyls; Alternatively, the aromatic hydrocarbon composition comprises: 2-methylbiphenyl and / or 3-methylbiphenyl; Toluene or xylene; and 4-Methylbiphenyl and / or biphenyl.

6. A hydrogen bond, wherein: The hydrocombination product is obtained by hydrogenating the aromatic hydrocarbon composition according to any one of claims 1 to 5 with hydrogen; wherein the hydrogenation reaction is achieved by using a fixed bed reactor in which a hydrogenation catalyst is loaded; Preferably, the hydrogenation catalyst is an alumina-supported ruthenium catalyst, a nickel-molybdenum two-component oxide non-supported catalyst, or the like.

7. A method for supplying hydrogen, wherein: The hydrogen supply method comprises subjecting the hydrogen compound of claim 6 to a dehydrogenation reaction to provide free hydrogen; Wherein the dehydrogenation reaction is preferably achieved by using a fixed bed reactor containing a dehydrogenation catalyst; Preferably, the dehydrogenation catalyst is an alumina-supported platinum catalyst, an alumina-supported palladium catalyst, or the like.

8. The hydrogen supply method according to claim 7, wherein: The mass of the obtainable free hydrogen is not less than 6.3wt% of the mass of the hydrogen-binding substance, and the purity of the hydrogen is not less than 99.99%.

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