Aromatic hydrocarbon compositions, hydrogenated compounds and uses thereof

Abstract

The present invention belongs to the field of hydrogen storage technology, and relates to a method for synthesizing an organic hydride hydrogen conjugate with high hydrogen content and good fluidity and a hydrogen supply method thereof. A new method for synthesizing an organic hydride hydrogen conjugate is provided, comprising initial material preparation of three or more specified types of aromatic compounds, material pretreatment, and hydrogenation reaction treatment of the materials to obtain a hydrogen conjugate. The hydrogen conjugate can obtain hydrogen and produce an aromatic hydrocarbon composition through a fixed bed reactor. The aromatic hydrocarbon composition, hydrogen conjugate, and liquid phase product after hydrogen supply of the hydrogen conjugate of the present invention can all remain in liquid form at a temperature not lower than 5°C. The hydrogen conjugate can obtain a hydrogen supply mass ratio of not less than 6.3wt%, and the hydrogen purity is high. The present invention provides a new formula and process method for the field of organic hydride hydrogen storage technology.

Description

Technical Field

[0001] The present 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 hydrogen energy industry has driven demand for high-density, safe hydrogen storage materials. Chemically stored hydrogen storage materials are primarily categorized into two main categories: liquid organic hydrides and metal hydrides. When selecting a hydrogen storage material, key considerations include hydrogen storage capacity, reaction kinetics, thermodynamic stability, and cost. For example, liquid organic hydrides such as cyclohexane and toluene offer high hydrogen storage capacity and good stability. Metal hydrides such as aluminum hydride and magnesium hydride, while offering high hydrogen storage capacity, suffer from slower reaction kinetics and relatively high costs. Organic liquid hydrogen storage technology is an efficient and safe method of hydrogen storage. Its principle is to utilize specific organic compounds as a hydrogen storage medium. Under mild conditions, chemical reactions bind hydrogen to organic molecules through chemical bonds. This technology offers high hydrogen storage density, low storage temperature, and low pressure. It can also be transported and stored using conventional liquid transportation and storage facilities, significantly improving the convenience of hydrogen storage and transportation. However, currently, it remains difficult to obtain organic hydride carriers with excellent overall performance.

[0003] Dodecahydrobenzyltoluene and octahydrodibenzyltoluene are two organic hydride hydrogen conjugates that have received much attention in the field. A journal article (Y.Suh et al., J.Catal.2022,413,127) reported a catalytic dehydrogenation study using these two materials as hydrogen carriers. A S-modified Pt / Al2O3 catalyst was used in the study. The S modification 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 complete dehydrogenation is difficult. At the same time, the hydrogen-poor product formed after dehydrogenation is solid at room temperature, and this property will make it inconvenient for storage and transportation 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 this field 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 comprising at least one 1-6 Alkyl-substituted biphenyl and at least one C 1-6 Alkyl-substituted benzenes.

[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, such as 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 There may be one or more, for example 1, 2, 3, 4, 5 or 6, alkyl-substituted biphenyls.

[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 One or more of the biphenyls substituted with alkyl. For example, the 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 optionally be substituted at any position other than the 1-position and the 1'-position in the biphenyl structure. Those skilled in the art will appreciate that the "any position other than 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-mentioned 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, 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 by 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 0 wt% or greater than 0 wt%, 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 55 wt% or higher, such as 55 wt% to 99 wt%, or such as 55 wt% to 95 wt%. 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 one of the alkyl biphenyls (such as 3-methyl biphenyl) is used, the "2-C 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-methyl biphenyl).

[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 there are two alkyl biphenyls (such as 3-methyl biphenyl), 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 Alkyl substituted benzenes may be selected from benzenes substituted with 1, 2, 3, 4, 5 or 6 C 1-6 One or more of the benzenes substituted with alkyl. For example, the 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 Alkyl groups may be optionally substituted at any position in the benzene structure. It will be understood by those skilled in the art that the aforementioned "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 will be understood by those skilled in the art that when benzene is replaced by two 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) benzene, 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 comprise di(C 1-6 Alkyl) biphenyl (such as dimethyl biphenyl), C 1-6 Alkylbenzenes (such as toluene) and di(C 1-6 One or more of 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 each of the alkyl)benzenes is 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 1 wt% to 15 wt%, for example 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%.

[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 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 When two of the two alkyl) benzenes (such as xylene) are present, 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 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) benzene (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 alkylbiphenyls (such as 4-methylbiphenyl), for example, 1, 2, 3, 4, 5 or 6. For example, the aromatic hydrocarbon composition comprises one of 4-methylbiphenyl 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 0.

[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 one of the alkyl biphenyls (such as 4-methyl biphenyl) is used, the "biphenyl and 4-C 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)benzenes; 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 4 wt% to 10 wt% (eg, 5 wt% to 9 wt%, 6 wt% to 8 wt% or 7.2 wt%).

[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 normal pressure and not lower 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 hydrogenating 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 of Group VIII of the Periodic Table, or may optionally further contain at least one metal of Groups I or VII 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, fuller's 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: nickel-based catalysts, palladium-based catalysts, platinum-based catalysts, ruthenium-based catalysts and rhodium-based catalysts.

[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 an effective amount required for the catalytic hydrogenation reaction. As an example, the content of the active ingredient in the hydrogenation catalyst can be 0.5 wt% to 10 wt% of the hydrogenation catalyst, such as 0.5 wt%, 1 wt%, 1.5 wt%, 2%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%.

[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, exemplified by 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 obtained by reducing at least some of the components in the aromatic hydrocarbon composition.

[0071] According to an embodiment of the present invention, the hydrocombinate comprises a product in which at least some 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 hydrogenated compound, 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 1 wt%, more than 2 wt%, more than 3 wt%, more than 4 wt%, more than 5 wt%, more than 6 wt%, more than 7 wt%, more than 8 wt%, more than 9 wt%, more than 10 wt%, more than 20 wt%, more than 30 wt%, more than 40 wt%, more than 50 wt%, more than 60 wt%, more than 70 wt%, more than 80 wt%, more than 90 wt%, more than 95 wt% or more of 99 wt% 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 alkyl ... 1-6 Alkyl-substituted cyclohexanes.

[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, such as 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 There may be one or more, for example, 1, 2, 3, 4, 5 or 6, alkyl-substituted bicyclohexanes.

[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 optionally be substituted at any position other than the 1- and 1'-positions in the bicyclohexyl structure. Those skilled in the art will appreciate that the "any position other than the 1- and 1'-positions" mentioned above may be independently selected from the 2-, 3-, 4-, 5-, 6-, 2'-, 3'-, 4'-, 5'-, and 6'-positions of the bicyclohexyl structure. The aforementioned substitution positions are known to those skilled in the art and may be specifically represented by the following formula:

[0079]

[0080] According to an embodiment of the present invention, 1 C 1-6 The alkyl-substituted bicyclohexyl 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 bicyclohexane, 3-methyl bicyclohexane, 4-methyl bicyclohexane, 5-methyl bicyclohexane, or 6-methyl bicyclohexane.

[0081] According to an embodiment of the present invention, 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'-dimethylbicyclohexane, 3,3'-dimethylbicyclohexane, 4,4'-dimethylbicyclohexane, 5,5'-dimethylbicyclohexane, 6,6'-dimethylbicyclohexane, 2,6'-dimethylbicyclohexane, 3,5'-dimethylbicyclohexane, 2,5'-dimethylbicyclohexane, 2,4'-dimethylbicyclohexane, 2,3-dimethylbicyclohexane, 2,4-dimethylbicyclohexane, 2,5-dimethylbicyclohexane, and 2,6-dimethylbicyclohexane.

[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 further comprise 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 cyclohexanes may be selected from cyclohexanes substituted with 1, 2, 3, 4, 5 or 6 C 1-6 One or more of the cyclohexane substituted with alkyl. 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 Alkyl groups may be optionally substituted at any position in the cyclohexane structure. It will be understood by those skilled in the art that the aforementioned "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 will be understood by those skilled in the art that when cyclohexane is replaced by two 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 cyclohexanes (such as 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 further comprise a compound selected from bicyclohexyl, 4-C 1-6 One or more alkyl bicyclohexanes (such as 4-methyl bicyclohexyl), for example 1, 2, 3, 4, 5 or 6. For example, the hydrogen bond 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)cyclohexanes; 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 hydrogen bond is 100 wt%.

[0100] According to an embodiment of the present invention, the hydrocombination product 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 hydrogenated product is obtained by hydrogenating the aromatic hydrocarbon composition and hydrogen; wherein the hydrogenation reaction is achieved by using a fixed bed reactor containing a hydrogenation catalyst;

[0102] Preferably, the hydrogenation catalyst is an alumina-supported ruthenium catalyst, a nickel-molybdenum two-component oxide unsupported 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 preparation method comprises reacting the aromatic hydrocarbon composition with hydrogen.

[0105] According to an embodiment of the present invention, the preparation method includes 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 before 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 hydrocarbon composition in the reactor to 0.1~6h -1 ;

[0113] and / or, the ratio of the mass flow rate of hydrogen to the mass flow rate of 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 hydrocarbon composition in the reactor to 0.2~1h -1 ;

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

[0119] and / or, the reactor pressure is 3 to 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 carried out 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 to be 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 an effective amount required to catalyze the dehydrogenation reaction. As an example, the content of the active ingredient in the dehydrogenation catalyst can be 0.5 wt% to 10 wt% of the dehydrogenation catalyst, such as 0.5 wt%, 1 wt%, 1.5 wt%, 2%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%.

[0126] According to an embodiment of the present invention, the specific surface area of ​​the dehydrogenation catalyst is not less than 120m 2 / g, for example, 140 to 220 m 2 / g, exemplified by 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 for supplying hydrogen include:

[0132] Control the space velocity of the hydrogen bond in the reactor to 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 reacts 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 product can be recycled to prepare the above-mentioned aromatic hydrocarbon composition or hydrogen bond.

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

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

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

[0140] S3: Hydrogenation to synthesize hydrogen conjugates;

[0141] Using a fixed bed reactor equipped 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 hydrogen conjugate is completed, the hydrogen conjugate 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 hydrogenated compound material is injected into the 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 hydrogenated compound is placed in a material storage tank and introduced into the reaction tube of a fixed bed reactor through a sampling pump, so that it passes through a bed 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 hydrocarbon product is collected in the liquid product tank, and the hydrogen produced at the same time is obtained from the gaseous product collection point;

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

[0152] The aromatic hydrocarbon composition, hydrogenated product, and liquid phase product after hydrogenation of the hydrogenated 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 steps S2 and / or S3.

[0155] According to an embodiment of the present invention, the hydrogen supply mass ratio of the hydrogen binder of the present invention (i.e., the ratio of the mass of free hydrogen to the mass of hydrogen binder) is not less than 6.3 wt %; the purity of the provided (free) hydrogen is not less than 99.97 v / v%, for example, not less than 99.99 v / 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 relevant technical solutions are also within the scope of protection.

[0157] Definitions and Explanations of Terms

[0158] Unless otherwise indicated, the numerical ranges recited in this specification and claims are equivalent to reciting at least each specific integer value therein. For example, the numerical range "1-10" should be understood to recite each integer value in the numerical range "1-10", namely, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, as well as the decimal values ​​between two adjacent values, such as at least reciting the sum of the smaller of the 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% to 99wt%” should be understood as recording each integer value in the numerical range of “55wt% to 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%, wt%, 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, such as 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] A fixed-bed reactor is a commonly used reaction device in the energy, chemical, and materials research and production fields. A fixed-bed reactor is characterized by a solid catalyst packed into a specific location within a reaction tube, forming a bed. Reactants, driven by a pump or pressure differential, enter the tube, flow through the bed, and exit the tube. The temperature, pressure, and flow rates of the reactant components within the tube can be controlled to meet specific needs.

[0164] The product gas from the reactor outlet is generally processed by 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 alkyl-substituted bicyclohexanes (or alkyl bicyclohexanes) is low, resulting in low dehydrogenation energy consumption in practical use. At low temperatures, higher hydrogen equilibrium pressures can be achieved than with commonly used organic hydrogen carriers (e.g., octahydrodibenzyltoluene and methylcyclohexane). Furthermore, the aromatic hydrocarbon compositions and hydrogen conjugates of the present invention can achieve higher actual hydrogen contents than similar hydrogen conjugates (e.g., methylcyclohexane can provide up to 6.2 wt% hydrogen, typically requiring a temperature of 320°C). They can also provide high-purity hydrogen, offering promising applications. 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, the various figure marks have the following meanings: 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, the various figure marks have the following meanings: 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 solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative 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 encompassed within the scope of protection 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 preparation method of the hydroconjugate comprises the following steps:

[0177] S1: Based on the weight percentage content of the following compounds in the aromatic hydrocarbon composition, they are mixed to obtain an aromatic hydrocarbon composition:

[0178]

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

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

[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. The material in storage tank 1 undergoes pretreatment in step S2 to produce an aromatic hydrocarbon composition. After filtering out possible particulate matter through filter device 2, it is pumped into fixed-bed reactor 8 by feed pump 3. Hydrogen is released from hydrogen source 5, its flow rate controlled by mass flow controller 6, and its pressure is measured by upstream pressure gauge 7. The hydrogen and aromatic hydrocarbon composition are combined and introduced into fixed-bed reactor 8 after passing through tee 4. The hydrogen passes through catalyst bed 9 in the reaction tube for hydrogenation. The reaction product is pressure-measured by downstream pressure gauge 10 and enters gas-liquid separation tank 12 through back pressure valve 11. The separated liquid product enters collection tank 13, and the gas enters tail gas treatment unit or discharge unit 14.

[0183] The catalyst 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 40-80 mesh; the specific surface area of ​​the catalyst is 137 m 2 / g; the ruthenium content on the catalyst is 5.0wt%.

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

[0185] The space velocity of the aromatic composition in the fixed bed reactor was controlled to be 0.4h -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 hydrocompounds are 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 hydrogenated compound is filtered out of possible particulate matter by a filter device 2' in a storage tank 1', it is injected into the reaction tube of a fixed bed reactor 4' using an injection pump 3' and passes through a catalyst bed 5' to obtain a reaction product. The reaction product is pressure-measured by a downstream pressure gauge 6' and enters a gas-liquid separation tank 7'. The separated liquid product enters a collection tank 8', and the gas enters a drying unit 9'. The gas flow rate is controlled by a mass flow meter 10' and is sent to a downstream use unit 11'.

[0189] The catalyst 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; the specific surface area of ​​the catalyst is 166 m 2 / g; the platinum content of the catalyst was 1.05wt%; the reaction pressure was 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℃; after the process parameters reach stability, the reaction products come out of the reaction tube and undergo gas-liquid separation, the hydrogen combination begins to fully or partially convert into aromatic hydrocarbon composition and is 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, hydrogenated product, and liquid product after hydrogenation of the hydrogenated product in this embodiment can all be kept in liquid form at a temperature not lower than 5°C.

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

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

[0195] The calculation method of the above hydrogen supply amount is: (mass of released hydrogen gas / mass of hydrogen complex)*100%.

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

[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: The aromatic composition existed in a near-solid, viscous state at room temperature. Sample injection through the injection pump at room temperature was difficult, making subsequent reactions in the fixed-bed reactor difficult. However, heating the feed tank and the injection area of ​​the injection pump to approximately 60°C allowed injection and subsequent reactions. This demonstrates that methylbiphenyl is crucial for maintaining the fluidity of the aromatic composition at room temperature.

[0200] During hydrogenation of the hydrogen conjugate of Comparative Example 1, the hydrogen supply mass ratio was 6.1 wt %, as measured by hydrogen flow and converted by mass. This indicates that the hydrogen conjugate formed from methylbiphenyl exhibits a superior kinetic hydrogen release advantage over the hydrogen conjugate formed from biphenyl, despite the fact that biphenyl hydride theoretically exhibits a superior total hydrogen supply mass ratio.

[0201] Example 2

[0202] Example 1 was repeated, except that:

[0203] In step S1 of 1A, the aromatic hydrocarbon composition comprises the following:

[0204] 2-Methylbiphenyl 45.0 wt%;

[0205] 3-Methylbiphenyl 22.0 wt%;

[0206] Biphenyl 26.0 wt%;

[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 compound in this embodiment, the hydrogen supply mass ratio was 6.44 wt % through hydrogen flow measurement and mass conversion; and the hydrogen purity was measured to be about 99.97%.

[0210] Example 3

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

[0212] Results: During the use of the hydrogen combination in this embodiment for hydrogen supply, the hydrogen supply mass ratio was 6.30 wt % as measured by hydrogen flow and converted by mass, which was basically consistent with that in 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: The hydrogen supply ratio of the hydrogen conjugate in this comparative example 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 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 60-100 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: During the use of the hydrogen combination in this embodiment for hydrogen supply, the hydrogen supply mass ratio was 6.38 wt % as obtained by hydrogen flow measurement and mass conversion.

[0219] The above is an exemplary description of the implementation methods of the technical solutions disclosed herein. It should be understood that the scope of protection of the present disclosure is not limited to the above-mentioned implementation methods. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present disclosure shall be included in the scope of protection of the claims of this application.

Claims

1. Application of an aromatic hydrocarbon composition in hydrogen storage, wherein: The aromatic hydrocarbon composition consists of the following components: 2-methylbiphenyl and / or 3-methylbiphenyl; Toluene or xylene; and Biphenyl and / or 4-methylbiphenyl; The aromatic hydrocarbon composition is in liquid state under normal pressure and temperature not lower than 5°C.

2. The use according to claim 1, wherein The aromatic hydrocarbon composition consists of the following components: 2-methylbiphenyl, 4-methylbiphenyl, biphenyl and toluene.

3. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-methylbiphenyl, 3-methylbiphenyl, biphenyl and xylene.

4. The use according to claim 1, wherein The sum of the contents of 2-methylbiphenyl and 3-methylbiphenyl is 55wt%~99wt%; And / or, the sum of the contents of biphenyl and 4-methylbiphenyl is 20 wt % to 44 wt %.

5. The use according to claim 1, wherein The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 40wt%~80wt%; 4-Methylbiphenyl 15wt%~25wt%; Biphenyl 8wt%~16wt%; and Toluene 4wt%~10wt%.

6. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 50wt%~70wt%; 4-Methylbiphenyl 17wt%~23wt%; Biphenyl 10wt%~14wt%; and Toluene 5wt%~9wt%.

7. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 55wt%~65wt%; 4-Methylbiphenyl 18wt%~22wt%; Biphenyl 11wt%~13wt%; and Toluene 6wt%~8wt%.

8. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 30wt%~60wt%; 3-Methylbiphenyl 15wt%~30wt%; Biphenyl 20wt%~35wt%; and Xylene 4wt%~10wt%.

9. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 35wt%~55wt%; 3-Methylbiphenyl 17wt%~27wt%; Biphenyl 22wt%~30wt%; and Xylene 5wt%~9wt%.

10. The use according to claim 1, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 40wt%~50wt%; 3-Methylbiphenyl 20wt%~24wt%; Biphenyl 25wt%~27wt%; and Xylene 6wt%~8wt%.

11. An aromatic hydrocarbon composition for an organic liquid hydrogen-carrying material, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 40wt%~80wt%; 4-Methylbiphenyl 15wt%~25wt%; Biphenyl 8wt%~16wt%; and Toluene 4wt%~10wt%.

12. The aromatic hydrocarbon composition according to claim 11, wherein The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 50wt%~70wt%; 4-Methylbiphenyl 17wt%~23wt%; Biphenyl 10wt%~14wt%; and Toluene 5wt%~9wt%.

13. The aromatic hydrocarbon composition according to claim 11, wherein The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 55wt%~65wt%; 4-Methylbiphenyl 18wt%~22wt%; Biphenyl 11wt%~13wt%; and Toluene 6wt%~8wt%.

14. An aromatic hydrocarbon composition for an organic liquid hydrogen-carrying material, wherein: The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 30wt%~60wt%; 3-Methylbiphenyl 15wt%~30wt%; Biphenyl 20wt%~35wt%; and Xylene 4wt%~10wt%.

15. The aromatic hydrocarbon composition according to claim 14, wherein The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 35wt%~55wt%; 3-Methylbiphenyl 17wt%~27wt%; Biphenyl 22wt%~30wt%; and Xylene 5wt%~9wt%.

16. The aromatic hydrocarbon composition according to claim 14, wherein The aromatic hydrocarbon composition consists of the following components: 2-Methylbiphenyl 40wt%~50wt%; 3-Methylbiphenyl 20wt%~24wt%; Biphenyl 25wt%~27wt%; and Xylene 6wt%~8wt%.

17. A hydrogen bond, wherein The hydrogen combination is prepared by hydrogenating the aromatic hydrocarbon composition according to any one of claims 1 to 10 with hydrogen; wherein the hydrogenation reaction is achieved by using a fixed bed reactor containing a hydrogenation catalyst.

18. The hydroconjugate according to claim 17, wherein The hydrogenation catalyst is an alumina-supported ruthenium catalyst or a nickel-molybdenum two-component oxide non-supported catalyst.

19. The hydroconjugate according to claim 17, wherein The hydroconjugate consists of the following components: 2-Methylbicyclohexyl and / or 3-methylbicyclohexyl; Methylcyclohexane or dimethylcyclohexane; and Bicyclohexyl and / or 4-methylbicyclohexyl.

20. The hydroconjugate according to claim 19, wherein The hydrogen bond consists of the following components: 2-methylbicyclohexyl, 4-methylbicyclohexyl, bicyclohexyl and methylcyclohexyl; Alternatively, the hydroconjugate consists of the following components: 2-methylbicyclohexyl, 3-methylbicyclohexyl, bicyclohexyl, and dimethylcyclohexyl.

21. A method for supplying hydrogen, wherein: The hydrogen supply method comprises subjecting the hydrogen conjugate according to any one of claims 17 to 20 to a dehydrogenation reaction to provide free hydrogen; The dehydrogenation reaction is achieved by using a fixed bed reactor in which the bed is filled with a dehydrogenation catalyst.

22. The hydrogen supply method according to claim 21, wherein: The dehydrogenation catalyst is an alumina-supported platinum catalyst or an alumina-supported palladium catalyst.

23. The hydrogen supply method according to claim 21 or 22, wherein: The mass of the obtained free hydrogen is not less than 6.3 wt % of the mass of the hydrogen-binding substance, and the purity of the hydrogen is not less than 99.99%.

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