CN117358258A - Catalyst for preparing hydrogen-rich organic hydrogen carrier and preparation method thereof - Google Patents

Catalyst for preparing hydrogen-rich organic hydrogen carrier and preparation method thereof Download PDF

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CN117358258A
CN117358258A CN202311305436.7A CN202311305436A CN117358258A CN 117358258 A CN117358258 A CN 117358258A CN 202311305436 A CN202311305436 A CN 202311305436A CN 117358258 A CN117358258 A CN 117358258A
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catalyst
hydrogen
carrier
active component
preparing
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郭磊
于飞
张文帅
李宗鸿
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Sinohydro Yuan'an Beijing Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/18—Reducing with gases containing free hydrogen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • C07—ORGANIC CHEMISTRY
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
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    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • C07C2602/14—All rings being cycloaliphatic
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    • C07C2602/28—Hydrogenated naphthalenes
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Abstract

The invention is suitable for the technical field of catalysts, and provides a catalyst for preparing a hydrogen-rich organic hydrogen carrier, which comprises an active component and a carrier; wherein the active component is nickel, or one or more of cobalt, palladium, platinum, lead, rhodium and ruthenium are combined with nickel; the carrier is one or more of metal oxide, molecular sieve and porous material; the active component is loaded on a carrier, the loading of the active component nickel on the carrier is 1-80 wt% of the total mass of the active component, and the loading of the second or third active component on the carrier is 0.1-5 wt% of the total mass of the active component. The prepared catalyst has high activity in the organic hydrogen storage reaction and good reaction stability, and provides a relatively mild hydrogenation environment for the organic hydrogen storage reaction; meanwhile, the preparation process of the catalyst is simple, the prepared catalyst is easy to mold, the cost of the catalyst is reduced, and the catalyst is easy to be used in industrial production.

Description

Catalyst for preparing hydrogen-rich organic hydrogen carrier and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing a hydrogen-rich organic hydrogen carrier and a preparation method thereof.
Background
In the rapid evolution of the current society and economy, the problems of energy shortage and environmental pollution caused by the traditional fossil fuels have become the core issues in the global energy and environmental fields. Among the many alternative energy strategies, hydrogen energy is increasingly being appreciated by scientific and industrial industries due to its unique characteristics. The hydrogen energy source not only has the environmental advantage of zero carbon emission, but also has remarkable benefit in energy conversion and utilization due to wide source and high energy density. Hydrogen energy is considered as the most potential energy carrier in the future energy system in long-term economic development, and is expected to become the dominant green energy in the 21 st century.
However, the large-scale commercial use of hydrogen energy is still limited by the technology of hydrogen storage and transport. For this reason, hydrogen storage materials have been rapidly developed and progressed in the past two decades as a novel functional material. The development and application of these materials are closely linked to the promotion of hydrogen energy and the strategy of global environmental protection.
Currently, hydrogen storage technologies are mainly classified into two main categories. First, conventional hydrogen storage technologies, such as high pressure gaseous hydrogen storage and low temperature liquid hydrogen storage, have had a certain basis in industrial applications, but still present technical and economic challenges. For example, although the equipment is relatively simple, the speed of charging and discharging hydrogen is high, but the safety risk is high, and the hydrogen storage density is low; the unit volume hydrogen storage density of the low-temperature liquid hydrogen storage is high, the safety is good, but the hydrogen liquefaction energy consumption is high, the cost is high, and meanwhile, the requirement on a hydrogen storage container is high. And the technology based on novel hydrogen storage materials, such as hydrogen storage alloy, coordination oxide hydrogen storage, carbon-based nano material hydrogen storage, organic liquid, oxide hydrogen storage, porous structure material hydrogen storage and the like. In particular, new hydrogen storage materials, their high energy density and excellent safety are considered as key technologies for future hydrogen storage. These new hydrogen storage modes are currently generally classified into solid material hydrogen storage and organic liquid hydrogen storage. The solid material has high hydrogen storage density, low energy consumption and good safety, but the prior art is not mature enough and still is in the laboratory research stage. The organic material has various structures, and the organic hydrogen storage material with various structures can meet different hydrogen storage requirements; secondly, the organic liquid has lighter mass relative to metal and inorganic materials, and the mass ratio of the organic liquid to the inorganic materials is relatively higher than the hydrogen storage capacity; in addition, the organic hydrogen storage material can be selected from green and environment-friendly organic materials, has high storage and transportation safety and mild hydrogen release condition, and has no strict requirement on a storage container.
The nature of the hydrogen storage process of the organic hydrogen storage material lean in hydrogen is catalytic hydrogenation reaction, and the activity of the active center of the hydrogenation catalyst directly determines the quality of hydrogenation performance. The current research focus of organic hydrogen storage catalysts is gradually changed from noble metals such as Pt, pd and Ir to non-noble metal active components such as Ni and Co. Noble metals have the advantages of high activity, low-temperature low-pressure reactivity, low load capacity and the like as active centers, but the wide application of the noble metals is limited by the characteristics of high price and cost, no sulfur resistance and no nitrogen resistance. In the commercialization of organic hydrogen carrier hydrogen storage technology, cost reduction is particularly important. Therefore, the non-noble metal active components (Co, mo, ni and the like) have the characteristics of low cost, good stability and strong sulfur resistance, so that the research of the non-noble metal active components is wider. However, non-noble metal catalysts cannot be used for hydrogenation reactions under milder conditions due to their inherent properties. The high temperature and pressure will be accompanied by carbon deposition on the catalyst surface, blocking the active sites of the catalyst, thereby reducing the activity and stability of the catalyst. And also causes cracking of a portion of the liquid hydrogen storage material, resulting in an increase in hydrogen storage costs.
The nickel catalyst has high activity and low cost, and is a common catalyst in hydrogenation industry. Nickel was found to have hydrogenation in 1897, and researchers subsequently found that Raney nickel was 4 times higher than normal nickel when hydrogenating cottonseed oil. The nickel catalyst can be applied to the hydrogenation of unsaturated hydrocarbon and the conversion processes of dehydrogenation, oxidative dehalogenation, desulfurization and the like. The nickel-based catalyst has high mechanical strength, insensitivity to poison and good thermal conductivity. However, there are disadvantages such as easy generation of carbon deposition in the reaction, deactivation, and insufficient stability at high temperature.
Disclosure of Invention
The embodiment of the invention aims to provide a catalyst for preparing a hydrogen-rich organic hydrogen carrier and a preparation method thereof, and aims to solve the problems in the background art.
The embodiment of the invention is realized in such a way that the catalyst for preparing the hydrogen-rich organic hydrogen carrier comprises an active component and a carrier;
wherein the active component is nickel, or one or more of cobalt, palladium, platinum, lead, rhodium and ruthenium are combined with nickel;
the carrier is one or more of metal oxide, molecular sieve and porous material;
the active component is loaded on a carrier, the loading of the active component nickel on the carrier is 1-80 wt% of the total mass of the active component, and the loading of the second or third active component on the carrier is 0.1-5 wt% of the total mass of the active component.
According to a further technical scheme, the metal oxide is one or more of aluminum oxide, silicon oxide, titanium oxide and cerium oxide.
According to a further technical scheme, the molecular sieve is MCM-41 or SBA-15.
According to a further technical scheme, the porous material is one or more of graphene, activated carbon and carbon nitride.
Another object of the embodiment of the present invention is a method for preparing a catalyst for preparing a hydrogen-rich organic hydrogen carrier, comprising the steps of:
step 1, providing an aqueous solution of soluble salt of an active component, and immersing a carrier in the aqueous solution;
step 2, drying the solution in the step 1, and then roasting;
and step 3, reducing the roasted product to obtain the catalyst.
According to a further technical scheme, in the step 1, the volume ratio of the aqueous solution of the soluble salt of the active component to the carrier is 2:1.
In a further technical scheme, in the step 1, the soluble salt of the active component is nickel nitrate, or one or more selected from cobalt nitrate, palladium chloride, platinum chloride, lead chloride, rhodium chloride and ruthenium chloride are combined with nickel nitrate.
According to a further technical scheme, the soluble salt of the active component is nickel nitrate or a combination of one or two of cobalt nitrate and palladium chloride and nickel nitrate.
In the step 2, the drying temperature is 80-120 ℃ and the drying time is 8-24 hours; roasting temperature is 300-600 ℃ and roasting time is 5-12 h.
In a further technical scheme, in the step 3, the reduction of the roasted product is performed by roasting under a hydrogen atmosphere.
Another object of the embodiment of the present invention is an application of a catalyst for preparing a hydrogen-rich organic hydrogen carrier, the catalyst being applied to hydrogenation of an organic hydrogen storage material, the application comprising the following specific steps:
filling the catalyst into a trickle bed reactor, and feeding the organic hydrogen storage material lean in hydrogen into a reaction system through a pump to react at the reaction temperature of 100-500 ℃ under the hydrogen pressure of 1-6 MPa, so as to prepare the organic hydrogen carrier rich in hydrogen.
Further technical proposal, the organic hydrogen storage material is selected from the group consisting of benzyl toluene (MBT, C) 14 H 14 ) Dibenzyltoluene (DBT, C) 21 H 20 ) Benzene (benzene, C 6 H 6 ) Toluene (tolene, C 7 H 8 ) Decalin (decahydroaphthaene)，C 10 H 18 ) Quinoline (leucoline, C 9 H 7 N), carbazole (C) 12 H 9 N), methyl carbazole (1-methyl carbazole, C 13 H 11 N) and N-ethylcarbazole (9-Ethyl-9H-carbazole, C) 14 H 13 N) one or more of the following.
The catalyst for preparing the hydrogen-rich organic hydrogen carrier and the preparation method thereof provided by the embodiment of the invention have the advantages that the prepared catalyst has high activity in the organic hydrogen storage reaction and good reaction stability, and a relatively mild hydrogenation environment is provided for the organic hydrogen storage reaction; meanwhile, the preparation process of the catalyst is simple, the prepared catalyst is easy to mold, the cost of the catalyst is reduced, and the catalyst is easy to be used in industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
The catalyst for preparing the hydrogen-rich organic hydrogen carrier comprises an active component and a carrier;
wherein the active component is nickel, or one or more of cobalt, palladium, platinum, lead, rhodium and ruthenium are combined with nickel;
the carrier is one or more of metal oxide, molecular sieve and porous material;
the active component is loaded on a carrier, the loading of the active component nickel on the carrier is 1-80 wt% of the total mass of the active component, and the loading of the second or third active component on the carrier is 0.1-5 wt% of the total mass of the active component.
In the embodiment of the invention, the loading of the active component nickel can be 10-50 wt% of the total mass. The loading of the second or third active component may be 0.1wt% to 1wt% of the total mass.
As a preferred embodiment of the present invention, the metal oxide is one or more of aluminum oxide, silicon oxide, titanium oxide, and cerium oxide.
As a preferred embodiment of the present invention, the molecular sieve is MCM-41 or SBA-15.
As a preferred embodiment of the present invention, the porous material is one or more of graphene, activated carbon, and carbon nitride.
The preparation method of the catalyst for preparing the hydrogen-rich organic hydrogen carrier provided by one embodiment of the invention comprises the following steps:
step 1, providing an aqueous solution of soluble salt of an active component, and immersing a carrier in the aqueous solution;
step 2, drying the solution in the step 1, and then roasting;
and step 3, reducing the roasted product to obtain the catalyst.
As a preferred embodiment of the present invention, the volume ratio of the aqueous solution of the soluble salt of the active ingredient in step 1 to the carrier is 2:1.
As a preferred embodiment of the present invention, the soluble salt of the active ingredient in the step 1 is nickel nitrate, or a combination of one or more selected from cobalt nitrate, palladium chloride, platinum chloride, lead chloride, rhodium chloride and ruthenium chloride with nickel nitrate.
As a preferred embodiment of the present invention, the soluble salt of the active ingredient is nickel nitrate, or a combination of one or both of cobalt nitrate and palladium chloride with nickel nitrate.
As a preferred embodiment of the present invention, in the step 2, the drying temperature is 80-120 ℃ and the drying time is 8-24 hours; roasting temperature is 300-600 ℃ and roasting time is 5-12 h.
In the embodiment of the invention, preferably, the drying temperature is 100-110 ℃ and the drying time is 10-20h; roasting temperature is 400-500 ℃ and roasting time is 8-10 h.
As a preferred embodiment of the present invention, in the step 3, the reduction of the calcined product is by calcination under a hydrogen atmosphere.
In the embodiment of the invention, a certain amount of nitrogen is mixed in the hydrogen atmosphere, wherein the ratio of the hydrogen to the nitrogen is (5-10) (90-95); the reduction process is carried out in situ in a fixed bed reactor or a trickle bed reactor, the flow rate of the reducing gas is 100-300 mL/min, the temperature is generally raised to 300-500 ℃ at the speed of 1 ℃/min, the temperature is kept for 2-6 h, and then the temperature is lowered to 20-50 ℃ below the reaction temperature to obtain the reduced catalyst.
The application of the catalyst for preparing the hydrogen-rich organic hydrogen carrier provided by one embodiment of the invention is applied to the hydrogenation of an organic hydrogen storage material, and comprises the following specific steps:
filling the catalyst into a trickle bed reactor, and feeding the organic hydrogen storage material lean in hydrogen into a reaction system through a pump to react at the reaction temperature of 100-500 ℃ under the hydrogen pressure of 1-6 MPa, so as to prepare the organic hydrogen carrier rich in hydrogen.
In the embodiment of the invention, the reaction temperature is 150-300 ℃, and the hydrogen pressure is 2-5 MPa.
As a preferred embodiment of the present invention, the organic hydrogen storage material has a liquid space velocity of 0.1 to 20 mL.g -1 ·h -1 . Preferably, the liquid space velocity of the organic hydrogen storage material is 0.5-10 mL.g -1 ·h -1 。
As a preferred embodiment of the present invention, in the reaction system, the hydrogen to oil ratio (H 2 Volume ratio with organic hydrogen storage liquid, V Hydrogen gas /V Organic liquid ) 100 to 10000. Preferably, the hydrogen to oil ratio is 500 to 5000.
As a preferred embodiment of the present invention, the organic hydrogen storage material is selected from the group consisting of benzyltoluene (MBT, C) 14 H 14 ) Dibenzyltoluene (DBT, C) 21 H 20 ) Benzene (benzene, C 6 H 6 ) Toluene (tolene, C 7 H 8 ) Decalin (decahydroaphthaene, C 10 H 18 ) Quinoline (leucoline, C 9 H 7 N, kakaOxazole (carbazole, C) 12 H 9 N), methyl carbazole (1-methyl carbazole, C 13 H 11 N) and N-ethylcarbazole (9-Ethyl-9H-carbazole, C) 14 H 13 N) one or more of the following.
The following specific examples are provided as experimental comparisons:
implementation example 1: 19.66g of nickel nitrate hexahydrate is weighed and added into deionized water, and the mixture is stirred uniformly at normal temperature, and 6g of Al is added 2 O 3 Stirring at normal temperature for 24h, then placing the mixture into an oil bath pot at 80 ℃ for 30min, then placing the sample into a baking oven at 100 ℃ for baking for 12h, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6h. The catalyst obtained is the calcined catalyst (Ni 40 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 2: 14.75g of nickel nitrate hexahydrate and 0.49g of cobalt nitrate hexahydrate are weighed and added into deionized water, and the mixture is stirred evenly at normal temperature, and 6.9g of Al is added 2 O 3 Stirring at room temperature for 24 hr, placing into 80 deg.C oil bath, stirring for 30min, placing sample into 100deg.C oven, baking for 12 hr, grinding, and transferring to 450 deg.CRoasting in a muffle furnace for 6h. The catalyst obtained is the calcined catalyst (Ni 30 Co 1 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 3: 14.75g of nickel nitrate hexahydrate and 0.17g of palladium chloride are weighed and added into deionized water, and the mixture is stirred evenly at normal temperature, and 6.9g of Al is added 2 O 3 Stirring at normal temperature for 24h, then placing the mixture into an oil bath pot at 80 ℃ for 30min, then placing the sample into a baking oven at 100 ℃ for baking for 12h, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6h. The catalyst obtained is the calcined catalyst (Ni 30 Pd 1 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 4: weighing 14.75g of nickel nitrate hexahydrate and 0.14g of platinum chloride, adding into deionized water, stirring at normal temperature, adding 1g of Al 2 O 3 Stirring at normal temperature for 24h, then placing the mixture into an oil bath pot at 80 ℃ for 30min, then placing the sample into a baking oven at 100 ℃ for baking for 12h, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6h. The catalyst obtained is the calcined catalyst (Ni 30 Pt 1 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 5: 19.66g of nickel nitrate hexahydrate is weighed and added into deionized water, and evenly stirred at normal temperature, and 6g of SiO is added 2 Stirring at room temperature for 24 hr, placing into an 80 deg.C oil bath, stirring for 30min, and placing into a 100deg.C ovenAnd (3) performing medium baking for 12 hours, fully grinding the dried catalyst, and then transferring the catalyst into a muffle furnace at 450 ℃ for roasting for 6 hours. The catalyst obtained is the calcined catalyst (Ni 40 /SiO 2 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 6: 19.66g of nickel nitrate hexahydrate is weighed and added into deionized water, and evenly stirred at normal temperature, and 6g of TiO is added 2 Stirring at normal temperature for 24h, then placing the mixture into an oil bath pot at 80 ℃ for 30min, then placing the sample into a baking oven at 100 ℃ for baking for 12h, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6h. The catalyst obtained is the calcined catalyst (Ni 40 /TiO 2 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 Gas reduction ofThe temperature-raising program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 7: 19.66g of nickel nitrate hexahydrate is weighed and added into deionized water to be uniformly stirred at normal temperature, 6g of MCM-41 molecular sieve is added to be stirred for 24 hours at normal temperature, then the mixture is put into an oil bath pot at 80 ℃ and is continuously stirred for 30 minutes, then a sample is put into a baking oven at 100 ℃ to be baked for 12 hours, and the dried catalyst is fully grinded and then is moved into a muffle furnace at 450 ℃ to be baked for 6 hours. The catalyst obtained is the calcined catalyst (Ni 40 MCM-41), grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. 1g of 40-60 mesh catalyst was weighed and mixed with 3g of quartz sand of the same mesh to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 8: 14.75g of nickel nitrate hexahydrate and 0.26g of ruthenium chloride trihydrate are weighed and added into deionized water, stirred evenly at normal temperature, and 6.9g of TiO is added 2 Stirring at room temperature for 24 hr, placing into 80 deg.C oil bath, stirring for 30min, placing sample into 100 deg.C oven, baking for 12 hr, grinding, and transferring into 450 deg.C muffle furnaceRoasting in a furnace for 6h. The catalyst obtained is the calcined catalyst (Ni 30 Pt 1 /TiO 2 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 9: 14.75g of nickel nitrate hexahydrate, 0.49g of cobalt nitrate hexahydrate and 0.26g of ruthenium chloride trihydrate are weighed and added into deionized water to be uniformly stirred at normal temperature, and 6.8g of Al is added 2 O 3 Stirring at normal temperature for 24 hours, then placing the mixture into an oil bath pot at 80 ℃ for continuous stirring for 30 minutes, then placing the sample into a baking oven at 100 ℃ for baking for 12 hours, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6 hours. The catalyst obtained is the calcined catalyst (Ni 30 Co 1 Ru 1 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is first passed through the originalBit reduction, reducing gas being pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Implementation example 10: weighing 14.75g of nickel nitrate hexahydrate, 0.49g of cobalt nitrate hexahydrate and 0.17g of palladium chloride, adding into deionized water, stirring at normal temperature, adding 6.8g of Al 2 O 3 Stirring at normal temperature for 24 hours, then placing the mixture into an oil bath pot at 80 ℃ for continuous stirring for 30 minutes, then placing the sample into a baking oven at 100 ℃ for baking for 12 hours, and after the dried catalyst is sufficiently grinded, transferring the catalyst into a muffle furnace at 450 ℃ for baking for 6 hours. The catalyst obtained is the calcined catalyst (Ni 30 Co 1 Pd 1 /Al 2 O 3 ) Grinding the roasted catalyst, tabletting and sieving to obtain particles of 40-60 meshes. Weighing a proper amount of 40-60 mesh catalyst, and mixing with 3g quartz sand with the same mesh number to prevent local overheating. The mixed catalyst is filled in a constant temperature zone of a reaction tube of the trickle bed device, the upper part and the lower part of the catalyst are filled with quartz sand, and the catalyst and the quartz sand are separated by quartz cotton. The reaction temperature is monitored in real time by a thermocouple embedded in the catalyst bed layer, so that the reaction temperature is ensured to be constant, and the reaction pressure is controlled by a back pressure valve. Fresh catalyst is firstly reduced in situ, and the reducing gas is pure H 2 The gas, the reducing and heating program is as follows: heating from room temperature to 120deg.C for 30min, and maintaining for 60min; then, the temperature was raised to a reduction temperature of 500℃at a heating rate of 1℃per minute, and the reaction was maintained for 5 hours. And cooling to 160 ℃ 5min after the reduction is completed, switching the gas into pure hydrogen, and starting back pressure to the required reaction pressure. And then starting a metering pump to start sample injection, analyzing tail gas by chromatography, and qualitatively and quantitatively analyzing hydrogen liquid by GC-MS.
Table 1 shows the activity and selectivity of the catalytic hydrogenation of different types of nickel-based catalysts. As can be seen from examples 1, 5, 6 and 7 in Table 1, the composition of Al 2 O 3 The catalyst has better conversion rate and selectivity for the hydrogen storage material dibenzyl toluene; the addition of the second and third active components can lead to a significant increase in the hydrogenation performance of the catalyst.
TABLE 1 catalytic hydrogenation Activity and selectivity comparison for different types of Nickel-based catalysts
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (10)

1. A catalyst for preparing a hydrogen-rich organic hydrogen carrier, which is characterized by comprising an active component and a carrier;
wherein the active component is nickel, or one or more of cobalt, palladium, platinum, lead, rhodium and ruthenium are combined with nickel;
the carrier is one or more of metal oxide, molecular sieve and porous material;
the active component is loaded on a carrier, the loading of the active component nickel on the carrier is 1-80 wt% of the total mass of the active component, and the loading of the second or third active component on the carrier is 0.1-5 wt% of the total mass of the active component.
2. The catalyst for preparing a hydrogen-rich organic hydrogen carrier according to claim 1, wherein the metal oxide is one or more of alumina, silica, titania and ceria.
3. The catalyst for preparing a hydrogen-rich organic hydrogen carrier according to claim 1, wherein the molecular sieve is MCM-41 or SBA-15.
4. The catalyst for preparing a hydrogen-rich organic hydrogen carrier according to claim 1, wherein the porous material is one or more of graphene, activated carbon, and carbon nitride.
5. A method for preparing a catalyst for preparing a hydrogen-rich organic hydrogen carrier, based on the catalyst for preparing a hydrogen-rich organic hydrogen carrier according to any one of the preceding claims 1 to 4, characterized by comprising the steps of:
step 1, providing an aqueous solution of soluble salt of an active component, and immersing a carrier in the aqueous solution;
step 2, drying the solution in the step 1, and then roasting;
and step 3, reducing the roasted product to obtain the catalyst.
6. The method for preparing a catalyst for hydrogen-enriched organic hydrogen carriers according to claim 5, wherein in the step 1, the volume ratio of the aqueous solution of the soluble salt of the active component to the carrier is 2:1.
7. The method for preparing a catalyst for hydrogen-rich organic hydrogen carriers according to claim 6, wherein in the step 1, the soluble salt of the active component is nickel nitrate, or a combination of one or more selected from cobalt nitrate, palladium chloride, platinum chloride, lead chloride, rhodium chloride and ruthenium chloride and nickel nitrate.
8. The method for preparing a catalyst for hydrogen-rich organic hydrogen carriers according to claim 5, wherein in the step 2, the drying temperature is 80-120 ℃ and the drying time is 8-24 hours; roasting temperature is 300-600 ℃ and roasting time is 5-12 h.
9. Use of a catalyst for the preparation of a hydrogen-rich organic hydrogen carrier, based on any of the above claims 1-4, characterized in that the catalyst is applied for the hydrogenation of an organic hydrogen storage material, comprising the following specific steps:
filling the catalyst into a trickle bed reactor, and feeding the organic hydrogen storage material lean in hydrogen into a reaction system through a pump to react at the reaction temperature of 100-500 ℃ under the hydrogen pressure of 1-6 MPa, so as to prepare the organic hydrogen carrier rich in hydrogen.
10. The use of the catalyst for preparing a hydrogen-rich organic hydrogen carrier according to claim 9, wherein the organic hydrogen storage material is selected from one or more of monobenzyl toluene, dibenzyl toluene, benzene, toluene, decalin, quinoline, carbazole, methyl carbazole, and N-ethyl carbazole.
CN202311305436.7A 2023-10-10 2023-10-10 Catalyst for preparing hydrogen-rich organic hydrogen carrier and preparation method thereof Pending CN117358258A (en)

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