CN106542955A - A kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent - Google Patents

A kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent Download PDF

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Publication number
CN106542955A
CN106542955A CN201510596877.6A CN201510596877A CN106542955A CN 106542955 A CN106542955 A CN 106542955A CN 201510596877 A CN201510596877 A CN 201510596877A CN 106542955 A CN106542955 A CN 106542955A
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China
Prior art keywords
hydrogen
naphthalene
reaction
decahydronaphthalene
catalyst
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CN201510596877.6A
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张叶
徐莉
樊玲
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

The invention discloses a kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent, it is characterised in that with naphthalene as carrier, with amorphous state Ni/Al alloy as catalyst, at 2.0~5.0MPa of pressure, 100 DEG C~280 DEG C of temperature, catalytic hydrogenation generates decahydronaphthalene to store hydrogen.The present invention has hydrogen storage equipment simple compared with prior art, hydrogen storage content is big, method is simple, and with low cost, hydrogen storage reaction height is reversible, the storage and release of hydrogen can conveniently be realized, and store, transport all very safe, reaction conversion ratio is high, up to 99.6%, the yield of decahydronaphthalene is up to 99.2% for the conversion ratio of naphthalene.

Description

A kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent
Technical field
The present invention relates to the hydrogen storage material field of technical field of chemical engineering, specifically a kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent.
Background technology
The energy is that the mankind have the material base with sustainable development.Because the alternative energy such as the not reusable edible of the traditional energies such as oil, coal, natural gas, solar energy, wind energy, geothermal energy, Hydrogen Energy is taken seriously and is continuously available exploitation already, wherein hydrogen energy source is acknowledged as one of most promising future source of energy.It is one of new method of Recent study hydrogen storage with organism hydride hydrogen storage, when hydrogen storage is needed, is reacted using unsaturated compoundses and hydrogen, form hydride, so as to by storing hydrogen;When needing to put hydrogen, metal hydride is made to put hydrogen by controlling temperature and/or pressure.The technology is compared with high pressure compressed hydrogen storage technology with traditional metal-oxide hydrogen storage, big with hydrogen storage content, and energy density is high, and hydrogen storage equipment is simple, and the storage of hydrogen, transport all unusual safe readies, hydrogen storage reaction height are reversible, the features such as hydrogen storage material can be recycled.In conventional organic liquid hydride, aromatic hydrocarbons is optimal hydrogen storing agent, mainly has benzene, toluene, naphthalene etc., and the high reversible chemical reaction hydrogen storage being hydrogenated with using naphthalene is the store hydrogen technology developed in recent years, and the theoretical hydrogen storage quality of naphthalene is up to 13%.The hydrogen storage system is made up of the hydrogenation reaction of hydrogen storing agent, 3 processes of the transport of hydrogen carrier and dehydrogenation reaction.Thus seek the first step that a kind of efficient naphthalene hydrogenation catalyst method is hydrogen storage system, have great significance.
The catalyst of arenes catalytic hydrogenation mainly has noble metal serial and base metal two big class of series at present, the catalyst of the noble metal series series such as including Pd, Pt, its high catalytic efficiency, but expensive, easily inactivates under the harsh reaction condition of High Temperature High Pressure.Base metal series refers mainly to nickel catalyst, including Raney's nickel and supported nickel catalyst etc., their relative inexpensiveness, but certain limitation is there is also, such as poor heat resistance, amorphous alloy have unique properties such as the easy modulation of structure, coordination height unsaturation and chemical homogeneous.Amorphous state Ni/Al alloy catalyst is compared with traditional Raney's nickel, loaded catalyst, its particle diameter is less, evenly, with higher specific surface area, its catalysis activity is higher, but amorphous state Ni/Al alloy is done catalyst at present yet there are no report for the chemical hydrogen storage method of naphthalene hydrogenation.
The content of the invention
The purpose of the present invention is a kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent provided for the deficiencies in the prior art, it adopts naphthalene for hydrogen storing agent catalytic hydrogenation reaction to store hydrogen, hydrogen storage reaction height is reversible, can conveniently realize the storage and release of hydrogen, and hydrogen storage content is big, energy density is high, hydrogen storage equipment is simple, and the storage of hydrogen, transport are all very safe, and reaction is with very high conversion ratio, hydrogen storage material and catalyst are reusable, low production cost.
Realize that concrete technical scheme of the invention is:A kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent, it is characterised in that with naphthalene as carrier, with amorphous state Ni/Al alloy as catalyst, at 2.0~5.0MPa of pressure, 100 DEG C~280 DEG C of temperature, catalytic hydrogenation generates decahydronaphthalene to store hydrogen.
A kind of typical preparation method of the present invention, comprises the following steps:
(1)Naphthalene hydrogenation reaction:During naphthalene is dissolved in decahydronaphthalene or naphthane solvent, preparation obtains reaction raw materials, reactor is inserted after adding Ni/Al catalyst, and with air in hydrogen exchange kettle, being then passed through the hydrogen that pressure is 4.0~5.0MPa into kettle carries out catalytic hydrogenation reaction, and reaction temperature is 100 DEG C~280 DEG C, response time is 4~8 hours, reaction is cooled to room temperature discharging after terminating, the product of reaction is decahydronaphthalene, conversion ratio more than 99%;
(2) The separation of catalyst:The decahydronaphthalene that above-mentioned reaction is generated is filtered, Ni/Al alloy catalysts are reclaimed.
The step(1)Solvent for use is decahydronaphthalene or naphthane, and decahydronaphthalene or naphthane and the percentage by weight of solid naphthalene are 20%~50% and 80%~50%.
Described to adopt amorphous state Ni/Al alloy for catalyst, the percentage by weight of Ni and Al is 40%~60% and 60%~40%.
The catalyst of recovery, is preserved in being dipped in ethanol or water, in case reusing.
The present invention has hydrogen storage equipment simple compared with prior art, hydrogen storage content is big, method is simple, and with low cost, hydrogen storage reaction height is reversible, the storage and release of hydrogen can conveniently be realized, and store, transport all very safe, reaction conversion ratio is high, up to 99.6%, the yield of decahydronaphthalene is up to 99.2% for the conversion ratio of naphthalene.
Specific embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
(1) Naphthalene hydrogenation reaction
12 grams of naphthalenes are added in 250ml autoclaves, 10 grams of decahydronaphthalenes and 0.2 gram of commercially available amorphous state Ni/Al alloy catalyst, are passed through air 3 times in hydrogen exchange kettle, are passed through 1 gram of hydrogen, its Hydrogen Vapor Pressure is 4.0MPa, the reacting by heating that heats up is hydrogenated with after finishing, oven temperature is set as 150 DEG C, the response time is 5 hours, after reaction terminates, reactor is taken out, room temperature discharging is cooled to, sampling measures naphthalene conversion ratio for 99.2%.
(2) The separation of catalyst
The decahydronaphthalene that above-mentioned reaction is generated is filtered, amorphous state Ni/Al alloy catalyst is reclaimed, is preserved in being dipped in ethanol or water, in case reusing.
Embodiment 2
(1)Naphthalene hydrogenation reaction
12 grams of naphthalenes are added in 250ml autoclaves, 8 grams of naphthanes and 0.5 gram of commercially available amorphous state Ni/Al alloy catalyst, are passed through air 3 times in hydrogen exchange kettle, are passed through 1 gram of hydrogen, its Hydrogen Vapor Pressure is 2.0MPa, the reacting by heating that heats up is hydrogenated with after finishing, oven temperature is set as 200 DEG C, the response time is 4 hours, after reaction terminates, reactor is taken out, room temperature discharging is cooled to, sampling measures naphthalene conversion ratio for 99.5%.
(2)The separation of catalyst
The decahydronaphthalene that above-mentioned reaction is generated is filtered, amorphous state Ni/Al alloy catalyst is reclaimed, is preserved in being dipped in ethanol or water, in case reusing.
Embodiment 3
(1)Naphthalene hydrogenation reaction
12 grams of naphthalenes are added in 250ml autoclaves, 5 grams of decahydronaphthalenes and 0.5 gram of commercially available amorphous state Ni/Al alloy catalyst, are passed through air 3 times in hydrogen exchange kettle, are passed through 1.5 grams of hydrogen, its Hydrogen Vapor Pressure is 5.0MPa, the reacting by heating that heats up is hydrogenated with after finishing, oven temperature is set as 150 DEG C, the response time is 8 hours, after reaction terminates, reactor is taken out, room temperature discharging is cooled to, sampling measures naphthalene conversion ratio for 99.3%.
(2)The separation of catalyst
The decahydronaphthalene that above-mentioned reaction is generated is filtered, amorphous state Ni/Al alloy catalyst is reclaimed, is preserved in being dipped in ethanol or water, in case reusing.

Claims (4)

1. a kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent, it is characterised in that with naphthalene as carrier, with Ni/Al alloys as catalyst, at pressure 2.0-5.0Mpa, 100 DEG C~280 DEG C of temperature, catalytic hydrogenation generates decahydronaphthalene to store hydrogen.
2. method according to claim 1, it is characterised in that comprise the following steps:
(1)Naphthalene hydrogenation reaction:During naphthalene is dissolved in decahydronaphthalene or naphthane solvent, preparation obtains reaction raw materials, reactor is inserted after adding Ni/Al catalyst, and with air in hydrogen exchange kettle, then being passed through the hydrogen that pressure is 4.0~5.0MPa into kettle carries out catalytic hydrogenation reaction, and reaction temperature is 100 DEG C~280 DEG C, and the response time is 4~8 hours, reaction is cooled to room temperature discharging after terminating, the product of reaction is decahydronaphthalene;
(2)The separation of catalyst:The decahydronaphthalene that above-mentioned reaction is generated is filtered, Ni/Al alloy catalysts are reclaimed.
3. method according to claim 2, it is characterised in that step(1)Solvent for use is decahydronaphthalene or naphthane, and decahydronaphthalene or naphthane and the percentage by weight of solid naphthalene are 20%~50% and 80%~50%.
4. method according to claim 1 and 2, it is characterised in that adopt amorphous state Ni/Al alloy for catalyst, the percentage by weight of Ni and Al is 40%~60% and 60%~40%.
CN201510596877.6A 2015-09-18 2015-09-18 A kind of catalytic hydrogenation method with naphthalene as hydrogen storing agent Pending CN106542955A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021143277A1 (en) * 2020-01-15 2021-07-22 华南理工大学 Method for storing hydrogen using structure-h hydrate
EP3950576A1 (en) * 2020-08-03 2022-02-09 Korea Research Institute of Chemical Technology Hydrogen storage materials comprising naphtalene group and the method for hydrogen storage and release using the same
WO2022076219A1 (en) * 2020-10-06 2022-04-14 The Claire Technologies Corporation Carbon-neutral process for generating electricity
WO2023128467A1 (en) * 2021-12-31 2023-07-06 경북대학교 산학협력단 Hydrogen storage material using naphthalene-based derivative and manufacturing method therefor
US11848468B2 (en) 2021-03-03 2023-12-19 CLAIRE Technologies Liquid carbon-neutral energy facility system
WO2024088128A1 (en) * 2022-10-27 2024-05-02 中国石油天然气股份有限公司 Underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, and preparation method and use method therefor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101575257A (en) * 2009-06-16 2009-11-11 华东师范大学 Catalytic hydrogenation method by taking toluene as hydrogen storing agent
CN101602644A (en) * 2009-07-16 2009-12-16 厦门大学 A kind of synthetic method of perhydronaphthalene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101575257A (en) * 2009-06-16 2009-11-11 华东师范大学 Catalytic hydrogenation method by taking toluene as hydrogen storing agent
CN101602644A (en) * 2009-07-16 2009-12-16 厦门大学 A kind of synthetic method of perhydronaphthalene

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021143277A1 (en) * 2020-01-15 2021-07-22 华南理工大学 Method for storing hydrogen using structure-h hydrate
EP3950576A1 (en) * 2020-08-03 2022-02-09 Korea Research Institute of Chemical Technology Hydrogen storage materials comprising naphtalene group and the method for hydrogen storage and release using the same
WO2022076219A1 (en) * 2020-10-06 2022-04-14 The Claire Technologies Corporation Carbon-neutral process for generating electricity
US11848468B2 (en) 2021-03-03 2023-12-19 CLAIRE Technologies Liquid carbon-neutral energy facility system
WO2023128467A1 (en) * 2021-12-31 2023-07-06 경북대학교 산학협력단 Hydrogen storage material using naphthalene-based derivative and manufacturing method therefor
WO2024088128A1 (en) * 2022-10-27 2024-05-02 中国石油天然气股份有限公司 Underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, and preparation method and use method therefor

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