CN112093775A - Hydrogen storage system and method for organic liquid hydrogen storage medium and industrial crude hydrogen source - Google Patents
Hydrogen storage system and method for organic liquid hydrogen storage medium and industrial crude hydrogen source Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims description 12
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- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
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- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
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- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 claims description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 3
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 3
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 3
- QAWLNVOLYNXWPL-UHFFFAOYSA-N 9-propylcarbazole Chemical compound C1=CC=C2N(CCC)C3=CC=CC=C3C2=C1 QAWLNVOLYNXWPL-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910002335 LaNi5 Inorganic materials 0.000 claims description 3
- 229910002674 PdO Inorganic materials 0.000 claims description 3
- 229910019020 PtO2 Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
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- 238000007599 discharging Methods 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a hydrogen storage and discharge system and a hydrogen storage and discharge method for an organic liquid hydrogen storage medium and an industrial crude hydrogen source, and belongs to the technical field of organic liquid hydrogen storage. The method comprises a first gas purification device, a gas compression device, an organic liquid hydrogen storage medium hydrogenation device, an organic liquid hydrogen storage medium storage tank, a hydrogen-rich hydrogen storage medium dehydrogenation device and a second gas purification device. The invention can effectively solve the problems of purification of industrial crude hydrogen source and safe storage and transportation of hydrogen while obtaining high-purity hydrogen.
Description
Technical Field
The invention belongs to the technical field of organic liquid hydrogen storage, and particularly relates to a hydrogen storage system and a hydrogen storage method based on an organic liquid hydrogen storage medium and an industrial crude hydrogen source.
Background
Hydrogen is an environmentally attractive fuel and a viable energy carrier to connect a range of energy forms to a variety of end uses in the future. The mass energy density of hydrogen was 120kJ · g-1Is gasolineThree times that of the original. It can be powered by combustion directly in the internal combustion engine, or can be powered by fuel cell to power the motor with high efficiency, and the process has only water as a product, so it will not cause environmental pollution or increase the emission of greenhouse gas. The industrial sources of hydrogen are very wide and large-scale industrial hydrogen production has been in existence for decades. In China, the powerful chemical industry also has a wide hydrogen production foundation. In 2015, the commercial surplus of hydrogen produced by domestic industry in China is about 38 ten thousand tons/year, and the fuel consumption of 190 ten thousand fuel cell vehicles per year (calculated according to two thousand kilometers of fuel cell vehicles per year). In China, 198 million tons/year of potential professional hydrogen production capacity can be used as subsequent hydrogen source supply. The above-described supply of about 240 million tons of hydrogen source does not require new capital investment, regardless of logistics transportation issues.
The storage and transportation of hydrogen become a bottleneck restricting the commercial breakthrough development, and is also a key and difficult problem of the current industrialization. In order to realize the large-scale application of hydrogen energy, it is crucial to develop a reliable hydrogen storage system that can simultaneously meet the requirements of cost and safety. Organic liquid hydrogen storage technology was first proposed and initiated extensive research in the 90's of the 20 th century and has now evolved into a very potential technology for the storage and transport of hydrogen. The organic liquid hydrogen storage system is composed of a pair of organic compounds (organic liquid hydrogen storage medium and hydrogen-rich hydrogen storage medium), and reversible storage of hydrogen is realized through circulation of hydrogenation reaction of the organic liquid hydrogen storage medium and dehydrogenation reaction of the hydrogen-rich hydrogen storage medium. The organic liquid hydrogen storage medium and the hydrogen-rich hydrogen storage medium have more stable, safe, reliable, simple and easy-to-use physical and chemical properties compared with hydrogen, and are convenient to transport as solid or liquid. Compared with high-pressure gaseous hydrogen storage and low-temperature liquefied hydrogen storage, the organic liquid hydrogen storage has higher safety and economy and higher popularization and application values.
Due to the uneven distribution of industrial areas and the policy of industrial capacity adjustment or the local characteristics of the industry, industrial hydrogen sources are not distributed uniformly in space at present, the fluctuation of the yield and the yield of time is large, and industrial hydrogen production hydrogen sources have low added value due to insufficient purity and have no practical value and no great waste due to low hydrogen content of industrial byproduct hydrogen sources. At present, no solution for hydrogen storage, transportation and application is reported so far, wherein the solution is coupled by an industrial crude hydrogen source containing impurity components and an organic liquid hydrogen storage medium. Therefore, the technical problem to be solved by the technical personnel in the field is to purify and safely store and transport the cheap and easily available industrial crude hydrogen source, supply high-purity hydrogen meeting the use standard for back-end application, and solve the problem of uneven distribution of the hydrogen source in space and time.
Disclosure of Invention
One of the objectives of the present invention is to provide a hydrogen storage and release system for an organic liquid hydrogen storage medium and an industrial crude hydrogen source, which can effectively solve the problems of purification of the industrial crude hydrogen source and safe storage and transportation of hydrogen, supply high-purity hydrogen meeting the use standard for back-end application, change the current development situations of low added value of the industrial hydrogen source for hydrogen production and great waste of industrial byproduct hydrogen source, and solve the problem of uneven distribution of hydrogen source in space and time.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrogen storage system based on organic liquid hydrogen storage media and industrial crude hydrogen sources comprises a first gas purification device, a gas compression device, a hydrogenation device for organic liquid hydrogen storage media, a storage tank for hydrogen-rich hydrogen storage media, a dehydrogenation device for hydrogen-rich hydrogen storage media and a second gas purification device, wherein:
the inlet of the first gas purification device is connected with an industrial crude hydrogen source, and the outlet of the first gas purification device is connected with the inlet of the gas compression device;
the organic liquid hydrogen storage medium hydrogenation device is provided with two inlets, wherein one inlet is connected with the outlet of the gas compression device, the other inlet is connected with the outlet of the organic liquid hydrogen storage medium storage tank, and the outlet of the organic liquid hydrogen storage medium hydrogenation device is connected with the inlet of the hydrogen-rich hydrogen storage medium storage tank;
the outlet of the hydrogen-rich hydrogen storage medium storage tank is connected with the inlet of the hydrogen-rich hydrogen storage medium dehydrogenation device; the hydrogen-rich hydrogen storage medium dehydrogenation device is provided with two outlets, wherein one outlet is connected with the organic liquid hydrogen storage medium storage tank, and the other outlet outputs hydrogen I;
the hydrogen enters the second gas purification device through the inlet of the second gas purification device, and high-purity hydrogen is output through the outlet of the second gas purification device.
The industrial crude hydrogen source is a special hydrogen production process hydrogen source or an industrial byproduct hydrogen source, and the volume percentage content of the original hydrogen is not higher than 95%.
In the hydrogen storage and discharge system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source, the volume percentage of hydrogen at the outlets of the first gas purification device and the second gas purification device is higher than that at the inlets of the respective devices.
In the hydrogen storage system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source, in the organic liquid hydrogen storage medium hydrogenation device, the organic liquid hydrogen storage medium is one or more of toluene, N-ethylcarbazole, N-propylcarbazole, N-methylindole, benzyltoluene and dibenzyltoluene.
In the hydrogen storage system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source, the organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device are devices for continuously inputting reaction raw materials and continuously outputting reaction products.
The hydrogen storage and release system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source is characterized in that a hydrogenation catalyst with hydrogenation activity is filled in the organic liquid hydrogen storage medium hydrogenation device, the hydrogenation catalyst is composed of an active component and a carrier, wherein the active component is Ru, Ni, Rh, Pt, Pd, Mo, Ag and LaNi5、YH3The carrier is carbon, graphene or Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride.
In the hydrogen storage system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source, in the organic liquid hydrogen storage medium hydrogenation device, the reaction temperature of catalytic hydrogenation is 80-250 ℃, and the reaction pressure is 0.5-12 MPa.
The hydrogen storage system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source is characterized in that the dehydrogenation device of the hydrogen-rich hydrogen storage medium is filled with a dehydrogenation catalyst with dehydrogenation activity, the dehydrogenation catalyst consists of an active component and a carrier, wherein the active component is Pt or PtO2Pd, PdO, Ru, Ni, nickel oxide, Rh, Cu, copper oxide, Co, Mo and Au, wherein the carrier is one or more of carbon, graphene and Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride.
In the hydrogen storage system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source, the reaction temperature of catalytic dehydrogenation in the hydrogen-rich hydrogen storage medium dehydrogenation device is 100-450 ℃, and the reaction pressure is 0.005-0.5 MPa.
Another object of the present invention is to provide a hydrogen storage method based on an organic liquid hydrogen storage medium and an industrial crude hydrogen source, which comprises the following steps in sequence:
s1, introducing the industrial crude hydrogen source into a gas compression device to compress the industrial crude hydrogen source;
s2, preheating the organic liquid hydrogen storage medium hydrogenation device to the temperature required by the reaction, and allowing the compressed crude hydrogen source to enter the preheated organic liquid hydrogen storage medium hydrogenation device for catalytic hydrogenation;
s3, sending the material obtained in the step S2 after catalytic hydrogenation into a hydrogen-rich hydrogen storage medium storage tank;
s4, preheating the hydrogen-rich hydrogen storage medium dehydrogenation device, and after the hydrogen-rich hydrogen storage medium dehydrogenation device reaches the dehydrogenation reaction temperature, sending the material in the hydrogen-rich hydrogen storage medium storage tank into the hydrogen-rich hydrogen storage medium dehydrogenation device for dehydrogenation;
and S5, after passing through the hydrogen-rich hydrogen storage medium dehydrogenation device, discharging high-purity hydrogen from one outlet, and feeding the other part of products into an organic liquid hydrogen storage medium storage tank.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a hydrogen storage system based on an organic liquid hydrogen storage medium and an industrial crude hydrogen source, which comprises a gas purification device I, a gas compression device, an organic liquid hydrogen storage medium hydrogenation device, an organic liquid hydrogen storage medium storage tank, a hydrogen-rich hydrogen storage medium dehydrogenation device and a gas purification device II.
The method can effectively solve the problems of purification of the industrial crude hydrogen source and safe storage and transportation of hydrogen, supplies high-purity hydrogen meeting the use standard for back-end application, changes the development situations of low additional value of the industrial hydrogen source for hydrogen production and great waste of industrial byproduct hydrogen source, and solves the problem of uneven distribution of the hydrogen source in space and time.
The method takes the organic liquid hydrogen storage medium as a medium, connects the industrial crude hydrogen source with huge capacity and wide source with the high-purity hydrogen demand of an application end, supplies high-purity hydrogen meeting the use standard for back-end application, changes the development current situations that the industrial hydrogen source for hydrogen production has low added value and industrial byproduct hydrogen source is wasted in a large amount, and simultaneously solves the safety problems of purification of the industrial crude hydrogen source and the safety of hydrogen in the storage and transportation processes.
The invention solves the problem of uneven distribution of hydrogen sources in space and time by taking the organic liquid hydrogen storage medium and the hydrogen-rich hydrogen storage medium as the characteristics of convenient storage and transportation of normal-temperature liquid or solid.
Drawings
The invention is further described below with reference to the accompanying drawings:
fig. 1 is a schematic diagram of a hydrogen storage system based on an organic liquid hydrogen storage medium and an industrial crude hydrogen source according to the present invention.
Detailed Description
The invention provides a hydrogen storage and release system and a hydrogen storage and release method for an organic liquid hydrogen storage medium and an industrial crude hydrogen source, and the invention is described in detail below by combining specific embodiments in order to make the advantages and technical scheme of the invention clearer and clearer.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
As a main improvement point of the present invention, the devices in the prior art are combined to form a hydrogen storage and storage system for the organic liquid hydrogen storage medium and the industrial crude hydrogen source, the system does not need additional hydrogen purification equipment to purify crude hydrogen, and the system connects the industrial crude hydrogen source with the high purity hydrogen requirement of an application end, thereby solving the technical problems that the technical personnel in the field want to solve all the time, and more importantly, the present invention also solves the problems of purification of the industrial crude hydrogen source and safety of hydrogen in the processes of storage and transportation.
The specific structures of the first gas purification device, the gas compression device, the organic liquid hydrogen storage medium hydrogenation device, the organic liquid hydrogen storage medium storage tank, the hydrogen-rich hydrogen storage medium dehydrogenation device and the second gas purification device are not described in detail, and the gas purification device can be realized by those skilled in the art by referring to the prior art.
As shown in fig. 1, in the hydrogen storage system of an organic liquid hydrogen storage medium and an industrial crude hydrogen source according to the present invention, the industrial crude hydrogen source is connected to an inlet of a first gas purification device, an outlet of the first gas purification device is connected to an inlet of a gas compression device, two inlets of a hydrogenation device of the organic liquid hydrogen storage medium are respectively connected to an outlet of the gas compression device and an outlet of a storage tank of the organic liquid hydrogen storage medium, an outlet of the hydrogenation device of the organic liquid hydrogen storage medium is connected to an inlet of the storage tank of the hydrogen-rich hydrogen storage medium, an outlet of the storage tank of the hydrogen-rich hydrogen storage medium is connected to an inlet of the storage tank of the hydrogen-rich hydrogen storage medium, the dehydrogenation device of the hydrogen-rich hydrogen storage medium has two outlets, one of which is connected to an inlet of the storage tank of the organic liquid hydrogen storage medium, one of which is used for conveying.
Industrial crude hydrogen source with the original hydrogen volume percentage not higher than 95% is input at the front end of the system, the source of the industrial crude hydrogen source can be special hydrogen production process hydrogen source (such as coal hydrogen production, natural gas hydrogen production, refining hydrogen production and the like) or industrial byproduct hydrogen source (chlor-alkali byproduct hydrogen, coke oven gas byproduct hydrogen and the like), and high-purity hydrogen with the hydrogen volume percentage higher than that of the industrial crude hydrogen source can be output on the same place or different places through system conversion.
As another main improvement point of the present invention, two gas purification devices are adopted in the system of the present invention, namely, the first gas purification device and the second gas purification device, which are both beneficial to hydrogen enrichment, including but not limited to devices capable of changing the composition or content of the gas passing through based on the principles of gas-liquid separation, pressure swing adsorption, etc., and particularly, the first gas purification device and the second gas purification device are combined with the system scheme of the organic liquid hydrogen storage technology, so that the fixed asset investment of a single gas purification device can be greatly reduced, and hydrogen can be safely transported through a hydrogen storage carrier in the middle transportation process.
The above gas compression device, for example, adopts the existing piston compressor, diaphragm compressor, metal hydride thermocompressor in the prior art or adopts several serial or parallel connection, the technicians in the field can select the compressor according to the needs, the compressor should meet the explosion-proof requirement, and the gas compression device comprises a hydrogen buffer tank.
The organic liquid hydrogen storage medium in the system is one or more of toluene, N-ethyl carbazole, N-propyl carbazole, N-methylindole, benzyl toluene and dibenzyl toluene, and all the organic liquid hydrogen storage media are cyclic compounds which can be hydrogenated by using unsaturated double bonds of the medium.
The system is provided with two devices for chemical reaction, namely an organic liquid hydrogen storage medium hydrogenation device for absorbing hydrogen and a hydrogen-rich hydrogen storage medium dehydrogenation device for releasing hydrogen, wherein the two devices are reaction devices for continuously inputting reaction raw materials and continuously outputting reaction products, the reaction devices can integrate various accessories for assisting the reaction, but the device principle is not changed, and the specific organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device for releasing hydrogen have the structure and the working principle.
The hydrogenation device of organic liquid hydrogen storage medium is filled with hydrogenation catalyst with hydrogenation activity, the hydrogenation catalyst with hydrogenation activity is composed of active component and carrier, wherein the active component is Ru, Ni, Rh, Pt, Pd, Mo, Ag, LaNi5、YH3The carrier is carbon, graphene or Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride. The reaction temperature of catalytic hydrogenation is 80-250 ℃, and the reaction pressure is 0.5-12 MPa. The organic liquid hydrogen storage medium is preheated to the temperature required by the reaction before entering the hydrogenation device, and the heat quantity can be generated by electric heating, partition wall medium heating, fuel (such as industrial waste gas with a certain heat value, industrial crude hydrogen raw material gas or partial organic liquid dehydrogenation) combustion direct heat release or tail gas (flue gas) heat supply. The temperature maintaining mode of the organic liquid hydrogen storage medium hydrogenation device can be a mode of introducing cold hydrogen flow into the middle section of the device, cooling a wall dividing medium and the like.
Further, the dehydrogenation device of the hydrogen-rich hydrogen storage medium is filled with a dehydrogenation catalyst with dehydrogenation activity, and the dehydrogenation catalyst with dehydrogenation activity consists of an active component and a carrier, wherein the active component is Pt and PtO2Pd, PdO, Ru, Ni, nickel oxide, Rh, Cu, copper oxide, Co, Mo and Au, wherein the carrier is one or more of carbon, graphene and Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride. The reaction temperature of the catalytic dehydrogenation is 100-450 ℃, and the reaction pressure is 0.005-0.5 MPa. The temperature maintaining mode of the hydrogen-rich hydrogen storage medium dehydrogenation device can be an electric heating mode, a partition wall medium heating mode, a mode of directly releasing heat by burning fuel (such as industrial waste gas with a certain heat value, industrial crude hydrogen raw material gas or partial organic liquid dehydrogenation) or a mode of supplying heat by tail gas (flue gas) and the like. The released hydrogen combustion heat supply mode is mainly suitable for non-power supply in a remote placement modeHeat source supply or costly application scenarios.
When the system disclosed by the invention faces different requirements and application scenes, the organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device are in a co-location mode and a non-location mode.
In the same-place mode, the organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device are placed in the same region, and the hydrogen is safely stored in place in a space-saving manner by adjusting the capacity of the medium contained in the connected organic liquid hydrogen storage medium storage tank and the hydrogen-rich hydrogen storage medium storage tank, so that the hydrogen is more stably output and supplied with high quality compared with the industrial crude hydrogen source. The mode is suitable for the scenes that the capacity of various industrial hydrogen sources fluctuates, or the scenes that the industrial hydrogen sources are stored in a large scale and stored in a warehouse, or the scenes that the quality and the stability of the hydrogen sources requiring the hydrogen on the same site exceed those of the hydrogen producing on the same site.
In a different place placing mode, the organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device are placed in different area ranges, and the storage and transportation of the contained medium are realized through the organic liquid hydrogen storage medium storage tank and the hydrogen-rich hydrogen storage medium storage tank, so that the hydrogen is safely stored and conveniently transported. The mode is suitable for scenes with industrial hydrogen sources far away from a demand end, and the distance is more than 10-50 kilometers.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto.
Although terms such as organic liquid hydrogen storage medium hydrogenation unit, hydrogen rich hydrogen storage medium dehydrogenation unit, etc. are used more generally herein, the possibility of using other terms is not excluded, and these terms are used only for the purpose of more conveniently describing and explaining the essence of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
It is further understood that the specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A store hydrogen system based on organic liquid hydrogen storage medium and industry crude hydrogen source which characterized in that: the device comprises a gas purification device I, a gas compression device, an organic liquid hydrogen storage medium hydrogenation device, an organic liquid hydrogen storage medium storage tank, a hydrogen-rich hydrogen storage medium dehydrogenation device and a gas purification device II, wherein:
the inlet of the first gas purification device is connected with an industrial crude hydrogen source, and the outlet of the first gas purification device is connected with the inlet of the gas compression device;
the organic liquid hydrogen storage medium hydrogenation device is provided with two inlets, wherein one inlet is connected with the outlet of the gas compression device, the other inlet is connected with the outlet of the organic liquid hydrogen storage medium storage tank, and the outlet of the organic liquid hydrogen storage medium hydrogenation device is connected with the inlet of the hydrogen-rich hydrogen storage medium storage tank;
the outlet of the hydrogen-rich hydrogen storage medium storage tank is connected with the inlet of the hydrogen-rich hydrogen storage medium dehydrogenation device; the hydrogen-rich hydrogen storage medium dehydrogenation device is provided with two outlets, wherein one outlet is connected with the organic liquid hydrogen storage medium storage tank, and the other outlet outputs hydrogen I;
the hydrogen enters the second gas purification device through the inlet of the second gas purification device, and high-purity hydrogen is output through the outlet of the second gas purification device.
2. A hydrogen storage system based on organic liquid hydrogen storage media and industrial crude hydrogen source according to claim 1, characterized in that: the industrial crude hydrogen source is a special hydrogen source for a hydrogen production process or an industrial byproduct hydrogen source, and the volume percentage of the original hydrogen is not higher than 95%.
3. A hydrogen storage system based on organic liquid hydrogen storage media and industrial crude hydrogen source according to claim 1, characterized in that: the volume percentage of hydrogen at the outlets of the first gas purification device and the second gas purification device is higher than that at the inlets of the respective devices.
4. A hydrogen storage system based on organic liquid hydrogen storage media and industrial crude hydrogen source according to claim 1, characterized in that: in the organic liquid hydrogen storage medium hydrogenation device, the organic liquid hydrogen storage medium is one or more of toluene, N-ethyl carbazole, N-propyl carbazole, N-methyl indole, benzyl toluene and dibenzyl toluene.
5. A hydrogen storage system based on organic liquid hydrogen storage media and a source of industrial raw hydrogen according to claim 4, characterized in that: the organic liquid hydrogen storage medium hydrogenation device and the hydrogen-rich hydrogen storage medium dehydrogenation device are devices for continuously inputting reaction raw materials and continuously outputting reaction products.
6. A hydrogen storage system based on organic liquid hydrogen storage media and a source of industrial raw hydrogen according to claim 5, characterized in that: the hydrogenation device of the organic liquid hydrogen storage medium is filled with a hydrogenation catalyst with hydrogenation activity, the hydrogenation catalyst consists of an active component and a carrier, wherein the active component is Ru, Ni, Rh, Pt, Pd, Mo, Ag or LaNi5、YH3The carrier is carbon, graphene or Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride.
7. A hydrogen storage system based on organic liquid hydrogen storage media and a source of industrial raw hydrogen according to claim 6, characterized in that: in the hydrogenation device for the organic liquid hydrogen storage medium, the reaction temperature of catalytic hydrogenation is 80-250 ℃, and the reaction pressure is 0.5-12 MPa.
8. A hydrogen storage system based on organic liquid hydrogen storage media and a source of industrial raw hydrogen according to claim 5, characterized in that: the dehydrogenation device is filled with dehydrogenation catalyst with dehydrogenation activity, the dehydrogenation catalyst is composed of active components and carriers, wherein the active components are Pt and PtO2Pd, PdO, Ru, Ni, nickel oxide, Rh, Cu, copper oxide, Co, Mo and Au, wherein the carrier is one or more of carbon, graphene and Al2O3、SiO2、TiO2、ZrO2、g-C3N4One or more of zeolite, molybdenum carbide, silicon carbide and boron nitride.
9. A hydrogen storage system based on organic liquid hydrogen storage media and a source of industrial raw hydrogen according to claim 8, characterized in that: in the hydrogen-rich hydrogen storage medium dehydrogenation device, the reaction temperature of catalytic dehydrogenation is 100-450 ℃, and the reaction pressure is 0.005-0.5 MPa.
10. A hydrogen storage method based on an organic liquid hydrogen storage medium and an industrial crude hydrogen source is characterized in that: the hydrogen storage and discharge system based on the organic liquid hydrogen storage medium and the industrial crude hydrogen source as claimed in any one of claims 1 to 9 is adopted, and the method sequentially comprises the following steps:
s1, introducing the industrial crude hydrogen source into a gas purification device to carry out primary purification on the industrial crude hydrogen source;
s2, introducing the primarily purified hydrogen source into a gas compression device to compress the primarily purified hydrogen source;
s3, preheating the organic liquid hydrogen storage medium hydrogenation device to the temperature required by the reaction, and introducing the compressed hydrogen source into the preheated organic liquid hydrogen storage medium hydrogenation device for catalytic hydrogenation;
s4, sending the material after catalytic hydrogenation in the step S3 into a hydrogen-rich hydrogen storage medium storage tank;
s5, preheating the hydrogen-rich hydrogen storage medium dehydrogenation device, and after the hydrogen-rich hydrogen storage medium dehydrogenation device reaches the dehydrogenation reaction temperature, sending the material in the hydrogen-rich hydrogen storage medium storage tank into the hydrogen-rich hydrogen storage medium dehydrogenation device for dehydrogenation;
s6, after passing through the hydrogen-rich hydrogen storage medium dehydrogenation device, discharging the first hydrogen from one of the outlets, and feeding the other part of the products into an organic liquid hydrogen storage medium storage tank;
s7, introducing the hydrogen gas obtained in the step S6 into a gas purification device II for purification, and outputting high-purity hydrogen after purification by the gas purification device.
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| CN112780944A (en) * | 2021-01-04 | 2021-05-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Hydrogen storage and transportation network |
| CN113926462A (en) * | 2021-11-19 | 2022-01-14 | 苏州金宏气体股份有限公司 | Hydrogenation catalytic material, preparation method and application |
| CN114874800A (en) * | 2022-05-10 | 2022-08-09 | 东南大学 | Biomass-based organic liquid hydrogen storage system and method |
| CN115849300A (en) * | 2022-12-23 | 2023-03-28 | 中国天辰工程有限公司 | Hydrogen storage and release process and system with toluene as hydrogen storage agent |
| CN113926462B (en) * | 2021-11-19 | 2024-05-14 | 金宏气体股份有限公司 | Hydrogenation catalytic material, preparation method and application |
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