CN114058408A - Supercritical water hydrogen production device - Google Patents

Supercritical water hydrogen production device Download PDF

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Publication number
CN114058408A
CN114058408A CN202111367633.2A CN202111367633A CN114058408A CN 114058408 A CN114058408 A CN 114058408A CN 202111367633 A CN202111367633 A CN 202111367633A CN 114058408 A CN114058408 A CN 114058408A
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Prior art keywords
supercritical
reaction
heat exchanger
water
hydrogen
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CN202111367633.2A
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Chinese (zh)
Inventor
杨家华
杨晨滈
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Jiangsu Hehai New Energy Technology Development Co ltd
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Individual
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • C10J3/485Entrained flow gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02Fixed-bed gasification of lump fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0973Water
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a supercritical water hydrogen production device, which comprises a supercritical boiler, an air-flotation bed reaction kettle and a reaction material feeding device, wherein the supercritical boiler provides supercritical water; the reaction material feeding device receives the reaction materials and discharges the reaction materials; reaction material and supercritical water that reaction material feeding device discharged mix and get into air supporting bed reation kettle, and in air supporting bed reation kettle, reaction material and supercritical water reaction generate supercritical mixture, and supercritical mixture contains supercritical carbon dioxide, supercritical hydrogen, the supercritical water that has not reacted, and the supercritical mixture of production discharges from air supporting bed reation kettle. The method does not need to prepare pure oxygen or externally arrange electric heating, has simple system control and lower hydrogen production cost; only supercritical water is used as a heat source in the whole process, air or oxygen is not required to be added, explosion danger is avoided, and the safety is higher; the produced hydrogen and carbon dioxide are in supercritical state, and liquid carbon dioxide and hydrogen can be obtained only by expansion and temperature reduction, thereby thoroughly solving the problem of hydrogen transportation.

Description

Supercritical water hydrogen production device
Technical Field
The invention belongs to the technical field of hydrogen production, and particularly relates to a supercritical water hydrogen production device.
Background
Since the invention of fire, people all adopt the oxygen-enriched (air) combustion mode to extract energy for the energy use modes of carbon-based fuels such as coal, petroleum, biomass, garbage and the like.
Traditional chemical industry coal gasification mode all adopts the pure oxygen as the gasification agent, adds water through the pure oxygen and generates carbon monoxide, hydrogen etc. under the condition of oxygen deficiency burning, and this mode needs the water to spray purification gasification gas and helps arranging the sediment, can lead to a large amount of water pollution, and the inefficiency is less than 60% simultaneously, causes a large amount of energy extravagant.
The traditional hydrogen production by electrolyzing water has high hydrogen production cost, low hydrogen pressure and difficult pressurization and liquefaction, is difficult to solve the transportation problem of hydrogen energy, and cannot support the rapid development of the hydrogen energy industrial chain.
The traditional supercritical water coal steaming mode adopts an electric heating or oxygen adding combustion mode to provide reaction heat in order to solve the endothermic energy of water and coal reaction.
Disclosure of Invention
In view of the above problems, the present invention provides a supercritical water hydrogen production apparatus, wherein supercritical water reacts with reaction materials to produce hydrogen in a supercritical state.
The technical scheme for realizing the invention is as follows
A device for producing hydrogen by supercritical water comprises a supercritical boiler, an air-float bed reaction kettle and a reaction material feeding device, wherein the supercritical boiler provides supercritical water;
the reaction material feeding device receives the reaction materials and discharges the reaction materials;
reaction material and supercritical water that reaction material feeding device discharged mix and get into air supporting bed reation kettle, and in air supporting bed reation kettle, reaction material and supercritical water reaction generate supercritical mixture, and supercritical mixture contains supercritical carbon dioxide, supercritical hydrogen, the supercritical water that has not reacted, and the supercritical mixture of production discharges from air supporting bed reation kettle.
The device also comprises a fixed bed reaction kettle and a middle transition ash bin, wherein the discharge end of the air floatation bed reaction kettle is communicated with the inlet end of the fixed bed reaction kettle, the supercritical mixture discharged from the air floatation bed reaction kettle enters the fixed bed reaction kettle for continuous reaction, and after the reaction is finished, the supercritical mixture is discharged from the discharge end of the fixed bed reaction kettle;
the slag discharge port of the fixed bed reaction kettle is communicated with the intermediate transition ash bin, a discharge control valve for controlling ash in the fixed bed reaction kettle to enter the intermediate transition ash bin is arranged between the slag discharge port of the fixed bed reaction kettle and the intermediate transition ash bin, and a slag discharge control valve for controlling the discharge of the ash in the intermediate transition ash bin is arranged at the slag discharge port of the intermediate transition ash bin.
The reaction material feeding device comprises a hopper, a middle transition bin and a feeding valve, wherein a feeding port is arranged on the hopper, the lower part of the hopper is communicated with the top of the middle transition bin, and a control valve for controlling the reaction materials in the hopper to enter the middle transition bin is arranged between the hopper and the middle transition bin; the feeding valve is arranged at the discharge end of the intermediate transition bin to control the discharge of reaction materials in the intermediate transition bin.
Reaction materials discharged by the reaction material feeding device and supercritical water discharged by the supercritical boiler are injected by the injector and then enter the air-floating bed reaction kettle from the bottom of the air-floating bed reaction kettle.
The device also comprises a water melting tank, a first heat exchanger and a second heat exchanger, wherein the water melting tank is internally stored with melting water;
the discharge end of the water melting water tank is communicated with the heat-gaining inlet end of the first heat exchanger, the heat-gaining discharge end of the first heat exchanger is communicated with the heat-gaining inlet end of the second heat exchanger, and the heat-gaining discharge end of the second heat exchanger is communicated with the supercritical water pipeline in the supercritical boiler;
the temperature in the first heat exchanger is lower than the temperature in the second heat exchanger; the temperature of the water in the water tank is gradually increased after the water passes through the first heat exchanger and the second heat exchanger.
The device still includes liquid carbon dioxide storage tank, hydrogen storage tank, and fixed bed reation kettle's discharge end forms the intercommunication with the heat supply inlet end of second heat exchanger, and the heat supply discharge end of second heat exchanger forms the intercommunication with the heat supply inlet end of first heat exchanger, and the heat supply discharge end of first heat exchanger is provided with two the tunnel, and with hydrogen storage tank intercommunication all the way, during gaseous hydrogen gets into the hydrogen storage tank, another way forms the intercommunication with the liquid carbon dioxide storage tank, supplies during liquid carbon dioxide gets into the liquid carbon dioxide storage tank.
The invention provides a method for producing hydrogen by reacting reaction materials (coal and/or biomass and/or garbage) with supercritical water to generate hydrogen and carbon dioxide in a water supercritical state, wherein the supercritical water fed by a supercritical boiler provides heat required by gasification reaction in the reaction process, so that the aim of converting chemical energy of the coal (biomass, garbage and the like) into hydrogen energy and producing hydrogen is fulfilled. The hydrogen production device has the following advantages:
1. the invention does not need to prepare pure oxygen or externally arrange electric heating, has simple system control and lower hydrogen production cost.
2. The gasification method only uses supercritical water as a heat source in the whole process, does not need to add air or oxygen, has no explosion hazard and has higher safety.
3. The hydrogen and the carbon dioxide produced by the method are both in a supercritical state, and the liquid carbon dioxide and the hydrogen can be obtained only by expansion and temperature reduction, so that the problem of hydrogen transportation is thoroughly solved.
Drawings
FIG. 1 is a schematic diagram of a hydrogen plant according to the present invention;
in the attached figure 1, 100 parts of a supercritical boiler, 101 parts of an air-float bed reaction kettle, 102 parts of a reaction material feeding device, 103 parts of a fixed bed reaction kettle, 104 parts of a middle transition ash bin, 105 parts of a filter, 106 parts of a discharge control valve, 107 parts of a slag discharge control valve, 108 parts of a hopper, 109 parts of a middle transition bin, 110 parts of a feeding valve, 111 parts of a control valve, 112 parts of an ejector, 113 parts of a water melting tank, 114 parts of a first heat exchanger, 115 parts of a second heat exchanger, 116 parts of a liquid carbon dioxide storage tank, 117 parts of a hydrogen storage tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Referring to fig. 1, a supercritical water hydrogen production apparatus includes a supercritical boiler 100, an air-flotation bed reactor 101, and a reactant feeding device 102, where the supercritical boiler 100 provides supercritical water, that is, external water passes through the supercritical boiler 100 to form supercritical pressure and temperature, and then is fed into the air-flotation bed reactor 101 to provide supercritical reaction conditions.
The reaction material feeding device receives the reaction materials and discharges the reaction materials, and the reaction materials can be carbon-containing solid materials such as coal and/or biomass and/or garbage. And after the reaction materials are dried, forming dry materials and feeding the dry materials into a reaction material feeding device.
Reaction material and supercritical water that reaction material feeding device discharged mix and get into air supporting bed reation kettle 101, and in air supporting bed reation kettle 101, reaction material and supercritical water reaction generate supercritical mixture, and supercritical mixture contains supercritical carbon dioxide, supercritical hydrogen, the supercritical water that has not reacted, and the supercritical mixture of production discharges from air supporting bed reation kettle 101.
One embodiment in this application: the device also comprises a fixed bed reaction kettle 103 and a middle transition ash bin 104, wherein the discharge end of the air floatation bed reaction kettle 101 is communicated with the inlet end at the bottom of the fixed bed reaction kettle 103, a supercritical mixture discharged from the air floatation bed reaction kettle 101 enters the fixed bed reaction kettle 103 for continuous reaction, after the reaction is finished, the generated gas is discharged from the discharge end of the fixed bed reaction kettle 103, and the formed ash falls towards the bottom of the fixed bed reaction kettle 103 under the action of gravity; from the air supporting bed reation kettle 101 exhaust mixture, continue the reaction in fixed bed reation kettle 103, make the reaction more complete, can add filter 105 in fixed bed reation kettle 103 or outside, reduce the discharge of adulterating other objects in the discharge mixture, promote the purity of discharge mixture. The air-float bed reaction kettle is combined with the fixed bed reaction kettle 103, and the double advantages of high reaction rate of the air-float bed and high gasification rate of the fixed bed are compatible, so that the complete reaction and the hydrogen generation rate are ensured.
One embodiment in this application: a slag discharge port of the fixed bed reaction kettle 103 is communicated with the intermediate transition ash bin 104, a discharge control valve 106 for controlling ash in the fixed bed reaction kettle 103 to enter the intermediate transition ash bin 104 is arranged between the slag discharge port of the fixed bed reaction kettle 103 and the intermediate transition ash bin 104, and a slag discharge control valve 107 for controlling the discharge of the ash in the intermediate transition ash bin 104 is arranged at the slag discharge port of the intermediate transition ash bin 104. The ash formed after the reaction in the fixed bed reactor 103 is discharged from the discharge control valve 106, enters the intermediate transition ash bin 104, and is finally discharged from the slag discharge control valve 107.
One embodiment in this application: the reaction material feeding device comprises a hopper 108, a middle transition bin 109 and a feeding valve 110, wherein a feeding port is formed in the top of the hopper 108, reaction materials are fed into the hopper 108 from the feeding port, the lower part of the hopper 108 is communicated with the top of the middle transition bin 109, a control valve 111 for controlling the reaction materials in the hopper 108 to enter the middle transition bin 109 is arranged between the hopper 108 and the middle transition bin 109, and the reaction materials in the hopper 108 can enter the middle transition bin 109 through switching of the control valve; the feed valve 110 is installed at the discharge end of the intermediate transition bin 109 to control the discharge of the reaction material in the intermediate transition bin 109. The bottom of the hopper 108 and the bottom of the intermediate transition bin 109 are respectively provided with a tapered bin which gradually shrinks so as to enable the reaction materials to better flow to the next stage.
One embodiment in this application: the reaction material discharged from the reaction material feeding device and the supercritical water discharged from the supercritical boiler 100 are injected by the injector 112, and then enter the air-floating bed reaction kettle 101 from the bottom of the air-floating bed reaction kettle 101. Supercritical water and reaction materials can be premixed in the ejector 112, and preparation is made for more sufficient reaction in the air floatation bed reaction kettle 101.
One embodiment in this application: the device also comprises a water melting tank 113, a first heat exchanger 114 and a second heat exchanger 115, wherein the water melting tank 113 is internally provided with water melting; the first heat exchanger and the second heat exchanger adopt shell-and-tube heat exchangers, the discharge end of the water melting water tank 113 is communicated with the heat-gaining inlet end of the first heat exchanger 114, the heat-gaining discharge end of the first heat exchanger 114 is communicated with the heat-gaining inlet end of the second heat exchanger 115, and the heat-gaining discharge end of the second heat exchanger 115 is communicated with the supercritical water pipeline in the supercritical boiler 100; in the present application, the temperature in the first heat exchanger 114 is lower than the temperature in the second heat exchanger 115; the temperature of the water in the water tank 113 is gradually increased after passing through the first heat exchanger 114 and the second heat exchanger 115, so as to stabilize the temperature of the water before entering the supercritical boiler 100, and reduce the energy consumption of the supercritical boiler 100.
One embodiment in this application: in order to utilize the heat energy contained in the mixture discharged from the fixed bed reaction kettle 103 and simultaneously separate and store the mixture, the hydrogen production device further comprises a liquid carbon dioxide storage tank 116 and a hydrogen storage tank 117, the discharge end of the fixed bed reaction kettle 103 is communicated with the heat supply inlet end of the second heat exchanger 115, the heat supply discharge end of the second heat exchanger 115 is communicated with the heat supply inlet end of the first heat exchanger 114, the heat supply discharge end of the first heat exchanger 114 is provided with two paths, one path is communicated with the hydrogen storage tank 117, the gaseous hydrogen enters the hydrogen storage tank 117, the other path is communicated with the liquid carbon dioxide storage tank 116, and the liquid carbon dioxide enters the liquid carbon dioxide storage tank 116. The mixture discharged from the fixed bed reaction kettle 103 sequentially passes through the second heat exchanger 115 and the first heat exchanger 114, so that the temperature of the water is gradually increased, meanwhile, the temperature of the mixture is gradually reduced, supercritical water in the second heat exchanger 115 is separated out in the reducing process and is sent back to the raw water tank, and supercritical carbon dioxide and hydrogen form a gas state and are sent into the first heat exchanger 114; after passing through the first heat exchanger 114, the gaseous carbon dioxide is cooled to be liquid carbon dioxide, and flows out from the bottom of the first heat exchanger 114 and enters the liquid carbon dioxide storage tank 116, and the hydrogen enters the hydrogen storage tank 117, so that the gaseous carbon dioxide and the liquid carbon dioxide can be stored respectively.

Claims (6)

1. A supercritical water hydrogen production device comprises a supercritical boiler, an air-float bed reaction kettle and a reaction material feeding device, and is characterized in that,
providing supercritical water by a supercritical boiler;
the reaction material feeding device receives the reaction materials and discharges the reaction materials;
reaction material and supercritical water that reaction material feeding device discharged mix and get into air supporting bed reation kettle, and in air supporting bed reation kettle, reaction material and supercritical water reaction generate supercritical mixture, and supercritical mixture contains supercritical carbon dioxide, supercritical hydrogen, the supercritical water that has not reacted, and the supercritical mixture of production discharges from air supporting bed reation kettle.
2. The supercritical water hydrogen production apparatus according to claim 1, further comprising a fixed bed reactor and an intermediate transition ash bin, wherein the discharge end of the air-floating bed reactor is communicated with the inlet end of the fixed bed reactor, the supercritical mixture discharged from the air-floating bed reactor enters the fixed bed reactor for continuous reaction, and after the reaction is completed, the supercritical mixture is discharged from the discharge end of the fixed bed reactor;
the slag discharge port of the fixed bed reaction kettle is communicated with the intermediate transition ash bin, a discharge control valve for controlling ash in the fixed bed reaction kettle to enter the intermediate transition ash bin is arranged between the slag discharge port of the fixed bed reaction kettle and the intermediate transition ash bin, and a slag discharge control valve for controlling the discharge of the ash in the intermediate transition ash bin is arranged at the slag discharge port of the intermediate transition ash bin.
3. The apparatus for producing hydrogen from supercritical water as defined in claim 1 wherein the reactant feeding means comprises a hopper, an intermediate transition bin, and a feeding valve, the hopper is provided with a feeding port, the lower part of the hopper is communicated with the top of the intermediate transition bin, and a control valve is provided between the hopper and the intermediate transition bin for controlling the reactant in the hopper to enter the intermediate transition bin; the feeding valve is arranged at the discharge end of the intermediate transition bin to control the discharge of reaction materials in the intermediate transition bin.
4. The supercritical water hydrogen production plant as defined in claim 1, wherein the reaction material discharged from the reaction material feeding device and the supercritical water discharged from the supercritical boiler are injected by the injector and then enter the air-flotation bed reaction kettle from the bottom of the air-flotation bed reaction kettle.
5. The supercritical water hydrogen production plant of claim 2 further comprising a water chemical tank, a first heat exchanger, a second heat exchanger, wherein water chemical is stored in the water chemical tank;
the discharge end of the water melting water tank is communicated with the heat-gaining inlet end of the first heat exchanger, the heat-gaining discharge end of the first heat exchanger is communicated with the heat-gaining inlet end of the second heat exchanger, and the heat-gaining discharge end of the second heat exchanger is communicated with the supercritical water pipeline in the supercritical boiler;
the temperature in the first heat exchanger is lower than the temperature in the second heat exchanger; the temperature of the water in the water tank is gradually increased after the water passes through the first heat exchanger and the second heat exchanger.
6. The apparatus for producing hydrogen from supercritical water as defined in claim 5, wherein the apparatus further comprises a liquid carbon dioxide storage tank, a hydrogen storage tank,
the discharge end of the fixed bed reaction kettle is communicated with the heat supply inlet end of the second heat exchanger, the heat supply discharge end of the second heat exchanger is communicated with the heat supply inlet end of the first heat exchanger, two paths of heat supply discharge ends of the first heat exchanger are arranged, one path of heat supply discharge ends of the first heat exchanger is communicated with the hydrogen storage tank, gaseous hydrogen enters the hydrogen storage tank, the other path of heat supply discharge ends of the first heat exchanger is communicated with the liquid carbon dioxide storage tank, and liquid carbon dioxide enters the liquid carbon dioxide storage tank.
CN202111367633.2A 2021-11-18 2021-11-18 Supercritical water hydrogen production device Pending CN114058408A (en)

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Application Number Priority Date Filing Date Title
CN202111367633.2A CN114058408A (en) 2021-11-18 2021-11-18 Supercritical water hydrogen production device

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Application Number Priority Date Filing Date Title
CN202111367633.2A CN114058408A (en) 2021-11-18 2021-11-18 Supercritical water hydrogen production device

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114876437A (en) * 2022-05-08 2022-08-09 太原理工大学 Coal bed in-situ hydrogen production method utilizing supercritical water
CN116590053A (en) * 2023-07-17 2023-08-15 太原理工大学 Method and device for producing hydrogen by efficiently gasifying coal
CN116606675A (en) * 2023-07-20 2023-08-18 太原理工大学 Method and device for improving gasification efficiency of lump coal

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114876437A (en) * 2022-05-08 2022-08-09 太原理工大学 Coal bed in-situ hydrogen production method utilizing supercritical water
CN114876437B (en) * 2022-05-08 2024-05-07 太原理工大学 Coal seam in-situ hydrogen production method by utilizing supercritical water
CN116590053A (en) * 2023-07-17 2023-08-15 太原理工大学 Method and device for producing hydrogen by efficiently gasifying coal
CN116590053B (en) * 2023-07-17 2023-09-08 太原理工大学 Method and device for producing hydrogen by efficiently gasifying coal
CN116606675A (en) * 2023-07-20 2023-08-18 太原理工大学 Method and device for improving gasification efficiency of lump coal
CN116606675B (en) * 2023-07-20 2023-09-29 太原理工大学 Method and device for improving gasification efficiency of lump coal

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