CN105154907B - A kind of electrolysis water oxygen generation system and method based on solid oxide electrolyte - Google Patents
A kind of electrolysis water oxygen generation system and method based on solid oxide electrolyte Download PDFInfo
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- CN105154907B CN105154907B CN201510609573.9A CN201510609573A CN105154907B CN 105154907 B CN105154907 B CN 105154907B CN 201510609573 A CN201510609573 A CN 201510609573A CN 105154907 B CN105154907 B CN 105154907B
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02E60/50—Fuel cells
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
A kind of electrolysis water oxygen generation system and method based on solid oxide electrolyte, AC conversion is provided for direct current to electrolytic tank of solid oxide；Poor H is provided to electrolytic tank of solid oxide2/H2O gaseous mixtures, rich H is exported in positive pole reaction2/H2O gaseous mixtures, in the high-purity O of negative pole output2；Gained richness H2/H2O gaseous mixtures deliver to the anode of SOFC, and poor H is exported by electrochemical reaction2/H2O gaseous mixtures；By air and the poor H of output2/H2O gaseous mixtures deliver to heat exchanger one, poor H2/H2O gaseous mixtures cool wherein；It is input in premixed device by pump after cooling, is mixed with make-up water；Air after being heated up in the tail gas and heat exchanger one of cathode of solid oxide fuel cell output is sent into heat exchanger two, and the air further heated up is recycled to cathode consumption O therein2, it is of the invention to be combined electrolytic cell with fuel cell, extensive high purity O can be realized2, system cost is reduced, is improved the life-span of electrolysis water oxygen generation system, and the electric energy caused by regenerative resource such as wind energy/solar energy can be utilized.
Description
Technical field
The invention belongs to technical field of oxygen generation, more particularly to a kind of electrolysis water oxygen system based on solid oxide electrolyte
System and method.
Background technology
The method of high purity oxygen mainly has three kinds：(1) Deep Cooling Method；(2) pressure swing adsorption method；(3) electrolysis water oxygen generation method.
Wherein electrolysis water method for producing oxygen through stability is higher, and power consumption is relatively low, and the capacity scope of application is wider.But current electrolysis water oxygen system
It is in system to use PEM electrolyte more, such a electrolyte operating temperature it is low (<100 DEG C), portability is preferable, but system is imitated
Rate and life-span are all relatively low.In order to overcome disadvantage mentioned above, this patent uses the electrolysis water method for producing oxygen through of solid oxide electrolyte,
Worked at 600 DEG C -1000 DEG C, without noble metal catalyst, cost can be reduced, improve efficiency and the life-span of system, and be
System small volume, oxygen scale processed are easy to amplify, and can obtain the high pure oxygen of high purity 99.995%.The input of electric power can utilize
The unstable electric power such as wind energy, solar energy, it is further able to reduce the cost of oxygen processed.
The content of the invention
The shortcomings that in order to overcome above-mentioned prior art, it is an object of the invention to provide one kind to be based on solid oxide electrolyte
The electrolysis water oxygen generation system and method for matter, it is possible to increase oxygen generation efficiency, realize extensive high purity oxygen (O2Purity >=
99.995%).
To achieve these goals, the technical solution adopted by the present invention is：
A kind of electrolysis water oxygen generation system based on solid oxide electrolyte, including：
AC/DC converters 1, it is direct current by AC conversion；
Electrolytic tank of solid oxide 2, the electric energy for receiving its output is connected with AC/DC converters 1, is connected and connects with premixed device 3
The poor H of its offer is provided2/H2O gaseous mixtures, the poor H2/H2O gaseous mixtures react to obtain rich H in the positive pole of electrolytic tank of solid oxide 22/
H2O gaseous mixtures, negative reaction obtain the O that purity is more than or equal to 99.995%2；
SOFC 4, it is connected with electrolytic tank of solid oxide 2 and receives its obtained rich H2/H2O gaseous mixtures,
The rich H2/H2O gaseous mixtures obtain poor H in the anode reaction of SOFC 42/H2O gaseous mixtures；
Heat exchanger 1, it is connected with SOFC 4 and receives its obtained poor H2/H2O gaseous mixtures, with air-source
Connection receives air, to poor H2/H2O gaseous mixtures are cooled, the poor H after cooling2/H2O gaseous mixtures are inputted extremely by the supercharging of pump 6
Premixed device 3, the air after heating are inputted to heat exchanger 7；
Heat exchanger 27, it is connected with heat exchanger 1 and its air provided is provided, be connected and connect with SOFC 4
The high-temperature tail gas of its negative electrode output is received, air is further heated up, the air after further heating up is inputted to solid oxidation
The negative electrode of thing fuel cell 4 provides it oxygen.
The SOFC 4 is connected with electrolytic tank of solid oxide 2 provides it direct current energy.
The premixed device 3 is connected with make-up water.
Present invention also offers a kind of electrolysis water method for producing oxygen through based on solid oxide electrolyte, including：
AC conversion is provided for direct current and to electrolytic tank of solid oxide 2 using AC/DC converters 1；
Using premixed device 3 poor H is provided to electrolytic tank of solid oxide 22/H2O gaseous mixtures, in its positive pole, by electrolytic cell just
React poor H pole2/H2H in O gaseous mixtures2O is converted into H2, export rich H2/H2O gaseous mixtures, at the same it is big in its negative pole output purity
In the O equal to 99.995%2；
By gained richness H2/H2O gaseous mixtures deliver to the anode of SOFC 4, by electrochemical reaction by richness
H2/H2H in O gaseous mixtures2It is converted into H2O, export poor H2/H2O gaseous mixtures；
The poor H that SOFC 4 is exported2/H2O gaseous mixtures deliver to heat exchanger 1, while to heat exchanger 1
Middle feeding air, poor H2/H2O gaseous mixtures cool in heat exchanger 1；
By the poor H after cooling in heat exchanger 12/H2O gaseous mixtures are sent into pump 6, after being pressurized in pump 6, are input to
In premixed device 3, mixed with the water of supply；
Air after being heated up in the tail gas and heat exchanger 1 of the output of the negative electrode of SOFC 4 is sent into heat exchange
Device 27, is further heated up to air, then empties tail gas；The air further heated up is sent into solid oxide fuel
The negative electrode of battery 4, in the cathode consumption of SOFC 4 O therein2。
Direct current energy is arrived DC supply input by DC/DC transformers 8 caused by the SOFC 4
In electrolytic tank of solid oxide 2.
The alternating current that the AC/DC converters 1 are converted is electric energy caused by wind energy or solar energy.
The electrolytic tank of solid oxide 2, single electrolytic cell is formed by positive pole, negative pole and solid oxide electrolyte,
Then extensive electrolytic tank of solid oxide is formed by connection in series-parallel combination by multiple electrolytic cells, operating temperature range is
600 DEG C -1000 DEG C, working pressure range 0.1MPa-20MPa；
The SOFC 4, single fuel electricity is formed by anode, negative electrode and solid oxide electrolyte
Pond, extensive SOFC, operating temperature are then formed by connection in series-parallel combination by multiple fuel cells
Scope is 600 DEG C -1000 DEG C, working pressure range 0.1MPa-20MPa.
The solid oxide electrolyte for stabilized with yttrium oxide zirconium oxide (Yttria Stabilized Zirconia,
YSZ), the cerium oxide of the stable zirconium oxide (Scandia Stabilized Zirconia, ScSZ) of scandium or oxidation Gd2 O3
(Gadolinia-Doped Ceria, GDC)；
The electrolytic cell positive pole uses Ni base catalyst, and is sintered together with solid oxide electrolyte；
The electrolytic cell negative pole uses the lanthanum manganate (LSM) of strontium doping, and is sintered together with solid oxide electrolyte；
The anode of fuel cell uses Ni base catalyst, and is sintered together with solid oxide electrolyte；
The fuel battery negative pole uses the lanthanum manganate (LSM) of strontium doping, and is sintered in one with solid oxide electrolyte
Rise.
Electrolytic cell positive pole reacts, and is H2O+2e-→H2+O2-, wherein O2-Electrolytic cell negative pole, electronics are transported to by electrolyte
Electrolytic cell positive pole is transported to from electrolytic cell negative pole by external circuit.
Electrolytic cell negative reaction, it is O2-→O2+2e-, wherein O2-Electrolytic cell is transported to by electrolyte from anode to bear
Pole, electronics are transported to electrolytic cell positive pole by external circuit from electrolytic cell negative pole.
Anode of fuel cell reacts, and is H2+O2-→H2O+2e-, wherein O2-Transported by electrolyte from fuel battery negative pole
To anode of fuel cell, electronics is transported to fuel battery negative pole by external circuit from anode of fuel cell.
Fuel battery negative pole reacts, and is O2+2e-→O2-, wherein O2-Transported from fuel battery negative pole and transported by electrolyte
To anode of fuel cell, electronics is transported to fuel battery negative pole by external circuit from anode of fuel cell.
The poor H2/H2O gaseous mixtures, 100 DEG C of H is more than for temperature2/H2O mixed gas, wherein H2Molar fraction be less than
0.3。
The rich H2/H2O gaseous mixtures, 100 DEG C of H is more than for temperature2/H2O mixed gas, wherein H2Molar fraction be more than
0.7。
Compared with prior art, the present invention is mutually tied electrolytic cell with fuel cell using soild oxide as electrolyte
Close, extensive high purity O can be realized2, system cost is reduced, is improved the life-span of electrolysis water oxygen generation system, and being capable of profit
The electric energy caused by the regenerative resources such as wind energy/solar energy.
Brief description of the drawings
Accompanying drawing 1 is a kind of electrolysis water oxygen generation system schematic diagram based on solid oxide electrolyte of the present invention.
Embodiment
Describe embodiments of the present invention in detail with reference to the accompanying drawings and examples.
Embodiment 1
As shown in figure 1, AC/DC converters 1 are input to by electric energy caused by wind-power electricity generation, will by AC/DC converters 1
220V AC conversions are 140V direct currents, and are input in the electrolytic tank of solid oxide 2 being made up of 100 batteries；Solid
The positive pole of oxide body electrolytic cell 2, reacted by electrolytic cell positive pole by the 30mol%H from premixed device 32700 DEG C of H2/H2O
H in gaseous mixture2O is converted into H2, export 80mol%H2800 DEG C of H2/H2O gaseous mixtures, while in electrolytic tank of solid oxide 2
The high-purity O of negative pole output2(O2>99.995%)；80mol%H2800 DEG C of H2/H2O gaseous mixtures enter solid oxide fuel electricity
The anode in pond 4, by electrochemical reaction by the H in gaseous mixture2It is converted into H2O, export 30mol%H2900 DEG C of H2/H2O is mixed
Gas, while the O in high temperature air of the cathode consumption of SOFC 4 from heat exchanger 272, at the same time
SOFC 4 outwards exports 70V direct current energies；The 30mol%H of the anode of SOFC 4 output2
900 DEG C of H2/H2O gaseous mixtures enter heat exchanger 1, and pump 6 is entered after being cooled to 700 DEG C, carry out being pressurized to 1.0MPa in pump 6
Afterwards, it is input in premixed device 3, is mixed with the water of supply；Tail gas (the N of cathode of solid oxide fuel cell output2、O2)
Into heat exchanger 27, cold air is preheated, then emptied；Normal temperature air initially enters heat exchanger 1 and is warming up to 200 DEG C,
Then enter back into heat exchanger 27 and be warming up to 600 DEG C, finally enter the negative electrode of SOFC 4.Soild oxide fires
70V direct current energies caused by material battery 4 boost to 140V by DC/DC transformers 8, by DC supply input to soild oxide
In electrolytic cell 2.
Embodiment 2
As shown in figure 1, being input to AC/DC converters 1 by electric energy caused by solar power generation, pass through AC/DC converters 1
It is 280V direct currents by 220V AC conversions, and is input in the electrolytic tank of solid oxide 2 being made up of 200 batteries, 100
Individual electrolytic tank of solid oxide carries out parallel operation；In the positive pole of electrolytic tank of solid oxide 2, being reacted by electrolytic cell positive pole will
20mol%H from premixed device 32750 DEG C of H2/H2H in O gaseous mixtures2O is converted into H2, export 70mol%H2850 DEG C
H2/H2O gaseous mixtures, while in the high-purity O of negative pole output of electrolytic tank of solid oxide 22(O2>99.995%)；70mol%H2's
850℃H2/H2O gaseous mixtures enter the anode of SOFC 4, by electrochemical reaction by the H in gaseous mixture2Turn
Turn to H2O, export 20mol%H2950 DEG C of H2/H2O gaseous mixtures, while come in the cathode consumption of SOFC 4
O from the high temperature air of heat exchanger 272, at the same time SOFC 4 outwards export 140V direct current energies；
The 20mol%H of the anode of SOFC 4 output2900 DEG C of H2/H2O gaseous mixtures enter heat exchanger 1, are cooled to
Enter pump 6 after 750 DEG C, carry out after being pressurized to 35.0MPa, be input in premixed device 3 in pump 6, mixed with the water of supply；
Tail gas (the N of cathode of solid oxide fuel cell output2、O2) enter heat exchanger 27, cold air is preheated, Ran Houpai
It is empty；Normal temperature air initially enters heat exchanger 1 and is warming up to 250 DEG C, then enters back into heat exchanger 27 and is warming up to 650 DEG C, most laggard
Enter the negative electrode of SOFC 4.140V direct current energies pass through DC/DC caused by SOFC 4
Transformer 8 boosts to 280V, by DC supply input into electrolytic tank of solid oxide 2.
Claims (8)
- A kind of 1. electrolysis water oxygen generation system based on solid oxide electrolyte, it is characterised in that including：AC/DC converters (1), it is direct current by AC conversion；Electrolytic tank of solid oxide (2), the electric energy for receiving its output is connected with AC/DC converters (1), is connected with premixed device (3) The poor H of its offer is provided2/H2O gaseous mixtures, the poor H2/H2O gaseous mixtures obtain richness in electrolytic tank of solid oxide (2) negative reaction H2/H2O gaseous mixtures, positive pole react to obtain the O that purity is more than or equal to 99.995%2；SOFC (4), it is connected with electrolytic tank of solid oxide (2) and receives its obtained rich H2/H2O gaseous mixtures, The rich H2/H2O gaseous mixtures obtain poor H in the anode reaction of SOFC (4)2/H2O gaseous mixtures；Heat exchanger one (5), it is connected with SOFC (4) and receives its obtained poor H2/H2O gaseous mixtures, with air-source Connection receives air, to poor H2/H2O gaseous mixtures are cooled, the poor H after cooling2/H2O gaseous mixtures are pressurized by pump (6) and inputted To premixed device (3), the air after heating is inputted to heat exchanger two (7)；Heat exchanger two (7), it is connected with heat exchanger one (5) and its air provided is provided, be connected with SOFC (4) The high-temperature tail gas of its negative electrode output is received, air is further heated up, the air after further heating up is inputted to solid oxygen Compound fuel cell (4) negative electrode provides it oxygen.
- 2. the electrolysis water oxygen generation system based on solid oxide electrolyte according to claim 1, it is characterised in that described solid Oxide body fuel cell (4) is connected with electrolytic tank of solid oxide (2) and provides it direct current energy.
- 3. the electrolysis water oxygen generation system based on solid oxide electrolyte according to claim 1, it is characterised in that described pre- Mixed device (3) is connected with make-up water.
- A kind of 4. electrolysis water method for producing oxygen through based on solid oxide electrolyte, it is characterised in that：AC conversion is direct current using AC/DC converters (1) and provided to electrolytic tank of solid oxide (2)；Using premixed device (3) poor H is provided to electrolytic tank of solid oxide (2)2/H2O gaseous mixtures, in its negative pole, born by electrolytic cell React poor H pole2/H2H in O gaseous mixtures2O is converted into H2, export rich H2/H2O gaseous mixtures, at the same it is big in its positive pole output purity In the O equal to 99.995%2；By gained richness H2/H2O gaseous mixtures deliver to the anode of SOFC (4), by electrochemical reaction by rich H2/ H2H in O gaseous mixtures2It is converted into H2O, export poor H2/H2O gaseous mixtures；The poor H that SOFC (4) is exported2/H2O gaseous mixtures deliver to heat exchanger one (5), while to heat exchanger one (5) air, poor H are sent into2/H2O gaseous mixtures cool in heat exchanger one (5)；Poor H after cooling in heat exchanger one (5)2/H2O gaseous mixtures are sent into pump (6), after being pressurized in pump (6), input Into premixed device (3), mixed with the water of supply；Air after being heated up in the tail gas and heat exchanger one (5) of the output of SOFC (4) negative electrode is sent into heat exchange Device two (7), is further heated up to air, then empties tail gas；The air further heated up is sent into soild oxide combustion The negative electrode of battery (4) is expected, in the cathode consumption O therein of SOFC (4)2。
- 5. the electrolysis water method for producing oxygen through based on solid oxide electrolyte according to claim 4, it is characterised in that described solid Direct current energy caused by oxide body fuel cell (4) is by DC/DC transformers (8), by DC supply input to soild oxide In electrolytic cell (2).
- 6. the electrolysis water method for producing oxygen through based on solid oxide electrolyte according to claim 4, it is characterised in that described The alternating current that AC/DC converters (1) are converted is electric energy caused by wind energy or solar energy.
- 7. the electrolysis water method for producing oxygen through based on solid oxide electrolyte according to claim 4, it is characterised in that described solid Oxide body electrolytic cell (2), single electrolytic cell is formed by positive pole, negative pole and solid oxide electrolyte, then by multiple electricity Xie Chi forms extensive electrolytic tank of solid oxide by connection in series-parallel combination, and operating temperature range is 600 DEG C -1000 DEG C, Working pressure range is 0.1MPa-20MPa；The SOFC (4), single fuel electricity is formed by anode, negative electrode and solid oxide electrolyte Pond, extensive SOFC, operating temperature are then formed by connection in series-parallel combination by multiple fuel cells Scope is 600 DEG C -1000 DEG C, working pressure range 0.1MPa-20MPa.
- 8. the electrolysis water method for producing oxygen through based on solid oxide electrolyte according to claim 4, it is characterised in thatThe poor H2/H2O gaseous mixtures, 100 DEG C of H is more than for temperature2/H2O mixed gas, wherein H2Molar fraction be less than 0.3.The rich H2/H2O gaseous mixtures, 100 DEG C of H is more than for temperature2/H2O mixed gas, wherein H2Molar fraction be more than 0.7.
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| CN105449250B (en) * | 2015-12-17 | 2018-03-06 | 中国科学院上海硅酸盐研究所 | A kind of multikilowatt reversible solid oxide fuel cell electrolytic cell test system |
| CN105845962B (en) * | 2016-03-30 | 2019-01-18 | 华中科技大学 | Solid oxide fuel cell and electrolytic tank of solid oxide combined generating system |
| CN105888787B (en) * | 2016-04-26 | 2018-06-19 | 淮南师范学院 | It is a kind of for device of vehicle maintenance service and preparation method thereof |
| CN109485044A (en) * | 2017-09-12 | 2019-03-19 | 陈志强 | Submarine fresh water air safeguards system and its method |
| CN111005029A (en) * | 2019-12-31 | 2020-04-14 | 广东省新材料研究所 | Electrolytic aquatic product gas pressure self-balancing device and application thereof |
| CN112410801A (en) * | 2021-01-22 | 2021-02-26 | 四川大学 | Water electrolysis hydrogen production system of current source type PWM rectifier and control method |
| WO2023082363A1 (en) * | 2021-11-12 | 2023-05-19 | 中国科学院大连化学物理研究所 | Efficient oxyhydrogen generation device for medical care, and method therefor |
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| CN205024329U (en) * | 2015-09-22 | 2016-02-10 | 中国华能集团清洁能源技术研究院有限公司 | Electrolysis water preparing oxygen system based on solid oxide electrolyte |
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| JP3294088B2 (en) * | 1995-11-15 | 2002-06-17 | 三菱重工業株式会社 | Fuel cell system |
| US6017646A (en) * | 1998-06-03 | 2000-01-25 | Praxair Technology, Inc. | Process integrating a solid oxide fuel cell and an ion transport reactor |
| US6610193B2 (en) * | 2000-08-18 | 2003-08-26 | Have Blue, Llc | System and method for the production and use of hydrogen on board a marine vessel |
| JP2002098009A (en) * | 2000-09-27 | 2002-04-05 | Honda Motor Co Ltd | Vehicle traveling mechanism and vehicle loaded with it |
| JP2003017083A (en) * | 2001-06-29 | 2003-01-17 | Toshiba Eng Co Ltd | Micro hydraulic-fuel cell power generating system |
| US7276306B2 (en) * | 2003-03-12 | 2007-10-02 | The Regents Of The University Of California | System for the co-production of electricity and hydrogen |
| JP2005232521A (en) * | 2004-02-18 | 2005-09-02 | Ebara Corp | Method and device for producing hydrogen |
| US7381313B2 (en) * | 2005-06-30 | 2008-06-03 | General Electric Company | Integrated hydrogen production and processing system and method of operation |
| US8293412B2 (en) * | 2007-11-20 | 2012-10-23 | Bloom Energy Corporation | Enhanced efficiency of a combined SORFC energy storage and fuel generation system |
| CN102695670B (en) * | 2009-09-08 | 2016-02-24 | 俄亥俄州立大学研究基金会 | There is the reformation/water-splitting of integrated carbon trapping and integrated for the electro-chemical systems that generates electricity |
| JP5792560B2 (en) * | 2011-08-25 | 2015-10-14 | シャープ株式会社 | Power generation system |
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