CN115650168A - Material and method for hydrogen production by methane chemical looping in cooperation with carbon dioxide capture - Google Patents
Material and method for hydrogen production by methane chemical looping in cooperation with carbon dioxide capture Download PDFInfo
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- CN115650168A CN115650168A CN202211180617.7A CN202211180617A CN115650168A CN 115650168 A CN115650168 A CN 115650168A CN 202211180617 A CN202211180617 A CN 202211180617A CN 115650168 A CN115650168 A CN 115650168A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 134
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000001257 hydrogen Substances 0.000 title claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 68
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000006722 reduction reaction Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 238000002309 gasification Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 239000012876 carrier material Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002407 reforming Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
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Abstract
The invention discloses a material and a method for the cooperation of methane chemical looping hydrogen production and carbon dioxide capture, relates to the technical field of chemical looping hydrogen production, and solves the problems of complex process flow and CO generation in the chemical looping hydrogen production process 2 The technical problem that the concentrated capture and separation are difficult is solved by adopting Ni and Fe 2 O 3 And Al 2 O 3 The composite oxygen carrier and methane are subjected to reduction reaction in a reduction reactor to generate high-purity carbon dioxide and water vapor; in the hydrogen production stage, the reduced oxygen carrier material reacts with water vapor to produce molten iron to produce hydrogen, and high-purity hydrogen is obtained. According to the process, the carbon deposition gasification and secondary reduction steps are increased by controlling the height-diameter ratio of the composite oxygen carrier material, and the problem of cycle performance reduction caused by serious carbon deposition is solved; further by chemical chainsThe hydrogen production and the carbon dioxide and hydrogen are synchronously separated, so that the purity and the yield of the carbon dioxide and the hydrogen are improved, and the carbon dioxide is synchronously separated and collected in the hydrogen production process, so that the low-carbon hydrogen production is realized.
Description
Technical Field
The application relates to the technical field of chemical-looping hydrogen production, in particular to a material and a method for co-trapping carbon dioxide in hydrogen production of a methane chemical looping.
Background
At present, the hydrogen production by methane steam reforming is the most widely applied hydrogen production technology in industry. Firstly, methane and water vapor are subjected to partial oxidation reaction to generate methane, and the methane is subjected to medium-temperature water vapor conversion and low-temperature water vapor conversion to generate CO 2 And H 2 And (3) decarbonizing the mixed gas through VPSA, PSA multistage pressure swing adsorption and other series of process flows to finally obtain the high-purity hydrogen. In conclusion, the hydrogen production by methane reforming is a very complicated process, a plurality of unit devices such as a reforming reactor, a medium-temperature shift converter, a low-temperature shift converter, an adsorption tower and the like are needed, the initial investment cost is huge, and the thermal efficiency of the system is generally less than 60%. In addition, because the reforming hydrogen production process has long flow and is difficult to realize miniaturization distribution, the scale of the established reforming hydrogen production project is generally in the ten-thousand ton class/year. The reforming and decarbonization links involve direct combustion of large amounts of methane and low concentrations of carbon dioxideAdsorption separation, the emission of carbon dioxide exceeds 12kg per 1kg of hydrogen produced, the carbon emission reduction intensity is very high, and at present, because the higher carbon emission of the ash hydrogen preparation technology such as reforming hydrogen production and the like is listed in partial regional restriction development catalogues, a clean, low-carbonization and low-cost multi-element hydrogen production system is urgently required to be constructed.
The chemical looping hydrogen production technology is a novel hydrogen production method derived from chemical looping combustion, and hydrogen with higher purity can be generally prepared by the method. The hydrogen production process is divided into a reduction stage and an oxidation stage, and in the reduction stage, fuel and oxygen carrier react in a reactor to generate CO 2 And H 2 O, the gas phase product of the stage can obtain high-purity CO after being condensed 2 (ii) a In the oxidation stage, water vapor reacts with the reduced oxygen carrier in the reactor, and outlet gas is condensed to generate high-purity H 2 And then, the oxygen carrier after the water vapor oxidation is reacted with air and further oxidized into an initial oxygen carrier, so that the next reaction cycle is carried out. The fuel used is typically methane or biomass. The chemical chain hydrogen production technology has the advantage that CO is produced 2 And H yield 2 The processes are respectively carried out, so that the separation of time and space for preparing the two gases is realized, the difficulty in carbon capture is greatly reduced, the problem that carbon emission is difficult to treat in the traditional hydrogen production process is solved, and the clean hydrogen production of fossil fuel is realized. And a large amount of heat released in the air oxidation process can be used for heat supply and power generation, so that the overall energy utilization efficiency of the system is improved.
The circulation reaction process route of the methane chemical looping hydrogen production also has obvious influence on the performance of the circulation reaction process route, and the current mainstream multi-reactor is found in the circulation continuous operation, on one hand, the mainstream methane chemical looping hydrogen production technology is easy to generate carbon deposition in the reduction stage and is difficult to separate in the process flow level; on the other hand, CO at the outlet of the reactor 2 The concentration is low, thereby CO in the process of preparing hydrogen from methane cannot be realized 2 Enrichment of gases, which leads to high CO 2 High H 2 The selectivity becomes a technical problem and is not favorable for CO 2 Concentrated capture and separation.
Disclosure of Invention
The application provides a material and a method for methane chemical looping hydrogen production and carbon dioxide capture, and the technical purpose is to solve the problems of complex process flow and CO in the chemical looping hydrogen production process 2 Difficult to collect and separate.
The technical purpose of the application is realized by the following technical scheme:
a material for the chemical chain hydrogen production of methane and the capture of carbon dioxide is prepared from Ni and Fe 2 O 3 And Al 2 O 3 In the composite oxygen carrier of (1), wherein Al 2 O 3 39-57% of Fe 2 O 3 The mass percentage of the content is 40-60%, and the mass percentage of the Ni content is 1-3%.
Further, the composite oxygen carrier is in a granular shape, and the diameter of the granules of the composite oxygen carrier is 2-3mm.
A method for the hydrogen production of methane chemical looping in coordination with the capture of carbon dioxide is realized by any one of the composite oxygen carriers, and comprises the following steps:
s1: loading the composite oxygen carrier into a reaction bed of a reactor 1 and a regeneration bed of a reactor 2, and heating both the reactor 1 and the reactor 2 to 850-950 ℃; opening a methane inlet valve and an air outlet valve of the reactor 1, replacing air in the reactor 1 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 1 when the oxygen concentration of an air outlet of the reactor 1 is lower than 1%;
s2: opening a methane inlet valve and a carbon dioxide outlet valve of the reactor 1, starting the reduction reaction of the reactor 1, condensing and compressing outlet gas at a carbon dioxide outlet of the reactor 1, and entering a carbon dioxide storage tank, and closing the methane inlet valve and the carbon dioxide outlet valve of the reactor 1 when the CO concentration detected at the carbon dioxide outlet of the reactor 1 exceeds 1%; opening a methane inlet valve and an air outlet valve of the reactor 2 while the reactor 1 is in reduction reaction, replacing air in the reactor 2 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 2 when the oxygen concentration of an air outlet of the reactor 2 is lower than 1%;
s3: opening a steam inlet valve and a carbon dioxide outlet valve of the reactor 1, performing a carbon deposition gasification stage, condensing and compressing gas at a carbon dioxide outlet of the reactor 1, and entering a carbon dioxide storage tank, and closing the carbon dioxide outlet valve of the reactor 1 when the concentration of the carbon dioxide at the carbon dioxide outlet of the reactor 1 is lower than 1%;
s4: opening a hydrogen outlet valve of the reactor 1, starting hydrogen production and air reaction in the reactor 1, introducing gas at a hydrogen outlet of the reactor 1 into a hydrogen storage tank through a condenser and purification, and closing a steam inlet valve and a hydrogen outlet valve of the reactor 1 after a hydrogen detector at the hydrogen outlet of the reactor 1 detects that the hydrogen concentration is lower than 3%; then opening an air inlet valve and an air outlet valve of the reactor 1, closing the air inlet valve of the reactor 1 after reacting for a period of time, opening a methane inlet valve of the reactor 1, replacing air in the reactor 1 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 1 when the oxygen concentration of an air outlet of the reactor 1 is lower than 1%; opening a methane inlet valve and a carbon dioxide outlet valve of the reactor 2 while the reactor 1 performs hydrogen production and air reaction, starting reduction reaction in the reactor 2, and closing the methane inlet valve and the carbon dioxide outlet valve of the reactor 2 after the CO concentration detected at the carbon dioxide outlet of the reactor 2 exceeds 1%;
s5: reactor 1 was operated interchangeably with reactor 2, and steps S3 to S5 were cycled.
Further, the composite oxygen carrier is filled in the reactor 1 and the reactor 2 in a fixed bed mode, and the height-diameter ratio of the bed layer is 5.
Further, in step S1, both the reactor 1 and the reactor 2 were heated to 900 ℃.
The beneficial effect of this application lies in: the material and the method for hydrogen production by methane chemical looping and carbon dioxide capture are characterized in that Ni and Fe are used 2 O 3 And Al 2 O 3 The composite oxygen carrier and methane are subjected to reduction reaction in a reduction reactor to generate high-purity carbon dioxide and water vapor, carbon is deposited on the surface of the composite oxygen carrier, and the high-purity dioxygen can be obtained through simple separationCarbonizing carbon; in the carbon deposition gasification and secondary reduction stage, the carbon deposition on the surface of the composite oxygen carrier material is subjected to carbohydrate reaction in a steam atmosphere and converted into carbon dioxide; in the hydrogen production stage, the reduced oxygen carrier material further reacts with water vapor to produce molten iron to prepare hydrogen, and high-purity hydrogen is obtained through simple condensation; and in the air oxidation stage, the oxygen carrier material is oxidized and regenerated in an air reactor to carry out the next cycle reaction.
Compared with the traditional methane chemical looping hydrogen production process, the process increases the steps of carbon deposition gasification and secondary reduction by controlling the height-diameter ratio of the composite oxygen carrier material, and solves the problem of cycle performance reduction caused by serious carbon deposition; the chemical chain is adopted for further hydrogen production, carbon dioxide and hydrogen are synchronously separated, the purity and the yield of the carbon dioxide and the hydrogen are improved, the concentration of the hydrogen and the concentration of the carbon dioxide reach more than 95%, and the carbon dioxide is synchronously separated and trapped in the hydrogen production process, so that low-carbon hydrogen production is realized.
Simultaneously, this application adopts switching formula fixed bed device design, need not frequent change and the interior compound oxygen carrier of mobile device, compares in mainstream circulating fluidized bed reactor design, and the device degree of wear reduces by a wide margin, and life improves 60%.
Drawings
FIG. 1 is a process flow diagram of a method described herein;
FIG. 2 is a schematic diagram of an apparatus used in the method of the present application;
in the figure: 1-reactor (reaction bed), 2-reactor (regeneration bed), 3-methane inlet, 4-steam inlet, 5-air inlet, 6-carbon dioxide outlet, 7-hydrogen outlet, 8-oxygen-deficient air outlet, 9-reactor 1 steam valve, 10-reactor 1 air valve, 11-reactor 1 methane valve, 12-reactor 2 steam valve, 13-reactor 2 air valve, 14-reactor 2 methane valve, 15-reactor 1 carbon dioxide valve, 16-reactor 1 oxygen-deficient air valve, 17-reactor 1 hydrogen valve, 18-reactor 2 carbon dioxide valve, 19-reactor 2 oxygen-deficient air valve, 20-reactor 2 hydrogen valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it should be noted that the described embodiments are part of the embodiments of the present invention, not all of the embodiments, and are not limited to laboratory operations.
Example 1:
the composite oxygen carrier material and the method process are utilized to carry out chemical looping hydrogen production, and 134g of the composite oxygen carrier material containing Ni and Fe is taken 2 O 3 And Al 2 O 3 The composite oxygen carrier is respectively arranged in a reactor 1 (reaction bed) and a reactor 2 (regeneration bed), and Al in the composite oxygen carrier is calculated according to the mass percentage content 2 O 3 Content of (2%) 39% Fe 2 O 3 The content of (2) is 60% and the content of Ni is 1%. The specific steps are shown in fig. 1 and comprise:
s1: opening a methane inlet valve and a carbon dioxide outlet valve of the reactor 1, controlling the temperature of the reactor 1 to be 850 ℃, introducing methane into a methane inlet of the reactor 1 at a flow rate of 200ml/min, starting the reduction reaction of the reactor 1, condensing and compressing outlet gas of a carbon dioxide outlet of the reactor 1 into a carbon dioxide storage tank, and closing a three-dimensional methane inlet valve and a three-dimensional carbon dioxide outlet valve of the reactor 1 when the CO concentration detected by the carbon dioxide outlet of the reactor 1 exceeds 1%.
S2: while the reactor 1 is carrying out the reduction reaction, the reactor 2 opens the methane inlet valve and the air outlet valve, replaces the air in the reactor 2 with methane, and closes the methane inlet valve and the air outlet valve of the reactor 2 when the oxygen concentration at the air outlet of the reactor 2 is lower than 1%.
S3: and opening a steam inlet valve and a carbon dioxide outlet valve of the reactor 1 to perform a carbon deposition gasification stage, condensing and compressing outlet gas at a carbon dioxide outlet of the reactor 1 into a carbon dioxide storage tank, and closing the carbon dioxide outlet valve of the reactor 1 when the concentration of carbon dioxide at the carbon dioxide outlet of the reactor 1 is lower than 1%.
S4: and opening a hydrogen outlet valve of the reactor 1, increasing the hydrogen concentration along with the reaction, allowing outlet gas at a hydrogen outlet of the reactor 1 to enter a hydrogen storage tank through a condenser and purification, and closing a steam inlet valve and a hydrogen outlet valve of the reactor 1 after a hydrogen detector at the hydrogen outlet of the reactor 1 detects that the hydrogen concentration is lower than 3%. And then opening an air inlet valve and an air outlet valve of the reactor 1, closing the air inlet valve of the reactor 1 after reacting for a period of time, opening a methane inlet valve of the reactor 1, replacing air in the reactor 1 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 1 when the oxygen concentration of an air outlet of the reactor 1 is lower than 1%. When the reactor 1 is used for hydrogen production and air reaction, a methane inlet valve and a carbon dioxide outlet valve of the reactor 2 are opened, the reactor 2 starts to perform reduction reaction, and the methane inlet valve and the carbon dioxide outlet valve of the reactor 2 are closed when the CO concentration detected at the carbon dioxide outlet of the reactor 2 exceeds 1 percent.
S5: and (3) operating the reactor 1 and the reactor 2 interchangeably, and circulating the processes of the steps S3, S4 and S5.
Example 2:
the procedure is as in example 1, except that the temperature of the reactor in step S1 is adjusted to 900 ℃.
Example 3:
the procedure is as in example 1, except that the temperature of the reactor in step S1 is adjusted to 950 ℃.
Example 4:
taking 134g of Ni and Fe 2 O 3 And Al 2 O 3 The composite oxygen carrier material is respectively filled into a reactor 1 (reaction bed) and a reactor 2 (regeneration bed), and Al in the composite oxygen carrier is calculated according to the mass percentage content 2 O 3 Content of (b) 50% Fe 2 O 3 The content of (B) is 50%.
The procedure is as in example 1, except that the temperature of the reactor in step S1 is adjusted to 900 ℃.
Example 5:
taking 134g of Fe 2 O 3 And Al 2 O 3 The composite oxygen carrier material is respectively filled into a reactor 1 (reaction bed) and a reactor 2 (regeneration bed) according to the massCalculating the content of the weight percentage, and Al in the composite oxygen carrier 2 O 3 Content of (1%) 57% Fe 2 O 3 The content of (2) is 40%, and the content of Ni is 3%.
The procedure is as in example 1, except that the temperature of the reactor in step S1 is adjusted to 900 ℃.
Comparative example 1:
chemical chain hydrogen production is carried out on a single reactor fixed bed, wherein the oxygen carrier contains Ni and Fe 2 O 3 And Al 2 O 3 The composite oxygen carrier material. Calculated according to the mass percentage content, al in the composite oxygen carrier 2 O 3 39% of (C), fe 2 O 3 The content of (2) is 60% and the content of Ni is 1%. Containing Ni and Fe 2 O 3 And Al 2 O 3 The composite oxygen carrier material 134g is loaded into a reactor, the temperature of the reactor is controlled to be 900 ℃, methane is introduced at the flow rate of 200ml/min, a methane inlet valve is closed after the CO concentration detected at the outlet of the reactor exceeds 1%, and then nitrogen is introduced to purge until the carbon dioxide concentration is below 3%. And then introducing water vapor at the flow rate of 1ml/min, wherein nitrogen is used as carrier gas, the flow rate is 300ml/min, and after the reaction is carried out until the concentration of hydrogen in outlet gas is reduced to 10%, the nitrogen is switched to purge until the concentration of hydrogen is below 3%. Subsequently, air was introduced at a flow rate of 1L/min until the oxygen concentration increased to 20.5%. And repeating the steps.
The gas concentrations were monitored using an ABB gas analyzer. The methane conversion and single cycle time in each example and comparative example are shown in table 1.
TABLE 1
| Serial number | CH 4 Conversion (%) | CO 2 Maximum concentration (%) | Single cycle time (min) |
| Example 1 | 100 | 97.2 | 31 |
| Example 2 | 100 | 98.5 | 25 |
| Example 3 | 100 | 98.4 | 23 |
| Example 4 | 90 | 93.6 | 27 |
| Example 5 | 98 | 98.1 | 34 |
| Comparative example 1 | 82 | 63.3 | 74 |
From table 1, it can be seen that the cycle time of the composite oxygen carrier passing through two reactors in the method of the present application is much shorter than that of a single reactor, and the conversion rate of methane can even reach 100%, and carbon dioxide with high concentration can be separated out.
Claims (5)
1. A material for co-capturing carbon dioxide in cooperation with hydrogen production through a methane chemical chain is characterized by comprising Ni and Fe 2 O 3 And Al 2 O 3 In the composite oxygen carrier of (1), wherein Al 2 O 3 The mass percentage of the content is 39-57 percent, fe 2 O 3 The mass percentage of the content is 40-60%, and the mass percentage of the Ni content is 1-3%.
2. The material of claim 1, wherein the composite oxygen carrier is in the form of particles having a particle diameter of 2-3mm.
3. A method for the hydrogen production by methane chemical looping in cooperation with carbon dioxide capture, which is realized by the composite oxygen carrier of any one of claims 1-2, and is characterized by comprising the following steps:
s1: loading the composite oxygen carrier into a reaction bed of a reactor 1 and a regeneration bed of a reactor 2, and heating the reactor 1 and the reactor 2 to 850-950 ℃; opening a methane inlet valve and an air outlet valve of the reactor 1, replacing air in the reactor 1 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 1 when the oxygen concentration of an air outlet of the reactor 1 is lower than 1%;
s2: opening a methane inlet valve and a carbon dioxide outlet valve of the reactor 1, starting the reduction reaction of the reactor 1, condensing and compressing outlet gas at a carbon dioxide outlet of the reactor 1 to enter a carbon dioxide storage tank, and closing the methane inlet valve and the carbon dioxide outlet valve of the reactor 1 when the CO concentration detected at the carbon dioxide outlet of the reactor 1 exceeds 1%; opening a methane inlet valve and an air outlet valve of the reactor 2 while the reactor 1 performs the reduction reaction, replacing air in the reactor 2 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 2 when the oxygen concentration of an air outlet of the reactor 2 is lower than 1%;
s3: opening a steam inlet valve and a carbon dioxide outlet valve of the reactor 1, carrying out a carbon deposition gasification stage, condensing and compressing gas at a carbon dioxide outlet of the reactor 1, and entering a carbon dioxide storage tank, and closing the carbon dioxide outlet valve of the reactor 1 when the concentration of the carbon dioxide at the carbon dioxide outlet of the reactor 1 is lower than 1%;
s4: opening a hydrogen outlet valve of the reactor 1, starting hydrogen production and air reaction in the reactor 1, introducing gas at a hydrogen outlet of the reactor 1 into a hydrogen storage tank through a condenser and purification, and closing a steam inlet valve and a hydrogen outlet valve of the reactor 1 after a hydrogen detector at the hydrogen outlet of the reactor 1 detects that the hydrogen concentration is lower than 3%; then opening an air inlet valve and an air outlet valve of the reactor 1, closing the air inlet valve of the reactor 1 after reacting for a period of time, opening a methane inlet valve of the reactor 1, replacing air in the reactor 1 with methane, and closing the methane inlet valve and the air outlet valve of the reactor 1 when the oxygen concentration of an air outlet of the reactor 1 is lower than 1%; opening a methane inlet valve and a carbon dioxide outlet valve of the reactor 2 while the reactor 1 performs hydrogen production and air reaction, starting reduction reaction in the reactor 2, and closing the methane inlet valve and the carbon dioxide outlet valve of the reactor 2 after the CO concentration detected at the carbon dioxide outlet of the reactor 2 exceeds 1%;
s5: reactor 1 and reactor 2 were operated interchangeably and step S3 to step S5 were cycled.
4. The method of claim 1, wherein the composite oxygen carrier is packed in the form of a fixed bed in the reactor 1 and the reactor 2, and the ratio of the height to the diameter of the bed is 5.
5. The method of claim 1, wherein in step S1, both reactor 1 and reactor 2 are warmed to 900 ℃.
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| CN103450966A (en) * | 2013-09-16 | 2013-12-18 | 华北电力大学 | Oxygen carrier for step-by-step methane catalysis for chemical looping combustion and preparation method thereof |
| CN107804824A (en) * | 2017-11-09 | 2018-03-16 | 东南大学 | A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method |
| CN111087026A (en) * | 2019-12-31 | 2020-05-01 | 天津大学 | Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof |
| CN113753857A (en) * | 2021-08-20 | 2021-12-07 | 清华大学 | Process for preparing high-purity hydrogen by methane-containing combustible gas reforming coupling chemical chain and application |
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- 2022-09-27 CN CN202211180617.7A patent/CN115650168A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450966A (en) * | 2013-09-16 | 2013-12-18 | 华北电力大学 | Oxygen carrier for step-by-step methane catalysis for chemical looping combustion and preparation method thereof |
| CN107804824A (en) * | 2017-11-09 | 2018-03-16 | 东南大学 | A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method |
| CN111087026A (en) * | 2019-12-31 | 2020-05-01 | 天津大学 | Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof |
| CN113753857A (en) * | 2021-08-20 | 2021-12-07 | 清华大学 | Process for preparing high-purity hydrogen by methane-containing combustible gas reforming coupling chemical chain and application |
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