CN105836705B - Integrated suitching type hydrogen production of chemical chain device and hydrogen production process - Google Patents
Integrated suitching type hydrogen production of chemical chain device and hydrogen production process Download PDFInfo
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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
Abstract
The invention discloses a kind of integrated suitching type hydrogen production of chemical chain devices, including an integrated chemical chain reaction device and two CaO reactors, it is divided into three reactors inside integrated chemical chain reaction device, each reactor is respectively equipped with five imports and five outlets, CaO reactors are respectively equipped with an import and two outlets, and the inlet and outlet is connected by valve from different gas pipings.Device using the present invention, hydrogen manufacturing is realized in the cyclic process can be reduced by oxygen carrier, aoxidized, it will react and be divided into three identical stages of reaction of reaction duration, and three reactors inside integrated chemical chain reaction device is controlled to be respectively at the different stages, so as to fulfill the cycle and continuous production of hydrogen manufacturing.The device of the invention realizes the immobilized reactant of oxygen carrier, avoids the abrasion that oxygen carrier flows initiation in each reactor, improves oxygen carrier utilization rate；It is ingenious in design, the heat transfer between reactor is strengthened, realizes continuous production.
Description
Technical field
The present invention relates to a kind of integrated suitching type hydrogen production of chemical chain apparatus and method, especially a kind of band CO2What is captured cuts
Change formula hydrogen production of chemical chain System and method for.
Background technology
19 generation are supported as fossil energies such as the important substance basis of human survival and development, coal, oil, natural gases
It records to 20th century progress of human civilization and socio-economic development over nearly 200 years.However, as the main of current whole world consumption
The energy, traditional fossil energy not only obtain energy during utilization, can also generate a large amount of CO2, cause " greenhouse effects ".
Therefore, strengthen CO2Trapping and sealing up for safekeeping seem and be even more important that there is an urgent need to the novel clean and effective usings energy source of research and development
Mode.
Nineteen eighty-three, Germany scientist Richter and Knoche are put forward for the first time burning chemistry chains（chemical looping
Combustion, CLC）Concept.The difference of the combustion technology and common combustion technology maximum is not directly using in air
Oxygen molecule, but the combustion process of fuel, combustion product are completed using the oxygen atom in oxygen carrier（Mainly CO2And water
Steam）It will not be diluted and very high concentrations by the nitrogen in air, be that can obtain almost pure CO by simple condensation2, it is simple and
Realize CO to low energy consumption2Separation and trapping；In addition, due to fuel reactor and the running temperature of air reactor relatively
It is low, generated in air reactor almost without thermal NO x and Quick-type NOx, and in fuel reactor, due to not with oxygen
Contact is generated without fuel type NOx.
Hydrogen receives close concern as pollution-free, the environmental-friendly economy energy, there is extensive purposes.Mirror
In the CO of burning chemistry chains method2The characteristics of interior separation, applied chemistry chain combustion method hydrogen manufacturing also become a current research heat
Point.It is similar with CLC processes, air reactor is introduced to complete the regeneration of oxygen carrier instead of air as oxidant with vapor,
Vapor is also reduced generation hydrogen simultaneously.A large amount of research is carried out to hydrogen production of chemical chain oxygen carrier, but right both at home and abroad at present
The research of hydrogen production of chemical chain apparatus and system is less.Chinese patent CN103113917A discloses a kind of solid fuel chemistry chain gasification
The System and method for of hydrogen manufacturing not only includes fuel reactor, air reactor, synthesis gas converting means, CO in system2Absorption is single
Member, calcining furnace etc., there are four gas-solid separating devices, and flow is complicated, and oxygen carrier recycles between different devices, and abrasion is tight
Weight, utilization rate are relatively low.Chinese patent CN102198934A discloses a kind of producing hydrogen by using chemical chain and its device, agent structure packet
Fuel reactor, vapor reactor and air reactor are included, oxygen carrier recycles in 3 reactors, and flow is relatively easy, but
There are the wear problems of oxygen carrier, thereby increases and it is possible to have portion gas back-mixing.The Fan L-S seminars in the U.S.（Fuel 103 2013：
495-505）The experimental rig of 25KWth scales has been built up, has employed counter-flow moving bed fuel reactor and vapor reactor
And the air reactor of fluid bed, the operating of 300h is completed, but there is also the problem of oxygen carrier abrasion.
For hydrogen production of chemical chain systematic account mostly all for mutually independent fluid bed or moving-burden bed reactor, mutually it
Between inhale heat release mismatch and oxygen carrier all inevitably result from wear problem in different reactor cyclic process, lead
Oxygen carrier utilization rate is caused to decline.It is had not been reported at present using integrated suitching type fixed bed hydrogen production of chemical chain system and method.
Invention content
There is suction heat release mismatch and oxygen carrier in differential responses to solve hydrogen production of chemical chain device in the prior art
Cycle can generate abrasion between device, and oxygen carrier utilization rate is led to problems such as to decline, and the present invention intends providing a kind of integrated suitching type chemistry
Chain device for producing hydrogen and the method using its hydrogen manufacturing strengthen the heat transfer between reactor, avoid oxygen carrier between each reactor
Circulate, improve the utilization rate of oxygen carrier and reactor.
For realization more than technical purpose, present invention firstly provides a kind of integrated suitching type hydrogen production of chemical chain device, including
One integrated chemical chain reaction device and two CaO reactors are divided into three parts in the integrated chemical chain reaction device, respectively change
Learn chain reaction device I, chemical chain reaction device II and chemical chain reaction device III；Each reactor is respectively equipped with five imports and five go out
Mouthful, five imports of chemical chain reaction device I respectively by valve a, valve b, valve c, valve d and valve e and fuel gas pipeline,
Vapor pipeline, air pipe line, CO2Pipeline and I pipeline of gaseous mixture communicate, and five outlets of chemical chain reaction device I pass through respectively
Valve f, valve g, valve h, valve i and valve j and CO2With vapor pipeline, I pipeline of gaseous mixture, II pipeline of gaseous mixture, H2With
Vapor pipeline and oxygen denuded air pipeline communicate；Each inlet and outlet of chemical chain reaction device II and chemical chain reaction device III is also led to
Valve each pipeline with more than is crossed to communicate；The CaO reactors be respectively equipped with an import and two outlet, CaO reactors I into
Mouth is communicated by valve A with II pipeline of gaseous mixture, two outlet passes through valve B, valve C and CO respectively2With vapor pipeline,
H2It is communicated with vapor pipeline；Also by valve, each pipeline with more than communicates each inlet and outlet of CaO reactors II；Each pipeline
Direction flowing of the middle gas from chemical chain reaction device to CaO reactors.
Further, the integrated chemical chain reaction device inner route clapboard is adjacent and mutual two-by-two for three by its equipartition
Independent chemical chain reaction device.
Further, the CO2Connect condenser I with vapor pipeline end, then with CO2Pipeline connects.
Further, the H2Condenser II is connected, then connect with hydrogen collecting apparatus with vapor pipeline end.
The present invention also provides the method using the suitching type hydrogen production of chemical chain device hydrogen manufacturing, first in integrated chemical chain
Oxygen carrier is loaded in three reactors of reactor, CaO is loaded in CaO reactors, is operated according to the following steps：
The first step：Close all valves, after chemical chain reaction device I first is warming up to default reaction temperature, open valve a and
Valve f connects fuel gas pipeline and is passed through fuel gas, and with oxygen carrier precursor reactant, oxygen carrier is reduced, and reaction generation gas is CO2And H2O,
Into CO2And vapor pipeline；
Second step：With the intensification of oxygen carrier reducing degree, incomplete oxidation product CO and H can be generated2, at this point, closing
Valve f, opens valve g, and reaction generation gas bag includes CO2, vapor, CO, H2The fuel gas of reaction is had not occurred with some, is entered
I pipeline of gaseous mixture；
Third walks：After oxygen carrier is completely reduced in chemical chain reaction device I 1, valve a is closed, valve d is opened and opens,
Connect CO2Pipeline is passed through CO2It is purged, purges in tail gas and include CO2、CO、H2, fuel gas and vapor, pass through valve g
Into I pipeline of gaseous mixture；
4th step：After purging, valve d and valve g is closed, valve b and valve h are opened, and connect vapor pipeline
Vapor, starting stage, the H of the oxygen carrier generation of vapor and reduction-state are passed through into chemical chain reaction device I 12, in tail gas also
Contain CO remaining in previous step2The vapor of purge gass and surplus, enters II pipeline of gaseous mixture, at this time by valve h
Open valve A, the gas in II pipeline of gaseous mixture enter CaO reactors I or（"or" deletes）By CO2Pass through valve B after absorption
Into H2And vapor pipeline；
5th step：It treats in chemical chain reaction device I without CO2During discharge, valve h is closed, valve i is opened, only contains H in tail gas2
With superfluous vapor, into H2And vapor pipeline；
6th step：Treat that oxygen carrier cannot be by H2When O is further aoxidized, valve b and valve i is closed, opens valve c and valve
Door j connects air pipe line and air is passed through into chemical chain reaction device I, and air further aoxidizes oxygen carrier, chemical chain reaction device
I outlet tail gas is vapor remaining in the air and previous step of oxygen deprivation, and entering oxygen denuded air pipeline heel row by valve j amplifies
Gas；
7th step：After oxygen carrier is by air complete oxidation, valve c is closed, opens valve b, vapor pipeline is connected and leads to
Enter vapor to be purged, tail gas is the air and vapor of oxygen deprivation, and entering oxygen denuded air pipeline heel row by valve j amplifies
Gas；
8th step：After purging, valve b and valve j is closed, valve e and valve f is opened, in I pipeline of gaseous mixture
CO2, vapor, CO, H2Enter in chemical chain reaction device I with fuel gas gaseous mixture carry out it is fully oxidized, outlet tail gas be CO2With
Vapor, into CO2And vapor pipeline；After gas reaction in I pipeline of gas to be mixed, valve e is closed；Again from first
Step proceeds by circular response；
Each chemical chain reaction device is recycled according to the step of first step ~ eight step, wherein the 8th step, the first step are
In the complete oxidation stage, second and third and four steps are the generation mixed gas stage, and the five, the six and seven steps are water and air oxidation stage,
By controlling the loadings of oxygen carrier and the throughput of each air inlet pipeline, the reaction time for controlling the three above stage is identical, makes
Three chemical chain reaction devices are respectively at the different stages of reaction and circular response.
Further, as it will be apparent to a skilled person that when the CaO in CaO reactors I disappears in the 4th step
After consumption, CaO reactors II are switched to, while CaO reactors I are subjected to calcination processing, open valve B, CaCO3Decompose production
Angry body enters CO2And vapor pipeline；
Further, as it will be apparent to a skilled person that H2It is condensed with the gas in vapor pipeline
Device II is pure H after condensing2Product connects hydrogen collecting apparatus；CO2Be pure after the condensed device I of gas in vapor pipeline
Net CO2Product can be collected or by being passed through CO2Pipeline is recycled.
Further, as preference, the combustion gas is carbon containing gaseous fuel or is carbon containing at the reaction temperatures
Gaseous fuel, as preference, for CH4。
Further, the selection of the oxygen carrier is known to the skilled person, and is common metal oxygen carrier, is made
To be preferred, the active component of the oxygen carrier is CuO, NiO, Fe2O3、MnO2Or CoO, non-active carrier Al2O3、
MgAl2O4、SiO2、TiO2、ZrO2Or YSZ.
Compared with prior art, the present invention has the following advantages：
First, the present invention is using chemical chain reaction device in parallel, by the reaction type being switched into gas control reactor,
The immobilized reactant of oxygen carrier is realized, the abrasion that oxygen carrier flows initiation in each reactor is avoided, improves oxygen carrier
Utilization rate；
Second, three chemical chain reaction devices are integrated into a big reactor by the present invention, anti-in water and air oxidation
The heat that the reactor in the stage of answering is released can pass to the reactor that another two is in the endothermic reaction stage, enhance heat
It transmits；
Third, the present invention utilize the different phase of chemical chain reaction, by control the amount of fill of oxygen carrier, reaction temperature,
Charge flow rate etc. can control the time of each elementary reaction, and the gas generated to reaction is collected and handled respectively, carry out weight
It is multiple to utilize, and obtain pure H2, it is ingenious in design, continuous production is realized, improves reactor utilization rate.
Description of the drawings
Fig. 1, integrated suitching type hydrogen production of chemical chain schematic device of the invention；
Wherein, 1. chemical chain reaction device I, 2. chemical chain reaction devices II, 3. chemical chain reaction devices III, 4.CaO reactors I,
5.CaO reactors II, 7. condensers II, 8. condensers I, 10. valve a, 11. valve b, 12. valve c, 13. valve d, 14. valves
E, 15. valve f, 16. valve g, 17. valve h, 18. valve i, 19. valve j, 41. valve A, 42. valve B, 43. valve C, 61.
Fuel gas pipeline, 62. vapor pipelines, 63. air pipe lines, 64.CO2Pipeline, 65.CO2And vapor pipeline, 66. gaseous mixtures I
Pipeline, 67. gaseous mixture, II pipeline, 68.H2And vapor pipeline, 69. oxygen denuded air pipelines.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
As shown in Figure 1, the integrated suitching type hydrogen production of chemical chain device for the present invention, including an integrated chemical chain reaction
Device and two CaO reactors are equally divided into three reactors inside integrated chemical chain reaction device, and three reactors are adjacent two-by-two,
Each reactor is respectively equipped with five imports and five outlets, five imports of chemical chain reaction device I 1 respectively by valve a10,
Valve b11, valve c12, valve d13 and valve e14 and fuel gas pipeline 61, vapor pipeline 62, air pipe line 63, CO2Pipe
Road 64 and I pipeline 66 of gaseous mixture communicate, and five outlets of chemical chain reaction device I 1 pass through valve f15, valve g16, valve respectively
H17, valve i18 and valve j19 and CO2With vapor pipeline 65, I pipeline 66 of gaseous mixture, II pipeline 67 of gaseous mixture, H2It is steamed with water
Air pipe 68 and oxygen denuded air pipeline 69 communicate；Each inlet and outlet of chemical chain reaction device II 2 and chemical chain reaction device III 3
By valve, each pipeline communicates with more than；The CaO reactors are respectively equipped with an import and two outlets, CaO reactors I 4
Import communicated by valve A41 with II pipeline 67 of gaseous mixture, two outlet passes through valve B42, valve C43 and CO respectively2
With vapor pipeline 65, H2It is communicated with vapor pipeline 68；Similarly, each inlet and outlet of CaO reactors II 5 is also by valve
Door is communicated with above each pipeline；Direction flowing of the gas from chemical chain reaction device to CaO reactors in each pipeline.The CO2With
65 end of vapor pipeline connect condenser I 8, then with CO2Pipeline 64 connects.The H2It is connected with 68 end of vapor pipeline cold
Condenser II 7, then connect with hydrogen collecting apparatus.
Using the method for the suitching type hydrogen production of chemical chain device hydrogen manufacturing of the present invention, include the following steps：
The Fe of 40 ~ 60 mesh is loaded first in chemical chain reaction device2O3/Al2O3Oxygen carrier, loadings 10mL, in CaO
CaO is loaded in reactor, is operated according to the following steps：
The first step：All valves are closed, chemical chain reaction device I 1 under inert gas shielding is first warming up to 850 DEG C, is beaten
Valve opening door a10 and valve f15 connects fuel gas pipeline 61 and is passed through CH4, gas is passed through flow velocity as 10mL/min, anti-with oxygen carrier
Should, oxygen carrier is reduced, and reaction generation gas is CO2And H2O, into CO2With vapor pipeline 65；
Second step：After five minutes, valve f15 is closed in the intensification of oxygen carrier reducing degree, opens valve g16, reaction generation
Gas bag includes CO2, vapor, CO, H2The CH of reaction is had not occurred with some4, into I pipeline 66 of gaseous mixture；
Third walks：After five minutes, oxygen carrier is largely reduced to FeO, and oxygenated fuel ability declines to a great extent, and closes valve
A10 opens valve d13 and opens, connects CO2Pipeline 64 is passed through CO2It is purged, CO2Gas is passed through flow velocity as 20 ml/min, blows
It winds up and includes CO in gas2、CO、H2、CH4And vapor, I pipeline 66 of gaseous mixture is entered by valve g16；
4th step：After five minutes, CO2Gaseous mixture displacement in reactor is complete, valve d13 and valve g16 is closed, valve
Door b11 and valve h17 is opened, and connects vapor pipeline 62, vapor is passed through into chemical chain reaction device I 1, and it is 30 to be passed through flow velocity
The H that the oxygen carrier of ml/min, starting stage, vapor and reduction-state generates2, also containing CO remaining in previous step in tail gas2
The vapor of purge gass and surplus, enters II pipeline 67 of gaseous mixture by valve h17, opens valve A41, gaseous mixture II at this time
Gas in pipeline 67 enters CaO reactors I 4 by CO2H is entered by valve B43 after absorption2With vapor pipeline 68；
5th step：After five minutes, CO in chemical chain reaction device I 1 is treated2Purge gass have been replaced completely, close valve h17,
Valve i18 is opened, only contains H in tail gas2With superfluous vapor, into H2It is cold by condenser II 7 with vapor pipeline 68
H is collected after solidifying2；
6th step：After five minutes, treat that oxygen carrier cannot be by H2When O is further aoxidized, valve b11 and valve i18 is closed,
Valve c12 and valve j19 is opened, air pipe line 63 is connected and is passed through air into chemical chain reaction device I 1, it is 40 to be passed through flow velocity
Ml/min, air further aoxidize oxygen carrier, and it is residual in the air and previous step of oxygen deprivation that chemical chain reaction device I 1, which exports tail gas,
Remaining vapor enters 69 heel row of oxygen denuded air pipeline by valve j19 and amplifies gas；
7th step：After five minutes, after oxygen carrier is by air complete oxidation, valve c12 is closed, opens valve b11, is connected
Vapor pipeline 62 is passed through vapor and is purged, and is passed through flow velocity as 30 ml/min, and tail gas is the air and vapor of oxygen deprivation,
69 heel row of oxygen denuded air pipeline is entered by valve j19 and amplifies gas；
8th step：After five minutes, purging finishes, and air is replaced completely by vapor, is closed valve b11 and valve j19, is beaten
Valve opening door e14 and valve f15, the CO in I pipeline 66 of gaseous mixture2, vapor, CO, H2And CH4Gaseous mixture enters chemical chain reaction
Carried out in device I 1 it is fully oxidized, outlet tail gas be CO2And vapor, into CO2With vapor pipeline 65；After ten minutes, it is to be mixed
After gas reaction in I pipeline 66 of gas, valve e14 is closed；Again circular response is proceeded by from the first step；
Each chemical chain reaction device is recycled according to the step of first step ~ eight step, wherein the 8th step, the first step are
Complete oxidation stage, total duration are 15 minutes, second and third and four steps are the generation mixed gas stage, and total duration is also 15 minutes,
Five, the six and seven steps are water and air oxidation stage, and similarly, total duration is 15 minutes, control three chemical chain reaction devices point
Other places are in three different stages of reaction and circular response.
Wherein, CaO reactors II 5 are switched to after the CaO in CaO reactors I 4 is exhausted in the 4th step, simultaneously will
CaO reactors I 4 carry out calcination processing, open valve B42, CaCO3It decomposes generation gas and enters CO2With vapor pipeline 65.
H2It is pure H after being condensed with the condensed device II 7 of gas in vapor pipeline 682Product connects Hydrogen collection
Device.
CO2Be pure CO after the condensed device I 8 of gas in vapor pipeline 652Product is passed into CO2Pipeline 64
It is recycled.
Claims (10)
1. integrated suitching type hydrogen production of chemical chain device, which is characterized in that described device include integrated chemical chain reaction device and
Two CaO reactors are divided into three parts, respectively chemical chain reaction device I in the integrated chemical chain reaction device（1）, chemical chain
Reactor II（2）With chemical chain reaction device III（3）；Each reactor is respectively equipped with five imports and five outlets, and chemical chain is anti-
Answer device I（1）Five imports pass through valve a respectively（10）, valve b（11）, valve c（12）, valve d（13）With valve e（14）
With fuel gas pipeline（61）, vapor pipeline（62）, air pipe line（63）、CO2Pipeline（64）With I pipeline of gaseous mixture（66）Phase
It is logical, chemical chain reaction device I（1）Five outlets pass through valve f respectively（15）, valve g（16）, valve h（17）, valve i（18）
With valve j（19）With CO2And vapor pipeline（65）, I pipeline of gaseous mixture（66）, II pipeline of gaseous mixture（67）、H2With vapor pipe
Road（68）And oxygen denuded air pipeline（69）It communicates；Chemical chain reaction device II（2）With chemical chain reaction device III（3）Each import and go out
Also by valve, each pipeline communicates mouth with more than；The CaO reactors are respectively equipped with an import and two outlets, CaO reactions
Device I（4）Import pass through valve A（41）With II pipeline of gaseous mixture（67）It communicates, two outlet passes through valve B respectively（42）、
Valve C（43）With CO2And vapor pipeline（65）、H2And vapor pipeline（68）It communicates；CaO reactors II（5）Each import and
Also by valve, each pipeline communicates with more than for outlet；Direction stream of the gas from chemical chain reaction device to CaO reactors in each pipeline
It is dynamic.
2. the apparatus according to claim 1, which is characterized in that the integrated chemical chain reaction device inner route clapboard is averaged
It is divided into three adjacent two-by-two and mutually independent chemical chain reaction devices.
3. the apparatus according to claim 1, which is characterized in that the chemical chain reaction device is fixed bed reactors.
4. the apparatus according to claim 1, which is characterized in that the CO2And vapor pipeline（65）End connects condenser
Ⅰ（8）, then with CO2Pipeline（64）Connection.
5. the apparatus according to claim 1, which is characterized in that the H2And vapor pipeline（68）End connects condenser
Ⅱ（7）, then connect with hydrogen collecting apparatus.
6. utilize the method for the device hydrogen manufacturing described in any one in claim 1 ~ 5, which is characterized in that include the following steps：
Oxygen carrier is loaded in three reactors of integrated chemical chain reaction device first, CaO is loaded in CaO reactors, presses
Following steps operate：
The first step：All valves are closed, first by chemical chain reaction device I（1）After being warming up to default reaction temperature, valve a is opened
（10）With valve f（15）, connect fuel gas pipeline（61）Fuel gas is passed through, with oxygen carrier precursor reactant, oxygen carrier is reduced, reaction life
It is CO into gas2And H2O, into CO2And vapor pipeline（65）；
Second step：With the intensification of oxygen carrier reducing degree, incomplete oxidation product CO and H can be generated2, at this point, closing valve f
（15）, open valve g（16）, react generation gas bag and include CO2, vapor, CO, H2The fuel gas of reaction is had not occurred with some, into
Enter I pipeline of gaseous mixture（66）；
Third walks：When chemical chain reaction device I（1）After middle oxygen carrier is completely reduced, valve a is closed（10）, open valve d（13）
It opens, connects CO2Pipeline（64）It is passed through CO2It is purged, purges in tail gas and include CO2、CO、H2, fuel gas and vapor,
Pass through valve g（16）Into I pipeline of gaseous mixture（66）；
4th step：After purging, by valve d（13）With valve g（16）It closes, valve b（11）With valve h（17）It opens, connects
Water flowing vapor line（62）To chemical chain reaction device I（1）In be passed through vapor, the starting stage, the oxygen carrier of vapor and reduction-state
The H that body generates2, also containing CO remaining in previous step in tail gas2The vapor of purge gass and surplus, passes through valve h（17）
Into II pipeline of gaseous mixture（67）, valve A is opened at this time（41）, II pipeline of gaseous mixture（67）In gas enter CaO reactors I
（4）, by CO2Pass through valve B after absorption（42）Into H2And vapor pipeline（68）；
5th step：Treat chemical chain reaction device I（1）Middle no CO2During discharge, valve h is closed（17）, open valve i（18）, in tail gas
Only contain H2With superfluous vapor, into H2And vapor pipeline（68）；
6th step：Treat that oxygen carrier cannot be by H2When O is further aoxidized, by valve b（11）With valve i（18）It closes, opens valve c
（12）With valve j（19）, connect air pipe line（63）To chemical chain reaction device I（1）In be passed through air, air is by oxygen carrier into one
Step oxidation, chemical chain reaction device I（1）Tail gas is exported as vapor remaining in the air and previous step of oxygen deprivation, passes through valve j
（19）Into oxygen denuded air pipeline（69）Heel row amplifies gas；
7th step：After oxygen carrier is by air complete oxidation, valve c is closed（12）, open valve b（11）, connect vapor pipe
Road（62）It is passed through vapor to be purged, tail gas is the air and vapor of oxygen deprivation, passes through valve j（19）Into oxygen denuded air pipe
Road（69）Heel row amplifies gas；
8th step：After purging, valve b is closed（11）With valve j（19）, open valve e（14）With valve f（15）, mixing
I pipeline of gas（66）In CO2, vapor, CO, H2Enter chemical chain reaction device I with fuel gas gaseous mixture（1）It is middle to carry out abundant oxygen
Change, outlet tail gas is CO2And vapor, into CO2And vapor pipeline（65）；I pipeline of gas to be mixed（66）In gas reaction
After, close valve e（14）；Again circular response is proceeded by from the first step；
Each chemical chain reaction device is recycled according to the step of first step ~ eight step, wherein the 8th step, the first step are complete
Oxidation stage, second and third and four steps are the generation mixed gas stage, and the five, the six and seven steps are water and air oxidation stage, are passed through
The loadings of oxygen carrier and the throughput of each air inlet pipeline are controlled, the reaction time for controlling the three above stage is identical, makes three
Chemical chain reaction device is respectively at the different stages of reaction and circular response.
7. according to the method described in claim 6, it is characterized in that, when CaO reactors I in the 4th step（4）In CaO run out of
Bi Hou switches to CaO reactors II（5）, while by CaO reactors I（4）Calcination processing is carried out, opens valve B（42）, CaCO3
It decomposes generation gas and enters CO2And vapor pipeline（65）.
8. according to the method described in claim 6, it is characterized in that, CO2And vapor pipeline（65）In the condensed device I of gas
（8）It is pure CO afterwards2Product is collected or by being passed through CO2Pipeline（64）It is recycled.
9. according to the method described in claim 6, it is characterized in that, the fuel gas is CH4。
10. according to the method described in claim 6, it is characterized in that, the oxygen carrier be metal oxygen carrier, the oxygen carrier
Active component is CuO, NiO, Fe2O3、MnO2Or CoO, non-active carrier Al2O3、MgAl2O4、SiO2、TiO2、ZrO2Or YSZ.
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| CN108869796B (en) * | 2018-06-15 | 2019-12-17 | 上海理工大学 | Rotary combination valve and method for fixed bed chemical looping hydrogen production |
| CN108726477B (en) * | 2018-06-15 | 2021-08-03 | 上海理工大学 | Chemical-looping hydrogen production and decarburization integrated device and method for heat balance compact fixed bed |
| CN111217380A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for synthesizing ammonia |
| CN115535963A (en) * | 2022-10-11 | 2022-12-30 | 山东理工大学 | Biomass chemical chain circulation hydrogen production system |
| CN115784256A (en) * | 2022-11-30 | 2023-03-14 | 东北大学 | Chemical-looping continuous ammonia production system and method utilizing biomass and solar energy |
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| CN102087048A (en) * | 2010-12-15 | 2011-06-08 | 华北电力大学（保定） | Process and device for fixed bed chemical-looping combustion reaction |
| CN102198934A (en) * | 2011-04-20 | 2011-09-28 | 中国科学院广州能源研究所 | Method and device for producing hydrogen by using chemical chain |
| CN102865669A (en) * | 2012-10-15 | 2013-01-09 | 上海锅炉厂有限公司 | Device and method for switching-type chemical-looping combustion |
| CN103785389A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity oxygen carrier and preparation method and application thereof |
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| CN102087048A (en) * | 2010-12-15 | 2011-06-08 | 华北电力大学（保定） | Process and device for fixed bed chemical-looping combustion reaction |
| CN102198934A (en) * | 2011-04-20 | 2011-09-28 | 中国科学院广州能源研究所 | Method and device for producing hydrogen by using chemical chain |
| CN102865669A (en) * | 2012-10-15 | 2013-01-09 | 上海锅炉厂有限公司 | Device and method for switching-type chemical-looping combustion |
| CN103785389A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity oxygen carrier and preparation method and application thereof |
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