CN113834897A - Method and device for testing bulk phase oxygen migration kinetics in chemical chain technology - Google Patents
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- 239000001301 oxygen Substances 0.000 title claims abstract description 231
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 231
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000000126 substance Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000005012 migration Effects 0.000 title claims abstract description 31
- 238000013508 migration Methods 0.000 title claims abstract description 31
- 238000012360 testing method Methods 0.000 title claims abstract description 24
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims abstract description 59
- 239000007789 gas Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- 239000002737 fuel gas Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 38
- 238000009792 diffusion process Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 239000012876 carrier material Substances 0.000 claims description 17
- 239000010416 ion conductor Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 13
- 230000003068 static effect Effects 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
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- 238000005406 washing Methods 0.000 claims description 6
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- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
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- 238000010998 test method Methods 0.000 abstract description 4
- 238000004364 calculation method Methods 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- -1 oxygen ions Chemical class 0.000 description 35
- 239000000047 product Substances 0.000 description 22
- 239000000446 fuel Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
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Abstract
The invention relates to a method and a device for testing bulk phase oxygen migration kinetics in a chemical looping technology, wherein the device comprises a chemical looping combustion system and a gas product detection system; the chemical looping combustion system structurally comprises a chemical looping combustion reactor, wherein the chemical looping combustion reactor comprises a reaction chamber and an inert chamber which are separated by an oxygen carrier, the inlet of the chemical looping combustion reactor is respectively connected with a fuel gas source and an inert gas source, and the outlet of the chemical looping combustion reactor is connected with the inlet of a gas product detection system. The test method comprises the following steps: preparing an oxygen carrier with a compact oxygen ion conducting membrane formed on one side surface; the oxygen carrier is placed in a chemical looping combustion reactor, fuel gas and inert gas are introduced to generate chemical looping combustion, gas at the outlet of a reaction chamber is introduced into a gas product detection system, the corresponding relation between the conversion rate of the oxygen carrier and time is obtained through calculation by analyzing the accumulated concentration of gaseous products, and the kinetic parameters of bulk oxygen migration of the oxygen carrier are solved, so that the related mechanism of the chemical looping combustion can be further disclosed.
Description
Technical Field
The invention relates to the technical field of chemical looping combustion testing, in particular to a method and a device for testing bulk phase oxygen migration dynamics in chemical looping combustion.
Background
The chemical looping combustion technology is a novel combustion technology based on a zero emission concept, fuel and air are isolated by means of an oxygen carrier material, and an oxygen supply mode of the traditional combustion technology is changed. The chemical looping combustion technology is divided into two steps, firstly, an oxygen carrier material reacts with fuel, lattice oxygen in the oxygen carrier material oxidizes the fuel, the oxygen carrier loses the lattice oxygen and is reduced, and the process is generally carried out in a fuel reactor; secondly, the oxygen carrier material reacts with air, the oxygen carrier material is oxidized by oxygen in the air to obtain lattice oxygen, and the process is generally carried out in an air reactor. Because only lattice oxygen exists, the flue gas at the outlet of the fuel reactor mainly comprises carbon dioxide and water vapor, and the high-concentration carbon dioxide gas can be obtained after the water vapor is condensed, so that the carbon capture cost is greatly reduced compared with the traditional combustion mode.
In chemical looping combustion technology, oxygen carriers play a key role, isolating fuel from air, and simultaneously realizing the transmission of lattice oxygen and heat. The gas-solid reaction is carried out on a reaction interface, oxygen ions are obtained by the oxygen carrier on the reaction interface in the oxidation reaction, and then the oxygen ions enter the oxygen carrier through bulk phase migration, so that the complete oxidation of the oxygen carrier is realized. In a similar way, in the reduction reaction, the oxygen carrier loses oxygen ions at the reaction interface, and the oxygen ions in the oxygen carrier reach the reaction interface through bulk phase migration, so that the oxygen carrier material is completely reduced. Therefore, the bulk oxygen ion transport process is a significant step in chemical looping combustion that is not negligible.
Researches show that the bulk oxygen migration process of the oxygen carrier material is the rate-limiting step of the chemical looping combustion process, and the researches on the bulk oxygen migration process of the oxygen carrier material have great significance in the aspects of designing the oxygen carrier, improving the reaction activity of the oxygen carrier, improving the chemical looping combustion process and the like. However, the existing research in the field is only on a qualitative level, and the dynamic research on the bulk oxygen transfer process is still lacked, so that the further development of the chemical-looping combustion technology is restricted.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for testing bulk phase oxygen migration kinetics in chemical looping combustion, solves the problem that the conventional research is limited in a theoretical qualitative level and lacks of an implementable specific test scheme, and provides a theoretical basis for design modification of an oxygen carrier and improvement of a chemical looping combustion process.
The technical scheme adopted by the invention is as follows:
a testing device for bulk phase oxygen migration kinetics in chemical looping technology comprises a chemical looping combustion system and a gas product detection system; the chemical looping combustion system structurally comprises a chemical looping combustion reactor, the chemical looping combustion reactor structurally comprises a reaction chamber and an inert chamber, the reaction chamber and the inert chamber are separated by an oxygen carrier, inlets of the reaction chamber and the inert chamber are respectively connected with a fuel gas source and an inert gas source, an outlet of the reaction chamber is connected with an inlet of a gas product detection system, and the gas product detection system structurally comprises a gas washing and drying device and a gas analyzer which are sequentially connected.
The further technical scheme is as follows:
the oxygen carrier is made of a sheet oxygen carrier material, and one side surface of the oxygen carrier is provided with a layer of compact oxygen ion conduction membrane.
The chemical looping combustion system further comprises a heating device for heating the chemical looping combustion reactor from the outside, and a temperature control device matched with the heating device.
A method for testing the bulk oxygen transfer kinetics of an oxygen carrier by using a test device of the bulk oxygen transfer kinetics in a chemical chain technology comprises the following steps:
s1, preparing a sheet-shaped oxygen carrier by using oxygen carrier powder and oxygen ion conductor powder, wherein the oxygen ion conductor powder forms a layer of compact oxygen ion conducting membrane on one side surface of the prepared oxygen carrier;
s2, placing the sheet-shaped oxygen carrier prepared in the step S1 into a chemical looping combustion reactor, wherein the sheet-shaped oxygen carrier separates a reaction chamber from an inert chamber in the chemical looping combustion reactor, and one side of the oxygen carrier, on which an oxygen ion conducting membrane is arranged, is positioned in the reaction chamber; respectively introducing fuel gas serving as reducing gas and inert gas serving as protective gas into the reaction chamber and the inert chamber, performing chemical looping combustion under a heating condition, introducing outlet gas of the reaction chamber into the gas product detection system for detection after the combustion reaction, and calculating to obtain the corresponding relation between the conversion rate of the oxygen carrier and the time by analyzing the accumulated concentration of gaseous products;
and S3, solving the bulk oxygen migration kinetic parameters of the oxygen carrier by using the result of the step S2 and combining the Fick second law and the Arrhenius law.
The further technical scheme is as follows:
in step S1, a sheet-like oxygen carrier is prepared from the oxygen carrier powder and the oxygen ion conductor powder, and the specific process is as follows:
putting oxygen carrier powder into a die, applying pressure, and placing under static pressure;
opening the mould, taking oxygen ion conductor powder, putting the oxygen ion conductor powder into the mould, covering the surface of the oxygen carrier powder subjected to static pressure treatment, applying pressure, and placing the oxygen carrier powder under static pressure to form a sheet-shaped oxygen carrier;
and taking the flaky oxygen carrier out of the die, putting the flaky oxygen carrier into a muffle furnace for calcining, and cooling to room temperature to obtain a final oxygen carrier finished product.
In step S3, the bulk oxygen transfer kinetic parameters include an oxygen ion diffusion coefficient of the oxygen carrier and an activation energy of the oxygen ion transfer process, and the oxygen ion diffusion coefficient D of the oxygen carriertComprises the following steps:
in the above formula, DtRepresents the oxygen ion diffusion coefficient at the time t, S represents a constant related to the oxygen ion diffusion of the material, and l represents the thickness of the oxygen carrier;
solving a constant S and a conversion rate X of the oxygen carrier according to the corresponding relation between the conversion rate of the oxygen carrier and the time obtained in the step S2tComprises the following steps:
the activation energy E of the oxygen ion migration process was calculated using the following formulaa：
In the above two formulae, DavgRepresents the average oxygen ion diffusion coefficient, Rg represents the universal gas constant, T represents the temperature, Davg，0Representing frequency factor, N representing total points in the discrete solving process, i representing point serial number, (D)t)iRepresents the oxygen ion diffusion coefficient corresponding to the point i at the time t.
The invention has the following beneficial effects:
the testing device comprises a reactor and a product gas analysis device, and establishes the corresponding relation between the conversion rate of the oxygen carrier and the time through the analysis of the product gas concentration, so that the parameters of bulk oxygen migration kinetics are obtained through calculation, and the bulk oxygen migration process of the oxygen carrier material is researched from the perspective of reaction kinetics. By utilizing the testing method, the bulk oxygen migration kinetic parameters of various oxygen carrier materials can be tested, the related mechanism of chemical looping combustion can be further disclosed, and theoretical basis is provided for design modification of the oxygen carrier and improvement of the chemical looping combustion process.
The surface of the oxygen carrier prepared and used by the invention is coated with a compact oxygen ion conduction membrane, so that the coupling of a gas diffusion process and a bulk oxygen migration process in a reaction is solved, and the obtained bulk oxygen migration kinetic result is more accurate.
Drawings
Fig. 1 is a schematic structural diagram of a testing apparatus according to an embodiment of the present invention.
FIG. 2 is a graph of the conversion of oxygen carriers obtained by the test method of the example of the present invention as a function of time and temperature.
FIG. 3 is a graph of oxygen ion diffusion coefficient of an oxygen carrier obtained by a testing method according to an embodiment of the present invention as a function of time and temperature.
FIG. 4 shows the average oxygen ion diffusion coefficients of oxygen carriers at different temperatures obtained by the testing method of the embodiment of the present invention.
FIG. 5 is a graph of the average oxygen ion diffusion coefficient of an oxygen carrier obtained by the test method of an example of the present invention as a function of temperature.
In the figure: 1. a volumetric flow controller; 2. a volumetric flow meter; 3. a pressure reducing valve; 4. a three-way valve; 5. an inert gas inlet; 6. an inert gas outlet; 7. an electric heating furnace; 8. an inert chamber; 9. a reaction chamber; 10. a fuel gas inlet; 11. a product gas outlet; 12. a gas analyzer; 13. drying the bottle; 14. a gas washing bottle; 15. a thermocouple temperature controller; 16. a gas cylinder.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
A testing device for bulk phase oxygen migration kinetics in chemical looping technology comprises a chemical looping combustion system and a gas product detection system; the chemical looping combustion system structurally comprises a chemical looping combustion reactor, as shown in fig. 1, the chemical looping combustion reactor structurally comprises a reaction chamber 9 and an inert chamber 8, the reaction chamber 9 and the inert chamber 8 are separated by a sheet-shaped oxygen carrier, inlets of the reaction chamber 9 and the inert chamber 8 are respectively connected with a fuel gas source and an inert gas source, an outlet of the reaction chamber 9 is connected with an inlet of a gas product detection system, and the gas product detection system structurally comprises a scrubbing and drying device and a gas analyzer 12 which are sequentially connected.
In the above embodiment, the flake oxygen carrier is a circular flake oxygen carrier material, and a layer of dense oxygen ion conducting membrane is coated on the surface of the oxygen carrier on one side of the reaction chamber 9.
In the above embodiment, the chemical looping combustion system further includes a heating device for heating the chemical looping combustion reactor from outside, and a temperature control device cooperating with the heating device.
Specifically, as shown in fig. 1, the reaction chamber 9 has a product gas outlet 11 and a fuel gas inlet 10, the inert chamber 8 has an inert gas inlet 5 and an inert gas outlet 6, the fuel gas source and the inert gas source are gas cylinders 16 for respectively storing fuel gas and inert gas, the fuel gas inlet 10 and the inert gas inlet 5 are respectively connected with the corresponding gas cylinders 16, a pressure reducing valve 3 and a volume flow meter 2 are respectively arranged on connecting pipelines, a three-way valve 4 can be further arranged as required, and the volume flow meter 2 is connected with the volume flow controller 1; the gas cylinder 16 provides fuel gas and inert gas required by the experiment, the gas flows out of the gas cylinder 16, is adjusted to the gas pressure required by the experiment through the pressure reducing valve 3, and then passes through the volume flow meter 2, and is controlled by the volume flow controller 1 to meet the flow required by the experiment. The heating device is an electric heating furnace 7 arranged outside the chemical looping combustion reactor, the temperature control device is a thermocouple temperature controller 15, the temperature required by the experiment of the chemical looping combustion reactor is controlled through the electric heating furnace 7 and the thermocouple temperature controller 15, chemical reaction does not occur in the inert chamber 8, the inert gas plays a role in protection, the chemical looping combustion reaction of reducing gas and an oxygen carrier occurs in the reaction chamber 9, and the combusted gas is discharged through a product gas outlet 11 of the reaction chamber 9. The inert chamber 8 is filled with inert gas to prevent the oxygen carrier from being oxidized by air.
Specifically, the gas washing and drying device of the gas product detection system comprises a gas washing bottle 14 and a drying bottle 13, wherein a reaction product is discharged from a product gas outlet 11, is washed by the gas washing bottle 14 and dried by the drying bottle 13, and then enters a gas analyzer 12, and the corresponding relation between the conversion rate of the oxygen carrier and the time is obtained by analyzing the accumulated concentration of the gaseous product.
A method for testing bulk oxygen transfer kinetics of an oxygen carrier by using the testing device of bulk oxygen transfer kinetics in the chemical looping technology of the embodiment comprises the following steps:
s1, preparing a sheet-shaped oxygen carrier by using oxygen carrier powder and oxygen ion conductor powder, wherein the oxygen ion conductor powder forms a layer of compact oxygen ion conducting membrane on one side surface of the prepared oxygen carrier;
s2, placing the sheet-shaped oxygen carrier prepared in the step S1 into a chemical looping combustion reactor, wherein the sheet-shaped oxygen carrier separates a reaction chamber 9 from an inert chamber 8 in the chemical looping combustion reactor, and an oxygen ion conducting membrane is positioned on one side in the reaction chamber 9; respectively introducing fuel gas serving as reducing gas and inert gas serving as protective gas into the reaction chamber 9 and the inert chamber 8, performing chemical looping combustion under a heating condition, introducing gas at the outlet of the reaction chamber 9 after the combustion reaction into a gas product detection system for detection, and calculating to obtain the corresponding relation between the conversion rate of the oxygen carrier and the time by analyzing the accumulated concentration of a gaseous product;
and S3, solving the bulk oxygen migration kinetic parameters of the oxygen carrier by using the result of the step S2 and combining the Fick second law and the Arrhenius law.
In the step S1, the oxygen carrier powder and the oxygen ion conductor powder are used to prepare the flake oxygen carrier, and the specific process is as follows:
putting oxygen carrier powder into a die, applying pressure, and placing under static pressure;
opening the mould, putting oxygen ion conductor powder into the mould, placing the oxygen carrier powder on the surface of the oxygen carrier powder subjected to static pressure treatment, applying pressure, and placing the oxygen carrier powder under static pressure to form a sheet-shaped oxygen carrier;
and taking the flaky oxygen carrier out of the die, putting the flaky oxygen carrier into a muffle furnace for calcining, and cooling to room temperature to obtain a final oxygen carrier finished product.
In step S3, the bulk oxygen migration kinetic parameters include the oxygen ion diffusion coefficient of the oxygen carrier and the activation energy of the oxygen ion migration process, and the oxygen ion diffusion coefficient D of the oxygen carriertComprises the following steps:
Dtrepresents the oxygen ion diffusion coefficient at the time t, S represents a constant related to the oxygen ion diffusion of the material, and l represents the thickness of the oxygen carrier;
solving a constant S and a conversion rate X of the oxygen carrier according to the corresponding relation between the conversion rate of the oxygen carrier and the time obtained in the step S2tComprises the following steps:
the activation energy Ea of the oxygen ion migration process was calculated using the following formula:
in the above two formulae, DavgRepresents the average oxygen ion diffusion coefficient, Rg represents the universal gas constant, T represents the temperature, Davg，0Representing the frequency factor, i.e. the fitting parameter; n represents the total number of points in the time range, i represents the serial number of points, and Dt)iRepresents the oxygen ion diffusion coefficient corresponding to the point i at the time t.
The following takes the red mud oxygen carrier coated with the GDC material as an example to further illustrate the test method of oxygen carrier bulk oxygen migration kinetics of the present application, which comprises the following steps:
s1: the method for preparing the required flaky oxygen carrier by using the red mud powder and the GDC powder specifically adopts a powder tabletting method to obtain the required oxygen carrier material, and comprises the following steps:
s11: taking a proper amount of red mud powder, putting the red mud powder into a mortar for fully grinding, then pouring the ground red mud powder into a mould, and pressing the red mud powder for 3 minutes by using a tablet press under the pressure of 60 MPa;
s12: opening the mould, taking a proper amount of GDC powder, fully grinding, pouring the powder into the mould to cover the surface of the red mud subjected to static pressure treatment, and pressing for 3 minutes under the pressure of 120 MPa;
s13: and taking the pressed flaky oxygen carrier out of the die, putting the flaky oxygen carrier into a muffle furnace, keeping the temperature rise rate of 2 ℃/min to 1350 ℃, keeping the temperature of 1350 ℃ for calcining for 6 hours, and then cooling to room temperature to obtain the required oxygen carrier material.
S2: the test device of the above embodiment is utilized to perform a chemical looping combustion experiment, and the corresponding relationship between the conversion rate of the oxygen carrier and the time is obtained:
the fuel gas used is carbon monoxide (CO) and nitrogen (N)2) The volume flow of the mixed gas is 50ml/min, the pressure is 1atm, and the temperature is normal temperature, whereinCarbon monoxide wherein the volume fraction is 5%; the inert gas used is argon (Ar), the volume flow of which is 50ml/min, the pressure is 1atm and the temperature is normal temperature.
The reaction pressure is 1atm, and the temperature is 700 ℃, 750 ℃, 800 ℃ and 850 ℃. Analysis of gaseous product CO in product gas using MRU gas analyzer2The cumulative concentration of (a) was obtained as a correlation between the conversion rate of the oxygen carrier at different temperatures and the time, and the result is shown in fig. 2.
S3: solving the oxygen carrier material bulk phase oxygen migration kinetic parameters by combining the Fick's second law and the Arrhenius law, wherein the oxygen carrier material bulk phase oxygen migration kinetic parameters are solved, the oxygen ion diffusion coefficients of the oxygen carrier at different time and different temperature are shown in figure 3, the average oxygen ion diffusion coefficient is shown in figure 4, and the Arrhenius relation in the oxygen ion migration process is shown in figure 5. The results show that the average oxygen ion diffusion coefficients of the red mud oxygen carrier coated with the GDC material are 0.24511 multiplied by 10 respectively at four different temperatures of 700 ℃, 750 ℃, 800 ℃ and 850 DEG C-10m2/s、0.55163×10-10m2/s、0.92845×10-10m2S and 1.74602X 10-10m2The activation energy for the oxygen ion migration process was 116.67 kJ/mol.
Claims (6)
1. A testing device for bulk phase oxygen migration dynamics in chemical looping technology is characterized by comprising a chemical looping combustion system and a gas product detection system; the structure of the chemical looping combustion system comprises a chemical looping combustion reactor, the structure of the chemical looping combustion reactor comprises a reaction chamber (9) and an inert chamber (8), the reaction chamber (9) and the inert chamber (8) are separated by an oxygen carrier, the inlets of the reaction chamber (9) and the inert chamber (8) are respectively connected with a fuel gas source and an inert gas source, the outlet of the reaction chamber (9) is connected with the inlet of a gas product detection system, and the structure of the gas product detection system comprises a gas washing and drying device and a gas analyzer (12) which are sequentially connected.
2. The device for testing bulk oxygen transfer kinetics in chemical looping technology according to claim 1, wherein the oxygen carrier is a sheet oxygen carrier material, and a dense oxygen ion conducting membrane is arranged on one side surface of the oxygen carrier.
3. The apparatus for testing bulk oxygen transfer kinetics in chemical looping technology according to claim 1, wherein the structure of the chemical looping combustion system further comprises a heating device for heating the chemical looping combustion reactor from the outside, and a temperature control device cooperating with the heating device.
4. A method for bulk oxygen transfer kinetics testing of an oxygen carrier using the apparatus for bulk oxygen transfer kinetics testing in chemical looping technology of claim 1, comprising the steps of:
s1, preparing a sheet-shaped oxygen carrier by using oxygen carrier powder and oxygen ion conductor powder, wherein the oxygen ion conductor powder forms a layer of compact oxygen ion conducting membrane on one side surface of the prepared oxygen carrier;
s2, placing the sheet-shaped oxygen carrier prepared in the step S1 into a chemical looping combustion reactor, wherein the sheet-shaped oxygen carrier separates a reaction chamber (9) from an inert chamber (8) in the chemical looping combustion reactor, and one side of the oxygen carrier, on which an oxygen ion conducting membrane is arranged, is positioned in the reaction chamber (9); respectively introducing fuel gas serving as reducing gas and inert gas serving as protective gas into the reaction chamber (9) and the inert chamber (8), performing chemical looping combustion under a heating condition, introducing gas at the outlet of the reaction chamber (9) after the combustion reaction into the gas product detection system for detection, and calculating the corresponding relation between the conversion rate of the oxygen carrier and the time according to the accumulated concentration of gaseous products;
and S3, solving the bulk oxygen migration kinetic parameters of the oxygen carrier by using the result of the step S2 and combining the Fick second law and the Arrhenius law.
5. The method according to claim 4, wherein in step S1, the oxygen carrier powder and the oxygen ion conductor powder are used to prepare the flake oxygen carrier, and the specific process is as follows:
putting oxygen carrier powder into a die, applying pressure, and placing under static pressure;
opening the mould, taking oxygen ion conductor powder, putting the oxygen ion conductor powder into the mould, covering the surface of the oxygen carrier powder subjected to static pressure treatment, applying pressure, and placing under static pressure to form a flaky oxygen carrier;
and taking the flaky oxygen carrier out of the die, putting the flaky oxygen carrier into a muffle furnace for calcining, and cooling to room temperature to obtain a final oxygen carrier finished product.
6. The method according to claim 4, wherein in step S3, the bulk oxygen transfer kinetic parameters include oxygen ion diffusion coefficient of oxygen carrier and activation energy of oxygen ion transfer process, and the oxygen ion diffusion coefficient D of oxygen carriertComprises the following steps:
in the above formula, DtRepresents the oxygen ion diffusion coefficient at the time t, S represents a constant related to the oxygen ion diffusion of the material, and l represents the thickness of the oxygen carrier;
solving a constant S and a conversion rate X of the oxygen carrier according to the corresponding relation between the conversion rate of the oxygen carrier and the time obtained in the step S2tComprises the following steps:
the activation energy Ea of the oxygen ion migration process was calculated using the following formula:
in the above two formulae, DavgRepresenting the mean oxygen ion diffusionCoefficient, Rg stands for general gas constant, T stands for temperature, Davg，0Representing frequency factor, N representing total points in the discrete solving process, i representing point serial number, (D)t)iRepresents the oxygen ion diffusion coefficient corresponding to the point i at the time t.
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