CN113834897B - Method and device for testing bulk oxygen migration dynamics in chemical chain technology - Google Patents
Method and device for testing bulk oxygen migration dynamics in chemical chain technology Download PDFInfo
- Publication number
- CN113834897B CN113834897B CN202110940222.1A CN202110940222A CN113834897B CN 113834897 B CN113834897 B CN 113834897B CN 202110940222 A CN202110940222 A CN 202110940222A CN 113834897 B CN113834897 B CN 113834897B
- Authority
- CN
- China
- Prior art keywords
- oxygen
- oxygen carrier
- gas
- carrier
- chemical chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 215
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 215
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000000126 substance Substances 0.000 title claims abstract description 56
- 230000005012 migration Effects 0.000 title claims abstract description 41
- 238000013508 migration Methods 0.000 title claims abstract description 41
- 238000012360 testing method Methods 0.000 title claims abstract description 25
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 33
- 239000007789 gas Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000002485 combustion reaction Methods 0.000 claims abstract description 53
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 18
- 239000002737 fuel gas Substances 0.000 claims abstract description 15
- 238000010998 test method Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 29
- 238000009792 diffusion process Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 21
- 239000012876 carrier material Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000010416 ion conductor Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000037427 ion transport Effects 0.000 claims 1
- 230000001186 cumulative effect Effects 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 2
- -1 oxygen ions Chemical class 0.000 description 35
- 239000000047 product Substances 0.000 description 19
- 239000000446 fuel Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 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 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 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
- 238000006722 reduction reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000009841 combustion method Methods 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- 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
- G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
本发明涉及一种化学链技术中体相氧迁移动力学的测试方法及装置，装置包括化学链燃烧系统和气体产物检测系统；化学链燃烧系统的结构包括化学链燃烧反应器，其包括之间由载氧体分隔开的反应室和惰性室，化学链燃烧反应器入口分别与燃料气源、惰性气源连接，出口与气体产物检测系统入口连接。测试方法包括：制备一侧面形成致密氧离子传导膜的载氧体；将载氧体放到化学链燃烧反应器中，通入燃料气和惰性气发生化学链燃烧，反应室出口气体通入气体产物检测系统，通过分析气态产物的累计浓度，计算获得载氧体的转化率与时间的对应关系，求解载氧体的体相氧迁移动力学参数，有助于进一步揭示化学链燃烧的有关机理。
The invention relates to a testing method and device for bulk phase oxygen migration kinetics in chemical chain technology. The device includes a chemical chain combustion system and a gas product detection system; the structure of the chemical chain combustion system includes a chemical chain combustion reactor, which includes a The reaction chamber and the inert chamber are separated by the oxygen carrier. The inlet of the chemical chain combustion reactor is connected to the fuel gas source and the inert gas source respectively, and the outlet is connected to the inlet of the gas product detection system. The test method includes: preparing an oxygen carrier with a dense oxygen ion conductive film formed on one side; placing the oxygen carrier into a chemical chain combustion reactor, introducing fuel gas and inert gas to cause chemical chain combustion, and passing the reaction chamber outlet gas into the gas The product detection system analyzes the cumulative concentration of gaseous products, calculates the relationship between the conversion rate of the oxygen carrier and time, and solves the bulk oxygen migration kinetic parameters of the oxygen carrier, which helps to further reveal the relevant mechanisms of chemical chain combustion. .
Description
技术领域Technical field
本发明涉及化学链燃烧测试技术领域，尤其是一种化学链燃烧中体相氧迁移动力学的测试方法与装置。The invention relates to the technical field of chemical chain combustion testing, in particular to a testing method and device for bulk phase oxygen migration kinetics in chemical chain combustion.
背景技术Background technique
化学链燃烧技术是一种基于零排放理念的新型燃烧技术，其借助载氧体材料将燃料与空气隔绝，改变了传统燃烧技术的供氧方式。化学链燃烧技术分为两步，一是载氧体材料与燃料发生反应，载氧体材料中的晶格氧将燃料氧化，载氧体失去晶格氧被还原，该过程一般在燃料反应器内进行；二是载氧体材料与空气反应，载氧体材料被空气中的氧气氧化得到晶格氧，该过程一般在空气反应器中进行。因为仅有晶格氧的存在，燃料反应器出口烟气主要是二氧化碳和水蒸气，将水蒸气冷凝后即可得到高浓度的二氧化碳气体，与传统燃烧方式相比大大降低了碳捕集成本。Chemical chain combustion technology is a new combustion technology based on the concept of zero emissions. It uses oxygen carrier materials to isolate fuel from air, changing the oxygen supply method of traditional combustion technology. Chemical chain combustion technology is divided into two steps. First, the oxygen carrier material reacts with the fuel. The lattice oxygen in the oxygen carrier material oxidizes the fuel. The oxygen carrier loses the lattice oxygen and is reduced. This process is generally in the fuel reactor. The second step is the reaction between the oxygen carrier material and the air. The oxygen carrier material is oxidized by the oxygen in the air to obtain lattice oxygen. This process is generally carried out in an air reactor. Because only lattice oxygen exists, the flue gas at the outlet of the fuel reactor is mainly carbon dioxide and water vapor. After condensing the water vapor, high-concentration carbon dioxide gas can be obtained, which greatly reduces the cost of carbon capture compared with traditional combustion methods.
在化学链燃烧技术中，载氧体发挥了关键作用，其将燃料与空气隔绝，同时实现了晶格氧与热量的传输。气固反应发生在反应界面，在氧化反应中，载氧体在反应界面得到氧离子，进而氧离子通过体相迁移进入载氧体内部，实现载氧体的完全氧化。同理，还原反应中，载氧体在反应界面失去氧离子，载氧体内部的氧离子通过体相迁移到达反应界面，进而实现载氧体材料的完全还原。因此，体相氧离子迁移过程是化学链燃烧中不可忽略的重要一步。In chemical chain combustion technology, the oxygen carrier plays a key role, insulating the fuel from the air and realizing the transmission of lattice oxygen and heat. The gas-solid reaction occurs at the reaction interface. During the oxidation reaction, the oxygen carrier obtains oxygen ions at the reaction interface, and then the oxygen ions enter the interior of the oxygen carrier through bulk phase migration, achieving complete oxidation of the oxygen carrier. In the same way, during the reduction reaction, the oxygen carrier loses oxygen ions at the reaction interface, and the oxygen ions inside the oxygen carrier reach the reaction interface through bulk phase migration, thereby achieving complete reduction of the oxygen carrier material. Therefore, the bulk oxygen ion migration process is an important step that cannot be ignored in chemical chain combustion.
已有研究表明，载氧体材料的体相氧迁移过程是化学链燃烧过程的限速步骤，对载氧体材料体相氧迁移过程的研究在载氧体的设计、提高载氧体反应活性以及改进化学链燃烧工艺等方面具有十分重要的意义。但是，该领域的现有研究均停留在定性层面，尚缺乏对体相氧迁移过程的动力学研究，制约了化学链燃烧技术的进一步发展。Studies have shown that the bulk phase oxygen migration process of oxygen carrier materials is the rate-limiting step in the chemical chain combustion process. The study of the bulk phase oxygen migration process of oxygen carrier materials plays an important role in the design of oxygen carriers and improving the reactivity of oxygen carriers. As well as improving the chemical chain combustion process, it is of great significance. However, existing research in this field remains at the qualitative level and lacks kinetic research on the bulk oxygen migration process, which restricts the further development of chemical chain combustion technology.
发明内容Contents of the invention
针对现有技术的缺陷，本发明提供一种化学链燃烧中体相氧迁移动力学的测试方法与装置，解决现有研究停留在理论定性层面缺少可实施的具体测试方案的问题，为载氧体的设计改性、化学链燃烧工艺改进提供理论依据。In view of the shortcomings of the existing technology, the present invention provides a testing method and device for bulk oxygen migration kinetics in chemical chain combustion, which solves the problem that existing research remains at the theoretical qualitative level and lacks implementable specific test solutions, and provides oxygen-carrying oxygen. It provides a theoretical basis for the design modification of the body and the improvement of the chemical chain combustion process.
本发明采用的技术方案如下：The technical solutions adopted by the present invention are as follows:
一种化学链技术中体相氧迁移动力学的测试装置，包括化学链燃烧系统和气体产物检测系统；所述化学链燃烧系统的结构包括化学链燃烧反应器，其结构包括反应室和惰性室，所述反应室与惰性室之间由载氧体分隔开，所述反应室与惰性室的入口分别与燃料气源、惰性气源连接，所述反应室出口与所述气体产物检测系统入口连接，所述气体产物检测系统的结构包括依次连接的洗气干燥装置和气体分析仪。A testing device for bulk oxygen migration kinetics in chemical chain technology, including a chemical chain combustion system and a gas product detection system; the structure of the chemical chain combustion system includes a chemical chain combustion reactor, and its structure includes a reaction chamber and an inert chamber , the reaction chamber and the inert chamber are separated by an oxygen carrier, the inlets of the reaction chamber and the inert chamber are connected to the fuel gas source and the inert gas source respectively, and the outlet of the reaction chamber is connected to the gas product detection system Inlet connection, the structure of the gas product detection system includes a gas scrubber drying device and a gas analyzer connected in sequence.
其进一步技术方案为：Its further technical solutions are:
所述载氧体采用片状载氧体材料，其一侧表面设置一层致密氧离子传导膜。The oxygen carrier is made of sheet oxygen carrier material, and a dense oxygen ion conductive film is provided on one side of the surface.
所述化学链燃烧系统的结构还包括对所述化学链燃烧反应器从外部加热的加热装置、以及与所述加热装置配合的温度控制装置。The structure of the chemical chain combustion system also includes a heating device that heats the chemical chain combustion reactor from the outside, and a temperature control device that cooperates with the heating device.
一种利用化学链技术中体相氧迁移动力学的测试装置进行载氧体的体相氧迁移动力学测试的方法，包括以下步骤：A method for testing the bulk oxygen migration kinetics of an oxygen carrier using a testing device for bulk oxygen migration kinetics in chemical chain technology, including the following steps:
S1、利用载氧体粉末与氧离子导体粉末制备片状载氧体，所述氧离子导体粉末在制成的载氧体一侧面形成一层致密氧离子传导膜；S1. Prepare a sheet-shaped oxygen carrier using oxygen carrier powder and oxygen ion conductor powder. The oxygen ion conductor powder forms a dense oxygen ion conductive film on one side of the prepared oxygen carrier;
S2、将步骤S1中所制备的片状载氧体放到化学链燃烧反应器中，使片状载氧体将所述化学链燃烧反应器中的反应室与惰性室分隔开，且所述载氧体的设置氧离子传导膜的一侧面位于所述反应室内；分别向反应室与惰性室内通入作为还原性气体的燃料气和作为保护气体的惰性气，并在加热条件下发生化学链燃烧，燃烧反应后反应室出口气体通入所述气体产物检测系统进行检测，通过分析气态产物的累计浓度，计算获得载氧体的转化率与时间的对应关系；S2. Place the flaky oxygen carrier prepared in step S1 into a chemical chain combustion reactor, so that the flaky oxygen carrier separates the reaction chamber and the inert chamber in the chemical chain combustion reactor, and the One side of the oxygen carrier with an oxygen ion conductive membrane is located in the reaction chamber; fuel gas as a reducing gas and inert gas as a protective gas are introduced into the reaction chamber and the inert chamber respectively, and chemical reactions occur under heating conditions. Chain combustion, after the combustion reaction, the outlet gas of the reaction chamber is passed into the gas product detection system for detection. By analyzing the cumulative concentration of the gaseous products, the corresponding relationship between the conversion rate of the oxygen carrier and time is calculated and obtained;
S3、利用步骤S2的结果，结合菲克第二定律和阿累尼乌斯定律求解载氧体的体相氧迁移动力学参数。S3. Use the results of step S2 and combine Fick's second law and Arrhenius' law to solve the bulk phase oxygen migration kinetic parameters of the oxygen carrier.
其进一步技术方案为：Its further technical solutions are:
步骤S1中，利用载氧体粉末与氧离子导体粉末制备片状载氧体，具体流程如下：In step S1, a sheet-shaped oxygen carrier is prepared using oxygen carrier powder and oxygen ion conductor powder. The specific process is as follows:
取载氧体粉末放入模具中，施加压力，静压放置；Take the oxygen carrier powder and put it into the mold, apply pressure and place it under static pressure;
打开模具，取氧离子导体粉末放入模具中，覆盖到静压处理后的载氧体粉末表面，施加压力，静压放置，形成片状载氧体；Open the mold, take the oxygen ion conductor powder and put it into the mold, cover it on the surface of the oxygen carrier powder after static pressure treatment, apply pressure, and place it under static pressure to form a flaky oxygen carrier;
从模具中取出所述片状载氧体，放入马弗炉内煅烧，降至室温得到最终的载氧体成品。The sheet-shaped oxygen carrier is taken out from the mold, placed in a muffle furnace, calcined, and lowered to room temperature to obtain the final finished oxygen carrier.
步骤S3中，所述体相氧迁移动力学参数包括载氧体的氧离子扩散系数和氧离子迁移过程的活化能，所述载氧体的氧离子扩散系数Dt为：In step S3, the bulk phase oxygen migration kinetic parameters include the oxygen ion diffusion coefficient of the oxygen carrier and the activation energy of the oxygen ion migration process. The oxygen ion diffusion coefficient D t of the oxygen carrier is:
上式中，Dt代表t时刻的氧离子扩散系数，S代表与材料的氧离子扩散有关的常数，l代表载氧体的厚度；In the above formula, D t represents the oxygen ion diffusion coefficient at time t, S represents the constant related to the oxygen ion diffusion of the material, and l represents the thickness of the oxygen carrier;
通过步骤S2所得载氧体的转化率与时间的对应关系，求解常数S，载氧体的转化率Xt为：Through the corresponding relationship between the oxygen carrier conversion rate and time obtained in step S2, the constant S is solved, and the oxygen carrier conversion rate X t is:
采用下式计算所述氧离子迁移过程的活化能Ea：The activation energy E a of the oxygen ion migration process is calculated using the following formula:
上两式中，Davg代表平均氧离子扩散系数，Rg代表通用气体常数，T代表温度，Davg，0代表频率因子，N代表离散求解过程中在所求时间范围内所取的总点数，i代表点数序号，(Dt)i代表t时刻第i号点所对应的氧离子扩散系数。In the above two formulas, D avg represents the average oxygen ion diffusion coefficient, Rg represents the universal gas constant, T represents the temperature, D avg, 0 represents the frequency factor, and N represents the total number of points taken within the required time range during the discrete solution process. i represents the point number, (D t ) i represents the oxygen ion diffusion coefficient corresponding to the i-th point at time t.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
本发明的测试装置包含反应器和产物气体分析装置，通过产物气体浓度分析，建立载氧体的转化率与时间的对应关系，从而计算获得体相氧迁移动力学参数，从反应动力学的角度研究了载氧体材料的体相氧迁移过程。利用本发明测试方法，可测试多种载氧体材料的体相氧迁移动力学参数，有助于进一步揭示化学链燃烧的有关机理，并为载氧体的设计改性、化学链燃烧工艺改进提供理论依据。The test device of the present invention includes a reactor and a product gas analysis device. Through product gas concentration analysis, the corresponding relationship between the conversion rate of the oxygen carrier and time is established, thereby calculating and obtaining the bulk phase oxygen migration kinetic parameters. From the perspective of reaction kinetics The bulk oxygen migration process of oxygen carrier materials was studied. The test method of the present invention can be used to test the bulk phase oxygen migration kinetic parameters of various oxygen carrier materials, which is helpful to further reveal the relevant mechanisms of chemical chain combustion, and provides opportunities for design modification of oxygen carriers and improvement of chemical chain combustion processes. Provide theoretical basis.
本发明制备和使用的载氧体表面涂覆了致密的氧离子传导膜，解决了反应中气体扩散过程与体相氧迁移过程的耦合，使得到的体相氧迁移动力学结果更为准确。The surface of the oxygen carrier prepared and used in the present invention is coated with a dense oxygen ion conductive film, which solves the coupling between the gas diffusion process and the bulk oxygen migration process in the reaction, making the obtained bulk oxygen migration kinetic results more accurate.
附图说明Description of drawings
图1是本发明实施例的测试装置的结构示意图。Figure 1 is a schematic structural diagram of a testing device according to an embodiment of the present invention.
图2是本发明实施例的测试方法所得载氧体的转化率与时间和温度的关系。Figure 2 is the relationship between the oxygen carrier conversion rate and time and temperature obtained by the testing method of the embodiment of the present invention.
图3是本发明实施例的测试方法所得载氧体的氧离子扩散系数与时间和温度的关系。Figure 3 is the relationship between the oxygen ion diffusion coefficient of the oxygen carrier and time and temperature obtained by the testing method of the embodiment of the present invention.
图4是本发明实施例的测试方法所得在不同温度下载氧体的平均氧离子扩散系数。Figure 4 is the average oxygen ion diffusion coefficient of the oxygen carrier at different temperatures obtained by the testing method of the embodiment of the present invention.
图5是本发明实施例的测试方法所得载氧料的平均氧离子扩散系数与温度的关系。Figure 5 is the relationship between the average oxygen ion diffusion coefficient and temperature of the oxygen-carrying material obtained by the testing method of the embodiment of the present invention.
图中：1、体积流量控制器；2、体积流量计；3、减压阀；4、三通阀；5、惰性气入口；6、惰性气出口；7、电加热炉；8、惰性室；9、反应室；10、燃料气入口；11、产物气体出口；12、气体分析仪；13、干燥瓶；14、洗气瓶；15、热电偶温度控制器；16、气瓶。In the picture: 1. Volume flow controller; 2. Volume flow meter; 3. Pressure reducing valve; 4. Three-way valve; 5. Inert gas inlet; 6. Inert gas outlet; 7. Electric heating furnace; 8. Inert chamber ; 9. Reaction chamber; 10. Fuel gas inlet; 11. Product gas outlet; 12. Gas analyzer; 13. Drying bottle; 14. Gas washing bottle; 15. Thermocouple temperature controller; 16. Gas cylinder.
具体实施方式Detailed ways
以下结合附图说明本发明的具体实施方式。Specific embodiments of the present invention will be described below with reference to the accompanying drawings.
一种化学链技术中体相氧迁移动力学的测试装置，包括化学链燃烧系统和气体产物检测系统；化学链燃烧系统的结构包括化学链燃烧反应器，如图1所示，其结构包括反应室9和惰性室8，反应室9与惰性室8之间由片状载氧体隔开，反应室9与惰性室8的入口分别与燃料气源、惰性气源连接，反应室9出口与气体产物检测系统入口连接，气体产物检测系统的结构包括依次连接的洗气干燥装置和气体分析仪12。A testing device for bulk oxygen migration kinetics in chemical chain technology, including a chemical chain combustion system and a gas product detection system; the structure of the chemical chain combustion system includes a chemical chain combustion reactor, as shown in Figure 1, and its structure includes a reaction Chamber 9 and inert chamber 8, reaction chamber 9 and inert chamber 8 are separated by a sheet oxygen carrier. The inlets of reaction chamber 9 and inert chamber 8 are connected to the fuel gas source and the inert gas source respectively, and the outlet of reaction chamber 9 is connected to The inlet of the gas product detection system is connected, and the structure of the gas product detection system includes a gas scrubbing and drying device and a gas analyzer 12 connected in sequence.
上述实施例中，片状载氧体为圆形片状载氧体材料，位于反应室9一侧的载氧体表面涂覆了一层致密氧离子传导膜。In the above embodiment, the sheet oxygen carrier is a circular sheet oxygen carrier material, and the surface of the oxygen carrier located on one side of the reaction chamber 9 is coated with a dense oxygen ion conductive film.
上述实施例中，化学链燃烧系统的结构还包括对化学链燃烧反应器从外部加热的加热装置、以及与加热装置配合的温度控制装置。In the above embodiment, the structure of the chemical chain combustion system also includes a heating device that heats the chemical chain combustion reactor from the outside, and a temperature control device that cooperates with the heating device.
具体地，如图1所示，反应室9具有产物气体出口11和燃料气入口10，惰性室8具有惰性气入口5和惰性气出口6，燃料气源、惰性气源为分别储备燃料气和惰性气的气瓶16，燃料气入口10、惰性气入口5分别和相应气瓶16连接，连接管路上分别设有减压阀3和体积流量计2，根据需要还可设置三通阀4，体积流量计2与体积流量控制器1连接；气瓶16提供实验所需的燃料气和惰性气，气体从气瓶16流出，经减压阀3调节至实验所需的气体压力，后通过体积流量计2，其受体积流量控制器1的控制使其满足实验所需流量。加热装置为设置在化学链燃烧反应器外部的电加热炉7、温度控制装置为热电偶温度控制器15，通过电加热炉7和热电偶温度控制器15控制化学链燃烧反应器至实验所需的温度，惰性室8内不发生化学反应，惰性气体起到保护的作用，反应室9内发生还原性气体与载氧体的化学链燃烧反应，燃烧后的气体通过反应室9的产物气体出口11排出。惰性室8内通过通入惰性气体来避免载氧体被空气氧化。Specifically, as shown in Figure 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, and the fuel gas source and the inert gas source are respectively stored fuel gas and The inert gas cylinder 16, the fuel gas inlet 10, and the inert gas inlet 5 are connected to the corresponding gas cylinders 16 respectively. The connecting pipelines are respectively provided with a pressure reducing valve 3 and a volume flow meter 2. A three-way valve 4 can also be provided as needed. The volume flow meter 2 is connected to the volume flow controller 1; the gas cylinder 16 provides the fuel gas and inert gas required for the experiment. The gas flows out from the gas cylinder 16, is adjusted to the gas pressure required for the experiment through the pressure reducing valve 3, and then passes through the volume Flowmeter 2, which is controlled by the volumetric flow controller 1 to meet the required flow rate for the experiment. The heating device is an electric heating furnace 7 installed outside the chemical chain combustion reactor, and the temperature control device is a thermocouple temperature controller 15. The electric heating furnace 7 and the thermocouple temperature controller 15 are used to control the chemical chain combustion reactor to the experimental requirements. At a temperature of 11 discharge. Inert gas is introduced into the inert chamber 8 to prevent the oxygen carrier from being oxidized by air.
具体地，气体产物检测系统的洗气干燥装置包括洗气瓶14，干燥瓶13，反应产物从产物气体出口11排出，经洗气瓶14洗气、干燥瓶13干燥后，进入气体分析仪12，通过分析气态产物的累计浓度得到载氧体转化率与时间的对应关系。Specifically, the gas washing and drying device of the gas product detection system includes a gas washing bottle 14 and a drying bottle 13. The reaction product is discharged from the product gas outlet 11. After being washed by the gas washing bottle 14 and dried by the drying bottle 13, it enters the gas analyzer 12 , by analyzing the cumulative concentration of gaseous products, the corresponding relationship between the oxygen carrier conversion rate and time is obtained.
一种利用上述实施例的化学链技术中体相氧迁移动力学的测试装置进行载氧体的体相氧迁移动力学测试的方法，包括以下步骤：A method for testing the bulk phase oxygen migration kinetics of an oxygen carrier using the bulk phase oxygen migration kinetics testing device in the chemical chain technology of the above embodiment, including the following steps:
S1、利用载氧体粉末与氧离子导体粉末制备片状载氧体，氧离子导体粉末在制成的载氧体一侧面形成一层致密氧离子传导膜；S1. Use oxygen carrier powder and oxygen ion conductor powder to prepare a sheet-shaped oxygen carrier. The oxygen ion conductor powder forms a dense oxygen ion conductive film on one side of the prepared oxygen carrier;
S2、将步骤S1中所制备的片状载氧体放到化学链燃烧反应器中，使片状载氧体将化学链燃烧反应器中的反应室9与惰性室8分隔开，且氧离子传导膜位于反应室9内一侧；分别向反应室9与惰性室8内通入作为还原性气体的燃料气和作为保护气体的惰性气，并在加热条件下发生化学链燃烧，燃烧反应后反应室9出口气体通入气体产物检测系统进行检测，通过分析气态产物的累计浓度，计算获得载氧体的转化率与时间的对应关系；S2. Place the flaky oxygen carrier prepared in step S1 into the chemical chain combustion reactor, so that the flaky oxygen carrier separates the reaction chamber 9 and the inert chamber 8 in the chemical chain combustion reactor, and the oxygen The ion conductive membrane is located on one side of the reaction chamber 9; fuel gas as a reducing gas and inert gas as a protective gas are introduced into the reaction chamber 9 and the inert chamber 8 respectively, and chemical chain combustion and combustion reactions occur under heating conditions. The gas at the outlet of rear reaction chamber 9 is passed into the gas product detection system for detection. By analyzing the cumulative concentration of gaseous products, the corresponding relationship between the conversion rate of the oxygen carrier and time is calculated and obtained;
S3、利用步骤S2的结果，结合菲克第二定律和阿累尼乌斯定律求解载氧体的体相氧迁移动力学参数。S3. Use the results of step S2 and combine Fick's second law and Arrhenius' law to solve the bulk phase oxygen migration kinetic parameters of the oxygen carrier.
上述步骤S1，利用载氧体粉末与氧离子导体粉末制备片状载氧体，具体流程如下：In the above step S1, oxygen carrier powder and oxygen ion conductor powder are used to prepare a sheet-shaped oxygen carrier. The specific process is as follows:
取载氧体粉末放入模具中，施加压力，静压放置；Take the oxygen carrier powder and put it into the mold, apply pressure and place it under static pressure;
打开模具，取氧离子导体粉末放入模具中静压处理后的载氧体粉末表面，施加压力，静压放置，形成片状载氧体；Open the mold, take the oxygen ion conductor powder and put it into the mold on the surface of the oxygen carrier powder after static pressure treatment, apply pressure, and place it under static pressure to form a flaky oxygen carrier;
从模具中取出所述片状载氧体，放入马弗炉内煅烧，降至室温得到最终的载氧体成品。The sheet-shaped oxygen carrier is taken out from the mold, placed in a muffle furnace, calcined, and lowered to room temperature to obtain the final finished oxygen carrier.
上述步骤S3中，体相氧迁移动力学参数包括载氧体的氧离子扩散系数和氧离子迁移过程的活化能，载氧体的氧离子扩散系数Dt为：In the above step S3, the bulk phase oxygen migration kinetic parameters include the oxygen ion diffusion coefficient of the oxygen carrier and the activation energy of the oxygen ion migration process. The oxygen ion diffusion coefficient D t of the oxygen carrier is:
Dt代表t时刻的氧离子扩散系数，S代表与材料的氧离子扩散有关的常数，l代表载氧体的厚度；D t represents the oxygen ion diffusion coefficient at time t, S represents the constant related to the oxygen ion diffusion of the material, and l represents the thickness of the oxygen carrier;
通过步骤S2所得载氧体的转化率与时间的对应关系，求解常数S，载氧体的转化率Xt为：Through the corresponding relationship between the oxygen carrier conversion rate and time obtained in step S2, the constant S is solved, and the oxygen carrier conversion rate X t is:
采用下式计算氧离子迁移过程的活化能Ea：Use the following formula to calculate the activation energy Ea of the oxygen ion migration process:
上两式中，Davg代表平均氧离子扩散系数，Rg代表通用气体常数，T代表温度，Davg，0代表频率因子，即拟合参数；N代表离散求解过程中在所求时间范围内所取的总点数，i代表点数序号，(Dt)i代表t时刻第i号点所对应的氧离子扩散系数。In the above two formulas, D avg represents the average oxygen ion diffusion coefficient, Rg represents the universal gas constant, T represents the temperature, D avg, 0 represents the frequency factor, that is, the fitting parameter; N represents the time range in the discrete solution process. The total number of points taken, i represents the point number, (D t ) i represents the oxygen ion diffusion coefficient corresponding to the i-th point at time t.
以下以涂覆GDC材料的红泥载氧体为例，进一步说明本申请的载氧体体相氧迁移动力学的测试方法，包括以下步骤：The following takes the red mud oxygen carrier coated with GDC material as an example to further illustrate the testing method of oxygen carrier bulk phase oxygen migration kinetics in this application, which includes the following steps:
S1：利用红泥粉末与GDC粉末制备所需的片状载氧体，具体采用粉末压片法得到所需的载氧体材料，包括：S1: Use red mud powder and GDC powder to prepare the required flaky oxygen carrier. Specifically, use the powder pressing method to obtain the required oxygen carrier material, including:
S11：取适量红泥粉末，放入研钵内充分研磨，然后倒入模具中，利用压片机在60MPa的压力下压制3分钟；S11: Take an appropriate amount of red mud powder, put it into a mortar and grind it thoroughly, then pour it into the mold, and press it with a tablet press under a pressure of 60MPa for 3 minutes;
S12：打开模具，取适量GDC粉末，充分研磨后倒入模具中覆盖到已静压处理的红泥表面，在120MPa的压力下压制3分钟；S12: Open the mold, take an appropriate amount of GDC powder, grind it thoroughly and pour it into the mold to cover the surface of the red mud that has been treated by static pressure, and press it under a pressure of 120MPa for 3 minutes;
S13：将压好的片状载氧体从模具中取出，放入马弗炉内，保持2℃/min的升温速率升至1350℃，保持1350℃的温度煅烧6个小时，然后冷却至室温得到所需载氧体材料。S13: Take out the pressed sheet oxygen carrier from the mold, put it into the muffle furnace, maintain a heating rate of 2℃/min to 1350℃, maintain the temperature of 1350℃ for calcination for 6 hours, and then cool to room temperature. Obtain the required oxygen carrier material.
S2：利用上述实施例的测试装置进行化学链燃烧实验，得到载氧体的转化率与时间的对应关系：S2: Use the test device of the above embodiment to conduct a chemical chain combustion experiment, and obtain the corresponding relationship between the conversion rate of the oxygen carrier and time:
使用的燃料气为一氧化碳(CO)与氮气(N2)混合气，其体积流量为50ml/min，压力为1atm，温度为常温，其中，一氧化碳其中体积分数为5％；使用的惰性气体为氩气(Ar)，其体积流量为50ml/min，压力为1atm，温度为常温。The fuel gas used is a mixture of carbon monoxide (CO) and nitrogen (N 2 ), with a volume flow rate of 50 ml/min, a pressure of 1 atm, and a temperature of normal temperature. The volume fraction of carbon monoxide is 5%; the inert gas used is argon. Gas (Ar), its volume flow rate is 50ml/min, the pressure is 1atm, and the temperature is normal temperature.
反应压力为1atm，温度为700℃、750℃、800℃和850℃四种不同温度。使用MRU气体分析仪分析产物气体中气态产物CO2的累计浓度，得到不同温度下载氧体的转化率与时间的对应关系，其结果如图2所示。The reaction pressure is 1 atm, and the temperature is four different temperatures: 700°C, 750°C, 800°C and 850°C. The MRU gas analyzer was used to analyze the cumulative concentration of the gaseous product CO 2 in the product gas, and the corresponding relationship between the conversion rate of oxygen at different temperatures and time was obtained. The results are shown in Figure 2.
S3：结合菲克第二定律和阿累尼乌斯定律求解载氧体材料体相氧迁移动力学参数，求解得到载氧体在不同时间、不同温度下的氧离子扩散系数如图3所示，平均氧离子扩散系数如图4所示，氧离子迁移过程的阿累尼乌斯关系如图5所示。结果表明，在700℃、750℃、800℃和850℃四种不同温度下，涂覆GDC材料的红泥载氧体平均氧离子扩散系数分别为0.24511×10-10m2/s、0.55163×10-10m2/s、0.92845×10-10m2/s和1.74602×10-10m2/s，氧离子迁移过程的活化能为116.67kJ/mol。S3: Combining Fick's second law and Arrhenius' law to solve the bulk phase oxygen migration kinetic parameters of the oxygen carrier material, and obtain the oxygen ion diffusion coefficient of the oxygen carrier at different times and temperatures, as shown in Figure 3 , the average oxygen ion diffusion coefficient is shown in Figure 4, and the Arrhenius relationship of the oxygen ion migration process is shown in Figure 5. The results show that at four different temperatures of 700°C, 750°C, 800°C and 850°C, the average oxygen ion diffusion coefficients of the red mud oxygen carrier coated with GDC materials are 0.24511×10 -10 m 2 /s and 0.55163× respectively. 10 -10 m 2 /s, 0.92845 ×10 -10 m 2 /s and 1.74602×10 -10 m 2 /s, the activation energy of the oxygen ion migration process is 116.67kJ/mol.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110940222.1A CN113834897B (en) | 2021-08-16 | 2021-08-16 | Method and device for testing bulk oxygen migration dynamics in chemical chain technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110940222.1A CN113834897B (en) | 2021-08-16 | 2021-08-16 | Method and device for testing bulk oxygen migration dynamics in chemical chain technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113834897A CN113834897A (en) | 2021-12-24 |
| CN113834897B true CN113834897B (en) | 2023-11-24 |
Family
ID=78960519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110940222.1A Active CN113834897B (en) | 2021-08-16 | 2021-08-16 | Method and device for testing bulk oxygen migration dynamics in chemical chain technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113834897B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118022855A (en) * | 2024-04-15 | 2024-05-14 | 昆明理工大学 | Chemical looping combustion enriched CO of blast furnace gas2Is a method of (2) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102200277A (en) * | 2011-04-27 | 2011-09-28 | 东南大学 | Chemical chain combustion method and device through solid fuel |
| CN104848207A (en) * | 2015-04-07 | 2015-08-19 | 东南大学 | Chemical looping combustion device for solid fuel grading oxidation and method thereof |
| CN104870894A (en) * | 2012-11-30 | 2015-08-26 | 沙特阿拉伯石油公司 | Staged chemical looping process with integrated oxygen generation |
| CN108821236A (en) * | 2018-06-04 | 2018-11-16 | 昆明理工大学 | A kind of method of the continuous producing synthesis gas of chemical chain |
| CN109438159A (en) * | 2018-10-26 | 2019-03-08 | 东南大学 | One kind being based on chemical chain Lattice Oxygen Transfer Technology methane oxidation coupling method |
| CN111477285A (en) * | 2020-04-24 | 2020-07-31 | 华中科技大学 | Method for obtaining thermal neutral oxygen carrier in chemical looping combustion process |
-
2021
- 2021-08-16 CN CN202110940222.1A patent/CN113834897B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102200277A (en) * | 2011-04-27 | 2011-09-28 | 东南大学 | Chemical chain combustion method and device through solid fuel |
| CN104870894A (en) * | 2012-11-30 | 2015-08-26 | 沙特阿拉伯石油公司 | Staged chemical looping process with integrated oxygen generation |
| CN104848207A (en) * | 2015-04-07 | 2015-08-19 | 东南大学 | Chemical looping combustion device for solid fuel grading oxidation and method thereof |
| CN108821236A (en) * | 2018-06-04 | 2018-11-16 | 昆明理工大学 | A kind of method of the continuous producing synthesis gas of chemical chain |
| CN109438159A (en) * | 2018-10-26 | 2019-03-08 | 东南大学 | One kind being based on chemical chain Lattice Oxygen Transfer Technology methane oxidation coupling method |
| CN111477285A (en) * | 2020-04-24 | 2020-07-31 | 华中科技大学 | Method for obtaining thermal neutral oxygen carrier in chemical looping combustion process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113834897A (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113834897B (en) | Method and device for testing bulk oxygen migration dynamics in chemical chain technology | |
| CN107973271B (en) | The reaction unit and application method of micro CO in a kind of removing hydrogen-rich gas | |
| CN111302302A (en) | Thermochemical hydrogen production system based on microwave heating and hydrogen production method and application thereof | |
| CN105967145B (en) | A kind of palladium/palladium alloy membrane purifier and its application method | |
| CN110155941B (en) | A kind of microwave heating hydrogen production device and hydrogen production method and application based on thermochemical cycle | |
| CN111593292A (en) | Vacuum furnace carbon potential dynamic detection device and detection method thereof | |
| JP3285511B2 (en) | Gas analysis test equipment | |
| CN107128896B (en) | Graphite fluoride tubular reaction furnace | |
| CN207689445U (en) | A kind of SCR denitration full-scale performance detection evaluating apparatus | |
| CN107265413B (en) | The system for preparing high-purity nitrogen efficiency for improving membrane separator | |
| Salanov et al. | Oxygen interaction with rhodium at low pressures | |
| Tsuchida et al. | Low-temperature hydrogen reduction of iron oxide by controlling the water potential using a CaH2 drying agent | |
| Hoffmann | The kinetics of CO dissociation on Ru (001): Time‐resolved vibrational spectroscopy at elevated pressures | |
| CN110935329A (en) | Preparation method of silver/alumina composite hollow fiber oxygen permeable membrane microreactor | |
| CN211741178U (en) | A thermal aging test platform for high temperature gas-cooled reactor ceramic reactor internal components | |
| CN212505037U (en) | Vacuum furnace carbon potential dynamic detection device | |
| CN114486794B (en) | Cogasification reaction detection device and method for coke, water vapor and carbon dioxide | |
| CN113122796B (en) | A vanadium-ferro-continuous nitriding device and process thereof | |
| CN213839523U (en) | Flange sealing device convenient for feeding and discharging of high-temperature tube furnace | |
| CN110865144A (en) | A thermal aging test platform for high temperature gas-cooled reactor ceramic reactor internal components | |
| CN208921584U (en) | It is a kind of for obtaining the capturing device of carbon soot particles in combustion process | |
| CN114904359B (en) | Device for selectively removing CO and application method thereof | |
| CN221426568U (en) | Methanol reforming hydrogen production catalyst evaluation integrated device | |
| Dong et al. | A self-catalytic mixed-conducting membrane reactor for effective production of hydrogen from methane | |
| CN221924560U (en) | Ammonia decomposition furnace device for powder sintering furnace |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |