催化剂微纳孔道内液体推进剂流动与分解反应过程研究

doi:10.11949/0438-1157.20240808

摘要/Abstract

摘要：

单组元能源属于燃气能源，不同于依赖氧气燃烧释能的常规能源，它是无须空气条件下通过催化分解含能液体化学品生成高温高压气体，流经拉瓦尔喷管产生推力或吹动涡轮输出轴功率。特点是高可靠，快响应，低成本，飞行高度不受限，常被用于为航空航天装备提供轨道维持和应急保障的动力。该类能源动力系统启动时，液体推进剂进入到反应催化床内与催化剂接触，并在毛细管力作用下，浸入载体微-纳孔道内被贵金属纳米粒子活化，发生催化分解反应生成高温高压小分子气相。受催化剂孔道结构、尺寸及表面活性影响，孔道内催化分解产气速率大于流体向外运动速度时，内部气相压力会急剧升高，甚至破坏载体毛细孔道结构导致失活。本文采用Poiseuille流描述催化剂孔道内的气相产物流动、毛细管力驱动牛顿第二定律解析气-液界面移动、反应物扩散-反应模型预测产气速率，揭示肼推进剂催化分解反应启动时在催化剂微纳孔道内的流动，催化反应以及气相压力形成过程，解析了启动过程中孔道内压过大导致催化剂破坏失活的物理现象，为单组元推进剂分解用催化剂孔道结构设计开发提供理论基础。

关键词: Poiseuille流, 毛细管, 肼分解, 扩散, 反应, 催化剂孔道, 传质

Abstract:

Monopropellant energy belongs to gas energy. Unlike conventional energy that relies on oxygen combustion to release energy, it generates high-temperature and high-pressure gas by catalytic decomposition of energetic liquid chemicals without air, which flows through the Laval nozzle to generate thrust or blow the turbine output shaft power. The characteristics are high reliability, fast response, low cost, and unrestricted flight altitude. It is often used to maintain the satellite orbit and provide the emergency power unit for aerospace equipment. With start-up of this power system, the liquid monopropellant enters the packed bed and contacts with the catalyst particles, and then immerses into the micro/nano pores of the catalyst carrier under the action of capillary force. The high-temperature and high-pressure small molecule gas phase is generated with being activated and decomposed by precious metal nanoparticles. With the influence of catalyst pore structure, size, and surface activity, when the gas production rate of catalytic decomposition inside the pore is greater than the outward movement speed of the fluid, the internal pressure in the pore will sharply increase, and even damage the carrier to deactivate. In this paper, the Poiseuille flow is used to describe the flow of gas-phase products in catalyst pores, the Newton’s second law is employed to analyze the movement of gas-liquid interface driven by capillary force, and the gas production rate is predicted through reactant diffusion reaction model. The phenomena of flow, catalytic reaction and gas-phase pressure formation process in the catalyst micro/nano pores is investigated during the initiation of hydrazine propellant catalytic decomposition reaction. The physical phenomenon of catalyst destruction and deactivation caused by the excessive pressure in the pores is analyzed during the initiation process, a theoretical basis for designing and optimizing the catalyst pore structures is provided for decomposing monopropellant.

Key words: Poiseuille flow, capillary, hydrazine decomposition, diffusion, reaction, catalyst pores, mass transfer

中图分类号:

TQ 032.4

侯宝林, 韩若曦, 王晓东. 催化剂微纳孔道内液体推进剂流动与分解反应过程研究[J]. 化工学报, 2024, 75(11): 4254-4263.

Baolin HOU, Ruoxi HAN, Xiaodong WANG. Process of monopropellant flow and catalytic decomposition reaction in micro/nano pores of catalyst[J]. CIESC Journal, 2024, 75(11): 4254-4263.

图/表 15

图1 液体单组元推进剂固定床催化分解过程

Fig.1 Catalytical decomposition of liquid monopropellant in packed bed

图2 液体推进剂与催化剂接触时毛细管力作用简化模型示意图

Fig.2 Schematic diagram of simplified model of capillary force action with monopropellant contacting with catalysts

图3 肼液滴与催化剂接触反应过程实验

Fig.3 Experimental investigation on the process of hydrazine droplet contacting with catalysts

图4 单组元发动机点火实验舱示意图1—真空舱;2—高压氮气阀门;3—推进剂储箱;4—单组元发动机;5—推力架;6—真空泵入口

Fig.4 Schematic diagram of monopropellant thruster ignition test chamber1—vacuum chamber; 2—high pressure nitrogen valve; 3—propellant storage tank; 4—monopropellant; 5—thrust force test; 6—vacuum pump inlet

图5 单组元发动机燃压曲线

Fig.5 The curve of combustion pressure in monopropellant thruster

图6 气-液界面移动与孔内压力随时间的变化曲线

Fig.6 The curves with various time on the gas-liquid interface displacement and pressure in pore

图7 不同孔道直径对孔道内气-液界面移动的影响

Fig.7 The effect of pore diameter on the gas-liquid interface displacement in the catalyst pores

图8 不同平均孔道直径对孔道内压的影响

Fig.8 The effect of pore diameter on the pressure in the catalyst pores

图9 催化剂孔道结构示意图

Fig.9 Schematic diagram of catalyst pore structure

图10 外小内大孔道结构对气-液界面位移的影响

Fig.10 The influence of external small and internal large pore structure on gas-liquid interface displacement

图11 外小内大孔道结构对孔道内压力的影响

Fig.11 The influence of external small and internal large pore structure on the pressure in catalyst pore

图12 外大内小孔道结构对气-液界面位移的影响

Fig.12 The influence of external large and internal small pore structure on gas-liquid interface displacement

图13 外大内小孔道结构对孔道内压力的影响

Fig.13 The influence of external large and internal small pore structure on the pressure in catalyst pores

图14 催化反应温度对气-液界面移动的影响

Fig.14 The influence of reaction temperature on the gas-liquid interface displacement

图15 催化反应温度对催化剂孔道内压力的影响

Fig.15 The influence of reaction temperature on the pressure in the catalyst pores

参考文献 30

1	Hwang C H, Lee S N, Baek S W, et al. Effects of catalyst bed failure on thermochemical phenomena for a hydrazine monopropellant thruster using Ir/Al₂O₃ catalysts[J]. Industrial & Engineering Chemistry Research, 2012, 51(15): 5382-5393.
2	Hou B L, Wang X D, Li T, et al. Steady-state behavior of liquid fuel hydrazine decomposition in packed bed[J]. AIChE Journal, 2015, 61(3): 1064-1080.
3	Spores R, Masse R, Kimbrel S, et al. GPIM AF-M315E propulsion system[C]//51st AIAA/SAE/ASEE Joint Propulsion Conference. Reston, Virginia: AIAA, 2015: 3753.
4	Chambreau S D, Popolan-Vaida D M, Kostko O, et al. Thermal and catalytic decomposition of 2-hydroxyethylhydrazine and 2-hydroxyethylhydrazinium nitrate ionic liquid[J]. The Journal of Physical Chemistry A, 2022, 126(3): 373-394.
5	Koerner M. Recent developments in aircraft emergency power[C]//35th Intersociety Energy Conversion Engineering Conference and Exhibit. Reston, Virginia: AIAA, 2000: 2802.
6	Masse R K, Glassy B A, Spores R A, et al. Hydrazine-based green monopropellant blends[C]//AIAA SCITECH 2024 Forum. Reston, Virginia: AIAA, 2024: 1619.
7	Thomas J C, Rodriguez F A, Teitge D S, et al. Lab-scale ballistic and safety property investigations of LMP-103S[J]. Combustion and Flame, 2023, 253: 112810.
8	Esparza A A, Chambreau S D, Vaghjiani G L, et al. Two-stage decomposition of 2-hydroxyethylhydrazinium nitrate (HEHN)[J]. Combustion and Flame, 2020, 220: 1-6.
9	杨敏, 曹炳阳. 微纳通道中牛顿流体毛细流动的研究进展[J]. 科学通报, 2016, 61(14): 1574-1584.
	Yang M, Cao B Y. Advances of capillary filling of Newtonian fluids in micro- and nanochannels[J]. Chinese Science Bulletin, 2016, 61(14): 1574-1584.
10	Ye G H, Wang H Z, Zhou X G, et al. Optimizing catalyst pore network structure in the presence of deactivation by coking[J]. AIChE Journal, 2019, 65(10): e16687.
11	Kerr D H, Karagozian A R, Bilyeu D, et al. Nondeterministic analysis of monopropellant catalyst bed model[J]. Journal of Propulsion and Power, 2021, 37(1): 126-138.
12	Sun D C, Liu J, Xiang W B. Numerical simulation of the transient process of monopropellant rocket engines[J]. Aerospace Science and Technology, 2020, 103: 105921.
13	Hwang C H, Baek S W, Cho S J. Experimental investigation of decomposition and evaporation characteristics of HAN-based monopropellants[J]. Combustion and Flame, 2014, 161(4): 1109-1116.
14	Walls P L L, Dequidt G, Bird J C. Capillary displacement of viscous liquids[J]. Langmuir, 2016, 32(13): 3186-3190.
15	Fries N, Dreyer M. An analytic solution of capillary rise restrained by gravity[J]. Journal of Colloid and Interface Science, 2008, 320(1): 259-263.
16	Bird B R, Stewart W E, Lightfoot E N. Transport Phenomena[M]. 2nd ed. New York: John Wiley & Sons, Inc., 2002:46.
17	Levenspiel O. Chemical Reaction Engineering [M]. 3rd ed. New York: John Wiley & Sons, Inc., 1999:105.
18	Washburn E W. The dynamics of capillary flow[J]. Physical Review, 1921, 17(3): 273-283.
19	Figliuzzi B, Buie C R. Rise in optimized capillary channels[J]. Journal of Fluid Mechanics, 2013, 731: 142-161.
20	Han A P, Mondin G, Hegelbach N G, et al. Filling kinetics of liquids in nanochannels as narrow as 27 nm by capillary force[J]. Journal of Colloid and Interface Science, 2006, 293(1): 151-157.
21	Wu P K, Ramakrishnan T S, Zhang H, et al. Closed-end capillary rise—an experimental study[J]. AIChE Journal, 2020, 66(6): e16964.
22	Wood J, Gladden L F. Modelling diffusion and reaction accompanied by capillary condensation using three-dimensional pore networks (Part 1): Fickian diffusion and pseudo-first-order reaction kinetics[J]. Chemical Engineering Science, 2002, 57(15): 3033-3045.
23	Wood J, Gladden L F, Keil F J. Modelling diffusion and reaction accompanied by capillary condensation using three-dimensional pore networks (Part 2): Dusty gas model and general reaction kinetics[J]. Chemical Engineering Science, 2002, 57(15): 3047-3059.
24	吕同富, 康兆敏, 方秀男. 数值计算方法[M]. 北京: 清华大学出版社, 2008: 281.
	Lyu T F, Kang Z M, Fang X N. Numerical Computation Method[M]. Beijing: Tsinghua University Press, 2008: 281.
25	Soares Neto T G, Dias F F, Cobo A J G, et al. Evolution of textural properties and performance of Ir/Al₂O₃ catalysts during hydrazine catalytic decomposition in a 2N satellite thruster[J]. Chemical Engineering Journal, 2011, 173(1): 220-225.
26	Heo S, Jo S, Yun Y, et al. Effect of dual-catalytic bed using two different catalyst sizes for hydrogen peroxide thruster[J]. Aerospace Science and Technology, 2018, 78: 26-32.
27	Wilhelm M, Negri M, Ciezki H, et al. Preliminary tests on thermal ignition of ADN-based liquid monopropellants[J]. Acta Astronautica, 2019, 158: 388-396.
28	Negri M, Lauck F. Hot firing tests of a novel green hypergolic propellant in a thruster[J]. Journal of Propulsion and Power, 2022, 38(3): 467-477.
29	吴越. 应用催化基础[M]. 北京: 化学工业出版社, 2009: 243.
	Wu Y. Basis of Applied Catalysis[M]. Beijing: Chemical Industry Press, 2009: 243.
30	Gugulothu R, Macharla A K, Chatragadda K, et al. Catalytic decomposition mechanism of aqueous ammonium dinitramide solution elucidated by thermal and spectroscopic methods[J]. Thermochimica Acta, 2020, 686: 178544.

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