CN111646870A - 一种应用于低温启动单组元推进剂的催化剂及其制备方法 - Google Patents
一种应用于低温启动单组元推进剂的催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000003380 propellant Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 claims abstract 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims 5
- 238000001354 calcination Methods 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/04—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by auto-decomposition of single substances
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种应用于低温启动单组元推进剂的催化剂及其制备方法，主要解决现有的催化剂在肼基推进剂低温冷启动时因催化剂初始活性低导致孔道微爆破碎的问题。该催化剂是在高强度多维孔结构氧化铝载体上负载两种贵金属。利用贵金属之间的协同效应，提高催化剂在低温条件下的催化活性。本发明涉及的催化剂可应用的催化分解反应温度为‑55～100℃。
Description
技术领域
本发明涉及一种催化剂应用技术领域，特别涉及用于低温启动肼基单组元推进剂的催化剂及制备方法。
背景技术
单组元液体推进系统具有系统简单、可靠性高等特点，广泛应用于航天推进系统，可用于航天飞行器调速、入轨、定点和姿控等。目前绝大部分运载火箭辅助动力系统均采用单组元推进系统，单组元推进剂在催化剂作用下进行稳定、高效分解是实现推进系统正常工作的关键。自上世纪60年代，美国Shell公司研制出了用于催化分解肼基推进剂的Shell405催化剂，成功应用于各种小型姿态控制发动机上。继美国之后，英、法、德、日等国也相继研制出了Ir/Al2O3催化剂，如德国的KCIRGA、法国的CNESRO-1和英国的RPE72/1。我国自上世纪60年代开始研制肼分解催化剂，先后研制成功了812、814、816、818、819等系列肼分解催化剂，并在我国多种卫星及其他航天飞行器中得到使用。
随着深空探测等任务的推进，要求宇航动力系统包括卫星、运载火箭飞船等航天器具有在低温苛刻环境条件工作的适用性，这对推进剂在低温快速启动提出了更高的要求。针对现用的肼分解催化剂，研究人员采用多种方法对催化剂活性的温度敏感性进行了研究。1968年，美国喷气实验室采用发动机试验研究了催化床温度对催化剂起活性能的影响，测试温度从-42℃到35℃，点火延迟期随催化床温度降低而增大，床温为19℃时点火延迟期5ms；床温-8℃时点火延迟期300ms。上世纪80年代，国内采用40N发动机和816催化剂，对DT-3推进剂进行了冷、热启动对比分解试验。1#发动机共进行21次冷启动，催化剂破碎9.1％，室压下降8.4％，床流阻增加60.9％。而2#、3#发动机经过连续热启动1249次，为1#发动机冷启动次数的60倍，催化剂破损仅6.7％，室压平均下降4.6％，床流阻平均增加45.1％。上世纪90年代，国内采用200N推力室，以多种比例装填国产816、814催化剂，在低温下分解H-70肼水推进剂，H70在-30℃以下未能成功实现低温启动，在-18℃～-26℃，H70起始分解时间是与温度有关的变量函数，温度越低，起始分解时间越长。
近年来，人们主要通过优化发动机结构改进推进系统的低温启动性能，如采用加热保温装置提高催化床温度，设计喷注器缓冲装置减少进入催化剂床的推进剂量，延长推进剂与催化剂接触时间等措施。但这些发动机结构的改进方法将导致推进系统复杂化，有效载荷降低。尤其对于已定型的发动机，结构改变成本较高。
本发明针对几种新型低温启动单组元肼基推进剂，有针对性地开发一种用于低温启动单组元肼基推进剂的催化剂，从根本上改善肼基催化剂的低温启动性能。
发明内容：
本发明的目的是针对背景技术中存在的现用肼分解催化剂低温活性低的问题，而提供一种用于低冰点单组元肼基推进剂的催化剂及其制备方法。
本发明解决其问题可以通过如下技术方案来达到：
(1)在载体上浸渍氯铱酸，经低温冷冻干燥、焙烧处理样品。
(2)交替浸渍氯金酸或氯铂酸或氯化铑或氯化钌，经液氮冷冻0.5-2h后冷冻干燥4-24h，在200-600℃范围内焙烧0.5-4h，重复(1)-(2)步，直至负载量达到5-40wt.％，停止浸渍过程，经还原及稳定化处理后得到目标催化剂。
本发明有益效果体现在：
(1)该催化剂的多维孔道结构，有利于低温下推进剂及分解产物的在孔道内的快速流动及扩散，避免分解气体聚集导致催化剂破碎，工作性能下降，适用于单组元推进剂在-10℃～-55℃下的低温启动。
(2)该催化剂的双金属配方，利用双金属协同效应，在低温条件下具有高催化活性，适用于单组元推进剂在-10℃～-55℃下的低温启动。
附图说明：
无
具体实施方式：
实施例1
(1)在强度为35MPa、比表面为220m2/g、堆密度为0.8g/cm3、孔结构为0-2nm、2-6nm、100-150nm的氧化铝载体上，浸渍氯铱酸中，经液氮低温冷冻0.5h，冷冻干燥6h，在500℃焙烧2h。
(2)交替浸渍氯化钉，经液氮低温冷冻0.5h，冷冻干燥6h，在500℃焙烧2h，重复(1)-(2)步，直至负载量达到25％，停止浸渍过程，经还原及稳定化处理后得到目标催化剂。
实施例2
(1)在强度为38MPa、比表面为200m2/g、堆密度为0.7g/cm3、孔结构为0-2nm、2-8nm、100-200nm的氧化铝载体上，浸渍氯铱酸中，经液氮低温冷冻1h，冷冻干燥8h，在500℃焙烧2h。
(2)交替浸渍氯化铑，经液氮低温冷冻1h，冷冻干燥4h，在500℃焙烧2h，重复(1)-(2)步，直至负载量达到30％，停止浸渍过程，经还原及稳定化处理后得到目标催化剂。
实施例3
(1)在强度为50MPa、比表面为150m2/g、堆密度为0.8g/cm3、孔结构为0-2nm、3-7nm、150-200nm的氧化铝载体上，浸渍氯铱酸中，经液氮低温冷冻1h，冷冻干燥8h，在400℃焙烧2h。
(2)交替浸渍氯化铑，经液氮低温冷冻1h，冷冻干燥4h，在400℃焙烧2h，重复(1)-(2)步，直至负载量达到38％，停止浸渍过程，经还原及稳定化处理后得到目标催化剂。
Claims (7)
1.一种应用于低温启动单组元推进剂的催化剂的制备方法，其特征是在高强度多维孔结构氧化铝载体上负载两种贵金属A、B。主要包括以下步骤：
(1)在载体上浸渍贵金属前驱体A中，经低温冷冻干燥、焙烧处理样品。
(2)交替浸渍贵金属前驱体B，冷冻干燥后焙烧，重复(1)-(2)步，直至负载量达到目标，停止浸渍过程，经还原及稳定化处理后得到目标催化剂。
2.根据权利要求1所述的高强度多维孔结构氧化铝载体，其特征在于所述的多维孔结构为0-2nm、2-10nm、100-500nm三级孔道结构，比表面积为100-300m2/g，载体堆密度为0.6-1.0g/cm3。
3.根据权利要求1所述的高强度多维孔结构氧化物载体，其特征在于所述的高强度为30-100MPa。
4.根据权利要求1所述的两种贵金属前驱体A、B，其特征在于所述的贵金属前驱体A为氯铱酸。贵金属前驱体B为氯金酸或氯铂酸或氯化铑或氯化钉。
5.根据权利要求1所述的冷冻干燥为经液氮冷冻0.5-2h处理后，冷干4-24h。
6.根据权利要求1所述的焙烧为在200-600℃范围内焙烧0.5-4h。
7.根据权利要求1所述的负载量目标为5-40wt.％。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950414A (zh) * | 2022-03-31 | 2022-08-30 | 北京航天试验技术研究所 | 一种用于肼基复合燃料分解的催化剂及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3732694A (en) * | 1968-01-18 | 1973-05-15 | Trw Inc | Method for the catalytic decomposition of monopropellant hydrazine |
| US3929682A (en) * | 1973-08-16 | 1975-12-30 | Kali Chemie Ag | Catalyst for decomposing hydrazine and its derivatives and process of making same |
| US4124538A (en) * | 1964-05-28 | 1978-11-07 | Shell Oil Company | Catalyst comprising Ir or Ir and Ru for hydrazine decomposition |
| JPH0285224A (ja) * | 1988-06-13 | 1990-03-26 | Mitsui Toatsu Chem Inc | ジメチルエーテルの製造方法 |
| CN101357336A (zh) * | 2007-08-03 | 2009-02-04 | 中国科学院成都有机化学有限公司 | 高温催化分解氧化亚氮(n2o)的方法 |
| CN101411975A (zh) * | 2007-10-19 | 2009-04-22 | 中国科学院大连化学物理研究所 | 一种炭载过渡金属碳化物催化剂在肼分解反应中的应用 |
-
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- 2020-05-06 CN CN202010379656.4A patent/CN111646870A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124538A (en) * | 1964-05-28 | 1978-11-07 | Shell Oil Company | Catalyst comprising Ir or Ir and Ru for hydrazine decomposition |
| US3732694A (en) * | 1968-01-18 | 1973-05-15 | Trw Inc | Method for the catalytic decomposition of monopropellant hydrazine |
| US3929682A (en) * | 1973-08-16 | 1975-12-30 | Kali Chemie Ag | Catalyst for decomposing hydrazine and its derivatives and process of making same |
| JPH0285224A (ja) * | 1988-06-13 | 1990-03-26 | Mitsui Toatsu Chem Inc | ジメチルエーテルの製造方法 |
| CN101357336A (zh) * | 2007-08-03 | 2009-02-04 | 中国科学院成都有机化学有限公司 | 高温催化分解氧化亚氮(n2o)的方法 |
| CN101411975A (zh) * | 2007-10-19 | 2009-04-22 | 中国科学院大连化学物理研究所 | 一种炭载过渡金属碳化物催化剂在肼分解反应中的应用 |
Non-Patent Citations (1)
| Title |
|---|
| 湛建阶等: "肼类分解催化剂研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114950414A (zh) * | 2022-03-31 | 2022-08-30 | 北京航天试验技术研究所 | 一种用于肼基复合燃料分解的催化剂及其制备方法 |
| CN114950414B (zh) * | 2022-03-31 | 2023-11-07 | 北京航天试验技术研究所 | 一种用于肼基复合燃料分解的催化剂及其制备方法 |
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