CN113348742B - Sub-nano dispersed IrRh bimetallic catalyst and application thereof - Google Patents
Sub-nano dispersed IrRh bimetallic catalyst and application thereof Download PDFInfo
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- CN113348742B CN113348742B CN201818004667.8A CN201818004667A CN113348742B CN 113348742 B CN113348742 B CN 113348742B CN 201818004667 A CN201818004667 A CN 201818004667A CN 113348742 B CN113348742 B CN 113348742B
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Abstract
The invention relates to a sub-nanometer dispersed IrRh bimetallic catalyst, in particular to an alumina-loaded IrRh bimetallic catalyst and preparation and application thereof. The precious metal IrRh is highly dispersed on the alumina carrier in the form of alloy, the IrRh bimetal can realize sub-nanometer dispersion in a wider mass ratio range, and the metal content of the IrRh bimetal is 1-20% of the total mass of the catalyst. The catalyst is suitable for catalytic decomposition of propellant hydrazine, and the low-temperature reaction activity of the catalyst is improved by 3-5 times compared with that of the traditional Ir catalyst. When the low-temperature starting frequency and the pulse working frequency of the power system are applied to the power system of a novel satellite, the low-temperature starting frequency and the pulse working frequency of the power system can be greatly increased from 4000 times and 20 ten thousand times to 8000 times and 60 ten thousand times respectively, and the on-orbit service life is expected to be prolonged to 8-10 years.
Description
The invention relates to a sub-nanometer dispersed IrRh bimetallic catalyst, in particular to an IrRh bimetallic catalyst which is highly dispersed on a carrier alumina in an alloy form and a sub-nanometer size and an application thereof.
Technical Field
Hydrazine is a stable liquid substance at ambient temperature and pressure, and thermal decomposition reactions occur when the temperature is raised to 250 ℃. Can realize rapid decomposition at lower temperature even room temperature in the presence of a catalyst to instantly generate a large amount of high-temperature high-pressure N2、H2、NH3And (4) mixing the gases. The high-energy gas is mainly used in an attitude control propulsion system and an auxiliary system of a satellite to realize speed regulation, orbit entering, fixed point and attitude control of the satellite.
The hydrazine decomposition reaction is very violent, and has high requirements on the low-temperature activity, the stability and the structure of the catalyst in practical application. It is generally required that the catalyst be able to initiate decomposition of hydrazine within tens of milliseconds at room temperature or even lower. As the hydrazine decomposition proceeds, the temperature of the catalyst bed immediately rises to 900 ℃, which requires that the hydrazine decomposition catalyst have high mechanical strength and resistance to quenching and quenching, providing excellent stability. At present, attitude control propulsion systems of satellites, particularly power systems with long service life, put higher requirements on the low-temperature activity and stability of hydrazine decomposition catalysts.
Since the successful development of shell405 catalyst in 1964 U.S. Pat. No. 4,124,538]The catalyst is still the most widely used hydrazine decomposition catalyst at present, and the catalyst adopts single metal Ir as an active component and Al as a carrier2O3Wherein the Ir supporting capacity is 20-40 wt%, the particle size is 3-5nm, and the Ir supporting material has the characteristics of mass transfer and heat transfer double-pore structure and good thermal stability, and is considered to be good at that timeIs a breakthrough in the true sense of the catalyst. Each country followed the development and the general trend was still to use single metal Ir. However, the Ir metal content is usually high, and as a rare precious metal, the Ir metal is also a high-grade strategic material, the stock capacity of south Africa of the main producing country is only about 400 tons, and China does not have any iridium stock capacity, so the price of the Ir metal is increasing day by day. With the development of aerospace technology, reducing the cost of catalysts has become a significant issue. The development of a low iridium or non-noble metal catalyst has been the goal of researchers in various countries. The catalyst adopted in the research shows hydrazine decomposition activity similar to that of iridium catalyst, but has low mechanical strength, limited operation stability and limited service life, and is only suitable for certain systems with low performance requirement. In general, the Shell405 catalyst is still considered to be the best overall hydrazine decomposition catalyst.
Ir is an important element of Pt group metal, the second Pt group metal is taken as an auxiliary agent, the catalytic activity of Ir can be maintained or improved while the content of Ir is expected to be reduced, and meanwhile, the second metal can stabilize Ir particles and enable the Ir particles to be highly dispersed. Balcon et al [ Ph. D Thesis, 1996] compared the hydrazine decomposition activity of Pt group metals, and found that Ir was the most active, followed by Rh, whereas Pt, Ru were less active than Rh. Since Ru is relatively inexpensive, some of the latter studies have focused on IrRu bimetallic catalysts. However, Ru in the bimetallic catalyst cannot effectively promote high dispersion of Ir, and the boiling point of Ru is low, so that the Ru may volatilize when the temperature of a reaction bed layer is high, and the stability of the catalyst is reduced.
In contrast, Rh, an important member of Pt group metals, has many excellent and unique catalytic properties compared to other metals, and the metal has higher stability and high temperature resistance compared to Ru, and plays an irreplaceable role in the field of heterogeneous catalysis represented by automobile exhaust three-way catalysts [ ACS catal.2012, 2, 1057 ]. In addition, Rh metal has itself better catalytic activity in hydrazine decomposition. The Rh metal is taken as an auxiliary agent, so that the high dispersion of Ir is promoted at high temperature, the Rh metal and the Ir form a bimetallic alloy, and the hydrazine decomposition efficiency can be improved. However, no research reports about the IrRh bimetallic alloy catalyst under the sub-nanometer size are found so far, and the application of the catalyst in hydrazine decomposition reaction is not reported.
Disclosure of Invention
The invention aims to provide a sub-nano dispersed IrRh bimetallic catalyst which can be used for low-temperature hydrazine decomposition reaction and a power system of a satellite.
In order to achieve the purpose, the invention adopts the technical scheme that;
a sub-nano dispersed IrRh bimetallic catalyst is prepared from IrRh bimetallic catalyst and Al carrier2O3The catalyst is composed of noble metal dispersed in sub-nanometer size, the total content of Ir and Rh is 1-20% of the total mass of the catalyst, and the mass ratio of Ir/Rh of the catalyst is 1: 4-4: 1, preferably 1: 1-2: 1.
The catalyst is prepared by an isometric co-impregnation method, an Ir precursor and an Rh precursor are prepared into a uniform solution according to a certain concentration, and the concentration of metal ions in the solution is 18-430 mM; using 0.1-2 mol/L HCl, H2SO4Adjusting the pH value of the solution to 3-7 by one acid; or adjusting the pH value of the solution to 7-10 by using 0.1-2 mol/L of one of NaOH and NH 3; adding the above mixed solution to Al in batches or gradually dropwise2O3Then standing and aging for 2-12h at room temperature, drying for 8-16h at 50-100 ℃, roasting for 4-10h at 200-1000 ℃, and reducing for 2-6h in hydrogen atmosphere at 200-800 ℃ to obtain the product.
The Ir precursor is chloroiridic acid or iridium chloride; the Rh precursor is rhodium chloride or rhodium nitrate, and the carrier is theta-Al2O3
The required standing and aging time is preferably 4-10 h; the drying temperature of the catalyst is preferably 60-80 ℃, the drying time is preferably 10-12h, the calcination temperature is preferably 400-600 ℃, and the calcination time is preferably 6-8 h.
The catalyst needs reduction treatment, and the preferable condition is that the reduction is carried out for 2 to 4 hours in a hydrogen atmosphere at the temperature of 200 ℃ and 400 ℃.
The catalyst can be used for catalytic decomposition reaction of hydrazine at low temperature. The hydrazine raw material is carried by argon in a bubbling mode at a certain temperatureFeeding into a fixed bed reactor with flow rate of 20-100mL min-1The hydrazine content is 1-30 vol%. In addition, the catalyst can also be used for a power system of a novel satellite, a quantitative catalyst is loaded into an engine catalytic bed in a thermal test evaluation device of the hydrazine-based single-component propellant, the propellant is supplied by adopting a gas extrusion and solenoid valve control mode, and the thermal test performance of the catalyst is investigated by measuring the temperature of an engine catalytic bed and the pressure of a combustion chamber.
Compared with the prior art, the invention has the substantial characteristics that:
1. the catalyst prepared by the method has the characteristics that the active components are in an alloy form, the iridium-rhodium bimetallic proportion is adjustable, and the iridium-rhodium bimetallic is highly dispersed in a sub-nanometer form.
2. The catalyst shows excellent low-temperature hydrazine decomposition reaction activity, and the hydrazine decomposition rate of unit metal at room temperature is improved by nearly four times compared with that of the traditional Ir catalyst.
3. The catalyst has good power propulsion performance, is applied to a novel satellite, and can greatly increase the low-temperature starting frequency and the pulse working frequency of a power system from 4000 times to 20 ten thousand times to 8000 times and 60 ten thousand times respectively.
Drawings
FIG. 1 shows Al2O3High resolution transmission electron microscopy images of bimetallic catalysts loaded with different Ir/Rh mass ratios. Wherein: the total mass content of Ir and Rh is 3 wt%, and (a) represents 2Ir1Rh/Al with the mass ratio of Ir/Rh of 2: 12O3Catalyst (example 1); (b) typically 1.5Ir1.5Rh/Al with a mass ratio of Ir/Rh of 1: 12O3Catalyst (example 2); (c) representative is 1Ir2Rh/Al with an Ir/Rh mass ratio of 1: 22O3Catalyst (example 3). As can be seen, the particles on the IrRh bimetallic catalyst are highly dispersed in a sub-nanometer (0.5-1 nm) form.
FIG. 2 shows 1Ir2Rh/Al with an Ir/Rh mass ratio of 1: 22O3The distribution of Ir and Rh in the catalyst (example 3). It can be seen that the Ir, Rh bi-metal is uniformly distributed, existing in the form of an alloy.
FIG. 3 shows examples 1 and 3 of IrRh catalyst,3, and H of comparative examples 2 and 32TPR (temperature programmed reduction) results. IrRh/Al can be seen regardless of the Ir/Rh mass ratio2O3The catalyst, which has only one reduction temperature and the temperature between the single metal Ir and the single metal Rh, shows the formation of an alloy between IrRh.
Fig. 4 shows the results of room temperature CO adsorption infrared of IrRh catalysts of examples 1 and 3, and comparative examples 2 and 3. It can be seen that the CO adsorption peak changes gradually with the change of the metal ratio between the IrRh alloys, which indicates that the surface of the catalyst is rich in Ir or Rh, but the wave number corresponding to the adsorption peak is between that of the single metal Ir and Rh.
FIG. 5 shows IrRh/Al in different Ir/Rh mass ratios2O3Catalyst examples 1, 2, 3, and comparative examples 2, 3, and reaction rates for hydrazine decomposition at room temperature. It can be seen that the addition of Rh can greatly increase the hydrazine decomposition reaction rate.
FIG. 6 shows IrRh/Al prepared by the present invention2O3The catalyst (example 6) catalyzes the engine steady-state 10s ignition result of the hydrazine propellant decomposition, where the curve labeled T in the figure is the engine catalyst bed temperature and the curve labeled Pc is the engine combustion chamber pressure. As can be seen from the figure, the engine can realize stable ignition at the low temperature of 60 ℃, the temperature of the catalytic bed and the combustion pressure of the engine rapidly rise and are stable, and the catalyst has higher activity and the capability of stably decomposing the propellant.
FIG. 7 shows the pressure profile (a) of the thrust chamber at 8000 start-ups and the results (b) of 60 ten thousand pulse ignitions for a powertrain loaded with a catalyst of the present invention (example 6). As can be seen from the figure, the pressure of the thrust chamber is stable in the 8000-time temperature starting process, the pulse combustion pressure is stable in 60 ten thousand times, and the thermal test performance of the catalyst can meet the requirements of a novel long-service-life satellite.
Detailed Description
Example 1:
2mL of 50mM H2IrCl6The solution was mixed with 2mL of 50mM RhCl2Mixing uniformly with 0.1mol/L H2SO4Adjusting the final pH value of the precursor solution to 5, and dropwise adding the solution to 1g of Al2O3Forming equal volume impregnation on the carrier, standing and aging for 4h at room temperature,standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 2Ir1Rh/Al with metal loading of 3%2O3A catalyst.
Example 2:
2mL of 38mM H2IrCl6The solution was mixed with 2mL of 75mM RhCl2Uniformly mixing, adjusting the final pH value of the precursor solution to 3 by using 1mol/L HCl solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 1.5Ir1.5Rh/Al with 3% metal loading2O3A catalyst.
Example 3:
2mL of 28mM H2IrCl6The solution was mixed with 2mL of 100mM RhCl2Mixing uniformly with 0.1mol/L NH3Adjusting the final pH value of the precursor solution to 7 by the solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 1Ir2Rh/Al with metal loading of 3%2O3A catalyst.
Example 4:
2mL of 18mM H2IrCl6The solution was mixed with 2mL of 18mM RhCl2Mixing uniformly with 0.1mol/L H2SO4Adjusting the final pH value of the precursor solution to 5, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 2Ir1Rh/Al with metal loading of 1%2O3A catalyst.
Example 5:
2mL of 160mM H2IrCl6The solution was mixed with 2mL of 160mM RhCl2Uniformly mixing, adjusting the final pH value of the precursor solution to 3 by using 1mol/L HCl solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier to form an equal volume, standing and aging at room temperature for 4h, standing at 60 deg.C for 12h to dry the catalystDrying, roasting at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 2Ir1Rh/Al with metal loading of 10%2O3A catalyst.
Example 6:
2mL of 320mM H2IrCl6The solution was mixed with 2mL of 320mM RhCl2Uniformly mixing, adjusting the final pH value of the precursor solution to 4 by using 1mol/L HCl solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 2Ir1Rh/Al with metal loading of 20%2O3A catalyst.
Example 7:
2mL of 100mM H2IrCl6The solution was mixed with 2mL of 760mM RhCl2Uniformly mixing, adjusting the final pH value of the precursor solution to 3 by using 1mol/L HCl solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 1Ir4Rh/Al with metal loading of 20%2O3A catalyst.
Example 8:
2mL of 400mM H2IrCl6The solution was mixed with 2mL of 200mM RhCl2Uniformly mixing, adjusting the final pH value of the precursor solution to 4 by using 1mol/L HCl solution, and dropwise adding the solution to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain 4Ir1Rh/Al with metal loading of 20%2O3A catalyst.
Examples 9 to 26:
the preparation method is the same as that of examples 1-8, and the specific conditions are shown in the following table.
Examples 27 to 35:
the preparation method is the same as that of examples 1-8, and the specific conditions are shown in the following table.
Comparative example 1:
the JB-3, sh-sb, CH54 catalysts used in the comparative examples were all monometallic Ir catalysts having a content of about 30 wt.%.
Comparative example 2:
3mL of 50mM H2IrCl6The solution was added dropwise to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain Ir/Al with metal loading of 3%2O3A catalyst.
Comparative example 3:
6mL of 50mM H2IrCl6The solution was added dropwise to 1g of Al2O3Soaking on the carrier in the same volume, standing at room temperature for aging for 4h, standing at 60 deg.C for 12h to dry the catalyst, calcining at 600 deg.C for 6h, and reducing at 400 deg.C for 2h to obtain Rh/Al with metal loading of 3%2O3A catalyst.
Table 1 shows the operating conditions of the catalyst of the invention (example 6) compared with the catalyst of comparative example 1 in a satellite power system. As can be seen from the table 1, the catalyst of the invention can greatly increase the low-temperature startup frequency and the pulse working frequency of a power system from 4000 times and 20 ten thousand times of the traditional catalyst to 8000 times and 60 ten thousand times respectively, and the working life is prolonged to 8-10 years.
In order to evaluate the catalytic performance of the prepared catalyst, a micro-reverse evaluation device is adopted to evaluate the activity of the hydrazine decomposition reaction of the catalyst. Hydrazine raw material is brought into the fixed bed reactor by argon gas in a bubbling mode at the temperature of 30 ℃, the hydrazine content is 3 vol%, and the flow is 100mL min-1The reaction temperature was 30 ℃.
A catalytic decomposition test of a hydrazine single-component propellant of a satellite power system is carried out, a quantitative catalyst is filled in an engine catalytic bed, a hydrazine propellant is supplied by adopting a gas extrusion and electromagnetic valve control mode, and the propellant enters the catalytic bed to be decomposed to generate high-temperature and high-pressure fuel gas. The thermal test stability of the catalyst is tested by measuring the pressure of the combustion chamber of the engine and the temperature of the catalyst bed. The power system filled with the catalyst can realize warm start times of 8000 and pulse working times of 60 ten thousand.
TABLE 1
Claims (4)
1. A sub-nanometer dispersed IrRh bimetallic catalyst is characterized in that: formed by IrRh bimetal and carrier Al2O3The total content of noble metal is 3-20% of total mass of catalyst, and the described carrier is theta-Al2O3；
The catalyst is prepared according to the following method: preparing an Ir precursor and an Rh precursor into a uniform solution according to a proportional concentration by adopting an isometric co-immersion method, wherein the concentration of metal ions in the solution is 18-430 mM; using 0.1-2 mol/L HCl, H2SO4Adjusting the pH value of the solution to 3-7 by one acid; or 0.1-2 mol/L NaOH and NH3Adjusting the pH value of the solution to 7-10 by using one alkali; dropwise adding the mixed solution to Al in batches2O3Then, standing at room temperature, aging, drying, roasting and hydrogen reduction treatment are carried out to obtain the product;
the standing and aging time is 2-12 h; the drying temperature is 50-100 ℃, and the drying time is 8-16 h; the roasting temperature is 600-1000 ℃, and the roasting time is 4-10 h; the hydrogen reduction temperature is 200-800 ℃, and the reduction time is 2-6 h;
the Ir precursor is chloroiridic acid or iridium chloride, and the Rh precursor is rhodium chloride or rhodium nitrate.
2. Use of a catalyst according to claim 1, wherein: the catalyst can be used for catalytic decomposition reaction of hydrazine at low temperature; when the method is applied to low-temperature hydrazine decomposition, hydrazine raw material is brought into a fixed bed reactor by argon gas in a bubbling mode at the temperature of 20-100 ℃, and the flow is 20-100mL min-1The hydrazine content is 1-30 vol%.
3. The use of the catalyst according to claim 2, wherein the catalyst is used in a satellite power system, namely the catalyst is filled in an engine to realize stable catalytic decomposition of a propellant, and engine steady state and pulse ignition are completed.
4. The use of the catalyst according to claim 3, wherein the power system filled with the catalyst can realize 60 ℃ low-temperature startup times of 8000 and 60 ten thousand pulse operation times.
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| CN114950414A (en) * | 2022-03-31 | 2022-08-30 | 北京航天试验技术研究所 | Catalyst for decomposing hydrazine-based composite fuel and preparation method thereof |
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| CN114950414A (en) * | 2022-03-31 | 2022-08-30 | 北京航天试验技术研究所 | Catalyst for decomposing hydrazine-based composite fuel and preparation method thereof |
| CN114950414B (en) * | 2022-03-31 | 2023-11-07 | 北京航天试验技术研究所 | Catalyst for decomposing hydrazine-based composite fuel and preparation method thereof |
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