Preparation method of catalyst for removing oxygen from hydrogen at low temperature, catalyst and application thereof

Abstract

The application discloses a preparation method of a catalyst for removing oxygen in hydrogen at low temperature, the catalyst obtained by the method and application of the catalyst. The catalyst is prepared by stirring nickel-based metal precursors, such as nickel nitrate or nickel chloride, other transition metal precursors, such as manganese salt, and a precipitator in an aqueous solution, and then through steps of standing, filtering, washing, drying and calcining. The amount of the nickel-based metal precursors and the other transition metal precursors is calculated according to metal atomic weight, and the atomic molar ratio is 1:0.25; the amount of the precipitator is calculated according to molar amount, and the molar ratio of the amount to the total metal atom molar amount is (1-4):1. The catalyst can efficiently remove oxygen in hydrogen at low temperature (80-140 DEG C) to obtain high-purity hydrogen, has high deoxidation activity, high stability and long service life; the method does not use noble metal, and has simple and controllable synthesis process, low preparation cost and convenience in industrial popularization and use.

Description

Technical Field

[0001] This invention relates to the field of gas purification, specifically to a method for preparing a catalyst for removing oxygen from hydrogen at low temperatures, the catalyst itself, and its applications. Background Technology

[0002] In order to curb the development of the global greenhouse effect, the research and exploration of new energy technologies has become a hot topic of international concern.

[0003] As one of the most promising renewable energy sources, hydrogen fuel can not only provide an efficient fuel supply system, but also achieve zero carbon emissions throughout the entire fuel use process.

[0004] Although hydrogen fuel is a very clean fuel, there are still some limitations in hydrogen production. Fossil fuel-based hydrogen production holds the largest market share, and its technology is mature and inexpensive.

[0005] However, the feedstocks for fossil fuel-based hydrogen production are mostly methane, coal, and methanol, and the byproducts (CO and CO2) are often generated during hydrogen production. The diversity of byproduct gases results in insufficient purity of hydrogen, necessitating subsequent purification processes.

[0006] The process of producing hydrogen through photocatalysis using renewable energy is clean and yields hydrogen of relatively high purity. However, this technology is still in the laboratory stage and cannot be used for large-scale production in the short term.

[0007] Currently, water electrolysis is one of the most promising hydrogen production processes because it uses water as a raw material and has zero carbon emissions.

[0008] However, the presence of oxygen (O2) impurities can pose a potential safety hazard when H2 is used as a power source for combustion. Therefore, oxygen (O2) impurities must be removed from the H2 stream to meet stringent requirements. After deoxygenation, the hydrogen produced by the water electrolysis process can be used for subsequent downstream applications.

[0009] However, currently, the metals commonly used in the market to prepare deoxidizers are usually metals from Group VII of the periodic table (such as Pd, Pt, and Ag), which possess high activity and high ductility, exhibiting good performance in deoxidation applications. However, the high price of precious metals limits their widespread industrial application, thus necessitating the development of non-precious metal deoxidation catalysts. Furthermore, the environment, especially temperature, for removing oxygen from hydrogen significantly impacts production costs. Low-temperature conditions greatly reduce equipment and environmental requirements, thereby lowering production costs. Therefore, the development of non-precious metal, low-temperature deoxidation catalysts holds a broader market prospect. Summary of the Invention

[0010] Therefore, one objective of this invention is to provide a method for preparing a catalyst for removing oxygen from hydrogen at low temperatures, comprising the following steps:

[0011] (1) Dissolve the weighed nickel-based metal precursor and other transition metal precursor in deionized water to obtain an aqueous solution containing mixed salts.

[0012] (2) Add the weighed precipitant to the above aqueous solution, stir and then let stand;

[0013] (3) Filter the solid-liquid mixture after it has been left to stand, and rinse it with deionized water;

[0014] (4) Dry the precipitate obtained after rinsing;

[0015] (5) The dried solid is roasted.

[0016] The amounts of the nickel-based metal precursor and other transition metal precursors are calculated based on the atomic weight of the metals, with an atomic molar ratio of 1:0.25; the amount of the precipitant added is calculated based on the molar weight, with a ratio of (1-4):1 to the total molar weight of the metal atoms.

[0017] The nickel-based metal precursor is nickel nitrate or nickel chloride;

[0018] The other transition metal precursors are manganese salts;

[0019] The manganese salt is one of manganese acetate, manganese nitrate, and manganese sulfate;

[0020] The precipitant is one of ammonium bicarbonate, oxalic acid, ammonium carbonate, and ammonium oxalate.

[0021] Preferably, the settling time in step (2) is 8-24 hours.

[0022] Preferably, the rinsing with deionized water in step (3) involves repeated rinsing until the filtrate becomes neutral.

[0023] Preferably, the drying temperature in step (4) is 75-105℃ and the drying time is 8-24h.

[0024] Preferably, the calcination atmosphere in step (5) is air, the calcination temperature rise rate is 2-5℃ / min, the calcination temperature is 350-550℃, and the calcination time is 3-5h.

[0025] A second objective of this invention is to provide a catalyst prepared by the above-described method.

[0026] A third objective of this invention is to provide the application of the catalyst prepared by the above method in removing oxygen from hydrogen, thereby obtaining high-purity hydrogen.

[0027] Preferably, the removal of oxygen from hydrogen is carried out under low-temperature conditions, namely 80-140°C.

[0028] Preferably, the process of removing oxygen from hydrogen involves removing oxygen from the hydrogen obtained after water electrolysis, thereby preparing high-purity hydrogen.

[0029] Beneficial Effects: This invention provides a catalyst for removing oxygen from hydrogen gas. The catalyst is prepared by stirring a nickel-based metal precursor (nickel nitrate or nickel chloride), a manganese salt of another transition metal precursor, and a precipitant in an aqueous solution, followed by standing, filtration, rinsing, drying, and calcination. The amounts of the nickel-based metal precursor and the other transition metal precursor are calculated by atomic weight, with a molar ratio of 1:0.25. The amount of precipitant added is calculated by molar weight, with a ratio of (1-4):1 to the total molar weight of the metal atoms. The catalyst prepared by this invention can efficiently remove oxygen from hydrogen gas at low temperatures (80-140℃) to obtain high-purity hydrogen. It exhibits high deoxygenation activity, strong stability, and long service life. Furthermore, this invention does not use precious metals, has a simple and controllable synthesis process, low preparation cost, and is easy to promote and use industrially. Attached Figure Description

[0030] Figure 1 A graph showing the oxygen removal rate of low-temperature hydrogen deoxygenation using the catalyst of the present invention.

[0031] Figure 2 This is a comparison graph showing the oxygen removal rate of hydrogen deoxygenation at different temperatures using the catalysts of Example 3 and Comparative Examples 4-6 of the present invention.

[0032] Figure 3 This is a stability diagram of hydrogen deoxygenation of the catalyst of the present invention.

[0033] Figure 4 This is a phase structure diagram of the catalyst prepared in this invention.

[0034] Figure 5 This is a phase comparison diagram of the catalysts prepared by different proportions of nickel and manganese metal according to the present invention.

[0035] Figure 6 This is a phase structure diagram of the catalyst prepared using cobalt salts.

[0036] Figure 7 This is a phase structure diagram of the catalyst prepared using copper salts. Detailed Implementation

[0037] The endpoints of any range and any value disclosed herein are not limited to the precise range and / or value, and such ranges and / or values ​​can and should be understood to include values ​​close to such ranges and / or values. For numerical ranges, endpoint values ​​of various ranges, endpoint values ​​of various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] This application provides a method for preparing a catalyst for removing oxygen from hydrogen gas, comprising the following steps:

[0039] (1) Dissolve the weighed nickel-based metal precursor and other transition metal precursors other than nickel in deionized water to obtain an aqueous solution containing mixed salts.

[0040] (2) Add the weighed precipitant to the above aqueous solution, stir and then let stand;

[0041] (3) Filter the solid-liquid mixture after it has been left to stand, and rinse it with deionized water;

[0042] (4) Dry the precipitate obtained after rinsing;

[0043] (5) The dried solid is roasted.

[0044] The amounts of nickel-based metal precursors and other transition metal precursors are calculated based on their atomic weights, with an atomic molar ratio of 1:0.25. The amount of precipitant added is calculated based on its molar weight, with a ratio of (1–4):1 to the total molar weight of the metal atoms. The nickel-based metal precursor is nickel nitrate or nickel chloride; the other transition metal precursors are manganese salts; the manganese salt is one of manganese acetate, manganese nitrate, and manganese sulfate; the precipitant is one of ammonium bicarbonate, oxalic acid, ammonium carbonate, and ammonium oxalate.

[0045] The catalyst prepared by this method can efficiently remove oxygen from hydrogen at low temperatures (80-140℃) to obtain high-purity hydrogen. This method does not use precious metals and has a simple synthesis process, which greatly reduces the production complexity and cost of catalysts for removing oxygen from hydrogen.

[0046] In a preferred embodiment, the settling time in step (2) is 8-24h; the rinsing with deionized water in step (3) is repeated rinsing until the filtrate becomes neutral; the drying temperature in step (4) is 75-105℃ and the drying time is 8-24h; the calcination atmosphere in step (5) is air, the calcination temperature rise rate is 2-5℃ / min, the calcination temperature is 350-550℃, and the calcination time is 3-5h.

[0047] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0048] The following embodiments describe the present invention in detail:

[0049] Example 1

[0050] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0051] (2) Add the weighed ammonium bicarbonate (NH4HCO3) precipitant to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements is 1:1. Then stir for 0.5 h.

[0052] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0053] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0054] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0055] Example 2

[0056] (1) Dissolve the weighed nickel chloride (NiCl2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0057] (2) Add the weighed ammonium bicarbonate (NH4HCO3) precipitant to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements is 1:1. Then stir for 0.5 h.

[0058] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0059] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0060] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0061] Example 3

[0062] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0063] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0064] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0065] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0066] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0067] Example 4

[0068] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0069] (2) Add the weighed ammonium carbonate ((NH4)2CO3) precipitant to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements is 1:1. Then stir for 0.5 h.

[0070] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0071] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0072] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0073] Example 5

[0074] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese sulfate (Mn(SO4)2·H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0075] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0076] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0077] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0078] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0079] Example 6

[0080] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0081] (2) The weighed ammonium oxalate ((NH4)2C2O4·H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0082] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0083] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0084] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0085] Example 7

[0086] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese nitrate (Mn(NO3)2(50wt%.in H2O)) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0087] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitate was added to the above aqueous solution. The molar ratio of the precipitant to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0088] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0089] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0090] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0091] Comparative Example 1

[0092] (1) Dissolve the weighed nickel sulfate (Ni(SO4)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.25.

[0093] (2) Add the weighed ammonium bicarbonate (NH4HCO3) precipitant to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements is 1:1. Then stir for 0.5 h.

[0094] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0095] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0096] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0097] Comparative Example 2

[0098] (1) Dissolve the weighed manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing manganese salt;

[0099] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to manganese metal was 1:1. Then the mixture was stirred for 0.5 h.

[0100] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0101] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0102] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0103] Comparative Example 3

[0104] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) in 120mL of deionized water to obtain an aqueous solution containing nickel salt;

[0105] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0106] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0107] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0108] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0109] Comparative Example 4

[0110] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and manganese acetate ((CH3COO)2Mn·4H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to manganese metal elements of 1:0.50.

[0111] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and manganese metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0112] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0113] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0114] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0115] Comparative Example 5

[0116] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and cobalt nitrate (Co(NO3)2·6H2O) in 120 mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to cobalt metal elements of 1:0.25.

[0117] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and cobalt metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0118] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0119] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0120] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0121] Comparative Example 6

[0122] (1) Dissolve the weighed nickel nitrate (Ni(NO3)2·6H2O) and copper nitrate (Cu(NO3)2·3H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts, with a molar ratio of nickel to copper metal elements of 1:0.25.

[0123] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the nickel and copper metal elements was 1:1. Then the mixture was stirred for 0.5 h.

[0124] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0125] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0126] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0127] Comparative Example 7

[0128] (1) Dissolve the weighed cobalt nitrate (Co(NO3)2·6H2O) in 120mL of deionized water to obtain an aqueous solution containing mixed salts;

[0129] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to the cobalt metal element was 1:1. Then the mixture was stirred for 0.5 h.

[0130] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0131] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0132] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0133] Comparative Example 8

[0134] (1) Dissolve the weighed copper nitrate (Cu(NO3)2·6H2O) in 120mL of deionized water to obtain an aqueous solution containing copper salt;

[0135] (2) The weighed oxalic acid (H2C2O4·2H2O) precipitant was added to the above aqueous solution. The molar ratio of the amount of precipitant added to copper metal element was 1:1. Then the mixture was stirred for 0.5 h.

[0136] (4) Filter the solid-liquid mixture after standing for 24 hours and rinse it with deionized water until the filtrate becomes neutral.

[0137] (5) The precipitate obtained after filtration is dried at a temperature of 60°C for 24 hours.

[0138] (6) The dried solid is calcined at a temperature of 450°C, a heating rate of 5°C / min, and a calcination time of 3h.

[0139] Performance testing: The catalytic effect of the catalysts prepared in the above examples / comparative examples was tested.

[0140] The deoxygenation performance of the catalyst was investigated in a fixed-bed reactor with an inner diameter of 6 mm and an outer diameter of 8 mm. At atmospheric pressure, the simulated gas consisted of 1000 ppm O2 and high-purity H2 using N2 as the balance gas. The total flow rate was set to 100 mL / min in each experiment. -1 The catalyst dosage was 100 mg. The weight hourly space velocity (WHSV) was controlled at 60,000 mL. -1 ·h -1 ·g -1 The inlet and outlet oxygen concentrations were detected using gas chromatography (Hisense GC-950). The oxygen removal rate was calculated using the following formula:

[0141] Oxygen removal rate (%) = (c O2,inlet -c O2,outlet ) / c O2,in *100%, c O2,inlet and c O2,outlet These represent the oxygen inlet and outlet concentrations, respectively.

[0142] Table 1 shows the specific composition of the precursors and precipitants used in the catalysts prepared in Examples 1-7 and Comparative Examples 1-8. Table 2 shows the oxygen removal rates of these catalysts at low temperatures. It is evident that the catalysts obtained by the method of this invention (Examples 1-7) exhibit good deoxygenation effects at both 100℃ and 140℃, with most exceeding 90% deoxygenation rates; while the comparative examples showed no deoxygenation ability at 100℃, and at 140℃, most had poor or no deoxygenation ability (Table 1). Figure 1 The experiment also showed the trend of deoxygenation rate of the catalyst of the present invention from 80-140℃, all of which have deoxygenation capacity. At 100℃, the deoxygenation capacity rapidly increases and maintains a good deoxygenation effect.

[0143] From the appendix Figure 2 It is known that catalysts obtained by using other nickel-manganese ratios in the precursor (such as 1:0.50 in Example 4) or by using non-manganese salts as other transition metal precursors (such as cobalt salts in Example 5 and copper salts in Example 6) do not exhibit the same deoxygenation effect at low temperatures as the catalyst of this invention (such as the nickel-manganese ratio of 1:0.25 in Example 3, and the use of manganese salts as other transition metal precursors). Furthermore, these catalysts have no catalytic activity at 100°C and below. The catalyst of this invention (such as Example 3) not only exhibits good deoxygenation effect at low temperatures but also maintains a stable deoxygenation effect, retaining a high oxygen removal level over time, indicating that the catalyst of this invention has a stable deoxygenation effect (see Appendix). Figure 3 ).

[0144] Appendix Figure 4-7 The phase diagram of the catalyst is attached. Figure 4As shown, the catalyst phase obtained using nickel sulfate as the nickel metal precursor in Comparative Example 1 is not as good as the phase obtained using nickel nitrate or nickel chloride in this invention (Examples 1-7), thus affecting the catalytic effect. (See attached...) Figure 5 As shown, in Examples 3 and 4, the metal precursors and precipitants are the same, but the nickel-manganese metal ratios are different, resulting in different phases and thus different catalytic effects. (See attached image) Figure 6 and attached Figure 7 The figures show the phase diagrams of other transition metal precursors using cobalt and copper salts, respectively. Obviously, they are different from those of the manganese salt used in this invention.

[0145] Table 1. Catalyst Synthesis Precursors

[0146]

[0147] Table 2 Deoxygenation efficiency of catalysts in Examples / Comparative Examples

[0148]

[0149] The conventional techniques and solutions not described in detail in the above embodiments are all well known in the art, and therefore will not be elaborated upon here. The above embodiments and / or experimental examples describe the preferred embodiments of the present invention in detail. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. Furthermore, various different embodiments of the present invention can also be arbitrarily combined, as long as they do not violate the spirit of the present invention, they should also be considered as the content disclosed by the present invention.

Claims

1. A method for preparing a catalyst for low-temperature removal of oxygen from hydrogen, characterized in that, Includes the following steps: (1) Dissolve the weighed nickel-based metal precursor and other transition metal precursor in deionized water to obtain an aqueous solution containing mixed salts. (2) Add the weighed precipitant to the above aqueous solution, stir and then let stand; (3) Filter the solid-liquid mixture after it has been left to stand, and rinse it with deionized water; (4) Dry the precipitate obtained after rinsing; (5) The dried solid is roasted. The amounts of the nickel-based metal precursor and other transition metal precursors are calculated based on the atomic weight of the metals, with an atomic molar ratio of 1:0.25; the amount of the precipitant added is calculated based on the molar weight, with a ratio of (1-4):1 to the total molar weight of the metal atoms. The nickel-based metal precursor is nickel nitrate or nickel chloride; The other transition metal precursors are manganese salts; The manganese salt is one of manganese acetate, manganese nitrate, and manganese sulfate; The precipitant is one of ammonium bicarbonate, oxalic acid, ammonium carbonate, and ammonium oxalate.

2. The preparation method according to claim 1, characterized in that, The settling time in step (2) is 8-24 hours.

3. The preparation method according to claim 1, characterized in that, The rinsing with deionized water in step (3) involves repeated rinsing until the filtrate becomes neutral.

4. The preparation method according to claim 1, characterized in that, The drying temperature in step (4) is 60-105℃ and the drying time is 8-24h.

5. The preparation method according to claim 1, characterized in that, In step (5), the calcination atmosphere is air, the calcination temperature rise rate is 2-5℃ / min, the calcination temperature is 350-550℃, and the calcination time is 3-5h.

6. The catalyst prepared by any one of the preparation methods described in claims 1-5.

7. The application of the catalyst as claimed in claim 6, characterized in that, Used to remove oxygen from hydrogen gas to produce high-purity hydrogen.

8. The application as described in claim 7, characterized in that, The removal of oxygen from hydrogen is carried out under low-temperature conditions, namely 80-140°C.

9. The application as described in claim 7, characterized in that, The process of removing oxygen from hydrogen to prepare high-purity hydrogen involves electrolyzing water and then removing oxygen from the resulting hydrogen.

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