Nickel-based catalyst for hydrogen production through methanol reforming and preparation and application thereof

Abstract

The invention relates to the technical field of catalysis technology and energy chemical industry, in particular to a nickel-based catalyst for hydrogen production through methanol reforming and preparation and application thereof. In the invention, the composition of the nickel-based catalyst is xNi / In2O3, x represents the mass percent of Ni, and x is 0.5-35; the nickel-based catalyst is an untreated nickel-based catalyst or a nickel-based catalyst subjected to gas pretreatment. The nickel-based catalyst has the characteristics of low metal usage amount, high activity, high selectivity, good cycle stability and the like, the indium oxide carrier is adopted, the highest Ni dispersity is achieved, the strong interaction of metal and the carrier in the nickel-based catalyst is greatly enhanced, the critical defect of poor selectivity generally existing in the nickel-based catalyst is effectively overcome, and the nickel-based catalyst is suitable for industrial production. The catalyst has excellent low-temperature activity, realizes complete conversion of methanol at 350 DEG C, and has CO selectivity far better than that of other oxide carriers.

Description

Technical Field

[0001] The present invention relates to the fields of catalytic technology and energy chemical technology, and in particular to a nickel-based catalyst for hydrogen production by methanol reforming, and the preparation and application thereof. Background Art

[0002] With the continuous growth of the global population and limited resources, and the low energy efficiency, high pollution and large amount of greenhouse gas emissions of traditional energy systems, how to develop more efficient and cleaner energy to meet people's growing energy needs has become a research hotspot. Hydrogen has the advantages of high energy density and no pollution after combustion, and is considered to be one of the substitutes for traditional fossil fuels. Hydrogen fuel polymer electrolyte membrane fuel cells (PEMFC) can convert the chemical energy of substances into electrical energy through electrochemical reactions, and have the advantages of high efficiency and "zero emissions". Since hydrogen is not easily compressed and liquefied, there are still technical barriers in transportation and storage. Liquid fuels can be explored to provide hydrogen-rich raw materials for polymer electrolyte membrane fuel cell (PEMFC) systems.

[0003] Methanol is considered a promising fuel for liquid hydrogen storage due to its high H / C, easy access and high energy density. Compared with other hydrogen production pathways, methanol steam reforming has the highest hydrogen production rate and mature industrial technology. However, in addition to the overall reaction, there are two side reactions: direct decomposition of methanol to produce CO and further hydrogenation to produce CH4, which lead to the production of by-products. Therefore, in order to inhibit the side reactions of direct decomposition of methanol to produce CO and further hydrogenation to produce CH4, it is necessary to develop a highly active and highly selective catalyst system.

[0004] At present, the catalyst system widely studied for hydrogen production from methanol steam reforming is copper-based catalyst. Copper-based catalysts are cheap and the raw materials are easily available, but they are prone to sintering and agglomeration at high temperatures and lose their catalytic activity. Precious metal catalysts have entered the field of vision of researchers due to their excellent catalytic activity and good thermal stability, but they are expensive and costly, and are easily poisoned by CO, making it difficult to maintain long-term stability.

[0005] Non-precious metal Ni catalysts have entered the field of vision of researchers because of their low cost. The study (DOI: 10.1039 / d4gc00397g) proposed a new and stable nickel-based catalyst loaded on mesoporous sponge alumina, and achieved an increase in hydrogen production efficiency, with a hydrogen production flow rate increased by 23.8%, but the catalyst can only achieve complete methanol conversion at 450°C, and the selectivity for CO at 400°C is higher than 25%. The study (DOI: 10.1039 / d3ra02891g) used polyethylene oxide-polypropylene oxide-polyethylene oxide as a triblock copolymer template and tetrabutyl titanate as a gel to prepare a nickel-titanium oxide catalyst at room temperature, but the nickel-titanium oxide catalyst can only achieve a methanol conversion rate of 99.2% at 600°C, and the CO selectivity is as high as 90%.

[0006] Therefore, how to improve the catalytic activity and stability, reduce the reaction temperature and ensure good product selectivity of Ni-based catalysts used in methanol steam reforming to produce hydrogen (also referred to as "methanol reforming to produce hydrogen") still faces huge challenges. Summary of the invention

[0007] In order to solve the above problems, the purpose of the present invention is to provide a nickel-based catalyst for hydrogen production by methanol reforming and its preparation and application. In the present invention, the composition of the nickel-based catalyst is xNi / In2O3, wherein x represents the mass percentage of Ni, and x is 0.5-35; the nickel-based catalyst is an untreated nickel-based catalyst or a gas-pretreated nickel-based catalyst. The nickel-based catalyst of the present invention has the characteristics of low metal usage, high activity, high selectivity and good cycle stability. The indium oxide carrier is used, which not only has the highest Ni dispersion, but also greatly enhances the strong metal-carrier interaction in the nickel-based catalyst, effectively overcoming the fatal defect of poor selectivity commonly existing in nickel-based catalysts. The catalyst has excellent low-temperature activity, achieves complete conversion of methanol at 350°C, and CO selectivity is far better than other oxide carriers. The nickel-based catalyst is activated by different pretreatment methods, and it is found that different pretreatment methods have a significant effect on the activity of the nickel-based catalyst. The catalyst raw materials of the present invention are easy to obtain, the preparation process is simple, and the reaction conditions are mild, and it has a good application prospect.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] The first object of the present invention is to provide a nickel-based catalyst for hydrogen production by methanol reforming, wherein the composition of the nickel-based catalyst is xNi / In2O3, wherein x represents the mass percentage of Ni, and x is 0.5 to 35 (preferably, x is 1 to 10);

[0010] The nickel-based catalyst is an untreated nickel-based catalyst or a gas-pretreated nickel-based catalyst;

[0011] The gas is selected from one or more of hydrogen, raw gas, CO2 / H2 or inert gas (preferably, the gas is raw gas).

[0012] The second object of the present invention is to provide a method for preparing a nickel-based catalyst for hydrogen production by methanol reforming, comprising the following steps:

[0013] (S1) Precipitating an In precursor salt with aqueous ammonia, drying and calcining the In2O3 carrier after heating in a water bath;

[0014] (S2) loading the Ni precursor salt onto the In2O3 carrier prepared in step (S1), drying and calcining to obtain an untreated nickel-based catalyst;

[0015] (S3) Pretreating an untreated nickel-based catalyst with a gas to obtain a gas-pretreated nickel-based catalyst.

[0016] In one embodiment of the present invention, in step (S1), the precursor salt of In is selected from one of indium (III) nitrate hydrate, In(NO3)3, and InCl3;

[0017] In step (S2), the Ni precursor salt is selected from one or more of Ni basic carbonate, nitrate, sulfate, chloride or acetate.

[0018] In one embodiment of the present invention, in step (S1), the molar ratio of ammonia water to In in the precursor salt of In is 10 to 30:1; wherein, the ammonia water needs to be excessive until In is completely precipitated.

[0019] During the water bath, the temperature is 60-85°C and the time is 1-3h;

[0020] During the drying process, the temperature is 60-100°C and the time is 5-12h;

[0021] During the calcination process, the temperature is 300-500°C and the time is 3-12 hours.

[0022] In one embodiment of the present invention, in step (S2), during loading, the loading method is selected from a hydrothermal method, a precipitation method or an impregnation method.

[0023] In one embodiment of the present invention, in step (S2), during the drying process, the temperature is 60 to 100° C. and the time is 5 to 12 h;

[0024] During the roasting process, the temperature is 300-500°C and the time is 3-12 hours.

[0025] In one embodiment of the present invention, in step (S2) and step (S3), during the pretreatment process, the temperature is 250 to 500° C. and the time is 0.5 to 2 h.

[0026] The third object of the present invention is to provide a nickel-based catalyst for producing hydrogen through methanol reforming.

[0027] A fourth object of the present invention is to provide a method for producing hydrogen by reforming methanol, comprising the following steps:

[0028] The nickel-based catalyst is screened and loaded into a fixed bed reactor to catalyze methanol steam reforming to produce hydrogen;

[0029] During the catalytic reaction, the temperature is 150-375°C, and the molar ratio of water vapor to methanol (also referred to as "water-to-methanol ratio") is 0.8-3.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) Compared with traditional nickel-based catalysts, the nickel-based catalyst provided by the present invention has not only high catalytic activity in the methanol reforming hydrogen production reaction, but also good methanol conversion rate and product selectivity at a relatively low temperature, and is a new type of hydrogen production catalyst with high efficiency and low loading;

[0032] (2) The nickel-based catalyst provided by the present invention is sintering-resistant and has good stability, and can maintain activity at 325°C for more than 30 hours;

[0033] (3) The present invention successfully prepared a nickel-based catalyst for methanol reforming to produce hydrogen through an easy-to-operate precipitation method and impregnation method, and simultaneously adjusted the pretreatment conditions and the Ni loading amount to achieve high catalytic activity, high selectivity and high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The hydrogen production rate and CO selectivity of the catalysts prepared in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 for hydrogen production from methanol reforming;

[0035] Figure 2 The hydrogen production rate, CO selectivity and CH4 selectivity of the catalysts prepared in Example 2, Comparative Example 4, Comparative Example 5 and Comparative Example 6 for hydrogen production from methanol reforming;

[0036] Figure 3 The hydrogen production rate and CO selectivity of the catalysts prepared in Example 1, Example 2 and Example 5 for hydrogen production from methanol reforming;

[0037] Figure 4The hydrogen production rate and CO selectivity of the catalysts prepared in Example 5, Example 10 and Example 12 for hydrogen production from methanol reforming;

[0038] Figure 5 The hydrogen production rate and CO selectivity diagram of the catalysts prepared in Example 5, Example 14, Example 16 and Example 18 for hydrogen production from methanol reforming.

[0039] Figure 6 The relationship between the catalytic activity and the space velocity of the catalyst prepared in Example 5 for hydrogen production by methanol reforming is shown in FIG.

[0040] Figure 7 The relationship between the catalytic activity of the catalyst prepared in Example 5 for hydrogen production from methanol reforming and the water-to-methanol ratio;

[0041] Figure 8 This is a graph showing the stability test results of the catalyst prepared in Example 5 for use in methanol reforming to produce hydrogen. DETAILED DESCRIPTION

[0042] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0043] In the following examples, unless otherwise specified, all reagents used are commercially available reagents, and all detection means and methods used are conventional detection means and methods in the art.

[0044] Example 1

[0045] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (1Ni / In2O3-W), comprising the following steps:

[0046] (S1) 4 g of hydrated indium nitrate (Aladdin, I105869) was dissolved in deionized water to prepare an indium nitrate solution with a concentration of 0.173 mol / L; 12.8 mL of ammonia water was added dropwise to the indium nitrate solution under vigorous stirring, and the mixture was stirred in a water bath at 80° C. for 1 h to obtain a mixed solution; the mixed solution was taken out, cooled to room temperature, and centrifuged to obtain a precipitate, which was washed with deionized water 3 times and ethanol 3 times in sequence, and then placed in an oven at 60° C. to dry for 12 h, and then calcined at 450° C. for 3 h to obtain an In2O3 carrier (0.7 g of the In2O3 carrier was taken, and its water absorption was measured with deionized water to be 230 μL);

[0047] (S2) 0.0351 g of nickel nitrate hexahydrate was dissolved in 230 μL of deionized water, and the mixture was evenly added dropwise to 0.7 g of the In2O3 carrier prepared in step (S1), and then ultrasonically mixed for 30 min; the mixture was then dried in an oven at 60°C for 12 hours, and calcined at 450°C for 3 hours to obtain an indium oxide-supported nickel-based catalyst: 1Ni / In2O3-W.

[0048] Comparative Example 1

[0049] This comparative example provides a method for preparing a cerium oxide-supported nickel-based catalyst (1Ni / CeO2-W), comprising the following steps:

[0050] (S1) 4 g of hydrated cerium nitrate (Aladdin, C105376) was dissolved in deionized water to prepare a cerium nitrate solution with a concentration of 0.173 mol / L; 8.88 mL of ammonia water was added dropwise to the cerium nitrate solution under vigorous stirring, and the mixture was stirred in a water bath at 80° C. for 1 h to obtain a mixed solution; the mixed solution was taken out, cooled to room temperature, and centrifuged to obtain a precipitate, and the precipitate was washed with deionized water 3 times and ethanol 3 times in sequence, and then placed in an oven at 60° C. to dry for 12 h, and then calcined at 450° C. for 3 h to obtain a CeO2 carrier (0.7 g of CeO2 carrier was taken, and its water absorption was measured with deionized water to be 150 μL);

[0051] (S2) Dissolve 0.0351 g of nickel nitrate hexahydrate in 150 μL of deionized water, ultrasonically dissolve it for 10 min, then evenly add it dropwise to 0.7 g of the CeO2 carrier prepared in step (S1), and then ultrasonically mix it for 30 min; then place it in an oven at 60°C and dry it for 12 hours, and calcine it at 450°C for 3 hours to obtain a cerium oxide-supported nickel-based catalyst: 1Ni / CeO2-W.

[0052] Comparative Example 2

[0053] This comparative example provides a method for preparing a titanium oxide-supported nickel-based catalyst (1Ni / TiO2-W), comprising the following steps:

[0054] 0.0351 g of nickel nitrate hexahydrate was dissolved in 100 μL of deionized water, and then evenly added to 0.7 g of a commercial TiO2 carrier (Aladdin, T164497) by ultrasonic dissolution for 10 min, and then ultrasonically mixed for 30 min; then, it was placed in an oven at 60°C for 12 hours and calcined at 450°C for 3 hours to obtain a titanium oxide-supported nickel-based catalyst: 1Ni / TiO2-W.

[0055] Comparative Example 3

[0056] This comparative example provides a method for preparing a zirconium oxide-supported nickel-based catalyst (1Ni / ZrO2-W), comprising the following steps:

[0057] 0.0351 g of nickel nitrate hexahydrate was dissolved in 140 μL of deionized water, and after ultrasonic dissolution for 10 min, it was evenly added dropwise to 0.7 g of a commercial ZrO2 carrier (Aladdin, Z104402), and then ultrasonically mixed for 30 min; then it was placed in an oven at 60°C for 12 hours and calcined at 450°C for 3 hours to obtain a zirconium oxide-supported nickel-based catalyst: 1Ni / ZrO2-W.

[0058] Example 2

[0059] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (1Ni / In2O3-H-350), comprising the following steps:

[0060] The 1Ni / In2O3-W prepared in Example 1 was pretreated with H2 (20 mL / min) at 350°C for 1 h to obtain an indium oxide-supported nickel-based catalyst: 1Ni / In2O3-H-350.

[0061] Comparative Example 4

[0062] This comparative example provides a method for preparing a cerium oxide-supported nickel-based catalyst (1Ni / CeO2-H-350), comprising the following steps:

[0063] The 1Ni / CeO2-W prepared in Comparative Example 1 was pretreated with H2 (20 mL / min) at 350°C for 1 h to obtain a cerium oxide nickel-based catalyst: 1Ni / CeO2-W-350.

[0064] Comparative Example 5

[0065] This comparative example provides a method for preparing a titanium oxide-supported nickel-based catalyst (1Ni / TiO2-H-350), comprising the following steps:

[0066] The 1Ni / TiO2-W prepared in Comparative Example 2 was pretreated with H2 (20 mL / min) at 350°C for 1 h to obtain a titanium oxide-supported nickel-based catalyst: 1Ni / TiO2-H-350.

[0067] Comparative Example 6

[0068] This comparative example provides a method for preparing a zirconium oxide-supported nickel-based catalyst (1Ni / ZrO2-H-350), comprising the following steps:

[0069] The 1Ni / ZrO2-W prepared in Comparative Example 3 was pretreated with H2 (20 mL / min) at 350°C for 1 h to obtain a zirconium oxide-supported nickel-based catalyst: 1Ni / ZrO2-H-350.

[0070] Example 3

[0071] 1) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-W) prepared in Example 1 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 1 In the catalytic reaction, the temperature was 350°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0072] 2) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-W) prepared in Example 1 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 3 In the catalytic reaction, the temperature was 275°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0073] Comparative Example 7

[0074] The cerium oxide supported nickel-based catalyst (1Ni / CeO2-W) prepared in Comparative Example 1 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 1 In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0075] Comparative Example 8

[0076] The titanium oxide supported nickel-based catalyst (1Ni / TiO2-W) prepared in Comparative Example 2 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 1 In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0077] Comparative Example 9

[0078] The zirconium oxide supported nickel-based catalyst (1Ni / ZrO2-W) prepared in Comparative Example 3 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 1In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0079] pass Figure 1 It can be found that the nickel-based catalyst supported by indium oxide has the highest hydrogen production rate and the lowest CO selectivity, which indicates that the use of indium oxide as a carrier to support nickel-based catalysts can improve the activity and selectivity defects of traditional nickel-based catalysts, and complete conversion can be achieved at 350°C with low CO selectivity.

[0080] Example 4

[0081] 1) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-H-350) prepared in Example 2 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 2 In the catalytic reaction, the temperature was 350°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0082] 2) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-H-350) prepared in Example 2 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 3 In the catalytic reaction, the temperature was 275°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0083] Comparative Example 10

[0084] The cerium oxide supported nickel-based catalyst (1Ni / CeO2-H-350) prepared in Comparative Example 4 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 2 In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0085] Comparative Example 11

[0086] The titanium oxide supported nickel-based catalyst (1Ni / TiO2-H-350) prepared in Comparative Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 2In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0087] Comparative Example 12

[0088] The zirconium oxide supported nickel-based catalyst (1Ni / CrO2-H-350) prepared in Comparative Example 6 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 2 In the catalytic reaction, the temperature is 350°C, the water-to-alcohol ratio is 1.4, and the gas phase space velocity is 24232h -1 .

[0089] pass Figure 2 It can be found that hydrogen pretreatment improves the hydrogen production rate of nickel-based catalysts with zirconium oxide and titanium oxide as carriers, but at the same time the CO selectivity is as high as over 80%; the hydrogen production rate of the catalyst with cerium oxide as carrier decreases after hydrogen pretreatment, and the CH4 selectivity is as high as over 60%; and the nickel-based catalyst supported on indium oxide after hydrogen pretreatment still maintains excellent hydrogen production rate and low by-product selectivity when fully converted at 350°C.

[0090] Example 5

[0091] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-350), comprising the following steps:

[0092] The 1Ni / In2O3-W prepared in Example 1 was pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 350°C for 1 h to obtain 1Ni / In2O3-M-350.

[0093] Example 6

[0094] 1) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-350) prepared in Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 3 and Figure 4 In the catalytic reaction, the temperature was 275°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0095] pass Figure 3It can be found that different pretreatment methods can effectively improve the catalytic activity of indium oxide-loaded nickel-based catalysts at low temperatures; among them, the hydrogen production rate of the catalyst after raw gas pretreatment at low temperatures can reach 3 to 4 times the hydrogen production rate of the catalyst without pretreatment.

[0096] 2) The indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-350) prepared in Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 5 In the catalytic reaction, the temperature was 325°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0097] Example 7

[0098] The indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) prepared in Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 6 In the catalytic reaction, the temperature was 350°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 19385h -1 、24232h -1 、32309h -1 、48464h -1 and 96974h -1 .

[0099] pass Figure 6 It can be found that with the increase of space velocity, the conversion rate of methanol and CO selectivity of indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) gradually decreased, and the selectivity of H2 always remained above 99%. It shows that as the contact time between the raw material and the catalyst surface becomes shorter, the methanol conversion rate and CO selectivity gradually decrease, proving that the selectivity of CO at high temperature in the indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) system mainly comes from the reverse water gas shift of CO2 and H2 produced by the reaction.

[0100] Example 8

[0101] The indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) prepared in Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 7In the catalytic reaction, the temperature was 325°C, the water-to-alcohol ratios were 1.0, 1.2, 1.4, and 1.6, respectively, and the gas phase space velocity was 24232 h -1 .

[0102] pass Figure 7 It can be found that the water-to-alcohol ratio also affects the catalytic activity of the indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-350) system. As the water-to-alcohol ratio increases, the methanol conversion rate and CO selectivity show a downward trend, the CO2 selectivity shows an upward trend, and the H2 selectivity and CH4 selectivity do not change significantly. This is because when there is more methanol in the raw material, methanol is more easily decomposed to produce CO and H2. As the water vapor partial pressure increases, the methoxyl group formed by methanol is oxidized and eventually decomposed into CO2 and H2. Therefore, the water-to-alcohol ratio has a certain effect on the activity of the catalyst, and choosing a suitable water-to-alcohol ratio is more conducive to improving the catalytic activity of the catalyst.

[0103] Example 9

[0104] The indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) prepared in Example 5 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 8 As shown), stability test was carried out; during the catalytic reaction, the temperature was 350°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 , time is 0~1870min.

[0105] pass Figure 8 It can be found that after 31 hours of continuous injection test, the indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) still maintains good catalytic activity and stability. Its methanol conversion rate can still reach more than 90%, the selectivity for CO is less than 9%, and the hydrogen selectivity is greater than 99%, which shows that the indium oxide supported nickel-based catalyst (1Ni / In2O3-M-350) has excellent activity and high stability at high temperature and has good application prospects.

[0106] Example 10

[0107] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-250), comprising the following steps:

[0108] The 1Ni / In2O3-W prepared in Example 1 was pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 250°C for 1 h to obtain 1Ni / In2O3-M-250.

[0109] Embodiment 11

[0110] The indium oxide supported nickel-based catalyst (1Ni / In2O3-M-250) prepared in Example 10 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 4 In the catalytic reaction, the temperature was 275°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0111] Example 12

[0112] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (1Ni / In2O3-M-500), comprising the following steps:

[0113] The 1Ni / In2O3-W prepared in Example 1 was pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 500°C for 1 h to obtain 1Ni / In2O3-M-500.

[0114] Embodiment 13

[0115] The indium oxide supported nickel-based catalyst (1Ni / In2O3-M-500) prepared in Example 12 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 4 In the catalytic reaction, the temperature was 275°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0116] pass Figure 4 It can be found that different pretreatment temperatures have an effect on the catalytic activity of indium oxide-supported nickel-based catalysts. Selecting a suitable reduction temperature in the range of 250°C to 500°C is more conducive to improving the catalytic activity of indium oxide-supported nickel-based catalysts.

[0117] Embodiment 14

[0118] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (5Ni / In2O3-M-350), comprising the following steps:

[0119] (S1) 4 g of hydrated indium nitrate (Aladdin, I105869) was dissolved in deionized water to prepare an indium nitrate solution with a concentration of 0.173 mol / L; 12.8 mL of ammonia water was added dropwise to the indium nitrate solution under vigorous stirring, and the mixture was stirred in a water bath at 80° C. for 1 h to obtain a mixed solution; the mixed solution was taken out, cooled to room temperature, and centrifuged to obtain a precipitate, which was washed with deionized water 3 times and ethanol 3 times in sequence, and then placed in an oven at 60° C. to dry for 12 h, and then calcined at 450° C. for 3 h to obtain an In2O3 carrier (0.7 g of the In2O3 carrier was taken, and its water absorption was measured with deionized water to be 230 μL);

[0120] (S2) dissolving 0.183 g of nickel nitrate hexahydrate in 230 μL of deionized water, dissolving by ultrasonication for 10 min, and then uniformly adding the solution to 0.7 g of the In2O3 carrier prepared in step (S1), and then ultrasonically mixing the solution for 30 min; then drying the solution in an oven at 60° C. for 12 hours, and calcining the solution at 450° C. for 3 hours to obtain an indium oxide-supported nickel-based catalyst: 5Ni / In2O3-W;

[0121] (S3) The 5Ni / In2O3-W obtained in step (S2) is pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 350°C for 1 h to obtain 5Ni / In2O3-M-350.

[0122] Embodiment 15

[0123] The indium oxide-supported nickel-based catalyst (5Ni / In2O3-M-350) prepared in Example 14 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 5 In the catalytic reaction, the temperature was 325°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0124] Example 16

[0125] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (10Ni / In2O3-M-350), comprising the following steps:

[0126] (S1) 4 g of hydrated indium nitrate (Aladdin, I105869) was dissolved in deionized water to prepare an indium nitrate solution with a concentration of 0.173 mol / L; 12.8 mL of ammonia water was added dropwise to the indium nitrate solution under vigorous stirring, and the mixture was stirred in a water bath at 80° C. for 1 h to obtain a mixed solution; the mixed solution was taken out, cooled to room temperature, and centrifuged to obtain a precipitate, which was washed with deionized water 3 times and ethanol 3 times in sequence, and then placed in an oven at 60° C. to dry for 12 h, and then calcined at 450° C. for 3 h to obtain an In2O3 carrier (0.7 g of the In2O3 carrier was taken, and its water absorption was measured with deionized water to be 230 μL);

[0127] (S2) dissolving 0.386 g of nickel nitrate hexahydrate in 230 μL of deionized water, dissolving by ultrasonication for 10 min, and then uniformly adding the solution to 0.7 g of the In2O3 carrier prepared in step (S1), and then ultrasonically mixing the solution for 30 min; then drying the solution in an oven at 60° C. for 12 hours, and calcining the solution at 450° C. for 3 hours to obtain an indium oxide-supported nickel-based catalyst: 10Ni / In2O3-W;

[0128] (S3) The 10Ni / In2O3-W obtained in step (S2) is pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 350°C for 1 h to obtain 10Ni / In2O3-M-350.

[0129] Embodiment 17

[0130] The indium oxide supported nickel-based catalyst (10Ni / In2O3-M-350) prepared in Example 16 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 5 In the catalytic reaction, the temperature was 325°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0131] Embodiment 18

[0132] This embodiment provides a method for preparing an indium oxide-supported nickel-based catalyst (33Ni / In2O3-M-350), comprising the following steps:

[0133] (S1) 4 g of hydrated indium nitrate (Aladdin, I105869) was dissolved in deionized water to prepare an indium nitrate solution with a concentration of 0.173 mol / L; 12.8 mL of ammonia water was added dropwise to the indium nitrate solution under vigorous stirring, and the mixture was stirred in a water bath at 80° C. for 1 h to obtain a mixed solution; the mixed solution was taken out, cooled to room temperature, and centrifuged to obtain a precipitate, which was washed with deionized water 3 times and ethanol 3 times in sequence, and then placed in an oven at 60° C. to dry for 12 h, and then calcined at 450° C. for 3 h to obtain an In2O3 carrier (0.7 g of the In2O3 carrier was taken, and its water absorption was measured with deionized water to be 230 μL);

[0134] (S2) dissolving 1.709 g of nickel nitrate hexahydrate in 230 μL of deionized water, dissolving by ultrasonication for 10 min, and then uniformly adding the solution to 0.7 g of the In2O3 carrier prepared in step (S1), and then ultrasonically mixing the solution for 30 min; then drying the solution in an oven at 60° C. for 12 hours, and calcining the solution at 450° C. for 3 hours to obtain an indium oxide-supported nickel-based catalyst: 33Ni / In2O3-W;

[0135] (S3) The 33Ni / In2O3-W obtained in step (S2) is pretreated with a mixed gas of raw gas (0.02 mL / min) / N2 (20 mL / min) at 350°C for 1 h to obtain 33Ni / In2O3-M-350.

[0136] Embodiment 19

[0137] The indium oxide-supported nickel-based catalyst (33Ni / In2O3-M-350) prepared in Example 18 was sieved to obtain 40-60 mesh particles, which were then loaded into a fixed reactor to catalyze methanol steam reforming to produce hydrogen (the product was analyzed by online gas chromatography, as shown in FIG. Figure 5 In the catalytic reaction, the temperature was 325°C, the water-to-alcohol ratio was 1.4, and the gas phase space velocity was 24232h -1 .

[0138] pass Figure 5 It can be found that changing the nickel loading amount also affects the activity and selectivity of indium oxide-loaded nickel-based catalysts. Among them, only 1% loading of indium oxide-loaded nickel-based catalysts can show excellent catalytic performance, effectively reduce the catalyst cost, and have good industrial production application prospects.

[0139] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the explanation of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A nickel-based catalyst for hydrogen production from methanol reforming, characterized in that: The composition of the nickel-based catalyst is xNi / In2O3, wherein x represents the mass percentage of Ni and x is 0.5 to 35; The nickel-based catalyst is an untreated nickel-based catalyst or a gas-pretreated nickel-based catalyst; The gas is selected from one or more of hydrogen, raw gas, CO2 / H2 or inert gas.

2. A nickel-based catalyst for hydrogen production by methanol reforming according to claim 1, characterized in that: The x is 1-10.

3. A method for preparing a nickel-based catalyst for hydrogen production by methanol reforming as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: (S1) Precipitating an In precursor salt with aqueous ammonia, drying and calcining the In2O3 carrier after heating in a water bath; (S2) loading the Ni precursor salt onto the In2O3 carrier prepared in step (S1), drying and calcining to obtain an untreated nickel-based catalyst; (S3) Pretreating an untreated nickel-based catalyst with a gas to obtain a gas-pretreated nickel-based catalyst.

4. The method for preparing a nickel-based catalyst for hydrogen production by methanol reforming according to claim 3, characterized in that: In step (S1), the precursor salt of In is selected from one of indium (III) nitrate hydrate, In(NO3)3, and InCl3; In step (S2), the Ni precursor salt is selected from one or more of Ni basic carbonate, nitrate, sulfate, chloride or acetate.

5. The method for preparing a nickel-based catalyst for hydrogen production by methanol reforming according to claim 3, characterized in that: In step (S1), the molar ratio of ammonia water to In in the In precursor salt is 10 to 30:1; During the water bath, the temperature is 60-85°C and the time is 1-3h; During the drying process, the temperature is 60-100°C and the time is 5-12h; During the calcination process, the temperature is 300-500°C and the time is 3-12 hours.

6. The method for preparing a nickel-based catalyst for hydrogen production by methanol reforming according to claim 3, characterized in that: In step (S2), during loading, the loading method is selected from a hydrothermal method, a precipitation method or an impregnation method.

7. The method for preparing a nickel-based catalyst for hydrogen production by methanol reforming according to claim 3, characterized in that: In step (S2), during the drying process, the temperature is 60 to 100° C. and the time is 5 to 12 hours; During the calcination process, the temperature is 300-500°C and the time is 3-12 hours.

8. The method for preparing a nickel-based catalyst for hydrogen production by methanol reforming according to claim 3, characterized in that: In step (S3), during the pretreatment process, the temperature is 250-500°C and the time is 0.5-2h.

9. Use of the nickel-based catalyst for producing hydrogen by reforming methanol as claimed in any one of claims 1 to 2 in producing hydrogen by reforming methanol.

10. A method for producing hydrogen by reforming methanol, characterized in that: The following steps are involved: The nickel-based catalyst for hydrogen production from methanol reforming according to any one of claims 1 to 2 is screened and loaded into a fixed bed reactor to catalyze methanol steam reforming to produce hydrogen; During the catalytic reaction, the temperature is 150-375°C and the water-to-alcohol ratio is 0.8-3.

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