CN112675865B - High-activity and high-stability supported nickel catalyst and preparation method and application thereof - Google Patents
High-activity and high-stability supported nickel catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-activity and high-stability supported nickel catalyst, and a preparation method and application thereof, and belongs to the field of energy and chemical industry. The catalyst is made of Al2O3‑SiO2‑La2O3Or a composite oxide formed by any two oxides of the three oxides is taken as a carrier, metallic nickel is taken as an active component, and the specific surface area of the catalyst is 100-500m2Per g, pore volume of 0.2-1.4cm3The pore diameter is 5-25nm, the molar ratio of Al-Si-La in the catalyst is any value, the total content of nickel is 30-90 wt%, and the particle diameter of Ni metal in the catalyst is 5-15 nm. The invention can improve the Ni loading to more than 30 wt% by a coprecipitation method, and reduce the agglomeration of the nickel, thereby increasing the dispersion of the Ni and controlling the particle size of the nickel particles to be in a nanometer level. The process is simple and convenient, the equipment requirement is low, and the prepared catalyst has high activity and stability for hydrogenation of the organic liquid hydrogen storage material.
Description
Technical Field
The invention belongs to the field of energy and chemical engineering, and particularly relates to a high-activity and high-stability supported nickel catalyst, and a preparation method and application thereof.
Background
The hydrogen storage technology is the key to realize the use of hydrogen energy, and compared with the traditional hydrogen storage technology, the organic liquid hydrogen storage technology has a plurality of advantages. The liquid organic hydrogen storage is characterized in that the organic liquid hydrogen storage materials are generally in liquid state at normal temperature, are similar to gasoline, can directly use the existing infrastructure, and are convenient to transport and store hydrogen energy. However, the Ru-based catalyst is generally used for hydrogenation of the organic liquid hydrogen storage material at present, and the catalyst is expensive, so that the cost of the organic liquid hydrogen storage technology is increased, and the development of the organic liquid hydrogen storage technology is greatly limited.
Research and development of a non-noble metal catalyst to replace a noble metal catalyst applied to hydrogenation reaction in an organic Liquid Hydrogen Storage (LOHCs) technology has great significance for reducing cost and popularizing the liquid organic hydrogen storage technology. The nickel catalyst has the advantages of high activity, low price and the like, and is widely applied to hydrogenation reaction. However, nickel supported oxides have been rarely reported for hydrogenation reactions in organic liquid hydrogen storage materials. The coprecipitation method is a method of simultaneously precipitating a plurality of components required for a catalyst, and is commonly used to prepare a high-content multi-component catalyst. For example, shenthrio et al at Nanjing university reported in the patent CN 105618058A that the co-precipitation method for preparing Ni-based catalyst with high content has good catalytic activity in preparing sorbitol by hydrogenating aqueous glucose solution. As the catalyst preparation method reported in CN 101733106A, CN 104084209 a patent, in general, when the catalyst is prepared by coprecipitation, a direct calcination reduction method is usually adopted after obtaining a precipitate precursor. However, various metal salts formed by metals and anions in the process of precipitate formation can be directly deposited in the catalyst precursor, and the metal is difficult to reduce by directly using the dried precipitate, so that the utilization rate of the metal is reduced. Meanwhile, the catalyst prepared by the direct reduction method has large particle size and uneven distribution, which can significantly affect the activity of the catalyst. The document reports (modern chemical industry, volume 38 in 2018, pages 87-92) that the specific surface area of pore volume and pore diameter of the catalyst is remarkably increased, the density of active centers is increased, and the catalytic activity is improved after hydrothermal treatment in the preparation process of the catalyst. Therefore, the preparation method combines the two, and adopts a hydrothermal treatment method to carry out 6h hydrothermal treatment on the precipitate on the basis of coprecipitation, and adopts lower hydrogen pressure to ensure that the precipitate does not generate nickel salt which is difficult to reduce. The prepared catalyst has smaller particle size distribution and particle size, and the metallic nickel has excellent crystal form and good dispersion. In addition, compared with a single oxide, the composite oxide has unique physical and chemical properties, the larger pore diameter and the larger specific surface area ensure that Ni can be uniformly dispersed on the carrier, and meanwhile, the rare earth La element is introduced, so that the stability of the catalyst is facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-activity and high-stability supported nickel catalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-activity and high-stability carried Ni catalyst is prepared from Al2O3-SiO2-La2O3Or a composite oxide formed by any two oxides of the three oxides is used as a carrier, metallic nickel is used as an active component, and the specific surface area of the catalyst is 100-500m2Per g, pore volume of 0.2-1.4cm3The pore diameter is 5-25nm, the molar ratio of Al-Si-La in the carrier in the catalyst is any value, the total content of nickel is 30-90 wt%, and the particle diameter of Ni metal in the catalyst is 5-15 nm.
The preparation process of the catalyst is as follows:
(1) weighing more than two substances in A, B, C in a certain amount, dissolving in deionized water to form a solution A ', weighing D and/or E in a certain amount, dissolving in deionized water to form a solution B ', weighing F, and dissolving in deionized water to form a solution C ';
(2) slowly dripping the solution A ' and the solution B ' into the solution C ' at the same time under the condition of 80-90 ℃ water bath, continuously stirring to form light green precipitate, filtering the precipitate, and continuously washing the precipitate with deionized water and absolute ethyl alcohol until the eluate is neutral;
(3) dispersing the precipitate obtained in the step (2) in absolute ethyl alcohol, and carrying out azeotropic evaporation on water and the absolute ethyl alcohol under the oil bath condition of 110-150 ℃;
(4) dispersing the precipitate obtained in the step (3) in deionized water to form a suspension, introducing 0.5-1.2MPa hydrogen pressure into a reaction kettle, reducing at the temperature of 130-170 ℃ for 5-8h at the speed of 150r/min to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and drying in an oven at the temperature of 40-70 ℃ for 4-6 h;
(5) grinding into powder, introducing inert gas and H into the catalyst in a tube furnace2Heating the mixed gas to 420-800 ℃, reducing the mixed gas for 5-12h with the flow rate of the mixed gas being 40-80mL/min, closing the mixed gas, and standing and cooling to obtain the nickel-supported catalyst;
a is Ni (NO)3)2·6H2O、NiCl2·6H2O or NiSO4·6H2O；
B is Al (NO)3)3·9H2O or Al2(SO4)3；
C is La (NO)3)3·6H2O or LaCl3·7H2O；
D is Na2SiO3·9H2O or K2SiO3；
E is Na2CO3、NaHCO3Or NaOH;
the F is PEG2000, PEG200, PEG600 or PEG 20000.
Further, the oil bath in the step (3) is 120 ℃.
Further, the hydrogen pressure in the step (4) is 1 MPa.
Further, the reduction time in the step (4) is 6 h.
Further, the oven drying temperature in the step (4) is 50 ℃.
Further, Ar/H in the step (5)2The volume fraction of hydrogen in the mixed gas was 10%.
Further, the reduction temperature in the step (5) is 450 ℃.
Further, the reduction time in the step (5) is 6 h.
The Ni-based catalyst provided by the invention has the advantages of high activity, low price and the like. The non-noble metal catalyst prepared by selecting the transition metal Ni as an active component to replace the Ru-based catalyst can greatly reduce the cost of the catalyst, and meanwhile, the coprecipitation method can improve the loading capacity of Ni to more than 30 wt% on one hand, reduce the agglomeration of the nickel on the other hand, increase the dispersion of the Ni and control the particle size of the nickel particles to be in a nanometer level. The process is simple and convenient, the equipment requirement is low, and the prepared catalyst has high activity and stability for hydrogenation of the organic liquid hydrogen storage material.
The invention also provides application of the supported nickel catalyst in hydrogenation reaction of an organic liquid hydrogen storage material.
Further, the application is that the reaction is carried out in a high-temperature high-pressure reaction kettle, and the experimental process is as follows: introducing pure hydrogen to evacuate air in the reaction kettle (avoid explosion in the reaction process), heating the reaction kettle to 160 ℃ for adding the organic solvent, introducing the hydrogen, starting the reaction, sampling and testing the reaction rate at intervals, wherein the reaction temperature is 160 ℃ for adding the organic solvent, the hydrogen pressure is 5-8MPa, and the reaction speed is 600r/min for adding the organic solvent at 400 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Ni-supported catalyst prepared by the invention can be applied to hydrogenation reaction of organic liquid hydrogen storage materials, has high catalytic activity and good stability, and can be repeatedly used for many times.
(2) The catalyst prepared by the method is a non-noble metal catalyst, and noble metals are not added, so that the cost of the catalyst is greatly reduced.
(3) The high-loading Ni still has good dispersibility on the carrier, and the grain diameter of the Ni is kept at a nanometer level.
(4) The invention has simple synthesis process and lower equipment requirement, and can be produced and applied in large scale.
Drawings
FIG. 1 is a representation of the X-ray diffraction analysis of the catalyst of example 1.
FIG. 2 is a transmission electron microscope and elemental map of the catalyst of example 1.
FIG. 3 is a graph showing the comparison of the hydrogenation activity of 5 catalysts in comparative example 3.
FIG. 4 is a graph comparing the hydrogenation of N-N-propylcarbazole (NPCZ) catalyzed by 8 catalysts in comparative example 4.
FIG. 5 is a comparative graph showing the hydrogenation of ethylcarbazole (NECZ) catalyzed by 2 catalysts in comparative example 5.
FIG. 6 is a comparative graph showing the hydrogenation of Dibenzyltoluene (DBT) catalyzed by 2 catalysts in comparative example 6.
FIG. 7 is a transmission electron micrograph of the catalyst of example 5.
FIG. 8 is a graph of the hydrogen uptake rate of N-N-propylcarbazole catalyzed by the catalyst of example 11 repeated 5 times.
Detailed Description
Commercial 0.5 wt% Ru/Al as used in the following comparative examples2O3The catalyst was purchased from Shanxi Kaida chemical Co., Ltd, analytically pure AR.
Example 1
Weighing 17.263gNi (NO)3)2·6H2O and 5.068gAl (NO)3)3·9H2O, dissolved in 100mL of deionized water, designated solution A'. Weighing 3.837gNa2SiO3·9H2O and 8.755g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B'. 0.5g of PEG2000 was weighed out and dissolved in 200mL of deionized water to name solution C'. Slowly dripping the solution A ' and the solution B ' into the solution C ' at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate with deionized water until the eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form turbid liquid, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ at 120r/min to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, drying for 4 hours in a 50 ℃ drying oven, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H (argon/hydrogen) furnace2Mixed gas (H)2Volume content of 10%), heating to 450 deg.C at a rate of 3 deg.C/min, and mixingThe flow rate of the resultant gas is 60mL/min, reduction is carried out for 6H, and Ar/H is closed2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni70/Al1Si1La0The characterization chart of the X-ray diffraction analysis of the supported nickel catalyst O (representing that the Ni loading is 70 and the molar ratio of Al/Si/La is 1/1/0) is shown in figure 1, and the transmission electron microscope and the element mapping chart are shown in figure 2.
Example 2
Weighing 17.263gNi (NO)3)2·6H2O and 2.435gAl (NO)3)3·9H2O, dissolved in 100mL of deionized water, designated solution A. Weighing 5.532gNa2SiO3·9H2O and 8.735g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 450 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni70/Al1Si3La0O (representing a catalyst with a Ni content of 70 and an Al/Si/La molar ratio of 1/3/0).
Comparative example 1
Weighing 17.263gNi (NO)3)2·6H2O and 11.029gAl (NO)3)3·9H2O, dissolved in 100mL of deionized water, designated solution a'. 16.447g of Na were weighed2CO3Dissolved in 100mL of deionized water and designated as solution B'. 0.5g of PEG2000 was weighed out and dissolved in 200mL of deionized water to name solution C'. Slowly dripping the solution A ' and the solution B ' into the solution C ' at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate with deionized water until the eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form turbid liquid, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ at 120r/min to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, drying for 4 hours in a 50 ℃ drying oven, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H (argon/hydrogen) furnace2Mixed gas (H)2Volume content of 10 percent), heating to 450 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2 Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni70/Al2O3。
Comparative example 2
Weighing 17.263gNi (NO)3)2·6H2O was dissolved in 100mL of deionized water and designated solution A'. Weighing 7.100gNa2SiO3·9H2O and 5.457g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B'. 0.5g of PEG2000 was weighed out and dissolved in 200mL of deionized water to name solution C'. Slowly dripping the solution A ' and the solution B ' into the solution C ' at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate with deionized water until the eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ at 120r/min to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and washing with deionized water and absolute ethyl alcoholDrying in 50 deg.C oven for 4 hr, grinding into powder, and placing the catalyst in tubular furnace with Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 450 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2 Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni70/SiO2。
Comparative example 3
0.2g of each of the catalysts prepared in example 1, example 2, comparative example 1 and comparative example 2 and commercial 0.5 wt% Ru/Al were weighed2O3The catalyst was subjected to a hydrogenation experiment with benzene. Wherein, 10mL of raw material benzene and 40mL of solvent n-hexane are added, the hydrogen pressure of the reaction is 7MPa, the reaction temperature is 150 ℃, and the rotating speed is 600 r/min. The results of the comparison of the catalytic benzene hydrogenation activities of the above 5 catalysts are shown in FIG. 3. It can be seen that Ni prepared in example 170/Al1Si1La0The O catalyst catalyzes the benzene hydrogenation to completely react in 60 minutes, and under the proper Al/Si molar ratio, the catalytic hydrogenation activity of the composite carrier loaded with nickel to catalyze the benzene is higher than that of Al2O3And SiO2Loaded Ni catalyst and having catalytic activity much higher than commercial 0.5 wt% Ru/Al2O3。
Example 3
Weighing 12.331gNi (NO)3)2·6H2O and 8.446gAl (NO)3)3·9H2O, dissolved in 100mL of deionized water, designated solution A. Weighing 6.396gNa2SiO3·9H2O and 8.528g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate with deionized water until the eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating the water and the ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1Ma hydrogen pressure into a high-temperature high-pressure reaction kettle, and introducing 120r/minReducing at 150 deg.C for 6H to form catalyst precursor, suction filtering, washing with deionized water and anhydrous ethanol, drying in 50 deg.C oven for 4H, grinding into powder, and placing the catalyst in tubular furnace2Mixed gas (H)2Volume content of 10 percent), heating to 450 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni50/Al1Si1La0O (representing a catalyst with 50 Ni content and 1/1/0 Al/Si/La molar ratio).
Example 4
Weighing 22.195gNi (NO)3)2·6H2O and 1.689gAl (NO)3)3·9H2O, dissolved in 100mL of deionized water, designated solution A. Weighing 1.279g Na2SiO3·9H2O and 12.485g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 450 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni90/Al1Si1La0O (representing a catalyst with a Ni content of 90 and an Al/Si/La molar ratio of 1/1/0).
Example 5
Weighing 7.433gNi (NO)3)2·6H2O、22.075gAl(NO3)3·9H2O and 1.329gLa (NO)3)3·6H2O was dissolved in 100mL of deionized water and designated solution A. 18.834g of Na were weighed2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 750 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al6Si0La1O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 6/0/1). The transmission electron microscopy of the catalyst is shown in FIG. 7.
Example 6
Weighing 7.433gNi (NO)3)2·6H2O、14.717gAl(NO3)3·9H2O and 3.988gLa (NO)3)3·6H2O was dissolved in 100mL of deionized water and designated solution A. 15.6165g of Na were weighed2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of water bath at the temperature of 90 ℃, and continuously stirring to form light greenPrecipitating, filtering, continuously washing the precipitate with deionized water until the eluate is neutral, dispersing the precipitate in 150mL of anhydrous ethanol, azeotropically evaporating water and ethanol at 120 ℃ in an oil bath, dispersing the precipitate in 200mL of deionized water to form a suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing at 120r/min and 150 ℃ for 6 hours to form a catalyst precursor, performing suction filtration, washing with deionized water and anhydrous ethanol, drying in a 50 ℃ oven for 4 hours, grinding into powder, and placing the catalyst in a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 750 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al4Si0La3O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 4/0/3).
Example 7
Weighing 7.433gNi (NO)3)2·6H2O、2.612gAl(NO3)3·9H2O and 5.320gLa (NO)3)3·6H2O was dissolved in 100mL of deionized water and designated solution A. Weighing 4.073gNa2SiO3·9H2O and 7.2564g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)210% by volume),heating to 750 deg.C at a rate of 3 deg.C/min, reducing for 6 hr with the flow rate of mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al1Si1La1O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 1/1/1).
Example 8
Weighing 7.433gNi (NO)3)2·6H2O and 3.122gLa (NO)3)3·6H2O was dissolved in 100mL of deionized water and designated solution A. Weighing 5.454gNa2SiO3·9H2O and 11.005g of Na2CO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g PEG2000 was weighed out and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 750 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al0Si4La3O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 0/4/3).
Example 9
Weighing 6.058g NiCl2·6H2O、2.184gAl2(SO4)3And 4.515gLaCl3·7H2O was dissolved in 100mL of deionized water and designated as solutionA. Weighing 1.967gK2SiO3And 13.928g of NaHCO3Dissolved in 100mL of deionized water and designated as solution B. 0.5g of PEG200 was weighed out and dissolved in 200mL of deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the condition of 90 ℃ water bath, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating water and ethyl alcohol under the condition of 120 ℃ oil bath, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, reducing for 6 hours at the temperature of 150 ℃ to form a catalyst precursor, then carrying out suction filtration, washing by deionized water and absolute ethyl alcohol, putting into a 50 ℃ drying oven for drying for 4 hours, grinding into powder, and then putting the catalyst into a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 750 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al1Si1La1O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 1/1/1).
Example 10
Weighing 6.686g NiSO4·6H2O、2.184gAl2(SO4)3And 4.515gLaCl3·7H2O was dissolved in 100mL of deionized water and designated solution A. Weighing 4.073gK2SiO3And 6.63g of NaOH, dissolved in 100mL of deionized water, designated as solution B. 0.5g PEG20000 was weighed and dissolved in 200mL deionized water to name solution C. Slowly dripping the solution A and the solution B into the solution C at the same time under the water bath condition of 90 ℃, continuously stirring to form light green precipitate, filtering and continuously washing the precipitate by deionized water until eluate is neutral, then dispersing the precipitate into 150mL of absolute ethyl alcohol, azeotropically evaporating the water and the ethyl alcohol under the oil bath condition of 120 ℃, then dispersing the precipitate into 200mL of deionized water to form suspension, introducing 1MPa of hydrogen pressure into a high-temperature high-pressure reaction kettle, controlling the temperature at 150 ℃ at 120r/minReducing for 6H to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, drying in a 50 ℃ oven for 4H, grinding into powder, and putting the catalyst in a tubular furnace Ar/H2Mixed gas (H)2Volume content of 10 percent), heating to 750 ℃ at the heating rate of 3 ℃/min, reducing for 6H with the flow rate of the mixed gas of 60mL/min, and closing Ar/H2Mixed gas (H)2Volume content 10%), placed in a tube furnace and cooled for 24h to obtain Ni30/Al1Si1La1O (representing a catalyst with a Ni content of 30 and an Al/Si/La molar ratio of 1/1/1).
Comparative example 4
0.2g of each of example 1, 3, 4, 6, 7, 8, 9, commercial 0.5 wt% Ru/Al was weighed2O3The catalyst was subjected to hydrogenation experiments with N-propylcarbazole (NPCZ). Wherein, 2g of raw material NPCZ is added, 40mL of solvent cyclohexane is added, the hydrogen pressure of the reaction is 7MPa, the reaction temperature is 150 ℃, and the rotating speed is 600 r/min. The amount of absorbed hydrogen for NPCZ catalyzed by the above catalyst varies with time as shown in FIG. 4, which shows that the hydrogenation activity of the catalysts prepared in examples 1, 3, 4, 6, 7, 8, and 9 on NPCZ is higher than that of commercial 0.5 wt% Ru/Al2O3Catalyst, especially Ni prepared in example 730/Al1Si1La1O high catalytic activity was obtained at the same reaction conditions using lower loadings, NPCZ reacted completely at 60 minutes compared to commercial 0.5 wt% Ru/Al2O3The catalyst took 240 minutes to complete the reaction.
Comparative example 5
0.2g of example 1, commercial 0.5 wt% Ru/Al were weighed out separately2O3The catalyst was subjected to a hydrogenation experiment with ethyl carbazole (NECZ). Wherein, 2g of raw material NECZ is added, 40mL of solvent cyclohexane is added, the hydrogen pressure of the reaction is 7MPa, the reaction temperature is 150 ℃, and the rotating speed is 600 r/min. The amount of hydrogen absorbed by the above catalyst to catalyze the NECZ as a function of time is shown in FIG. 5, which shows that the catalyst prepared in example 1 only requires about 90 minutes for hydrogenation of the NECZ at 150 ℃ and 7MPa to obtain commercially 0.5 wt% Ru/Al2O3For comparison, 240 minutes did not occur under the same experimental conditionsThe reaction can be completed.
Comparative example 6
0.2g of example 1, commercial 0.5 wt% Ru/Al were weighed out separately2O3The catalyst was subjected to hydrogenation experiments with Dibenzyltoluene (DBT). Wherein, 2g of DBT is added as raw material, 40mL of cyclohexane solvent is added, the hydrogen pressure of the reaction is 7MPa, the reaction temperature is 150 ℃, and the rotating speed is 600 r/min. The amount of hydrogen absorbed by the DBT catalyzed by the above catalyst as a function of time is shown in FIG. 6, which shows that the catalyst prepared in example 1 only requires about 90 minutes for the hydrogenation of DBT at 150 ℃ and 7MPa to obtain commercial 0.5 wt% Ru/Al2O3By way of comparison, 240 minutes failed to react completely under the same experimental conditions.
In conclusion, the catalyst prepared by the invention has good catalytic activity on benzene, N-N-propyl carbazole, ethyl carbazole and dibenzyl toluene, and can be used as a general catalyst for hydrogenation of organic liquid hydrogen storage molecules to a certain extent.
Example 11
A cyclically repeated hydrogenation experiment of NPCZ was carried out using 0.2g of the catalyst prepared in example 1. Wherein, 2g of raw material NPCZ is added, 40mL of solvent cyclohexane is added, the hydrogen pressure of the reaction is 7MPa, the reaction temperature is 150 ℃, the rotating speed is 600r/min, and the next cycle reaction is carried out after the reaction is finished. The hydrogen absorption rate of the obtained five times of N-N-propylcarbazole is shown in FIG. 8, and it can be known that NPCZ can completely react in 90 minutes in the fifth cycle, and the catalyst activity is not obviously attenuated, thus showing good stability.
Comparative example 7
Asahi peak, Zhejiang university, and others performed a hydrogenation test of ethylcarbazole using Raney nickel, which is highly active in nickel-based catalysts, by placing ethylcarbazole and activated Raney nickel (Raney-Ni) catalysts in a stainless steel autoclave, and continuously monitoring the stirring speed, temperature, and pressure. The reactor was then sealed, evacuated for about 15 minutes, and then heated to the desired temperature. Subsequently, the reaction was started at the desired temperature and hydrogen pressure while stirring at 1000 rpm. As the reaction proceeded, the pressure in the reactor remained constant throughout the experiment, with hydrogen being continuously added from the hydrogen storage tank. By pressure gaugesThe hydrogen consumption and reaction time were recorded. The liquid reaction products were analyzed using a gas chromatography-mass spectrometer (HP6890/5973 GC-MS). (journal of alloysan dCompouns 2011 volume 509, page 152-156). Wuyowa et Al, Beijing university general Ni/Al2O3And YH3The powders were mixed in a mass ratio of 4:1 to prepare 1 wt% Ni/Al2O3-YH3The catalyst was used for the ethylcarbazole hydrogenation test (journal of materials chemistry a2019, volume 7, pp 16677-16684). The reaction conditions and the results obtained are shown in table 1 for the catalyst pairing ratio of example 1:
TABLE 1
| Sample (I) | Hydrogen storage molecules | Reaction conditions | Time | Yield of |
| Raney-Ni | NECZ | 10wt％a,433K,5MPa H2 | 2.5 | 86.2 |
| 1wt％ Ni/Al2O3-YH3 | NECZ | 12.5wt％,453K,10MPa H2 | 1.5 | 100 |
| Ni70/Al1Si1La0O | NECZ | 10wt％,423K,7MPa H2 | 1.5 | 100 |
aMass ratio of catalyst to reactants.
As can be seen from Table 1, under similar reaction conditions, hydrogenation of NECZ by Raney-Ni did not completely react within 2.5h, and 1 wt% Ni/Al reacted within the same time2O3-YH3The higher reaction conditions are required, which indicates that the catalyst prepared in example 1 has high catalytic activity, superior to raney nickel catalyst and previously reported nickel-based catalyst.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. A high-activity high-stability supported nickel catalyst is characterized in that the catalyst uses Al2O3、SiO2、La2O3The composite oxide formed by more than two oxides is used as a carrier, the metallic nickel is used as an active component, and the specific surface area of the catalyst is 100-500m2Per g, pore volume of 0.2-1.4cm3The pore diameter is 5-25nm, the total content of nickel is 30-90 wt%, and the particle diameter of Ni metal as a catalyst is 5-15 nm;
the preparation method of the catalyst comprises the following steps:
(1) weighing A, B, C in certain amount and dissolving in deionized water to form solution A ', weighing D and/or E in certain amount and dissolving in deionized water to form solution B ', weighing F and dissolving in deionized water to form solution C ';
(2) slowly dripping the solution A ' and the solution B ' into the solution C ' at the same time under the condition of 80-90 ℃ water bath, continuously stirring to form light green precipitate, filtering the precipitate, and continuously washing the precipitate with deionized water and absolute ethyl alcohol until the eluate is neutral;
(3) dispersing the precipitate obtained in the step (2) in absolute ethyl alcohol, and carrying out azeotropic evaporation on water and the absolute ethyl alcohol under the oil bath condition of 110-150 ℃;
(4) dispersing the precipitate obtained in the step (3) in deionized water to form a suspension, introducing 0.5-1.2MPa hydrogen pressure into a reaction kettle, reducing at the temperature of 130-170 ℃ for 5-8h at the speed of 150r/min to form a catalyst precursor, then carrying out suction filtration, washing with deionized water and absolute ethyl alcohol, and drying in an oven at the temperature of 40-70 ℃ for 4-6 h;
(5) grinding into powder, introducing inert gas and H into the catalyst in a tube furnace2Heating the mixed gas to 420-800 ℃, reducing the mixed gas for 5-12h with the flow rate of the mixed gas being 40-80mL/min, closing the mixed gas, and standing and cooling to obtain the nickel-supported catalyst;
a is Ni (NO)3)2·6H2O、NiCl2·6H2O or NiSO4·6H2O；
B is Al (NO)3)3·9H2O or Al2(SO4)3；
C is La (NO)3)3·6H2O or LaCl3·7H2O；
D is Na2SiO3·9H2O or K2SiO3；
E is Na2CO3、NaHCO3Or NaOH;
the F is PEG2000, PEG200, PEG600 or PEG 20000.
2. The supported nickel catalyst of claim 1, wherein the oil bath in step (3) is 120 ℃.
3. The supported nickel catalyst according to claim 1, wherein the hydrogen pressure in the step (4) is 1 MPa.
4. The supported nickel catalyst of claim 1, wherein the reduction time in step (4) is 6 hours.
5. The supported nickel catalyst of claim 1, wherein the oven drying temperature in step (4) is 50 ℃.
6. The supported nickel catalyst according to claim 1, wherein the volume fraction of hydrogen in the mixed gas in the step (5) is 10%.
7. The supported nickel catalyst of claim 1, wherein the reduction temperature in step (5) is 450 ℃.
8. The supported nickel catalyst of claim 1, wherein the reduction time in step (5) is 6 hours.
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