CN109999801B - M-B@Pd-B@Al2O3Catalyst and preparation method and application thereof - Google Patents
M-B@Pd-B@Al2O3Catalyst and preparation method and application thereof Download PDFInfo
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The invention belongs to the technical field of hydrogenation catalysts, and particularly relates to M-B @ Pd-B @ Al2O3A catalyst, a preparation method and application thereof. M-B @ Pd-B @ Al of the invention2O3The catalyst comprises an active component inner core, an active component middle layer wrapped outside the active component inner core and an auxiliary agent outer layer wrapped outside the active component middle layer; the active component inner core is M-B amorphous alloy, and M is selected from one of Zn, Cu, Fe, Co and Ni; the active component interlayer is Pd-B amorphous alloy; the outer layer of the auxiliary agent is alumina. The invention provides a novel catalyst which has higher activity and selectivity when being used for preparing gamma-valerolactone by selective hydrogenation of levulinic acid in a water phase.
Description
Technical Field
The invention belongs to the technical field of hydrogenation catalysts, and particularly relates to a hydrogenation catalystM-B @ Pd-B @ Al2O3A catalyst, a preparation method and application thereof.
Background
Fossil fuels are used as energy sources and fuel sources, so that the reserves are reduced day by day, and sulfur oxides and nitrogen oxides generated in the consumption process easily cause environmental pollution. The lignocellulose biomass and the derivatives thereof are used as substitutes of fossil fuels, so that the method has sustainability, and the produced fine chemicals and fuels have the characteristic of environmental friendliness.
The preparation of gamma-valerolactone by hydrogenation of levulinic acid is an important reaction in the biomass chemical process, and is an important intermediate reaction for preparing liquid fuel from cellulose or hemicellulose. Meanwhile, formic acid is used as a common product for preparing levulinic acid from cellulose and can be used as a hydrogen source in the hydrogenation process, so that the utilization rate of carbon atoms is improved. In addition, the method has very important significance in efficiently converting small molecules after lignocellulose hydrolysis by utilizing a water phase reaction process: the process of separating organic micromolecules from the water phase is avoided, and the production cost is reduced; compared with pyrolysis reaction and gasification reaction, the temperature of the water phase reaction is reduced, and energy loss is reduced. Therefore, the development of a high-activity and high-selectivity catalyst capable of catalyzing the reaction of levulinic acid and formic acid in a water-phase reaction system to prepare gamma-valerolactone has important economic and social significance.
《Co/γ-Al2O3The research on the catalytic hydrogenation of levulinic acid to gamma-valerolactone discloses a catalytic hydrogenation process, wherein the process prepares Co/gamma-Al by an isometric impregnation method2O3Adding a catalyst, 1.67g of levulinic acid and 40mL of methanol into an autoclave, introducing hydrogen to replace air in the autoclave, introducing the hydrogen to the reaction pressure, slowly heating to the reaction temperature, and starting the reaction (Zhang Lin and the like, industrial catalysis, volume 21, No. 7, 68-71). When the catalyst is used for catalyzing levulinic acid to prepare gamma-valerolactone through hydrogenation, the selectivity of the valerolactone can only reach 81.4 percent at the highest level, and the selectivity is poor. In addition, in the prior art, the gamma-valerolactone prepared by hydrogenating levulinic acid is mostly carried out in an organic phase, and the levulinic acid serving as a raw material is generally generated by biomass hydrolysis and is prepared by organic materialsIn phase, the levulinic acid generated by hydrolysis needs to be separated, the polarity of the gamma-valerolactone is low, and the difficulty of separating the product from the system is increased by adopting an organic phase.
Disclosure of Invention
The first purpose of the invention is to provide M-B @ Pd-B @ Al2O3The catalyst can improve the selectivity of gamma-valerolactone when used for preparing the gamma-valerolactone by hydrogenating levulinic acid.
The second purpose of the invention is to provide M-B @ Pd-B @ Al with simple process2O3A method for preparing the catalyst.
The third purpose of the invention is to provide M-B @ Pd-B @ Al2O3The catalyst has better hydrogenation activity in the application of hydrogenation reduction reaction.
In order to achieve the purpose, the invention adopts the technical scheme that:
M-B@Pd-B@Al2O3the catalyst comprises an active component inner core, an active component middle layer wrapped outside the active component inner core and an auxiliary agent outer layer wrapped outside the active component middle layer; the active component inner core is M-B amorphous alloy, and M is selected from one of Zn, Cu, Fe, Co and Ni; the active component interlayer is Pd-B amorphous alloy; the outer layer of the auxiliary agent is alumina.
The catalyst of the invention takes M-B amorphous alloy and Pd-B amorphous alloy as active components, and the outer layer is coated by alumina, thereby avoiding the direct contact of the active components and water molecules during aqueous phase reaction and being more stable in the aqueous phase. The active components of the catalyst of the invention consist of noble metals and non-noble metals, which not only ensures the hydrogenation activity of the catalyst, but also reduces the cost to a certain extent. The catalyst of the invention has higher selectivity and activity when being used for preparing gamma-valerolactone by selective hydrogenation of levulinic acid in water phase.
The mass ratio of M atoms in the M-B amorphous alloy, Pd atoms in the Pd-B amorphous alloy and Al atoms in the alumina is 1: (0.05-1.5): (0.05-1.5). At the above ratio, M-B @ Pd-B @ Al2O3Catalyst performanceBetter activity and selectivity are obtained.
To ensure sufficient contact between the catalyst and the reactants, the M-B @ Pd-B @ Al2O3The average particle size of the catalyst is 3-8 nm.
M-B @ Pd-B @ Al mentioned above2O3The preparation method of the catalyst comprises the following steps:
1) mixing the M-B amorphous alloy and the Pd sol, gelatinizing under a protective atmosphere to change the Pd sol into Pd gel and coat the Pd gel on the surface of the M-B amorphous alloy, then adding borohydride to react to change the Pd gel into the Pd-B amorphous alloy, and washing an obtained precipitate after the reaction is completed to obtain the Pd-B coated M-B amorphous alloy;
2) mixing the prepared Pd-B coated M-B amorphous alloy with Al sol, gelatinizing under a protective atmosphere to enable the Al sol to be changed into Al gel and to be coated on the surface of the Pd-B coated M-B amorphous alloy, then carrying out solid-liquid separation, and washing the solid to obtain the Pd-B coated M-B amorphous alloy.
The invention provides a preparation method of a novel catalyst, which is simple and can be used for preparing a catalyst with a core-shell structure.
In order to realize uniform coating of the gel, the gelation in the step 1) and the step 2) is kept for 1-5 hours under the conditions that the temperature is 50-150 ℃ and the pressure of protective gas is 1-5 MPa.
The preparation method of the M-B amorphous alloy for facilitating the subsequent process comprises the following steps: adding borohydride into a soluble salt water solution of the metal M for reaction, and washing the generated precipitate to be neutral after the reaction is completed to obtain the metal M.
In order to completely reduce M atoms, the ratio of the mass of M atoms in the soluble salt water solution of the metal M to the mass of B atoms in the borohydride is 1: (5-50).
In order to completely reduce Pd atoms, the ratio of the amount of Pd atoms in the Pd sol to the amount of B atoms in borohydride in step 1) is 1: (5-50).
M-B@Pd-B@Al2O3The application of the catalyst in hydrogenation reduction reaction. The catalyst of the present invention has high hydrogenating activity and may be usedIn common hydrogenation reduction reactions such as furfural hydrogenation, benzene hydrogenation, etc.
The hydrogenation reduction reaction is to hydrogenate levulinic acid to generate gamma-valerolactone. M-B @ Pd-B @ Al of the invention2O3When the catalyst is used for preparing gamma-valerolactone by hydrogenating levulinic acid, when hydrogen is taken as a hydrogen source, the conversion rate of the levulinic acid is 100 percent and the selectivity of the gamma-valerolactone reaches over 99 percent in 5 hours of reaction, so that the catalyst has important industrial application value.
Drawings
FIG. 1 shows M-B @ Pd-B @ Al2O3Example 1 of catalyst Zn-B @ Pd-B @ Al2O3TEM images of the catalyst;
FIG. 2 shows M-B @ Pd-B @ Al2O3Cu-B @ Pd-B @ Al of example 2 of the catalyst2O3TEM images of the catalyst;
FIG. 3 shows M-B @ Pd-B @ Al2O3Example 3 Co-B @ Pd-B @ Al of catalyst2O3TEM images of the catalyst;
FIG. 4 is M-B @ Pd-B @ Al2O3Example 4 of catalyst Ni-B @ Pd-B @ Al2O3TEM images of the catalyst;
FIG. 5 is M-B @ Pd-B @ Al2O3Example 5 of catalyst Fe-B @ Pd-B @ Al2O3TEM images of the catalyst.
Detailed Description
M-B @ Pd-B @ Al of the invention2O3The catalyst comprises an active component inner core, an active component middle layer wrapped outside the active component inner core and an auxiliary agent outer layer wrapped outside the active component middle layer; the active component inner core is M-B amorphous alloy, and M is selected from one of Zn, Cu, Fe, Co and Ni; the active component interlayer is Pd-B amorphous alloy; the outer layer of the auxiliary agent is alumina. Wherein the mass content of B is 0.02-0.04%.
Preferably, the mass ratio of M atoms in the M-B amorphous alloy, Pd atoms in the Pd-B amorphous alloy and Al atoms in the alumina is 1: 0.4: 0.2. at the above ratio, M-B @ Pd-B @ Al2O3The performance of the catalyst is optimal.
M-B @ Pd-B @ Al of the invention2O3The preparation method of the catalyst comprises the following steps:
1) mixing the M-B amorphous alloy and the Pd sol, gelatinizing under a protective atmosphere to change the Pd sol into Pd gel and coat the Pd gel on the surface of the M-B amorphous alloy, then adding borohydride to react to change the Pd gel into the Pd-B amorphous alloy, and washing an obtained precipitate after the reaction is completed to obtain the Pd-B coated M-B amorphous alloy;
2) mixing the prepared Pd-B coated M-B amorphous alloy with Al sol, gelatinizing under a protective atmosphere to enable the Al sol to be changed into Al gel and to be coated on the surface of the Pd-B coated M-B amorphous alloy, then carrying out solid-liquid separation, and washing the solid to obtain the Pd-B coated M-B amorphous alloy.
Preferably, the protective atmosphere is at least one of hydrogen, nitrogen, argon and helium. Further preferably, the protective gas is hydrogen.
The preparation method of the M-B amorphous alloy comprises the following steps: adding borohydride into a soluble salt water solution of the metal M for reaction, and washing the generated precipitate to be neutral after the reaction is completed to obtain the metal M. The reaction temperature is 0-50 ℃. The borohydride is an aqueous solution of an alkali metal borohydride.
The preparation method of the Pd sol in the step 1) comprises the following steps: adding an alkali solution into a Pd soluble salt solution until no precipitate is generated any more, and then adding a citric acid solution until the precipitate is completely dissolved to obtain the Pd/Pd alloy catalyst.
OH in the alkali solution-The concentration of (A) is 0.1-10 mol/L; the concentration of the citric acid in the citric acid solution is 0.01-5 mol/L. The soluble salt of Pd is soluble salt of + 2-valent Pd. The alkali solution is at least one solution of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.
In the step 2), the preparation method of the Al sol comprises the following steps: in the presence of Al3+Adding strong alkali solution into the solution to generate precipitate, and continuously strengthening the alkali solution until the precipitate is completely dissolved to obtain the product. The Al sol was confirmed to be finally produced by the tyndall effect. The strong base is sodium hydroxide or sodium hydroxideAt least one of potassium.
The invention is further described with reference to the following specific embodiments and the accompanying drawings.
M-B@Pd-B@Al2O3Example 1 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Zn-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Zn-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the mass ratio of Zn, Pd and Al elements is 1: 0.4: 0.2. the catalyst of this example had a mass content of B of 0.03% as measured by ICP. Zn-B @ Pd-B @ Al of the present example2O3The morphology of the catalyst is shown in FIG. 1, and it is understood from FIG. 1 that the average particle diameter of the catalyst particles is about 5 nm.
M-B@Pd-B@Al2O3Example 2 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Cu-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Cu-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the ratio of the amounts of Cu, Pd and Al elements is 1: 0.4: 0.2. the catalyst of this example had a mass content of B of 0.04% as measured by ICP. Cu-B @ Pd-B @ Al of the present example2O3The morphology of the catalyst is shown in FIG. 2, and it is understood from FIG. 2 that the average particle diameter of the catalyst particles is about 5 nm.
M-B@Pd-B@Al2O3Example 3 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Co-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Co-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, CoThe ratio of the amounts of Pd and Al elements is 1: 0.4: 0.2. the catalyst of this example had a mass content of B of 0.03% as measured by ICP. Co-B @ Pd-B @ Al of this example2O3The morphology of the catalyst is shown in FIG. 3, and it is understood from FIG. 3 that the average particle diameter of the catalyst particles is about 5 nm.
M-B@Pd-B@Al2O3Example 4 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Ni-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Ni-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the mass ratio of Ni, Pd and Al elements is 1: 0.4: 0.2. Ni-B @ Pd-B @ Al of the present example2O3The morphology of the catalyst is shown in FIG. 4, and it is understood from FIG. 4 that the average particle diameter of the catalyst particles is about 5 nm.
M-B@Pd-B@Al2O3Example 5 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Fe-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Fe-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the ratio of the amounts of Fe, Pd and Al elements is 1: 0.4: 0.2. Fe-B @ Pd-B @ Al of the present example2O3The morphology of the catalyst is shown in FIG. 5, and it is understood from FIG. 5 that the average particle diameter of the catalyst particles is about 5 nm.
M-B@Pd-B@Al2O3Example 6 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Zn-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Zn-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a Catalyst and process for preparing sameIn the formula, the mass ratio of Zn, Pd and Al elements is 1: 0.07: 1.3.
M-B@Pd-B@Al2O3example 7 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Zn-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Zn-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the mass ratio of Zn, Pd and Al elements is 1: 1.5: 1.
M-B@Pd-B@Al2O3example 8 of the catalyst
M-B @ Pd-B @ Al of the present example2O3The catalyst is Zn-B @ Pd-B @ Al2O3The catalyst comprises an active component inner core Zn-B amorphous alloy, an active component intermediate layer Pd-B amorphous alloy coated outside the active component inner core and an auxiliary agent outer layer Al coated outside the active component intermediate layer2O3(ii) a In the catalyst, the mass ratio of Zn, Pd and Al elements is 1: 1: 0.08.
M-B@Pd-B@Al2O3example 1 of the preparation method of the catalyst
The catalyst in this example was Zn-B @ Pd-B @ Al2O3The preparation method specifically comprises the following steps:
1) 2.1g of ZnCl was taken2Dissolving in 50mL of distilled water to prepare ZnCl2Taking 5.8g of NaBH4Dissolving the NaBH in 50mL of distilled water to prepare NaBH4Solution, NaBH4And ZnCl2The mass ratio of (a) to (b) is 10: 1, NaBH is stirred at 30 DEG C4Dropwise addition of the solution to ZnCl2And (3) stirring the solution for reaction until no black solid is generated, filtering, and washing the black solid with distilled water until the filtrate is neutral to obtain the Zn-B amorphous alloy.
2) 1.1g of PdCl are taken2Dissolved in 50mL of distilled water to prepare PdCl2Solution, 4mol/L NaOH solution is added to PdCl2In solution until no more precipitate is formed, andadding 1mol/L citric acid solution until the precipitate is completely dissolved to obtain Pd sol; adding Zn-B amorphous alloy into Pd sol, and keeping the mixture for 3 hours under the conditions that the temperature is 150 ℃, the hydrogen pressure is 1MPa and the stirring speed is 800r/min, so that the Pd sol is changed into Pd gel and is wrapped on the surface of the M-B amorphous alloy to obtain mixed solution; in the mixed solution, the ratio of the amount of Zn to Pd is 1: 0.4;
3.5g of NaBH are taken4Dissolving the NaBH in 50mL of distilled water to prepare NaBH4Solution, adding NaBH at 30 deg.C under stirring4And dropwise adding the solution into the mixed solution (the mass ratio of B to Pd in the system is 15: 1), continuously stirring for 30min to complete the reduction reaction, filtering until no black solid is generated in the system, and washing the black solid with distilled water until the filtrate is neutral to obtain the Pd-B coated Zn-B amorphous alloy.
3) 0.41g of AlCl is taken3Dissolving in 50mL of distilled water to prepare AlCl3Solution, 4mol/L NaOH solution is added to AlCl dropwise3Adding 4mol/L NaOH solution into the solution until no precipitate is generated, and dissolving the precipitate completely to obtain Al sol; adding the Pd-B coated Zn-B amorphous alloy into Al sol (in the system, the mass ratio of Zn to Al is 1: 0.2), keeping for 3h under the conditions that the temperature is 150 ℃, the hydrogen pressure is 1MPa and the stirring speed is 800r/min, so that the Al sol is changed into Al gel and is coated on the surface of the Pd-B coated M-B amorphous alloy, filtering, and washing the obtained black solid with distilled water until the filtrate is neutral, thus obtaining the Pd-B coated Zn-B amorphous alloy.
The catalyst prepared in this example had a B content of 0.02% by mass as measured by ICP, and it was confirmed by XRD that Al was present as Al in the catalyst prepared in this example2O3Exist in the form of (1).
M-B@Pd-B@Al2O3Example 2 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 2 catalyst Cu-B @ Pd-B @ Al2O3Is substantially the same as the operating procedure of example 1 of the process for the preparation of the catalyst, except that, in step 1), 2.1g of ZnCl are added2To 2.1gCuCl2Finally, the catalyst with the active component with Cu-B amorphous alloy as the kernel is prepared.
M-B@Pd-B@Al2O3Example 3 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 3 catalyst Co-B @ Pd-B @ Al2O3The preparation process of (1) is substantially the same as the operation procedure of example 1 of the preparation process of the catalyst except that, in the step 1), 2.1g of ZnCl is added2Change to 2.0g CoCl2Finally, the catalyst with the active component with the Co-B amorphous alloy as the kernel is prepared.
M-B@Pd-B@Al2O3Example 4 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 4 catalyst Ni-B @ Pd-B @ Al2O3The preparation process of (1) is substantially the same as the operation procedure of example 1 of the preparation process of the catalyst except that, in the step 1), 2.1g of ZnCl is added2To 2.0g NiCl2Finally, the catalyst with the active component with Ni-B amorphous alloy as the kernel is prepared. The mass content of B in the catalyst prepared in this example was measured by ICP to be 0.03%.
M-B@Pd-B@Al2O3Example 5 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 5 catalyst Fe-B @ Pd-B @ Al2O3The preparation process of (1) is substantially the same as the operation procedure of example 1 of the preparation process of the catalyst except that, in the step 1), 2.1g of ZnCl is added2Changed to 2.0g FeCl2Finally, the catalyst with the active component with Fe-B amorphous alloy as the kernel is prepared. The mass content of B in the catalyst prepared in this example was 0.03% by ICP.
M-B@Pd-B@Al2O3Example 6 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 6 catalyst Zn-B @ Pd-B @ Al2O3The preparation method of (1) is substantially the same as the operation procedure of example 1 of the preparation method of the catalyst except that in the step 1), when the M-B amorphous alloy is prepared, ZnCl is used2Middle Zn and NaBH4The ratio of the amounts of the substances of B in (1): 7, the reaction temperature is room temperature; in the step 2), adding the Zn-B amorphous alloy into the Pd sol, and keeping the mixture for 5 hours under the conditions that the temperature is 100 ℃, the hydrogen pressure is 3MPa and the stirring speed is 800 r/min; adding NaBH4The temperature of the solution after reaction is room temperature; pd and NaBH in Pd sol4The ratio of the amounts of the substances of B in (1): 25; in the step 3), the Zn-B amorphous alloy wrapped by the Pd-B is added into the Al sol and kept for 5 hours under the conditions that the temperature is 100 ℃, the hydrogen pressure is 3MPa and the stirring speed is 800 r/min.
M-B@Pd-B@Al2O3Example 7 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 7 catalyst Zn-B @ Pd-B @ Al2O3The preparation method of (1) is substantially the same as the operation procedure of example 1 of the preparation method of the catalyst except that in the step 1), when the M-B amorphous alloy is prepared, ZnCl is used2Middle Zn and NaBH4The ratio of the amounts of the substances of B in (1): 20, the reaction temperature is 15 ℃; in the step 2), adding the Zn-B amorphous alloy into the Pd sol, and keeping the mixture for 2 hours under the conditions that the temperature is 80 ℃, the hydrogen pressure is 5MPa and the stirring speed is 800 r/min; adding NaBH4The temperature of the solution after reaction is 15 ℃; pd and NaBH4The ratio of the amounts of the substances of B in (1): 8; in the step 3), the Zn-B amorphous alloy wrapped by the Pd-B is added into the Al sol and kept for 2h under the conditions that the temperature is 80 ℃, the hydrogen pressure is 5MPa and the stirring speed is 800 r/min.
M-B@Pd-B@Al2O3Example 8 of the preparation method of the catalyst
This example is M-B @ Pd-B @ Al2O3Catalyst example 8 catalyst Zn-B @ Pd-B @ Al2O3The preparation method of (1) is substantially the same as the operation procedure of example 1 of the preparation method of the catalyst except that in the step 1), when the M-B amorphous alloy is prepared, ZnCl is used2Middle Zn and NaBH4The ratio of the amounts of the substances of B in (1): 15, the reaction temperature is 35 ℃; in the step 2), adding the Zn-B amorphous alloy into the Pd sol, and keeping the mixture for 4 hours under the conditions that the temperature is 150 ℃, the hydrogen pressure is 2MPa and the stirring speed is 800 r/min; adding NaBH4The temperature of the solution post-reaction is 35 ℃; pd and NaBH in Pd sol4The ratio of the amounts of the substances of B in (1): 12; in the step 3), the Zn-B amorphous alloy wrapped by the Pd-B is added into the Al sol and kept for 4 hours under the conditions that the temperature is 150 ℃, the hydrogen pressure is 2MPa and the stirring speed is 800 r/min.
M-B @ Pd-B @ Al in the invention2O3In other embodiments of the catalyst preparation method, other soluble M salts, such as ZnSO, may be used in preparing the M-B amorphous alloy4Etc.; other soluble Pd salts, such as Pd (NO), may be used in the preparation of Pt sols3)2For example, the concentrations of the respective reaction materials can be adjusted within the range defined in the present invention depending on the reaction conditions, the capacity of the reaction apparatus, and the like, and the test effects equivalent to those in the examples can be obtained.
M-B@Pd-B@Al2O3Examples of the use of the catalysts
In this example, M-B @ Pd-B @ Al was examined separately using hydrogen and formic acid as hydrogen sources2O3The catalysts of embodiments 1 to 8 have catalytic effects in the reaction of preparing gamma-valerolactone by hydrogenating levulinic acid.
When hydrogen is used as a hydrogen source, the reaction process is as follows: adding 0.5g of catalyst and 12.5g of levulinic acid into a reaction kettle, adding 250mL of distilled water, replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle until the pressure is 1.0MPa, heating to 150 ℃ at the heating rate of 1 ℃/min, and controlling the stirring speed to be 800 r/min.
When formic acid is used as a hydrogen source, the reaction process is as follows: 0.5g of catalyst, 10.4g of levulinic acid and 1.4g of formic acid are added into a reaction kettle, 250mL of distilled water is added, the temperature is raised to 150 ℃ at the temperature rise rate of 1 ℃/min, and the stirring speed is controlled to be 800 r/min.
After the reaction was completed, the product composition was analyzed by a gas chromatograph using an FID detector, and the product concentration was calculated by an area calibration method, and the conversion of levulinic acid and the selectivity of γ -valerolactone were calculated, and the results are shown in table 1.
TABLE 1 evaluation of catalytic Properties of catalysts
As can be seen from the results in Table 1, Zn-B @ Pd-B @ Al2O3Catalyst, Cu-B @ Pd-B @ Al2O3Catalyst, Fe-B @ Pd-B @ Al2O3Catalyst, Co-B @ Pd-B @ Al2O3Catalyst and Ni-B @ Pd-B @ Al2O3The catalyst takes hydrogen as a hydrogen source, the conversion rate of levulinic acid reaches 100%, and the selectivity of gamma-valerolactone reaches over 99% when the reaction time is 5 hours. This indicates that the catalyst prepared by the invention has important industrial application value. Formic acid as hydrogen source, Zn-B @ Pd-B @ Al2O3When the catalyst reacts for 24 hours, the conversion rate of the levulinic acid can still reach 100%, and the selectivity of the gamma-valerolactone reaches 99.5%, which shows that the catalyst has better stability.
Claims (9)
1. M-B@Pd-B@Al2O3The catalyst is characterized by comprising an active component inner core, an active component middle layer coated outside the active component inner core and an auxiliary agent outer layer coated outside the active component middle layer; the active component inner core is M-B amorphous alloy, and M is selected from one of Zn, Cu, Fe, Co and Ni; the active component interlayer is Pd-B amorphous alloy; the outer layer of the auxiliary agent is aluminum oxide; the mass ratio of M atoms in the M-B amorphous alloy, Pd atoms in the Pd-B amorphous alloy and Al atoms in the alumina is 1: 0.4: 0.2.
2. according to claim1 said M-B @ Pd-B @ Al2O3Catalyst, characterized in that said M-B @ Pd-B @ Al2O3The average particle size of the catalyst is 3-8 nm.
3. The M-B @ Pd-B @ Al of claim 12O3The preparation method of the catalyst is characterized by comprising the following steps:
1) mixing the M-B amorphous alloy and the Pd sol, gelatinizing under a protective atmosphere to change the Pd sol into Pd gel and coat the Pd gel on the surface of the M-B amorphous alloy, then adding borohydride to react to change the Pd gel into the Pd-B amorphous alloy, and washing an obtained precipitate after the reaction is completed to obtain the Pd-B coated M-B amorphous alloy;
2) mixing the prepared Pd-B coated M-B amorphous alloy with Al sol, gelatinizing under a protective atmosphere to enable the Al sol to be changed into Al gel and to be coated on the surface of the Pd-B coated M-B amorphous alloy, then carrying out solid-liquid separation, and washing the solid to obtain the Pd-B coated M-B amorphous alloy.
4. M-B @ Pd-B @ Al as in claim 32O3The preparation method of the catalyst is characterized in that the gelation in the step 1) and the step 2) is kept for 1-5 hours under the conditions that the temperature is 50-150 ℃ and the pressure of protective gas is 1-5 MPa.
5. M-B @ Pd-B @ Al as in claim 32O3The preparation method of the catalyst is characterized in that the preparation method of the M-B amorphous alloy comprises the following steps: adding borohydride into a soluble salt water solution of the metal M for reaction, and washing the generated precipitate to be neutral after the reaction is completed to obtain the metal M.
6. M-B @ Pd-B @ Al as in claim 52O3The preparation method of the catalyst is characterized in that the mass ratio of M atoms in the soluble salt water solution of the metal M to B atoms in borohydride is 1: 10.
7. M-B @ Pd-B @ Al as in claim 32O3The preparation method of the catalyst is characterized in that the mass ratio of Pd atoms in the Pd sol in the step 1) to B atoms in borohydride is 1: 15.
8. the M-B @ Pd-B @ Al of claim 12O3The application of the catalyst in hydrogenation reduction reaction.
9. The M-B @ Pd-B @ Al of claim 82O3The application of the catalyst in hydrogenation reduction reaction is characterized in that the hydrogenation reduction reaction is that levulinic acid is hydrogenated to generate gamma-valerolactone.
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