CN113441143A - Nickel-cobalt-aluminum ternary metal composite catalyst and preparation method and application thereof - Google Patents
Nickel-cobalt-aluminum ternary metal composite catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nickel-cobalt-aluminum ternary metal composite catalyst and a preparation method and application thereof, wherein a urea hydrolysis coprecipitation method is adopted, and then the catalyst is calcined and reduced to form a Ni-Co-Al composite ternary metal catalyst, the label of the catalyst is xNiyCoAl, wherein x represents the molar ratio of nickel element to Al element, x is 1.5-2.5, y represents the molar ratio of Co element to Al element, and y is 0.25-2. The catalyst can efficiently catalyze levulinic acid to hydrogenate and synthesize gamma-valerolactone in 1, 4-dioxane under mild reaction conditions. The catalyst has high catalytic activity at the temperature of 120-130 ℃ and 3‑4MPa H2The reaction is carried out for 2 to 3 hours under the catalytic reaction condition, and the yield of the gamma-valerolactone can reach 100 percent; other non-noble metal catalysts reported at present usually need to be at a reaction temperature of 140 ℃ and 200 ℃ to achieve similar catalytic effects.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a nickel-cobalt-aluminum ternary metal composite catalyst and a preparation method and application thereof.
Background
The biomass is a natural clean renewable carbon resource with wide source, abundant reserves and low price. Biomass can be converted into various important high value-added fuels, chemical products and materials, has great potential for replacing traditional fossil resources, and methods for exploring more effective utilization of biomass resources are receiving wide attention. Among them, converting biomass raw materials into various biomass-based platform compounds and then converting the biomass-based platform compounds to prepare high value-added chemicals is generally considered as an important biomass resource utilization mode. Levulinic acid is an important biomass-based platform molecule, can be used for preparing gamma-valerolactone through catalytic hydrogenation, and has wide application in the aspects of green solvents, organic synthesis, fuel additives and the like.
At present, a solvent system for preparing gamma-valerolactone by directly hydrogenating levulinic acid mainly comprises organic solvents such as 1, 4-dioxane. Because of the higher solubility of hydrogen in 1, 4-dioxane, 1, 4-dioxane is considered to be a relatively ideal hydrogenation solvent and enables higher yields of gamma-valerolactone to be achieved (ACS Catalysis,2016,6(8): 5462-. However, the reaction conditions of the 1, 4-dioxane system are harsh at present, and particularly when a non-noble metal catalyst is used, the reaction temperature is mostly between 140 ℃ and 200 ℃ (Fuel,2020,259: 116208.1-116208.4; Catalysis Letters,2017,147(3): 1-7; Catalysis, 2015,6(1): 6-15; Catalysis Today,2016,274: 55-59; Catalysis Today,2017,309: 189) and 194), and the efficiency of levulinic acid for preparing gamma-valerolactone under milder conditions is lower. Other non-noble metal catalysts reported at present usually need to be at a reaction temperature of 140 ℃ and 200 ℃ to achieve similar catalytic effects.
The non-noble metal has more application prospect than the noble metal due to the abundant reserves and the relatively lower cost. The development of a non-noble metal catalyst with high-efficiency catalytic activity and the realization of the high-efficiency hydrogenation reduction of levulinic acid in a 1, 4-dioxane system under mild conditions have become a great technical difficulty in the industrial production of gamma-valerolactone.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nickel-cobalt-aluminum ternary metal composite catalyst and a preparation method and application thereof. The nickel-cobalt-aluminum ternary metal composite hydrogenation catalyst provided by the invention can efficiently catalyze levulinic acid to be hydrogenated and synthesized into gamma-valerolactone in a 1, 4-dioxane system under mild conditions.
One of the technical schemes of the invention provides the nickel-cobalt-aluminum ternary metal composite catalyst prepared by the preparation method. The catalyst is marked as xNiyCoAl, wherein x represents the molar ratio of Ni element to Al element in the catalyst, x is 1.5-2.5, y represents the molar ratio of Co element to Al element in the catalyst, and y is 0.25-2.
The second technical scheme of the invention is to provide a preparation method of a nickel-cobalt-aluminum ternary metal composite catalyst, which comprises the following steps: dissolving cobalt nitrate hexahydrate, urea, nickel nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water; reacting at 100 ℃ and 140 ℃ for 3-5h, carrying out solid-liquid separation, drying solid precipitate, and grinding into powder; calcining at the temperature of 400-.
In a preferred embodiment of the invention, the catalyst is labeled xNiyCoAl, where x represents the molar ratio of the Ni element to the Al element and y represents the molar ratio of the Co element to the Al element in the catalyst.
In a preferred embodiment of the invention, the molar ratio of the nickel element to the aluminum element is 1.5-2.5: 1.
In a preferred embodiment of the invention, the molar ratio of the cobalt element to the aluminum element is 0.25-2: 1.
In the preferred embodiment of the invention, the total molar ratio of the urea to the three elements of nickel, cobalt and aluminum is 13-14: 1.
In a preferred embodiment of the invention, in the aqueous solution containing nickel nitrate, cobalt nitrate, aluminum nitrate and urea, the concentration of urea is 3-5mol/L, and the concentration of cobalt nitrate is 0.015-0.15 mol/L.
In a preferred embodiment of the invention, the calcination is carried out in an air atmosphere.
In a preferred embodiment of the invention, the shielding gas is 10% vol hydrogen + 90% vol nitrogen.
The third technical scheme of the invention is to provide an application of a nickel-cobalt-aluminum ternary metal composite catalyst in preparation of gamma-valerolactone.
The fourth technical scheme of the invention is to provide a method for preparing gamma-valerolactone by using a nickel-cobalt-aluminum ternary metal composite catalyst, which comprises the following steps: mixing levulinic acid and a solvent 1, 4-dioxane, placing the mixture into a reaction vessel, adding a nickel-cobalt-aluminum ternary metal composite catalyst, sealing the reactor, and filling hydrogen, wherein the hydrogen pressure is 1-4MPa, the reactor temperature is 100-130 ℃, and the reaction time is 1-3 h. More preferably, the hydrogen pressure is 2-4MPa, the reaction temperature is 120-130 ℃, and the reaction time is 2-3 h. Under the above conditions, the yield of gamma-valerolactone is about 90.7-100%.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
As used herein, "about" or "about" and the like refer to a range or value within plus or minus 20 percent of the stated range or value.
In the present invention, the "room temperature", i.e., the normal ambient temperature, may be 10 to 30 ℃.
Compared with the background technology, the technical scheme has the following advantages:
(1) the invention forms the Ni-Co-Al composite ternary metal catalyst by urea hydrolysis coprecipitation method and then calcining and reducing;
(2) the catalyst prepared by the invention has high-efficiency catalytic activity, and efficiently catalyzes levulinic acid to synthesize gamma-valerolactone by hydrogenation in 1, 4-dioxane under mild reaction conditions;
(3) the catalyst prepared by the invention has the H at the temperature of 120-130 ℃ and the H of 3-4MPa2The reaction is carried out for 2 to 3 hours under the catalytic reaction condition, and the yield of the gamma-valerolactone can reach 100 percent; the catalytic reaction temperature is lower than the reaction temperature of 140 ℃ and 200 ℃ of the non-noble metal catalyst in the prior art, and the similar catalytic effect can be achieved.
Detailed Description
The invention provides a preparation method of a nickel-cobalt-aluminum ternary metal composite catalyst, which specifically comprises the following steps: dissolving cobalt nitrate hexahydrate, urea, nickel nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water, wherein the concentration of the urea is 3-5mol/L, the concentration of the cobalt nitrate is 0.015-0.15mol/L, the molar ratio of nickel element to aluminum element is 1.5-2.5:1, the molar ratio of cobalt element to aluminum element is 0.25-2:1, and the total molar ratio of the urea to the three elements of nickel, cobalt and aluminum is 13-14: 1; reacting at 100 ℃ and 140 ℃ for 3-5h, carrying out solid-liquid separation, drying the solid precipitate, and grinding into powder; calcining at 400-600 ℃ for 3-5h in the air atmosphere, and reducing at 550-750 ℃ for 4-6h in the protective atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst is labeled xNiyCoAl, where x represents the molar ratio of the Ni element to the Al element, x is 1.5 to 2.5, y represents the molar ratio of the Co element to the Al element in the catalyst, and y is 0.25 to 2.
The invention provides a method for preparing gamma-valerolactone by using a nickel-cobalt-aluminum ternary metal composite catalyst, which comprises the following steps: mixing levulinic acid and a solvent 1, 4-dioxane, placing the mixture into a reaction vessel, adding a nickel-cobalt-aluminum ternary metal composite catalyst, sealing the reactor, and filling hydrogen, wherein the hydrogen pressure is 1-4MPa, the reactor temperature is 100-130 ℃, and the reaction time is 1-3 h. More preferably, the hydrogen pressure is 2-3MPa, the reaction temperature is 120-130 ℃, and the reaction time is 2-3 h.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following will describe the contents of the present invention in more detail by way of examples, but the scope of the present invention is not limited to these examples.
Example 1
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 0.364g of cobalt nitrate hexahydrate (0.00125mol) and 13.5g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst was labeled 2 Ni0.25CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni0.25CoAl is added as a catalyst, the reaction kettle is sealed, 3MPa of hydrogen is introduced, the mixture is magnetically stirred, the mixture is heated to 100 ℃ and kept for 2 hours, the reaction is finished, the mixture is cooled to room temperature and sampled for detection, and the detection result is shown as the serial number 1 in the table 1.
Example 2
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 0.7275g of cobalt nitrate hexahydrate (0.0025mol) and 14.4g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst was labeled 2 Ni0.5CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni0.5CoAl is added as a catalyst, the reaction kettle is sealed, 3MPa of hydrogen is introduced, the mixture is magnetically stirred, the mixture is heated to 100 ℃ and kept for 2 hours, the reaction is finished, the mixture is cooled to room temperature and sampled for detection, and the detection result is shown as the serial number 2 in the table 1.
Example 3
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 1.455g of cobalt nitrate hexahydrate (0.005mol) and 16.2g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst is labeled 2Ni1 CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni1CoAl is added as a catalyst, the reaction kettle is sealed, 3MPa of hydrogen is introduced, the mixture is magnetically stirred, the mixture is heated to 100 ℃ and kept for 2 hours, the reaction is finished, the mixture is cooled to room temperature, and sampling detection is carried out, wherein the detection result is shown as a serial number 3 in Table 1.
Example 4
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 2.91g of cobalt nitrate hexahydrate (0.01mol) and 19.8g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst is labeled 2Ni2 CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni2CoAl is added as a catalyst, the reaction kettle is sealed, 3MPa of hydrogen is introduced, the mixture is magnetically stirred, the mixture is heated to 100 ℃ and kept for 2 hours, the reaction is finished, the mixture is cooled to room temperature and is sampled for detection, and the detection result is listed as the serial number 4 in the table 1.
Examples 5 to 8
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 0.7275g of cobalt nitrate hexahydrate (0.0025mol) and 14.4g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst was labeled 2 Ni0.5CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane were added into a 25mL autoclave, 0.075g of 2Ni0.5CoAl was added as a catalyst, the reaction vessel was sealed, 3MPa of hydrogen was introduced, the mixture was magnetically stirred, heated to 100 ℃, 110 ℃, 120 ℃ and 130 ℃ for 2 hours, the reaction was completed, cooled to room temperature, sampled and examined, and the examination results are listed as serial numbers 5 to 8 in Table 1.
Examples 9 to 12
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 0.7275g of cobalt nitrate hexahydrate (0.0025mol) and 14.4g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst was labeled 2 Ni0.5CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni0.5CoAl is added as a catalyst, the reaction kettle is sealed, 1MPa, 2MPa, 3MPa and 4MPa of hydrogen are introduced, the mixture is magnetically stirred, the mixture is heated to 120 ℃ and kept for 2 hours, the reaction is finished, the mixture is cooled to room temperature, sampling detection is carried out, and the detection results are listed as serial numbers 9-12 in Table 1.
Examples 13 to 15
Preparing a nickel-cobalt-aluminum ternary metal composite catalyst:
2.907g (0.01mol) of nickel nitrate hexahydrate and 1.88g (0.005mol) of aluminum nitrate nonahydrate, 0.7275g of cobalt nitrate hexahydrate (0.0025mol) and 14.4g of urea were dissolved in 70mL of deionized water; reacting the solution at 120 ℃ for 4 hours, and separating to obtain solid precipitate; grinding the dried solid into powder, calcining the powder for 4 hours at 500 ℃ in the air atmosphere, and calcining and reducing the calcined solid for 5 hours at 650 ℃ in the atmosphere of 10% vol% hydrogen and 90% vol% nitrogen to obtain the nickel-cobalt-aluminum ternary metal composite catalyst. The catalyst was labeled 2 Ni0.5CoAl.
The nickel-cobalt-aluminum ternary metal composite catalyst prepared by the method is used for preparing the following gamma-valerolactone:
0.125g of levulinic acid and 5mL of 1, 4-dioxane are added into a 25mL autoclave, 0.075g of 2Ni0.5CoAl is added as a catalyst, the reaction kettle is sealed, 3MPa of hydrogen is introduced, the mixture is magnetically stirred, the mixture is heated to 120 ℃ and kept for 1 hour, 2 hours and 3 hours, the reaction is finished, the mixture is cooled to room temperature and sampled for detection, and the detection result is listed as serial numbers 13-15 in Table 1.
TABLE 1 test results in examples
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. The catalyst is marked as xNiyCoAl, wherein x represents the molar ratio of Ni element to Al element, x is 1.5-2.5, y represents the molar ratio of Co element to Al element, and y is 0.25-2.
2. The nickel-cobalt-aluminum ternary metal composite catalyst of claim 1 is applied to preparation of gamma-valerolactone.
3. A preparation method of a nickel-cobalt-aluminum ternary metal composite catalyst is characterized by comprising the following steps: dissolving cobalt nitrate hexahydrate, urea, nickel nitrate hexahydrate and aluminum nitrate nonahydrate in deionized water; reacting at 100 ℃ and 140 ℃ for 3-5h, carrying out solid-liquid separation, drying the solid precipitate, and grinding into powder; calcining at the temperature of 400-.
4. The method for preparing a nickel-cobalt-aluminum ternary metal composite catalyst according to claim 3, wherein the molar ratio of the nickel element to the aluminum element is 1.5-2.5: 1.
5. The method of claim 3, wherein the molar ratio of cobalt to aluminum is 0.25-2: 1.
6. The method of claim 3, wherein the molar ratio of urea to the total of the nickel, cobalt, and aluminum is 12.5-14.5: 1.
7. The method for preparing a nickel-cobalt-aluminum ternary metal composite catalyst according to claim 3, wherein the concentration of urea in the aqueous solution containing nickel nitrate, cobalt nitrate, aluminum nitrate and urea is 3 to 5mol/L, and the concentration of cobalt nitrate is 0.015 to 0.15 mol/L.
8. The method of claim 3, wherein the calcination is performed in an air atmosphere.
9. The method of claim 3, wherein the shielding gas is 10 vol% hydrogen +90 vol% nitrogen.
10. The method for preparing gamma-valerolactone by using the nickel-cobalt-aluminum ternary metal composite catalyst of claim 1, which is characterized by comprising the following steps: mixing levulinic acid and a solvent 1, 4-dioxane, placing the mixture into a reaction vessel, adding a nickel-cobalt-aluminum ternary metal composite catalyst, sealing the reactor, and filling hydrogen, wherein the hydrogen pressure is 1-4MPa, the reactor temperature is 100-130 ℃, and the reaction time is 1-3 h.
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| CN113441143B (en) | 2022-12-09 |
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