CN117019145A - Catalyst for preparing 1, 4-pentanediol through levulinate hydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing 1, 4-pentanediol through levulinate hydrogenation and preparation method and application thereof Download PDF

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CN117019145A
CN117019145A CN202311010583.1A CN202311010583A CN117019145A CN 117019145 A CN117019145 A CN 117019145A CN 202311010583 A CN202311010583 A CN 202311010583A CN 117019145 A CN117019145 A CN 117019145A
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catalyst
metal
levulinate
pentanediol
metal oxide
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高晓庆
朱善辉
郑洪岩
牛宇岚
王峰
薛彦峰
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Taiyuan Institute of Technology
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Abstract

The invention provides a catalyst for preparing 1, 4-pentanediol through levulinate hydrogenation, a preparation method and application thereof, and belongs to the technical field of catalytic hydrogenation. The invention provides a catalyst comprising Al 2 O 3 Nanoplatelets and supports on the Al 2 O 3 Metal nanoparticles on nanoplatelets. Al (Al) 2 O 3 The nano sheet is a two-dimensional material, and the surface of the sheet layer has high chemical bond unsaturation degree, so the nano sheet contains five-coordination Al with a plurality of oxygen defects and coordination unsaturation 3+ A site. And oxygen defect and pentadentate Al 3+ The sites are favorable for riveting the metal nano particles, and the dispersity of the metal nano particles is improved, so that the contact area with the reaction raw materials is increased, and the catalytic activity is improved; in addition, metal and Al 2 O 3 The nanosheets have strong metal-carrier interactions to form metal-Al 2 O 3 The interface, and thus the catalyst, has excellent stability.

Description

Catalyst for preparing 1, 4-pentanediol through levulinate hydrogenation and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a catalyst for preparing 1, 4-pentanediol by hydrogenating levulinate, a preparation method and application thereof.
Background
1, 4-pentanediol is an important organic and fine chemical raw material, and is widely applied to the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like, and the most important application is the synthesis of monomers of degradable polyester and resin materials. The preparation of the high added value 1, 4-pentanediol by catalytic hydrogenation of levulinate has important academic significance and great economic value.
At present, the catalyst for preparing 1, 4-pentanediol by directly hydrogenating levulinate is mainly a supported Cu-based catalyst. For example, jing et al (Chemistry Select,2020,5 (11), 924-930) employ Cu/ZrOCO 3 Catalyst for preparing 1, 4-pentanediol by catalyzing methyl levulinate hydrogenation, and 1, 4-pentanediol is prepared by catalyzing methyl levulinate to realize complete conversionThe yield is only 23.1 percent; tian et al (Catalysis Communications 2016,76,50-53) use Cu/ZrO 2 The catalyst is used for catalyzing methyl levulinate, and the yield of 1, 4-pentanediol is only 39%; fu et al (ChemSuschem, 2019,12 (16), 3837-3848) catalyzed the hydrogenation of ethyl levulinate with Cu-Fe/SBA-15, ethyl levulinate conversion of 99.3% and 1, 4-pentanediol yield of 64.4%. Despite the significant progress made in these previous works, these catalysts still suffer from the following drawbacks: (1) The yield of the target product 1, 4-pentanediol is low, generally lower than 70%. (2) The catalyst is easy to deactivate, cu nano particles are easy to aggregate, and the catalyst can run off in the reaction process, has poor stability and can not run for a long period.
Disclosure of Invention
The invention aims to provide a catalyst for preparing 1, 4-pentanediol by hydrogenating levulinate, a preparation method and application thereof, and the catalyst has excellent catalytic activity and stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst comprising Al 2 O 3 Nanoplatelets and supports on the Al 2 O 3 Metal nanoparticles on nanoplatelets.
Preferably, the metal nanoparticles comprise one or more of Ru, pt, pd, ni and Cu;
the particle size of the metal nano particles is 1-10 nm.
Preferably, the loading of the metal nano particles is 0.5 to 20wt%.
Preferably, the catalyst further comprises a catalyst supported on the Al 2 O 3 Metal oxide adjuvants on nanoplatelets.
Preferably, the metal oxide promoter comprises WO 3 、MoO 3 、CeO 2 、Ga 2 O 3 And Re (Re) 2 O 3 One or more of the following.
Preferably, the loading of the metal oxide auxiliary agent is 0.5-3 wt%.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
al is added with 2 O 3 The nanosheets are immersed in a precursor solution of the metal nanoparticles or a solution of a precursor containing the metal nanoparticles and a precursor of the metal oxide auxiliary agent, and then dried, baked and reduced in sequence to obtain the catalyst.
Preferably, the precursor of the metal nanoparticle comprises one or more of nitrate, hydrochloride and acid corresponding to the metal element;
the metal oxide auxiliary precursor comprises nitrate and/or ammonium salt corresponding to metal in the metal oxide auxiliary.
Preferably, the roasting temperature is 400-800 ℃ and the time is 1-4 hours;
the reduction is at H 2 The reduction is carried out in Ar mixed gas, the temperature of the reduction is 150-400 ℃, and the time is 1-3 h.
The invention also provides an application of the catalyst prepared by the scheme or the preparation method of the scheme in preparing 1, 4-pentanediol by hydrogenating levulinate.
The invention provides a catalyst comprising Al 2 O 3 Nanoplatelets and supports on the Al 2 O 3 Metal nanoparticles on nanoplatelets. Al (Al) 2 O 3 The nano sheet is a two-dimensional material, and the surface of the sheet layer has high chemical bond unsaturation degree, so the nano sheet contains five-coordination Al with a plurality of oxygen defects and coordination unsaturation 3+ A site. And oxygen defect and pentadentate Al 3+ The sites are favorable for riveting the metal nano particles, and the dispersity of the metal nano particles is improved, so that the contact area with the reaction raw materials is increased, and the catalytic activity is improved; in addition, metal and Al 2 O 3 The nanosheets have strong metal-carrier interactions to form metal-Al 2 O 3 The interface, and thus the catalyst, has excellent stability. The results of the examples show that when the catalyst of the invention catalyzes levulinate to prepare 1, 4-pentanediol by hydrogenation, the conversion rate of levulinate is 100%, and the yield of 1, 4-pentanediol is 85.4-95.2%; and the ethyl levulinate conversion was made 100%,1,after the catalyst with the yield of 91.7% of 4-pentanediol is recycled for 5 times, the conversion rate of levulinate is 100%, and the selectivity of 1, 4-pentanediol is 90.3%.
Drawings
FIG. 1 is Al in example 1 2 O 3 TEM image of the nanoplatelets;
FIG. 2 shows Ru-WO in example 1 3 /Al 2 O 3 TEM image of the catalyst.
Detailed Description
The invention provides a catalyst comprising Al 2 O 3 Nanoplatelets and supports on the Al 2 O 3 Metal nanoparticles on nanoplatelets.
In the present invention, the loading amount of the metal nanoparticles is preferably 0.5 to 20wt%, more preferably 1 to 10wt%, and still more preferably 1 to 5wt%. In the present invention, the loading refers to the mass fraction of the metal nanoparticles to the catalyst. In the present invention, the metal nanoparticles preferably include one or more of Ru, pt, pd, ni and Cu; the particle diameter of the metal nanoparticle is preferably 1 to 10nm, more preferably 1 to 5nm.
In the present invention, the catalyst preferably further comprises a catalyst supported on the Al 2 O 3 A metal oxide additive on the nanoplatelets; the loading of the metal oxide auxiliary is preferably 0.5 to 3wt%, more preferably 1 to 2.5wt%, and still more preferably 1.5 to 2wt%. In the present invention, the loading refers to the mass fraction of the metal oxide promoter in the catalyst. The catalyst also preferably comprises a catalyst supported on the Al 2 O 3 A metal oxide additive on the nanoplatelets; the metal oxide promoter preferably comprises WO 3 、MoO 3 、CeO 2 、Ga 2 O 3 And Re (Re) 2 O 3 One or more of the following. The metal oxide promoter can improve the acidity of the catalyst and improve the stability of the catalyst in high temperature aqueous solutions.
In the present invention, the Al 2 O 3 The specific surface area of the nano-sheet is preferably 160-260 m 2 Preferably 180 to 240m 2 Preferably 200 to 220m 2 And/g. The Al is 2 O 3 The thickness of the nanosheets is preferably 5-15 nm.
The Al is 2 O 3 The preparation method of the nano-sheet preferably comprises the following steps:
mixing aluminum salt, urea and water for hydrothermal reaction and roasting to obtain the Al 2 O 3 A nano-sheet.
In the present invention, the aluminum salt includes one or more of aluminum chloride, aluminum sulfate, and aluminum nitrate. The mass ratio of the aluminum salt to the urea is preferably 1:1 to 3, more preferably 1:2 to 2.5. The mass ratio of the aluminum salt to the water is preferably 1:10-20, more preferably 1:15-18.
In the invention, the temperature of the hydrothermal reaction is preferably 60 to 150 ℃, more preferably 80 to 120 ℃; the time is preferably 36 to 72 hours, more preferably 48 to 56 hours. Al in the aluminium salt during the hydrothermal reaction 3+ And hydroxide ions released from the aqueous urea solution produce aluminum hydroxide.
The present invention preferably sequentially cools the resulting hydrothermal reaction product to room temperature, filters and dries it before the calcination. The present invention is not particularly limited to the filtration and drying, and may be carried out by using a scheme well known to those skilled in the art.
In the present invention, the temperature of the calcination is preferably 400 to 800 ℃, more preferably 450 to 750 ℃, still more preferably 500 to 600 ℃; the time is preferably 1 to 4 hours, more preferably 2 to 3 hours.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
al is added with 2 O 3 The nanosheets are immersed in a precursor solution of the metal nanoparticles or a solution of a precursor containing the metal nanoparticles and a precursor of the metal oxide auxiliary agent, and then dried, baked and reduced in sequence to obtain the catalyst.
In the invention, the precursor of the metal nanoparticle comprises one or more of nitrate, hydrochloride and acid corresponding to the metal element; when the metal is nickel, the nitrate corresponding to the metal nickel is nickel nitrate; when the metal is copper, the nitrate corresponding to the metal copper is copper nitrate; when the metal is palladium, the hydrochloride corresponding to the metal palladium is palladium chloride; when the metal is ruthenium, the hydrochloride corresponding to the metal ruthenium is ruthenium chloride; when the metal is platinum, the acid corresponding to the metal platinum element is chloroplatinic acid; the concentration of the metal precursor solution is preferably 0.01 to 0.2mol/L, more preferably 0.1 to 0.15mol/L.
In the present invention, the metal oxide promoter precursor preferably includes a nitrate and/or ammonium salt corresponding to the metal in the metal oxide promoter; when the metal oxide auxiliary agent is cerium dioxide, the nitrate is cerium nitrate; when the metal oxide auxiliary agent is gallium trioxide, the nitrate is gallium nitrate; when the metal oxide auxiliary agent is tungsten trioxide, the ammonium salt is ammonium metatungstate; when the metal oxide auxiliary agent is molybdenum trioxide, the ammonium salt is ammonium molybdate; when the metal oxide promoter is rhenium trioxide, the ammonium salt is ammonium perrhenate. The concentration of the metal nanoparticle precursor in the solution containing the metal nanoparticle precursor and the metal oxide auxiliary precursor is preferably 0.01-0.2 mol/L, more preferably 0.1-0.15 mol/L; the concentration of the metal oxide auxiliary precursor is preferably 0.005 to 0.1mol/L, more preferably 0.06 to 0.08mol/L.
In the present invention, the impregnation mode is preferably a standing mode, and the time of the standing is preferably 5 to 30 hours, more preferably 10 to 25 hours, and even more preferably 15 to 20 hours.
In the present invention, the temperature of the drying is preferably 80℃and the time is preferably 10 hours.
In the present invention, the temperature of the calcination is preferably 400 to 800 ℃, more preferably 450 to 750 ℃, still more preferably 500 to 600 ℃; the time is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the roasting process, the metal precursor and the metal oxide additive precursor both generate corresponding metal oxides.
In the present invention, the reduction is preferably at H 2 In an Ar mixture, H in the mixture 2 Preferably 10% by volume; the temperature of the reduction is excellentThe temperature is selected to be 150-400 ℃, more preferably 200-350 ℃, and still more preferably 250-300 ℃; the time is preferably 1 to 3 hours, more preferably 1.5 to 2 hours.
The invention also provides an application of the catalyst prepared by the scheme or the preparation method of the scheme in preparing 1, 4-pentanediol by hydrogenating levulinate.
The hydrogenation of levulinate to prepare 1, 4-pentanediol preferably comprises the steps of:
mixing levulinate, a polar solvent and a catalyst, and then introducing hydrogen to carry out hydrogenation reaction to obtain 1, 4-pentanediol;
the catalyst is the catalyst described in the scheme or the catalyst prepared by the preparation method described in the scheme.
In the present invention, the levulinate preferably includes one or more of methyl levulinate, ethyl levulinate, propyl levulinate, and butyl levulinate.
In the present invention, the mass of the catalyst is preferably 3 to 15% of the mass of levulinate, more preferably 5 to 10%. The polar solvent preferably comprises water. The mass of the polar solvent is preferably 10 to 30 times of the mass of levulinate. The catalyst of the invention has high activity, thus reducing the dosage of the catalyst.
In the present invention, the hydrogenation temperature is preferably 200 to 300 ℃, more preferably 230 to 270 ℃; the pressure of the hydrogen is preferably 4-8 MPa, more preferably 5-6 MPa; the time is preferably 6 to 24 hours, more preferably 10 to 16 hours.
After the hydrogenation reaction, the obtained hydrogenation reaction product is cooled to room temperature and then is subjected to centrifugal separation, so that the 1, 4-pentanediol is obtained.
The catalyst for preparing 1, 4-pentanediol by hydrogenating levulinate, the preparation method and application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
Example 1
6.44g of aluminum nitrate and 9.28g of urea were added to 80mL of deionized water and vigorously stirred at room temperature for 25minHydrothermal holding at 100deg.C for 48 hr, cooling to room temperature, filtering, and drying in oven at 80deg.C. Roasting in a muffle furnace at 600 ℃ for 2h to obtain Al 2 O 3 A nano-sheet.
Will 2gAl 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-WO 3 /Al 2 O 3 Catalyst, ru loading of 1.5wt%, WO 3 Is 2.5wt%.
For Al prepared in example 1 2 O 3 The results of TEM analysis of the nanoplatelets are shown in FIG. 1. As can be seen from FIG. 1, al 2 O 3 The appearance of the nano sheet is presented, and the thickness is 5-10 nm. Testing of Al by BET method 2 O 3 The specific surface area of the nano-sheet is 230m 2 /g。
For Ru-WO prepared in example 1 3 /Al 2 O 3 The catalyst was subjected to TEM analysis and the results are shown in fig. 2. As can be seen from FIG. 2, all Ru nanoparticles were uniformly distributed in Al 2 O 3 The particle diameter of Ru nano particles on the surface of the nano sheet is 2-4 nm.
Application example 1
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02-gRu-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then the temperature is raised to 240 ℃, the temperature is kept for 10 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 91.7%. After the catalyst is recycled for 5 times, the conversion rate of ethyl levulinate is 100%, and the selectivity of 1, 4-pentanediol is 90.3%, which proves that the catalyst has high stability.
Comparative example 1
2g of Al purchased from national pharmaceutical group chemical reagent Co., ltd 2 O 3 (three-dimensional material without specific morphology) was added to 3mL containingRuCl 3 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-WO 3 /Al 2 O 3 The catalyst has Ru load of 1.5wt%, ru nanometer particle size of 3-6 nm and WO 3 Is 2.5wt%.
Comparative application example 1
The catalyst of comparative example 1 was subjected to performance test according to the reaction conditions of application example 1.
The Ru-WO 3 /Al 2 O 3 The evaluation results of the catalyst show that: ethyl levulinate conversion was 94.2% and 1, 4-pentanediol yield was 35.7%;
after 2 times of recycling, the conversion rate of ethyl levulinate is reduced to 95.6%, and the yield of 1, 4-pentanediol is reduced to 28.6%, which shows that the commercial Al 2 O 3 Supported Ru-WO 3 The catalyst had started to deactivate after 2 cycles.
Example 2
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets to 3mL containing RuCl 3 In the solution (0.1 mol/L), the mixture was allowed to stand for 12 hours, dried at 80℃for 10 hours, and then baked in a muffle furnace at 500℃for 3 hours. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru/Al 2 O 3 The catalyst has Ru load of 1.5wt% and Ru nanometer particle size of 2-5 nm.
Application example 2
The only differences from application example 1 are: ru/Al of example 2 was used 2 O 3 A catalyst.
The Ru/Al 2 O 3 The evaluation results of the catalyst show that: the ethyl levulinate conversion was 96.7% and the 1, 4-pentanediol yield was 42.8%.
Example 3
2g of the Al synthesized in example 1 2 O 3 Adding the nano-sheet into 3mL containing PdCl 2 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L)Standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Pd-WO 3 /Al 2 O 3 The catalyst has Pd load of 1.5wt%, pd nanometer particle size of 1-5 nm and WO 3 Is 2.5wt%.
Application example 3
Into a high-pressure reaction kettle, 2mmol of methyl levulinate, 5mL of water and 0.02g Pd-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then the temperature is raised to 240 ℃, the temperature is kept for 15 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The conversion of methyl levulinate was 100% and the yield of 1, 4-pentanediol was 92.2%.
Example 4
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets to 3mL containing H 2 PtCl 4 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 200 ℃ in Ar mixed gas to obtain Pt-WO 3 /Al 2 O 3 The catalyst has Pt loading of 1.5wt%, pt nanometer particle size of 2-6 nm and WO 3 Is 2.5wt%.
Application example 4
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02-gPt-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then the temperature is raised to 240 ℃, the temperature is kept for 15 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 94.8%.
Example 5
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets to 3mL of a solution containing Co (NO) 3 ) 2 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80deg.C for 10h, and baking at 500deg.C in muffle furnaceAnd (5) burning for 3 hours. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 400 ℃ in Ar mixed gas to obtain Co-WO 3 /Al 2 O 3 Catalyst, co loading of 5wt%, co nanometer particle size of 3-10 nm, WO 3 Is 2.5wt%.
Application example 5
Into a autoclave, 2mmol of propyl levulinate, 5mL of water and 0.02g of Co-WO were introduced 3 /Al 2 O 3 The catalyst was flushed with 5mpa h2, then warmed to 260 ℃, held for 15h, cooled to room temperature, centrifuged to separate the liquid product, and the product analyzed on a gas chromatograph. The conversion of propyl levulinate was 100% and the yield of 1, 4-pentanediol was 89.7%.
Example 6
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets into 3mL of Ni (NO) 3 ) 2 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 400 ℃ in Ar mixed gas to obtain Ni-WO 3 /Al 2 O 3 The catalyst has Ni loading of 5wt%, ni nanometer particle size of 2-10 nm and WO 3 Is 2.5wt%.
Application example 6
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02-gNi-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature is raised to 260 ℃, the temperature is kept for 15 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 86.9%.
Example 7
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets to 3mL of Cu (NO) 3 ) 2 (0.1 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Ar gas mixtureReducing at 300 ℃ for 2h to obtain Cu-WO 3 /Al 2 O 3 Catalyst, cu loading is 5wt%, cu nano particle size is 4-10 nm, WO 3 Is 2.5wt%.
Application example 7
Into a autoclave, 2mmol of ethyl levulinate, 5mL of water and 0.02g of Cu-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature is raised to 260 ℃, the temperature is kept for 15 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 85.4%.
Example 8
2g of the Al synthesized in example 1 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.05mol/L)、PdCl 2 (0.05 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample is reduced for 2 hours in a tube furnace at 300 ℃ in 10% H2/Ar mixed gas to obtain RuPd-WO 3 /Al 2 O 3 The catalyst has RuPd total load of 2wt%, ru and Pd nanometer particle sizes of 1-4 nm and 2-5 nm, and WO 3 Is 2.5wt%.
Application example 8
Into a autoclave, 2mmol of ethyl levulinate, 5mL of water and 0.02g of RuPd-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature is raised to 240 ℃, the temperature is kept for 12 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 93.3%.
Example 9
6.44g of aluminum nitrate and 9.28g of urea were added to 90mL of deionized water, vigorously stirred at room temperature for 25min, maintained hydrothermally at 120℃for 60h in a crystallization kettle, cooled to room temperature, filtered, and dried in an oven at 80 ℃. Roasting in a muffle furnace at 500 deg.C for 3 hr to obtain a powder with a surface area of 215m 2 Per g, al with thickness of 6-12 nm 2 O 3 Nanometer scaleAnd (3) a sheet.
Will 2gAl 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.05mol/L)、H 2 PtCl 4 (0.05 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain RuPt-WO 3 /Al 2 O 3 The catalyst has RuPt load of 2wt%, ru and Pt nanometer particle sizes of 1-4 nm, 2-6 nm and WO 3 Is 2.5wt%.
Application example 9
Into a high pressure reactor were introduced 3mmol of butyl levulinate, 5mL of water and 0.04g of RuPt-WO 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The conversion of butyl levulinate was 100% and the yield of 1, 4-pentanediol was 95.2%.
Example 10
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.05mol/L)、Co(NO 3 ) 2 (0.05 mol/L) and ammonium metatungstate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain RuCo-WO 3 /Al 2 O 3 The catalyst has RuCo load of 2wt%, ru and Co nanometer particle sizes of 1-3 nm and 2-6 nm, and WO 3 Is 2.5wt%.
Application example 10
Into a autoclave, 2mmol of ethyl levulinate, 5mL of water and 0.02g of RuCo-WO were introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 92.7%.
Example 11
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.1 mol/L) and ammonium molybdate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-MoO 3 /Al 2 O 3 The catalyst has Ru loading of 1wt%, ru nanometer particle size of 1-4 nm and MoO 3 Is 1.5wt%.
Application example 11
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02-gRu-MoO are introduced 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature is raised to 250 ℃, the temperature is kept for 12 hours, the temperature is reduced to room temperature, the liquid product is centrifugally separated, and the product analysis is carried out in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 91.6%.
Example 12
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.1 mol/L) and nitric acid decorations (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-CeO 2 /Al 2 O 3 The catalyst has Ru load of 1wt%, ru nanometer particle size of 1-6 nm and CeO 2 Is 1.5wt%.
Application example 12
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02gRu-CeO were introduced 2 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 90.4%.
Example 13
2g of example 8Al synthesized in the middle 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.1 mol/L) and gallium nitrate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-Ga 2 O 3 /Al 2 O 3 Catalyst, ru loading is 1wt%, ru nano particle size is 1-4 nm, ga 2 O 3 Is 1.5wt%.
Application example 13
Into a high-pressure reaction kettle, 2mmol of ethyl levulinate, 5mL of water and 0.02-gRu-Ga are introduced 2 O 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 92.4%.
Example 14
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.1 mol/L) and ammonium perrhenate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain Ru-Re 2 O 3 /Al 2 O 3 The catalyst has Ru loading of 1wt%, ru nanometer particle size of 1-5 nm and Re 2 O 3 Is 1.5wt%.
Application example 14
Into a high-pressure reaction kettle, 2mmol of methyl levulinate, 5mL of water and 0.02gRu-Re are introduced 2 O 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The conversion of methyl levulinate was 100% and the yield of 1, 4-pentanediol was 91.9%.
Example 15
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.05mol/L)、PdCl 2 (0.05 mol/L) and ammonium perrhenate (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 300 ℃ in Ar mixed gas to obtain RuPd-Re 2 O 3 /Al 2 O 3 The catalyst has RuPd load of 2wt%, ru and Pd nanometer particle sizes of 2-5 nm, 1-4 nm and Re respectively 2 O 3 Is 1.5wt%.
Application example 15
Into a high-pressure reaction vessel, 2mmol of ethyl levulinate, 5mL of water and 0.02g of RuPd-Re were introduced 2 O 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 15 hours, cooled to room temperature, and the liquid product was centrifugally separated and analyzed in a gas chromatograph. The ethyl levulinate conversion was 100% and the 1, 4-pentanediol yield was 94.7%.
Example 16
2g of Al synthesized in example 8 2 O 3 Adding nanosheets to 3mL containing RuCl 3 (0.03mol/L)、H 2 PtCl 4 (0.03mol/L)、Ni(NO 3 ) 2 (0.03 mol/L) and nitric acid decorations (0.01 mol/L), standing for 12h, drying at 80 ℃ for 10h, and roasting in a muffle furnace at 500 ℃ for 3h. Finally, the sample was heated in a tube furnace at 10% H 2 Reducing for 2h at 350 ℃ in Ar mixed gas to obtain RuPtNi-Ce 2 O 3 /Al 2 O 3 The load of RuPtNi is 4wt%, the grain sizes of Ru, pt and Ni nano particles are respectively 1-3 nm, 1-4 nm and 2-4 nm, ce 2 O 3 Is 2.5wt%.
Application example 16
Into a autoclave, 2mmol of ethyl levulinate, 5mL of water and 0.02g of RuPtNi-Ce were introduced 2 O 3 /Al 2 O 3 Catalyst and rinse into 5MPaH 2 Then, the temperature was raised to 240℃and kept for 14 hours, the temperature was lowered to room temperature, the liquid product was centrifugally separated, and the product was analyzed by a gas chromatograph. AcetylThe ethyl propionate conversion was 100% and the 1, 4-pentanediol yield was 93.9%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A catalyst, characterized by comprising Al 2 O 3 Nanoplatelets and supports on the Al 2 O 3 Metal nanoparticles on nanoplatelets.
2. The catalyst of claim 1, wherein the metal comprises one or more of Ru, pt, pd, ni and Cu;
the particle size of the metal nano particles is 1-10 nm.
3. The catalyst according to claim 1 or 2, characterized in that the loading of the metal nanoparticles is 0.5 to 20wt%.
4. The catalyst of claim 1, further comprising a catalyst supported on the Al 2 O 3 Metal oxide adjuvants on nanoplatelets.
5. The catalyst of claim 4 wherein the metal oxide promoter comprises WO 3 、MoO 3 、CeO 2 、Ga 2 O 3 And Re (Re) 2 O 3 One or more of the following.
6. The catalyst according to claim 4 or 5, wherein the loading of the metal oxide promoter is 0.5 to 3wt%.
7. The method for preparing the catalyst according to any one of claims 1 to 6, comprising the steps of:
al is added with 2 O 3 The nanosheets are immersed in a precursor solution of the metal nanoparticles or a solution of a precursor containing the metal nanoparticles and a precursor of the metal oxide auxiliary agent, and then dried, baked and reduced in sequence to obtain the catalyst.
8. The method of claim 7, wherein the precursor of the metal nanoparticle comprises one or more of nitrate, hydrochloride, and acid corresponding to the metal element;
the metal oxide auxiliary precursor comprises nitrate and/or ammonium salt corresponding to metal in the metal oxide auxiliary.
9. The method according to claim 7, wherein the baking temperature is 400 to 800 ℃ for 1 to 4 hours;
the reduction is at H 2 The reduction is carried out in Ar mixed gas, the temperature of the reduction is 150-400 ℃, and the time is 1-3 h.
10. Use of the catalyst of any one of claims 1 to 6 or the catalyst prepared by the preparation method of any one of claims 7 to 9 in the preparation of 1, 4-pentanediol by hydrogenation of levulinate esters.
CN202311010583.1A 2023-08-11 2023-08-11 Catalyst for preparing 1, 4-pentanediol through levulinate hydrogenation and preparation method and application thereof Pending CN117019145A (en)

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