CN117126124A - Ternary metal oxide catalyst and application thereof in catalytic synthesis of gamma-valerolactone - Google Patents

Ternary metal oxide catalyst and application thereof in catalytic synthesis of gamma-valerolactone Download PDF

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CN117126124A
CN117126124A CN202310130751.4A CN202310130751A CN117126124A CN 117126124 A CN117126124 A CN 117126124A CN 202310130751 A CN202310130751 A CN 202310130751A CN 117126124 A CN117126124 A CN 117126124A
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catalyst
reaction
valerolactone
gamma
ethyl levulinate
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邱佳容
张良清
吴巧妹
陈剑锋
刘乐冕
石新国
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Fuzhou University
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a ternary metal oxide catalyst and application thereof in catalyzing and synthesizing gamma-valerolactone, comprising the following steps: adding ethyl levulinate, a catalyst and an alcohol solvent into a reaction kettle, sealing the reaction kettle, carrying out airtight reaction at 200-270 ℃ under the stirring speed of 500rpm without adding hydrogen, and cooling to room temperature to obtain gamma-valerolactone; the catalyst is dried after centrifugal separation and is directly used for the next reaction. The catalyst provided by the invention prepares gamma-valerolactone in an in-situ hydrogen production mode, has higher selectivity and yield, does not need to add hydrogen in the whole process, reduces the cost of hydrogen conveying equipment, has excellent stability, and can overcome the problem of deactivation in the recycling process of the catalyst.

Description

Ternary metal oxide catalyst and application thereof in catalytic synthesis of gamma-valerolactone
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to preparation of a ternary metal oxide catalyst and application of the ternary metal oxide catalyst in catalytic synthesis of gamma-valerolactone.
Background
Gamma-valerolactone is a bio-based platform compound with wide application prospect, and has higher boiling point and flash point and lower melting point, so that the gamma-valerolactone can be stored in a large amount. The gamma-valerolactone has wide application, can be used as a green solvent with excellent performance, can completely dissolve cellulose under specific conditions, and can better dissolve lignin for extracting lignin. Gamma-valerolactone has unique flavor and taste, is often applied to the fields of food, cosmetics, fuel additives, synthesis of various chemical intermediates and the like, can also be directly used as fuel, and is considered as one of the most potential raw materials for producing renewable fuels and chemical products.
Gamma valerolactone can be synthesized by selective hydrogenation of biomass levulinic acid (ester). Levulinic acid (esters) are considered to be desirable starting materials for the production of gamma valerolactone. The reaction systems for preparing gamma valerolactone by catalyzing levulinic acid (ester) can be classified into three types according to the difference of hydrogen sources: h 2 As an external hydrogen source system, formic acid as an in-situ hydrogen source system, and alcohols as an in-situ hydrogen source system. Currently, H is used as 2 The preparation of gamma valerolactone by hydrogenation of levulinic acid (ester) as an external hydrogen source has been extensively studied. The catalyst prepared from noble metals such as Ru, pt and Ir can catalyze levulinic acid (esters) to obtain high-yield gamma-valerolactone under mild conditions, but the noble metal catalysts have the defects of high price, easy loss in the recovery process and the like. Non-noble metal catalysts such as Cu, mo 2 C. Ni and Co can also be used to catalyze levulinic acid (ester) hydrogenation, but the preparation process often requires reduction thereof with hydrogen. In combination, it can be seen that H 2 The recovery of the conventional hydrogenation system used as an external hydrogen source for preparing gamma valerolactone is easy to lose and the hydrogenation system is easy to pass throughLow economical efficiency and the like. In a catalytic system taking formic acid as an in-situ hydrogen source, the catalyst belongs to a double-function catalyst, and can catalyze the decomposition of formic acid to produce hydrogen and the hydrogenation reduction of levulinic acid (ester). Supported bifunctional catalysts such as Ru/C, ru-P/SiO 2 、Ni/Cu-SiO 2 Ag-Ni-ZrO 2 Can effectively catalyze the decomposition of formic acid to produce hydrogen and simultaneously reduce levulinic acid (ester) to synthesize gamma-valerolactone, however, the catalysts generally need to be in the presence of excessive formic acid to obtain high-yield gamma-valerolactone. The acid resistance requirements of the catalyst in the catalytic system are very high, and only a few noble or non-noble metal-based heterogeneous or homogeneous catalysts can meet the requirements.
In order to overcome the defects of the two catalytic systems, alcohols are used as in-situ hydrogen sources and solvents, and the preparation of gamma-valerolactone by adopting a transfer hydrogenation form has great research prospect. Zr-Beta, ru (OH) x/TiO reportedly 2 And Zr-HBA, etc. can catalyze levulinic acid (ester) to synthesize gamma-valerolactone in a system with alcohols as hydrogen donors, but the stability and activity of the catalyst still need to be further improved. Thus, there is an urgent need to find non-noble metal catalysts for the selective hydrogenation of levulinic acid (esters) to gamma valerolactone that overcome the above disadvantages.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and relates to preparation of a ternary metal oxide catalyst and application of the ternary metal oxide catalyst in catalytic synthesis of gamma-valerolactone.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for synthesizing gamma valerolactone, comprising: mixing ethyl levulinate, a catalyst and an alcohol solvent, adding the ethyl levulinate, the catalyst and the alcohol solvent into a reaction kettle, sealing the reaction kettle, carrying out airtight reaction for 1-5h at 200-270 ℃ at a stirring speed of 500rpm without adding hydrogen, and cooling to room temperature to obtain gamma-valerolactone; the catalyst is washed by ethanol after centrifugal separation, and is dried for 1h at 80 ℃ in a vacuum drying oven for the next reaction.
The preparation method of the catalyst comprises the following steps: dissolving a cationic active metal precursor in 150mL of deionized water according to a certain molar ratio, adding excessive urea into the mixed solution, hydrolyzing for 4 hours at 90 ℃, continuously stirring the mixed solution in the hydrolysis process at the stirring speed of 300-400rpm, aging the obtained slurry at 90 ℃ for 2 hours after the hydrolysis is finished, cooling to room temperature, filtering the slurry, drying the obtained filter residue at 110 ℃ overnight, grinding the dried product in a mortar, sieving with a 100-mesh sieve, and calcining for 4 hours at 300-400 ℃ in a muffle furnace to obtain the catalyst. The cation active metal precursor consists of soluble salts containing Zr, mg and Cu.
In a preferred embodiment of the invention, the mass ratio of the raw material ethyl levulinate to the alcohol solvent is 1:19.
In a preferred embodiment of the invention, the mass ratio of the catalyst to the starting ethyl levulinate is from 0.2 to 0.6:1.
In a preferred embodiment of the present invention, the molar ratio of Mg to Zr in the active metal precursor is 1.15:1-2, and the calcination temperature is 300 DEG C
In a preferred embodiment of the present invention, the molar ratio of Cu, mg, zr in the active metal precursor is 1:1.15:1-3, and the calcination temperature is 400 ℃.
In a preferred embodiment of the invention, the precursors of Zr, mg, cu are Cu (NO 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O。
In a preferred embodiment of the present invention, the alcoholic solvent is isopropanol.
The beneficial effects of the invention are as follows:
1. the yield of the gamma-valerolactone is higher, and the yield of the gamma-valerolactone reaches 88 percent under the reaction conditions of 240 ℃ and 3h and 500 rpm.
2. The metal precursor used by the catalyst prepared by the invention is non-noble metal, and the preparation cost is low and the recovery is convenient.
3. The non-noble metal catalyst prepared by the invention has the advantages of simple preparation method, no need of hydrogen reduction in the preparation process, low preparation cost and capability of maintaining excellent activity in the recycling process.
Drawings
FIG. 1 is a catalyst Cu 1 Mg 1.15 Zr 2 O x An XRD pattern of (a); in XRD patterns, cu prepared in this experiment 1 Mg 1.15 Zr 2 O x In the catalyst sample there is a catalyst containing ZrO 2 Similar characteristic diffraction peaks are at 2θ=30.5°,35.5 °,51.2 °,60.7 °, respectively. Cu (Cu) 1 Mg 1.15 Zr 2 O x Strong diffraction peaks of CuO and MgO are not observed in the XRD pattern of the catalyst, which may be due to low loading of CuO and MgO, high dispersibility, or amorphous phase caused by a lower calcination temperature (400 ℃), etc.
FIGS. 2 (a), 2 (b), 2 (c), 2 (d) and 2 (e) are Cu 1 Mg 1.15 Zr 2 O x XPS spectrum of catalyst; for Cu 1 Mg 1.15 Zr 2 O x The catalyst was subjected to X-ray photoelectron spectroscopy analysis, including Cu 2p,Mg 1s,Zr 3d,O 1s and C1s (fig. 2). As can be seen, cu 1 Mg 1.15 Zr 2 O x The catalyst contains element Cu, mg, zr, O. FIG. 2 (b) is Cu 1 Mg 1.15 Zr 2 O x As shown in FIG. 2 (b), the BE values of 934.1eV and 953.7eV respectively belong to Cu in the Cu 2p high-resolution spectrogram of the catalyst 1 Mg 1.15 Zr 2 O x Cu 2p in catalyst 3/2 And Cu 2p 1/2 . Each Cu 2p emission line can be fitted with 1 Gaussian line, indicating the possible presence of Cu 2+ . As can be seen from FIGS. 2 (c) and 2 (d), cu 1 Mg 1.15 Zr 2 O x Possible presence of Mg in the catalyst of Mg, zr 2+ 、Zr 4+ 。
FIG. 3 is a catalyst H 2 -a TPR profile; from FIG. 3H 2 TPR pattern reveals Cu 1 Mg 1.15 Zr 2 O x The catalyst being present as H 2 Adsorption peaks, possibly due to Cu 2+ Also described is Cu 1 Mg 1.15 Zr 2 O x Catalyst Cu 2+ Is the existence form of Cu element and is consistent with XPS result. Cu (Cu) 1 Mg 1.15 Zr 2 O x Maximum H of catalyst 2 Adsorption peak (226.5 ℃) to Cu 1 Zr 3 O x Maximum H of catalyst 2 Adsorption peak (149.2 ℃) and Cu 1 Mg 1.15 Maximum H of catalyst 2 High adsorption peak (158.9 ℃ C.) indicates Cu 1 Mg 1.15 Zr 2 O x The interaction force between three metals of the catalyst is stronger, cu 2+ Is not easily reduced, which may be Cu 1 Mg 1.15 Zr 2 O x The possible reason for the higher activity of the catalyst than the bimetallic catalyst.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
The preparation method of the catalyst in the following examples comprises:
cu (NO) 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O is dissolved in 150mL of deionized water according to a certain molar ratio, excessive urea is added into the mixed solution, and is hydrolyzed for 4 hours at 90 ℃, the mixed solution is continuously stirred in the hydrolysis process, the stirring speed is 300-400rpm, the obtained slurry is aged for 2 hours at 90 ℃ after the hydrolysis is finished, the slurry is cooled to room temperature, the obtained filter residue is filtered, dried overnight at 110 ℃, the dried product is ground in a mortar, and the dried product is calcined for 4 hours at 300-400 ℃ in a muffle furnace after being sieved by a 100-mesh sieve, so that the catalyst is prepared.
The catalyst is prepared by adopting a urea hydrolysis uniform precipitation method, and the urea is hydrolyzed at 90 ℃ by utilizing the characteristic of heated hydrolysis of the urea, and the hydrolysis reaction is CO (NH) 2 ) 2 +3H 2 O→2NH 4 + +2OH - +CO 2 . The precipitate is slowly generated in the solution through chemical reaction, and the formed catalyst particles are uniform and have good dispersibility by slow stirring. With ZrO 2 Has good thermal stability for the carrier, and Zr can inhibit CuO x The catalyst is not easy to deactivate due to the crystal growth. Whereas proper MgO can significantly improve the dispersibility of Cu. According to the invention, the optimal metal molar ratio is optimized by adjusting the molar ratio of each metal component, so that the prepared catalyst has high activity and high stability. The gas generated in the reaction process is detected by GC-TCD, and obvious H is detected 2 Peak, indicating that dehydrogenation of isopropanol over highly dispersed metallic Cu component produces H 2 . H generated in situ 2 So that the ethyl levulinate is hydrogenated and dehydrated into gamma-valerolactone.
Examples 1 to 5
And (3) preparing a catalyst: 1mol of Cu (NO) 3 ) 2 ·3H 2 O、1.15mol Mg(NO 3 ) 2 ·6H 2 O、2mol Zr(NO 3 ) 4 ·5H 2 O is dissolved in 150mL of deionized water, then excessive (42.5 g) urea is added into the mixed solution and hydrolyzed for 4 hours at 90 ℃, the mixed solution is continuously stirred during the hydrolysis process, the stirring speed is 300rpm, the obtained slurry is aged for 2 hours at 90 ℃ after the hydrolysis is finished, the slurry is cooled to room temperature, the obtained filter residue is dried overnight at 110 ℃, then the dried product is ground in a mortar, and the dried product is calcined for 4 hours at 400 ℃ in a muffle furnace after passing through a 100-mesh sieve, so that the catalyst is recorded as Cu 1 Mg 1.15 Zr 2 O x 。
1g of ethyl levulinate and 19g of isopropanol are added into a 100mL high-pressure reaction kettle, 0.5g of catalyst is added, the mol ratio of Cu, mg and Zr in the active metal precursor is 1:1.15:2, and after the catalyst precursor is calcined in air at 400 ℃, cu is recorded 1 Mg 1.15 Zr 2 O x The reaction vessel was closed by discharging nitrogen after replacing the air in the vessel with nitrogen, stirring at 500rpm, heating to 240℃and maintaining at 1, 2, 3, 4, 5 hours, cooling naturally to room temperature after completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis with GC-MS and GC, respectively, the results of the detection being shown in examples 1 to 5 of Table 1.
As is evident from the reactions of examples 1 to 5, the yield of gamma-valerolactone was 88% and the yield of gamma-valerolactone was higher at 3 hours. Continuing the reaction time thereafter, the yield of gamma valerolactone was reduced.
Examples 6 to 9
1g of ethyl levulinate and 19g of isopropanol are added into a 100mL high-pressure reaction kettle, 0.5g of the catalyst prepared in examples 1-5 is added, nitrogen is discharged after air in the kettle is replaced by nitrogen, the reaction kettle is sealed and stirred at 500rpm, the temperature is respectively heated to 200, 220, 260 and 270 ℃ and kept for 1h, the reaction kettle is naturally cooled to room temperature after the reaction is finished, the reaction liquid is centrifugally separated by a centrifugal machine, supernatant is taken, the supernatant is qualitatively analyzed by GC-MS, standard solutions of ethyl levulinate, isopropanol, gamma-valerolactone and the like are prepared, quantitative detection is carried out by GC, and the detection results are listed in examples 6-9 in table 1.
From the reactions of examples 6 to 9, it was found that the reaction temperature was increased from 200℃to 220℃and the yield of gamma-valerolactone was increased; the high reaction temperature (260 ℃ or higher) lowers the yield of gamma-valerolactone.
Example 10
And (3) preparing a catalyst: the molar ratio of Cu, mg and Zr in the active metal precursor is adjusted to be 1:1.15:1, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Mg 1.15 Zr 1 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 1.15 Zr 1 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 10 of Table 1.
Example 11
And (3) preparing a catalyst: the molar ratio of Cu, mg and Zr in the active metal precursor is adjusted to be 1:1.15:1.15, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Mg 1.15 Zr 1.15 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 1.15 Zr 1.15 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 11 of Table 1.
Example 12
And (3) preparing a catalyst: the molar ratio of Cu, mg and Zr in the active metal precursor is adjusted to be 1:1.15:1.5, and the rest operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Mg 1.15 Zr 1.5 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 1.15 Zr 1.5 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 12 of Table 1.
Example 13
And (3) preparing a catalyst: the catalyst Cu is prepared by adjusting the molar ratio of Cu, mg and Zr in the active metal precursor to be 1:1.15:3 and the rest of the operations are the same as in examples 1-5 1 Mg 1.15 Zr 3 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 1.15 Zr 3 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, subjecting the supernatant to qualitative and quantitative analysis with GC-MS and GC, respectively, and the results of the detection are shown in Table 1Example 13.
Example 14
To a 100mL autoclave, 1g of ethyl levulinate and 19g of isopropyl alcohol were added, 0.5g of CuO catalyst was added, the air in the autoclave was replaced with nitrogen, the nitrogen was discharged, the autoclave was closed, stirred at 500rpm, heated to 240℃and maintained for 3 hours, after the reaction was completed, naturally cooled to room temperature, the reaction mixture was centrifuged by a centrifuge, the supernatant was collected, and the supernatant was subjected to qualitative analysis and quantitative analysis by GC-MS and GC, respectively, and the results of the detection were shown in example 14 of Table 1.
Example 15
1g of ethyl levulinate and 19g of isopropanol are added into a 100mL high-pressure reaction kettle, 0.5g of MgO catalyst is added, the air in the kettle is replaced by nitrogen, the nitrogen is discharged, the reaction kettle is closed, the reaction kettle is stirred at a speed of 500rpm, the temperature is heated to 240 ℃ and kept for 3 hours, the reaction liquid is naturally cooled to room temperature after the reaction is finished, the reaction liquid is centrifugally separated by a centrifugal machine, the supernatant is taken, qualitative analysis and quantitative analysis are respectively carried out on the supernatant by using GC-MS and GC, and the detection results are listed in example 15 in Table 1.
Example 16
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of ZrO was added 2 The catalyst was replaced with nitrogen, the air in the reactor was purged with nitrogen, the reactor was closed, stirred at 500rpm, heated to 240℃and maintained for 3 hours, cooled naturally to room temperature after the completion of the reaction, the reaction mixture was centrifuged with a centrifuge, the supernatant was collected, and the supernatant was subjected to qualitative and quantitative analysis using GC-MS and GC, respectively, and the results of the detection were shown in example 16 of Table 1.
Example 17
And (3) preparing a catalyst: adjusting the active metal precursor to Mg (NO) 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O, wherein the molar ratio of Mg to Zr is 1.15:1, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Mg 1.15 Zr 1 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Mg was added 1.15 Zr 1 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 17 of Table 1.
Example 18
And (3) preparing a catalyst: adjusting the active metal precursor to Mg (NO) 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O, wherein the molar ratio of Mg to Zr is 1:1.15, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Mg 1 Zr 1.15 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Mg was added 1 Zr 1.15 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 18 of Table 1.
Example 19
And (3) preparing a catalyst: adjusting the active metal precursor to Mg (NO) 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O, wherein the molar ratio of Mg to Zr is 1:2, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Mg 1 Zr 2 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Mg was added 1 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, subjecting the supernatant to qualitative and quantitative analysis with GC-MS and GC, respectively, and the results of the detection are shown in Table 1 in examples19。
Example 20
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Zr(NO 3 ) 4 ·5H 2 O, wherein the molar ratio of Cu to Zr is 1:1, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Zr 1 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Zr 1 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 20 of Table 1.
Example 21
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Zr(NO 3 ) 4 ·5H 2 O, wherein the molar ratio of Cu to Zr is 1:2, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Zr 2 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 21 of Table 1.
Example 22
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Zr(NO 3 ) 4 ·5H 2 O, the molar ratio of Cu to Zr is 1:3, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Zr 3 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Zr 3 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 22 of Table 1.
Example 23
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O, wherein the molar ratio of Cu to Mg is 1:2, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Mg 2 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 23 of Table 1.
Example 24
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O, and the molar ratio of Cu to Mg is 1:3, and the rest of the operations are the same as in examples 1-5, so as to prepare the catalyst Cu 1 Mg 3 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 3 O x Replacing air in the reactor with nitrogen, discharging nitrogen, sealing the reactor, stirring at 500rpm, heating to 240 deg.C, holding for 3 hr, naturally cooling to room temperature, and centrifugingThe reaction solution was centrifuged, and the supernatant was collected and subjected to qualitative and quantitative analysis using GC-MS and GC, respectively, and the detection results are shown in example 24 of Table 1.
Example 25
And (3) preparing a catalyst: adjusting the active metal precursor to Cu (NO) 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O, and Cu and Mg in a molar ratio of 1:1.15, and the rest of the operations are the same as in examples 1-5, to prepare the catalyst Cu 1 Mg 1.15 O x 。
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, and 0.5g of catalyst Cu was added 1 Mg 1.15 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 25 of Table 1.
Example 26
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of methanol, and 0.4g of the catalyst Cu prepared in examples 1-5 was added 1 Mg 1.15 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 26 of Table 1.
Example 27
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of ethanol, and 0.4g of the catalyst Cu prepared in examples 1-5 was added 1 Mg 1.15 Zr 2 O x The nitrogen is used for replacing air in the kettle, then the nitrogen is discharged, the reaction kettle is closed, the stirring is carried out at 500rpm, the temperature is heated to 240 ℃ and kept for 3 hours, after the reaction is finished, the reaction liquid is naturally cooled to room temperature, the centrifugal separation is carried out on the reaction liquid by a centrifugal machine,the supernatant was taken and subjected to qualitative and quantitative analysis using GC-MS and GC, respectively, and the detection results are shown in example 27 of Table 1.
Example 28
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isobutanol, and 0.4g of the catalyst Cu prepared in examples 1-5 was added 1 Mg 1.15 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis using GC-MS and GC, respectively, the detection results being shown in example 28 of Table 1.
Example 29
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of sec-butanol, and 0.4g of Cu as a catalyst prepared in examples 1-5 was added 1 Mg 1.15 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis by GC-MS and GC, respectively, the results of the detection being shown in examples 1 to 29 of Table 1.
Table 1 examples 1-29 test results
From examples 1 to 29, the optimized metal molar ratio of the ternary metal oxide catalyst consisting of Cu, mg and Zr is 1:1.15:2, and when the alcohol solvent is isopropanol, the ternary metal oxide has the highest catalytic activity, and the yield of gamma-valerolactone can be obtained by 88%.
Examples 30 to 33
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, with varying amounts of catalyst Cu prepared in examples 1-5 1 Mg 1.15 Zr 2 O x The reaction vessel was closed by replacing the air in the vessel with nitrogen, discharging nitrogen, stirring at 500rpm, heating to 240℃and maintaining for 3 hours, cooling naturally to room temperature after the completion of the reaction, centrifuging the reaction solution with a centrifuge, collecting the supernatant, and subjecting the supernatant to qualitative and quantitative analysis by GC-MS and GC, respectively, the detection results being shown in examples 30 to 33 of Table 2.
TABLE 2 results of examples 30-33
Examples 30 to 33 show that the amount of the catalyst added was increased from 0.2g to 0.6g, and the conversion of EL to the reaction substrate and the yield of GVL were varied. Under uniform reaction conditions (240 ℃,3h,500 rpm), it was found that when the catalyst addition was increased from 0.1g to 0.5g, the conversion of EL and the yield of GVL increased, but the degree of increase in the conversion per 0.1g of EL and the yield of GVL were different in the overall trend of increase. When Cu is 1 Mg 1.15 Zr 2 O x When the catalyst addition was increased from 0.3g to 0.4g, the EL conversion was increased from 88.3% to 99.7%, 11.4% and the GVL yield was increased from 70.5% to 87.0% by a margin of 16.5%. The catalyst was continuously increased to 0.5g, the EL conversion was continuously increased to 99.8%, only 0.1%, and at the same time the GVL yield was continuously increased by 1%, reaching 88.0%. When the catalyst addition amount was increased to 0.6g, the EL yield and the GVL yield were rather decreased to 92.1% and 76.7%, respectively, indicating that the catalyst addition amount was not as large as possible. The catalyst addition was 0.5g at the highest GVL yield.
Examples 34 to 40
Into a 100mL autoclave were charged 1g of ethyl levulinate and 19g of isopropyl alcohol, using 0.4g of catalyst Cu prepared in examples 1-5 1 Mg 1.15 Zr 2 O x 7 times of catalyst circulation stability experiments are carried out according to the reaction conditions of Table 2, after the reaction is finished, the reaction solution is naturally cooled to room temperature, centrifugal separation is carried out by a centrifugal machine, and the solid catalyst recovered by the centrifugal separation is dried for 1h at 80 ℃ in a vacuum drying oven for the next experiment. The supernatant was analyzed qualitatively by GC-MS to prepare a standard solution of ethyl levulinate, isopropyl alcohol and gamma valerolactone, and quantitatively detected by GC, and the detection results are shown in examples 34 to 40 of Table 3. Where cycling for the first time means repeating the first experiment on the basis of example 32, the remainder and so on.
TABLE 3 results of examples 34-40
Examples 41 to 42
Cu used 1 time was detected by elemental analyzer 1 Mg 1.15 Zr 2 O x Catalyst and Cu after 8 uses 1 Mg 1.15 Zr 2 O x Catalyst carbon content. The results of the measurements are shown in Table 4, examples 41-42.
TABLE 4 Cu after use 1 Mg 1.15 Zr 2 O x Content of catalyst C element
As can be seen from examples 34-40, representative catalyst Cu 1 Mg 1.15 Zr 2 O x After 7 times of experiments on recycling, the yield of gamma-valerolactone and the conversion rate of ethyl levulinate have excellent stability. Indicating representative catalyst Cu 1 Mg 1.15 Zr 2 O x The excellent activity is maintained during the recycling process. Carbon deposition generated during the use of the catalyst in an organic solvent is an important factor causing the reduction of the catalytic activity of the catalyst. Carbon deposition covers the active sites of the catalyst or plugs the pores of the catalystThe active sites on the contact catalyst that result in failure of the reactants to enter are two forms of carbon deposition that result in deactivation of the catalyst. As is clear from examples 41 to 42, the content of C element in the catalyst recovered after 8 times of use was compared with the content of C element in the catalyst recovered after 1 time of use, indicating Cu 1 Mg 1.15 Zr 2 O x The content of C element is only slightly increased by 0.32% after 7 times of recycling of the catalyst. Analysis results show that Cu 1 Mg 1.15 Zr 2 O x The catalyst only generates a small amount of carbon deposit in the recycling process, does not influence the catalytic activity of the catalyst obviously, and shows Cu 1 Mg 1.15 Zr 2 O x The catalyst has excellent stability.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.

Claims (9)

1. A method for catalyzing and synthesizing gamma-valerolactone by using a ternary metal oxide catalyst, which is characterized by comprising the following steps of: adding ethyl levulinate, a ternary metal oxide catalyst and an alcohol solvent into a reaction kettle, sealing the reaction kettle, carrying out airtight reaction at 200-270 ℃ at a stirring speed of 500rpm without adding hydrogen, and cooling to room temperature to obtain gamma-valerolactone;
the preparation method of the catalyst comprises the following steps: dissolving an active metal precursor in deionized water according to a certain molar ratio, adding excessive urea into the mixed solution, hydrolyzing at 90 ℃ for 4h, continuously stirring the mixed solution in the hydrolysis process, wherein the stirring speed is 300-400rpm, aging the obtained slurry at 90 ℃ for 2h after the hydrolysis is finished, cooling to room temperature, filtering the slurry, drying the obtained filter residue at 110 ℃ overnight, grinding the dried product in a mortar, sieving with a 100-mesh sieve, and calcining in a muffle furnace at 300-400 ℃ for 4h to obtain the catalyst; the active metal precursor consists of soluble salts containing Zr, mg and Cu.
2. The method of claim 1, wherein: the mass ratio of the ethyl levulinate to the alcohol solvent is 1:19.
3. The method of claim 1, wherein: the mass ratio of the catalyst to the ethyl levulinate is 0.2-0.6:1.
4. The method of claim 1, wherein: the molar ratio of Mg to Zr in the active metal precursor is 1.15:1-2.
5. The method of claim 1, wherein: the air calcination temperature was 300 ℃.
6. The method of claim 1, wherein: the molar ratio of Cu, mg and Zr in the active metal precursor is 1:1.15:1-3.
7. The method of claim 1, wherein: the air calcination temperature was 400 ℃.
8. The method of claim 1, wherein: active metal precursors of Zr, mg and Cu are Cu (NO 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O。
9. The method of claim 1, wherein: the alcohol solvent is isopropanol.
CN202310130751.4A 2023-02-17 2023-02-17 Ternary metal oxide catalyst and application thereof in catalytic synthesis of gamma-valerolactone Pending CN117126124A (en)

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