CN110898837B - Catalyst for catalyzing levulinic acid and levulinate ester to prepare gamma-valerolactone - Google Patents

Catalyst for catalyzing levulinic acid and levulinate ester to prepare gamma-valerolactone Download PDF

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CN110898837B
CN110898837B CN201910972182.1A CN201910972182A CN110898837B CN 110898837 B CN110898837 B CN 110898837B CN 201910972182 A CN201910972182 A CN 201910972182A CN 110898837 B CN110898837 B CN 110898837B
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levulinic acid
valerolactone
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肖卫华
赵婷婷
韩鲁佳
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China Agricultural University
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-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
    • C07D307/30—Heterocyclic compounds containing five-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
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Abstract

The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing gamma-valerolactone by catalyzing levulinic acid and levulinate ester, which comprises the following steps: (1) preparing a mixed aqueous solution of AlCl3 and ZrOCl 2.8H 2O, adding nano Fe3O4, and uniformly mixing to obtain a mixed solution; (2) adding concentrated ammonia water (25-28 wt%) into the mixed solution obtained in the step (1) until the pH value of the solution is 10, standing and aging; (3) filtering and washing the solid obtained in the step (2); (4) and (4) roasting the washed catalyst filter cake in the step (3). The obtained catalyst has the characteristics of low price, simple preparation, low addition amount and high catalytic performance.

Description

Catalyst for catalyzing levulinic acid and levulinate ester to prepare gamma-valerolactone
Technical Field
The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing gamma-valerolactone by catalyzing levulinic acid and levulinate ester.
Background
Traditional fossil resources such as coal, petroleum and natural gas are still the synthetic basis of global energy products at present, but with the rapid development of economy, the problems of the gradual depletion of the fossil resources and the gradual deterioration of the ecological environment are increasingly highlighted. Therefore, the preparation of biofuel and biomass-based chemicals by using renewable biomass resources has a very important meaning for reducing the dependence of traditional fossil energy. Among the platform compounds, GVL is considered to be one of the most promising biomass-based platform compounds due to its non-toxic and biodegradable properties, and has recently received much attention from academic and industrial fields. The organic-inorganic composite material can be used as an edible spice to be added into food, and can be widely applied to biomass pretreatment as a green solvent in recent years. In addition, GVL has been shown to be a superior gasoline additive to ethanol because it has a lower saturated vapor pressure (3.5 kpa at 80 ℃), a higher boiling point (208 ℃) and a higher energy density (35 MJ/L). The downstream products of valeric ester, 5-nonanone, long-chain olefin and the like have high calorific value and are candidates of high-grade fuels.
Patent document 1 discloses an Ag/ZrO2The method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation has the optimum reaction temperature of 220 ℃, 4MPa hydrogen is filled into a high-pressure reaction kettle in the reaction, and the yield of the gamma-valerolactone can reach 99.3 percent to the maximum. However, the active metal of the catalyst is noble metal silver, and high hydrogenation selectivity can be realized only by adding high-pressure hydrogen and long reaction time (6 h).
Patent document 2 discloses a method for producing γ -valerolactone by mixing a reaction substrate with an organic alcohol and using a metal oxide as a catalyst. With an optimized single metal oxide ZrO22-propanol is taken as a hydrogen source to react for 1 hour at the temperature of 250 ℃ by taking the catalyst as a catalyst, and the yield of gamma-valerolactone is 80.6 percent. Although the method avoids using noble metal as a catalytic center, the reaction temperature is high, the conditions are severe, the yield is low, and the requirements of industrial production cannot be met.
Patent document 3 discloses a magnetic metal composite oxide ZrxFe10-x(x ═ 1-9) catalytic levulinic acid or esters thereof to gamma valerolactone, with 2-propanol as the hydrogen source, at 99% gamma valerolactone yield under preferred conditions. However, the catalyst required for the reaction is added in an extremely high amount (about 1.4 times of the substrate) and takes a long time (12 hours), so that the problem of high production cost still exists for industrialization.
Patent document 4 discloses a catalyst for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, wherein the gamma-valerolactone yield can reach 99% by catalytic reaction of a supported Co-Re bimetallic catalyst in a hydrogen atmosphere. The method utilizes the anchoring synergistic effect between the double metals, and can obtain higher yield under low loading. However, the metal Re in the catalyst belongs to one of the most rare elements in the earth crust, and the catalyst needs to be reduced in a hydrogen atmosphere at a high temperature (450-550 ℃) before use, so that the two factors greatly increase the production cost of the gamma-valerolactone, and meanwhile, the danger coefficient of the whole process is extremely large.
Documents of the prior art
Patent document
Patent document 1: CN109651304A
Patent document 2: CN103497168A
Patent document 3: CN109053640A
Patent document 4: CN107930642A
Disclosure of Invention
Technical problem to be solved by the invention
In general, the prior art for preparing gamma-valerolactone has the problem of hindering large-scale production. The invention aims to provide AlmZrn@Fe3O4The catalyst has the characteristics of low price, simple preparation, low addition amount and high catalytic performance, and is easy to magnetically recover and can be recycled.
Means for solving the technical problem
Aiming at the problems, the invention provides a preparation method and a use method of an AlmZrn @ Fe3O4 catalyst.
According to one embodiment of the invention, there is provided a method for preparing an AlmZrn @ Fe3O4 catalyst, comprising the steps of:
(1) preparing a mixed aqueous solution of AlCl3 and ZrOCl 2.8H 2O, adding nano Fe3O4, and uniformly mixing to obtain a mixed solution;
(2) adding concentrated ammonia water (25-28 wt%) into the mixed solution obtained in the step (1) until the pH value of the solution is 10, standing and aging;
(3) filtering and washing the solid obtained in the step (2);
(4) and (4) roasting the washed catalyst filter cake in the step (3).
In one embodiment, the molar ratio of Al to Zr in the step (1) is (3:1) - (1:3), the molar total amount of the two compounds is 20mmol, and the addition amount of the nano Fe3O4 is 5-15 mmol.
According to a second aspect of the present invention, there is provided an AlmZrn @ Fe3O4 catalyst prepared using the above method.
According to a third aspect of the present invention, there is provided a method for preparing gamma-valerolactone, comprising the following steps:
(1) adding levulinic acid or levulinic acid ester raw materials, alcohol and the catalyst into a high-pressure reaction kettle;
(2) setting the reaction temperature and the reaction time, reacting under stirring, and obtaining the gamma-valerolactone after the reaction is finished.
In one embodiment, the levulinic acid esters are one or more of methyl levulinate, ethyl levulinate and butyl levulinate.
In one embodiment, the alcohol is ethanol, n-propanol, isopropanol or sec-butanol.
In one embodiment, the mass ratio of the added amount of the catalyst to levulinic acid or levulinate ester is (2-6): 13.
In one embodiment, the temperature of the catalytic reaction is 170-230 ℃, and the reaction time is 0.5-3.0 h.
The invention has the advantages of
(1) The invention has the advantages that the bimetallic magnetic catalyst prepared by taking Al and Zr as active components has cheap and easily obtained raw materials, simple preparation process, good catalytic performance, low reaction addition amount, easy magnetic separation after reaction and accordance with the current green sustainable development strategy.
(2) The prepared catalyst can effectively catalyze levulinic acid and levulinate to prepare gamma-valerolactone in a system taking alcohol as a solvent and a hydrogen donor, and has the advantages of no need of inert gas protection in the reaction process, short reaction time, high gamma-valerolactone yield and almost no side reaction. Improves the safety and the economical efficiency of the preparation of the gamma-valerolactone and expands the application of the bimetallic magnetic catalyst in the industrial production of the gamma-valerolactone.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1 is a graph showing the yield of gamma valerolactone from methyl levulinate using multiple cycles of the catalyst of example 7 of the present invention.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
The AlmZrn @ Fe3O4 catalyst is prepared by a coprecipitation method, and a carrier is common commercially available nano ferroferric oxide. The preparation method comprises the following specific steps:
(1) respectively dissolving a certain amount of AlCl3 and ZrOCl2 & 8H2O in 100ml of deionized water to prepare a mixed solution, adding a certain amount of nano Fe3O4 after completely dissolving, and uniformly stirring in a mechanical stirring manner;
(2) then dropwise adding concentrated ammonia water (25-28%) under vigorous stirring until the pH value of the solution is 10, stopping dropwise adding, continuously stirring for a period of time, and standing for aging;
(3) the resulting solid was filtered and washed until no Cl "was detected by AgNO 3;
(4) and drying the catalyst, then placing the dried catalyst in a tubular furnace, roasting the catalyst at the temperature of 300 ℃, and naturally cooling the catalyst to obtain brown powder.
In the catalyst preparation step, a mixed solution of AlCl3 and ZrOCl 2.8H 2O is prepared, the molar ratio of Al to Zr is 3:1 and 1: 11: 3, and the molar total amount of the two compounds is 20 mmol. The addition amount of the nano Fe3O4 in the catalyst preparation step is 5mmol, 10mmol and 15 mmol. The prepared AlmZrn @ Fe3O4 catalyst can have catalytic activity without reduction pretreatment in a hydrogen atmosphere.
A method for preparing gamma-valerolactone by catalyzing levulinic acid and levulinate ester comprises the following specific steps:
(1) adding levulinic acid or levulinic acid ester raw materials, alcohol and the prepared catalyst into a quartz liner tube of a high-pressure reaction kettle;
(2) setting reaction temperature and reaction time, starting stirring, cooling after the reaction is finished, and taking out a reaction mixture;
(3) the liquid phase product was collected and analyzed by gas chromatography.
The levulinic acid esters are one or more of methyl levulinate, ethyl levulinate and butyl levulinate. The alcohol is ethanol, n-propanol, isopropanol or sec-butanol. The mass ratio of the addition amount of the catalyst to the levulinic acid or the levulinic acid ester is (2-6): 13. The temperature of the catalytic reaction is 170-230 ℃, and the reaction time is 0.5-3.0 h.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples.
Examples 1 to 3:
0.65g of ethyl levulinate and 40ml of isopropanol were added to a 100ml reaction vessel quartz liner, and 0.20g of Al was added thereto, respectively3Zr1@Fe3O4(2:1)、Al1Zr1@Fe3O4(2:1)、Al1Zr3@Fe3O4(2:1)(Fe3O4The addition amount is 10mmol, and the total metal oxide content and Fe are shown in brackets3O4Molar ratio of (d) as a catalyst, a stirrer was added, the reaction vessel was closed, the stirring rate was 500rpm, and the mixture was heated to 230 ℃ and held for 0.5 h. And after the reaction is finished, taking out the kettle body, and cooling by water. After the reaction mixture is subjected to magnetic separation, a liquid product is quantitatively analyzed through gas chromatography, and detection results of different reaction conditions are listed as serial numbers 1-3 in Table 1.
Examples 4 to 5:
0.65g of ethyl levulinate and 40ml of isopropanol were added to a 100ml reaction vessel quartz liner, and 0.20g of Al was added thereto, respectively1Zr3@Fe3O4(4:1)、Al1Zr3@Fe3O4(4:3)(Fe3O4The addition amounts are respectively 5mmol and 15mmol, and the total metal oxide content and Fe are shown in brackets3O4Molar ratio of (d) as a catalyst, a stirrer was added, the reaction vessel was closed, the stirring rate was 500rpm, and the mixture was heated to 230 ℃ and held for 0.5 h. To be treatedAnd after the reaction is finished, taking out the kettle body, and cooling by water. After the reaction mixture is subjected to magnetic separation, a liquid product is quantitatively analyzed through gas chromatography, and detection results of different reaction conditions are listed as serial numbers 4-5 in Table 1.
TABLE 1
Figure BDA0002232457970000051
Figure BDA0002232457970000061
Examples 6 to 13:
0.65g of levulinic acid or levulinic acid ester and 40ml of isopropanol are added into a 100ml reaction kettle quartz liner tube, and then 0.10g to 0.30g of Al is respectively added1Zr3@Fe3O4(4:1) (Total metal oxide content and Fe in brackets)3O4The molar ratio) as a catalyst, adding a stirrer, sealing the reaction kettle, heating to 170-230 ℃ at the stirring speed of 500rpm, and keeping the temperature for 0.5-3.0 h. And after the reaction is finished, taking out the kettle body, and cooling by water. After the reaction mixture is subjected to magnetic separation, a liquid product is quantitatively analyzed through gas chromatography, and detection results of different reaction conditions are listed as serial numbers 1-8 in Table 2.
TABLE 2
Figure BDA0002232457970000062
Examples 14 to 16:
to a 100ml reactor quartz liner was added 0.65g of methyl levulinate and 0.20g of Al1Zr3@Fe3O4(4:1) (Total metal oxide content and Fe in brackets)3O4In a molar ratio) as a catalyst, 40ml of different alcohols were added, a stirrer was added, and the reaction vessel was closed at a stirring rate of 500rpm, heated to 200 ℃ and held for 1.0 hour. And after the reaction is finished, taking out the kettle body, and cooling by water. The reaction mixture is magnetically separatedAnd (3) quantitatively analyzing the separated liquid product through gas chromatography, wherein detection results of different reaction conditions are listed as serial numbers 1-3 in Table 3.
TABLE 3
Figure BDA0002232457970000071
Example 17
After the reaction of example 7 (Table 2, No. 2), Al was added1Zr3@Fe3O4(4:1) the catalyst is recovered magnetically, washed with ethanol repeatedly for three times, dried at 60 ℃ and then put into the conditions of example 7 for recycling, the experimental result is shown in figure 1, and the yield of the gamma-valerolactone is still as high as 92.8% after the catalyst is recycled for five times.
Industrial applicability
The catalyst of the invention has simple and rapid synthesis process and high product yield, and provides a certain support for realizing the industrial preparation of the gamma-valerolactone.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (2)

1. A method for preparing gamma-valerolactone is characterized by comprising the following specific steps:
(1) adding levulinic acid or levulinic acid ester raw materials, alcohol and Al into a high-pressure reaction kettlemZrn@Fe3O4A catalyst;
(2) setting reaction temperature and reaction time, and reacting under stirring to obtain gamma-valerolactone;
wherein the levulinic acid esters are one or more of methyl levulinate, ethyl levulinate and butyl levulinate;
wherein the alcohol is ethanol, n-propanol, isopropanol or sec-butanol;
the Al ismZrn@Fe3O4The catalyst is prepared by adopting the following method,
(1) compounding AlCl3And ZrOCl2·8H2O mixed water solution, and nanometer Fe is added3O4Then evenly mixing to obtain mixed liquid;
(2) adding 25-28% wt of concentrated ammonia water into the mixed solution obtained in the step (1) until the pH of the solution is =10, standing and aging;
(3) filtering and washing the solid obtained in the step (2);
(4) roasting the washed catalyst filter cake in the step (3);
wherein the molar ratio of Al to Zr in the step (1) is 3: 1-1: 3, the molar total amount of the two compounds is 20mmol, and the nano Fe is3O4The addition amount of (2) is 5 mmol;
the temperature of the catalytic reaction is 170-230 ℃, and the reaction time is 0.5-3.0 h.
2. The method of claim 1, wherein: the mass ratio of the addition amount of the catalyst to the levulinic acid or the levulinic acid ester is (2-6): 13.
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Citations (4)

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CN106432144A (en) * 2016-09-05 2017-02-22 中国农业大学 Method for high-selectivity preparation of gamma-GVL by homogeneous catalysis
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CN106415919A (en) * 2014-03-31 2017-02-15 泰克年研究发展基金会公司 A method for passive metal activation and uses thereof
CN106432144A (en) * 2016-09-05 2017-02-22 中国农业大学 Method for high-selectivity preparation of gamma-GVL by homogeneous catalysis
CN109053640A (en) * 2018-06-19 2018-12-21 江南大学 A method of gamma-valerolactone is prepared by levulic acid and its esters

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"Direct Conversion of Sugars and Ethyl Levulinate into γ‑Valerolactone with Superparamagnetic Acid−Base Bifunctional ZrFeOx Nanocatalysts";Hu Li et al.;《ACS Sustainable Chem. Eng.》;20151203;第4卷;第236-246页 *
"New magnetic nanocomposites of ZrO2-Al2O3-Fe3O4 as green solid acid catalysts in organic reactions";Anqi Wang et al.;《Catal. Sci. Technol.》;20130924;第4卷;第71-80页 *
Anqi Wang et al.."New magnetic nanocomposites of ZrO2-Al2O3-Fe3O4 as green solid acid catalysts in organic reactions".《Catal. Sci. Technol.》.2013,第4卷 *

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