CN110898837A - 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 PDFInfo
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- CN110898837A CN110898837A CN201910972182.1A CN201910972182A CN110898837A CN 110898837 A CN110898837 A CN 110898837A CN 201910972182 A CN201910972182 A CN 201910972182A CN 110898837 A CN110898837 A CN 110898837A
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- catalyst
- levulinic acid
- valerolactone
- reaction
- levulinate
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 21
- -1 levulinate ester Chemical class 0.000 title claims abstract description 12
- 229940058352 levulinate Drugs 0.000 title claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 5
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 claims description 3
- 229940005460 butyl levulinate Drugs 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910020706 Co—Re Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
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- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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 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. 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 4-5 in Table 1.
TABLE 1
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
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) ofAdding 40ml of different alcohols as a catalyst, adding a stirrer, sealing the reaction kettle, heating to 200 ℃ at the stirring speed of 500rpm, and keeping the temperature for 1.0 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 quantified through gas chromatography, and detection results of different reaction conditions are listed as serial numbers 1-3 in Table 3.
TABLE 3
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 (8)
1. Al (aluminum)mZrn@Fe3O4The preparation method of the catalyst is characterized by comprising the following steps:
(1) compounding AlCl3And ZrOCl2·8H2O mixed water solution, and nanometer Fe is added3O4Then evenly mixing to obtain mixed liquid;
(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).
2. The preparation method of claim 1, 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 amount of (B) is 5 to 15 mmol.
3. An AlmZrn @ Fe3O4 catalyst prepared by the process of claim 1 or 2.
4. A method for preparing gamma-valerolactone comprises the following specific steps:
(1) charging levulinic acid or a levulinic acid ester feedstock, an alcohol and the catalyst of claim 3 into an autoclave;
(2) setting the reaction temperature and the reaction time, and reacting under stirring to obtain the gamma-valerolactone.
5. The method according to claim 4, wherein the levulinic acid esters are one or more of methyl levulinate, ethyl levulinate and butyl levulinate.
6. The process of claim 4, wherein the alcohol is ethanol, n-propanol, isopropanol or sec-butanol.
7. The method of claim 4, wherein the mass ratio of the catalyst addition amount to levulinic acid or levulinate ester is (2-6): 13.
8. The method of claim 4, wherein the temperature of the catalytic reaction is 170-230 ℃ and the reaction time is 0.5-3.0 h.
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| CN201910972182.1A CN110898837B (en) | 2019-10-14 | 2019-10-14 | Catalyst for catalyzing levulinic acid and levulinate ester to prepare gamma-valerolactone |
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| CN110898837B CN110898837B (en) | 2021-05-25 |
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Citations (4)
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| US8975421B2 (en) * | 2012-03-07 | 2015-03-10 | Council Of Scientific & Industrial Research | Process for preparation of γ-valerolactone via catalytic hydrogenation of levulinic acid |
| 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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2019
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Patent Citations (4)
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|---|---|---|---|---|
| US8975421B2 (en) * | 2012-03-07 | 2015-03-10 | Council Of Scientific & Industrial Research | Process for preparation of γ-valerolactone via catalytic hydrogenation of levulinic acid |
| 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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| ANQI WANG ET AL.: ""New magnetic nanocomposites of ZrO2-Al2O3-Fe3O4 as green solid acid catalysts in organic reactions"", 《CATAL. SCI. TECHNOL.》 * |
| HU LI ET AL.: ""Direct Conversion of Sugars and Ethyl Levulinate into γ‑Valerolactone with Superparamagnetic Acid−Base Bifunctional ZrFeOx Nanocatalysts"", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| JIAN HE ET AL.: ""Cascade catalytic transfer hydrogenation–cyclization of ethyllevulinate to γ-valerolactone with Al-Zr mixed oxides"", 《APPLIED CATALYSIS A: GENERAL》 * |
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