CN109694363B - Method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide - Google Patents
Method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide Download PDFInfo
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- CN109694363B CN109694363B CN201810791154.5A CN201810791154A CN109694363B CN 109694363 B CN109694363 B CN 109694363B CN 201810791154 A CN201810791154 A CN 201810791154A CN 109694363 B CN109694363 B CN 109694363B
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 229940116318 copper carbonate Drugs 0.000 title claims abstract description 15
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 title claims abstract description 15
- 230000009467 reduction Effects 0.000 title claims abstract description 13
- -1 levulinic acid ester Chemical class 0.000 title claims abstract description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 101
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 5
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 claims description 4
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229940005460 butyl levulinate Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 15
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 150000004730 levulinic acid derivatives Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
-
- 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
- B01J23/72—Copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/16—Reducing
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide, which comprises the following steps: mixing levulinic acid or its ester, secondary alcohol and basic copper carbonate/aluminum hydroxide (Cu) 2 (OH) 2 CO 3 AlOOH) is put into a high-pressure reaction kettle, is evenly mixed, reacts for 1 to 24 hours at the temperature of 140 to 220 ℃ after being sealed, and is cooled to obtain gamma-valerolactone solution. The reaction has good yield within a short time of 5 hours, the experimental process is simple and convenient to operate, the cost is low, the reaction temperature is low, and the method has a good industrial production prospect.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for catalyzing levulinic acid or levulinate ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide.
Background
Due to the limited natural resources and the increasing demand for energy, the selective conversion of biomass into fuels and chemicals is of great importance in the rapidly developing human society. The catalytic route is particularly important in various processes for biomass conversion, and many biomasses can be used to produce derivative chemicals and fuels by careful design of the catalytic system. Gamma valerolactone, which is considered one of the most promising platform compounds for sustainable production of fuels and high value added chemicals, can be obtained by hydrogenolysis of levulinic acid from lignocellulose or its esters.
The hydrogenolysis reaction has two distinct pathways. The first path is at H 2 Using a series of metals (e.g., pd, ru, rh, pt, re, ni, co, mo, and Cu) as catalysts for the hydrogenolysis reaction; the second route is by using alcohols or formic acid and transition metalsSubstitute for H 2 And noble metals are respectively used as a reaction hydrogen source and a catalyst, so that the reaction condition can be reduced, and the hydrogenolysis reaction can be realized. Recently, in the second method, catalytic Transfer Hydrogenation (CTH) reaction, which is an alternative to hydrogen hydrogenation reaction, has been considered as a highly efficient route for synthesizing γ -GVL. Catalysts for such reactions are metals, metal complexes, metal oxides or hydroxides, various zeolites, and the like. Among these catalysts, the supported catalyst of non-noble metal supported metal oxide is a kind of high-efficiency, cheap and easy-to-prepare catalyst.
At present, for this type of catalyst (e.g. Cu/ZrO) 2 、Cu-Ni/Al 2 O 3 And the like) are required to be subjected to high-temperature hydrogen reduction so as to participate in the reaction, so that the operation is complex and the requirement on equipment is high. Further, some researchers have found that CuO can be reduced to Cu by reforming methanol to catalyze the synthesis of γ -GVL. However, the reforming temperature of methanol is high and CuO is not easy to be reduced, so that the application of the methanol in catalyzing levulinic acid and ester thereof to synthesize gamma-GVL is limited.
CN 104693159A discloses a method for preparing gamma-valerolactone by liquid phase hydrogenation and a catalyst used by the method. The supported catalyst used in the method has high cost because the active metal is noble metal palladium or palladium-nickel alloy, and high hydrogenation selectivity can be realized only by adding certain hydrogen pressure.
CN 104829559A discloses a method for preparing gamma-valerolactone from methyl levulinate. Adding a copper-chromium oxide catalyst which is not subjected to hydrogenation pretreatment into a mixed solution of methyl levulinate and methanol, and catalyzing the reaction by reducing copper oxide in situ. The catalyst comprises chromium which is harmful to human bodies and the environment, comprehensive recovery of chromium in the catalyst needs to be considered due to environmental protection requirements, and the reaction temperature is high.
CN 107253937A discloses a method for synthesizing gamma-valerolactone. The method uses a copper-based bimetallic catalyst (Zr, al, mg, ca, zn, ba or Ni) to participate in the synthesis of gamma-valerolactone by in-situ reduction of copper oxide. The method has high reaction temperature (180-280 ℃) and increases the production cost.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for reducing basic copper carbonate/aluminum hydroxy oxide (Cu) in situ 2 (OH) 2 CO 3 AlOOH) to levulinic acid or levulinate esters to gamma valerolactone.
The invention achieves the above purpose through the following technical scheme:
the technical scheme adopted by the invention is that Cu is reduced in situ by low-temperature secondary alcohol 2 (OH) 2 CO 3 AlOOH to catalytically transfer the hydrogenated levulinic acid or ester thereof to gamma valerolactone, the specific experiment was carried out according to the following steps:
reacting levulinic acid or ester thereof, secondary alcohol and Cu 2 (OH) 2 CO 3 and/AlOOH is put into a high-pressure reaction kettle, mixed evenly, sealed and reacted for 1 to 24 hours at the temperature of 140 to 220 ℃, and cooled to obtain the gamma-valerolactone solution.
Further, after sealing, the reaction was carried out at 180 ℃ for 5 hours with stirring.
Further, the levulinic acid or the ester thereof: secondary alcohol: cu 2 (OH) 2 CO 3 AlOOH as (0.1-1 mmol): (10-30 mL): (0.01-0.4 g) in a certain proportion.
Further, the levulinic acid or the ester thereof: secondary alcohol: cu 2 (OH) 2 CO 3 The preferred ratio of/AlOOH is: 0.67mmol:20mL of: 0.1g.
Further, the levulinic acid or the ester thereof is levulinic acid, methyl levulinate, ethyl levulinate or butyl levulinate.
Further, the secondary alcohols are isopropanol, sec-butanol and cyclohexanol.
Further, the Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 1.208-4.832g of Cu (NO) 3 ) 2 ·3H 2 O and 1.500-9.378gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, 1mol of L is used -1 Na 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; followed byThen, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu 2 (OH) 2 CO 3 /AlOOH。
The invention has the beneficial effects that:
the invention relates to a method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide, which has the following advantages compared with the prior art:
1. the invention uses Cu 2 (OH) 2 CO 3 the/AlOOH compound is synthesized into a Cu/AlOOH catalyst through the in-situ reduction of a secondary alcohol, and then the gamma-valerolactone is synthesized through the catalytic transfer hydrogenation of levulinic acid or ester thereof.
2. The catalyst provided by the invention is cheap and easy to obtain, stable in catalytic performance and good in reusability, the whole reaction does not need hydrogenation in a hydrogen environment, the temperature of a series of processes is controlled below 200 ℃, the operation safety of industrial production is high, and the industrial application potential is very good.
3. The method uses secondary alcohol as a hydrogen donor and a reaction medium at the same time, does not need an external hydrogen source and other solvents, has a simple reaction system, and is beneficial to the separation of target products.
4. The invention synthesizes gamma-valerolactone by catalytically transferring and hydrogenating levulinic acid or ester thereof.
5. The catalyst has the advantages of cheap and easily obtained active metal and carrier, and good economical efficiency.
6. The Cu/AlOOH catalyst reduced in situ is a particle of 30-40nm, and has excellent catalytic activity.
Drawings
FIG. 1 is a gas chromatographic comparison of the product gamma valerolactone of example 1 of the invention and a gamma valerolactone standard. Wherein A is a gamma-valerolactone standard sample; b is a gas chromatogram of the product;
retention time 6.90min is gamma valerolactone;
retention time 6.50min is methyl levulinate;
retention time 8.84min is 1, 4-pentanediol;
FIG. 2 is a Transmission Electron Microscope (TEM) image of in-situ reduced Cu/AlOOH in example 1 of the present invention
In which figure 2A shows the catalyst particles around 30-40 nm. FIG. 2B shows the (111) crystal plane of Cu and the (031) crystal plane of AlOOH.
FIG. 3 is an X-ray powder diffraction (XRD) pattern of in situ Cu/AlOOH with different Cu/Al molar ratios in accordance with the present invention.
Wherein, the diffraction peak is a characteristic peak of Cu, and is respectively 2 theta =43.2 °, 50.4 ° and 74.1 °. Since AlOOH is a low crystallinity, XRD of other ratios does not see a characteristic peak of AlOOH except when the Cu/Al molar ratio is 0.
Detailed Description
The invention will be further described with reference to the accompanying drawings in which:
by in-situ reduction of Cu 2 (OH) 2 CO 3 The method for catalytically transferring the hydrogenated levulinic acid or the ester thereof to the gamma valerolactone by AlOOH comprises the following steps:
a certain amount of levulinic acid or ester thereof, secondary alcohol and a certain amount of Cu 2 (OH) 2 CO 3 The AlOOH catalyst is put into a high-pressure reaction kettle, mixed evenly, sealed and reacted for 1 to 24 hours at the temperature of 140 to 220 ℃, preferably for 5 hours at the temperature of 180 ℃, and cooled to obtain the gamma-valerolactone solution.
Wherein levulinic acid or an ester thereof: secondary alcohol: cu 2 (OH) 2 CO 3 AlOOH catalyst according to (0.1-1 mmol): (10-30 mL): (0.01-0.4 g) in a proportion.
Preferably, levulinic acid or an ester thereof: secondary alcohol: cu 2 (OH) 2 CO 3 AlOOH catalyst according to (0.67 mmol): (20 mL): (0.1 g) were mixed.
Preferably, the secondary alcohols are isopropanol, sec-butanol and cyclohexanol
Preferably, the levulinic acid or ester thereof is levulinic acid, methyl levulinate, ethyl levulinate or butyl levulinate.
Wherein, cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 1.208-4.832g of Cu (N)O 3 ) 2 ·3H 2 O and 1.500-9.378gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, 1mol of L- 1 Na 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and drying in an oven at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu 2 (OH) 2 CO 3 /AlOOH。
Preferred Cu 2 (OH) 2 CO 3 AlOOH is a Cu/Al molar ratio of 3/1.
The main product after the reaction is gamma-valerolactone, and the main byproduct is 1, 4-pentanediol.
Example 1
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 5 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring for a few minutes at room temperature; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS) as shown in FIG. 1. According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 90.51 percent.
FIG. 2 can be taken that the in-situ reduced Cu/AlOOH are nanoparticles and the crystal lattice of Cu and AlOOH is seen, which can be taken from FIG. 3 2 (OH) 2 CO 3 The Cu/AlOOH can be generated by in-situ reduction of the/AlOOH.
Example 2
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 1h, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring for a few minutes at room temperature; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and drying in an oven at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined by gas chromatography-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of the gamma-valerolactone in the product can be calculated to be 34.10%.
Example 3
0.67mmol of methyl levulinate and 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 24 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and drying in an oven at 80 ℃; then grinding and placingCalcining in 200 deg.C muffle furnace. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was detected using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 54.27%.
Example 4
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 140 ℃ for 24 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was detected using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 90.76%.
Example 5
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 220 ℃ for 24 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring for a few minutes at room temperature; subsequently, the reaction is carried out with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was detected using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 18.96%.
Example 6
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 160 ℃ for 12 hours, and cooling the reaction kettle for testing.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was detected using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 90.34%.
Example 7
0.67mmol of levulinic acid and 0.1g of Cu were added 2 (OH) 2 CO 3 The resulting mixture was put into a 35mL autoclave with AlOOH (Cu/Al = 3/1) and 20mL of isopropyl alcohol, the autoclave was closed, and the mixture was heatedStirring and reacting for 5h at 180 ℃, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, the reaction is carried out with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined by gas chromatography-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 17.8%.
Example 8
0.67mmol of ethyl levulinate and 0.1g of Cu were added 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 5 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, the reaction is carried out with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and drying in an oven at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined by gas chromatography-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 90.12%.
Example 9
0.67mmol of butyl levulinate and 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of isopropanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 5 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the/AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, the reaction is carried out with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was detected using a gas chromatograph-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 91.14%.
Example 10
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL sec-butyl alcohol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 5 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, the reaction is carried out with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining the Cu/Al molar ratio3/1 of Cu 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined by gas chromatography-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of the gamma-valerolactone in the product can be calculated to be 89.37%.
Example 11
0.67mmol of methyl levulinate, 0.1g of Cu 2 (OH) 2 CO 3 Putting AlOOH (Cu/Al = 3/1) and 20mL of cyclohexanol into a high-pressure reaction kettle with the volume of 35mL, sealing the reaction kettle, stirring and reacting at 180 ℃ for 5 hours, and cooling the reaction kettle to be tested.
Wherein Cu 2 (OH) 2 CO 3 The preparation method of the AlOOH catalyst comprises the following steps: 3.624g of Cu (NO) 3 ) 2 ·3H 2 O and 1.875gAl 2 (NO 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring for a few minutes at room temperature; subsequently, with 1mol/LNa 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and drying in an oven at 80 ℃; then grinding and placing in a muffle furnace at 200 ℃ for roasting. Finally obtaining Cu with the Cu/Al molar ratio of 3/1 2 (OH) 2 CO 3 /AlOOH。
The resulting solution was examined by gas chromatography-mass spectrometer (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the peak area of the product, the yield of gamma-valerolactone in the product can be calculated to be 40.92%.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A method for catalyzing levulinic acid ester to gamma valerolactone by in-situ reduction of basic copper carbonate/aluminum hydroxide oxide is characterized in that: levulinic acid esters, secondary alcohols and basic copper carbonate/aluminum hydroxy oxide (Cu) 2 (OH) 2 CO 3 The catalyst of/AlOOH) is put into a high-pressure reaction kettle, the secondary alcohol is isopropanol and sec-butyl alcohol, the mixture is evenly mixed, the mixture reacts for 5 hours at 180 ℃ after being sealed, and the product gamma-valerolactone is obtained after cooling;
the levulinic acid ester is as follows: secondary alcohol: basic copper carbonate/aluminum oxyhydroxide (Cu) 2 (OH) 2 CO 3 AlOOH) as per (0.1-1 mmol): (10-30 mL): (0.01-0.4 g);
the basic copper carbonate/aluminum hydroxy oxide (Cu) 2 (OH) 2 CO 3 The preparation method of the/AlOOH) catalyst comprises the following steps: 1.208-4.832g of Cu (NO) 3 ) 2 ·3H 2 O and 1.500-9.378g Al (NO) 3 ) 3 ·9H 2 Dissolving O in 40mL of deionized water, and stirring at room temperature for a few minutes; subsequently, 1mol of L is used -1 Na 2 CO 3 Adjusting the pH value of the solution to 8-9, stirring for ten minutes, and standing overnight; then, carrying out suction filtration, washing for four times and five times by using deionized water, and placing in an oven for drying at 80 ℃; grinding, and calcining in 200 deg.C muffle furnace to obtain basic copper carbonate/aluminum hydroxide (Cu) as catalyst 2 (OH) 2 CO 3 /AlOOH)。
2. A process for the in situ reduction of basic copper carbonate/aluminum hydroxy oxide catalyzed levulinic acid esters into gamma valerolactone according to claim 1, wherein the levulinic acid ester: secondary alcohol: basic copper carbonate/aluminum oxyhydroxide (Cu) 2 (OH) 2 CO 3 The ratio of/AlOOH) is: 0.67mmol:20mL of: 0.1g.
3. A process for the in situ reduction of basic copper carbonate/aluminum hydroxy oxide catalyzed levulinic acid esters into gamma valerolactone according to claim 1, wherein the levulinic acid esters are: one of methyl levulinate, ethyl levulinate or butyl levulinate.
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Selective hydrogenation of levulinic acid into γ-valerolactone over Cu/Ni hydrotalcite-derived catalyst;Shyam Sunder R. Gupta等;《Catalysis Today》;20170807;第309卷;189-194 * |
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