CN109694363A - In-situ reducing basic copper carbonate/aluminum oxyhydroxide is catalyzed levulic acid or levulinate to the method for gamma-valerolactone - Google Patents
In-situ reducing basic copper carbonate/aluminum oxyhydroxide is catalyzed levulic acid or levulinate to the method for gamma-valerolactone Download PDFInfo
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- CN109694363A CN109694363A CN201810791154.5A CN201810791154A CN109694363A CN 109694363 A CN109694363 A CN 109694363A CN 201810791154 A CN201810791154 A CN 201810791154A CN 109694363 A CN109694363 A CN 109694363A
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- Prior art keywords
- levulic acid
- valerolactone
- gamma
- basic copper
- copper carbonate
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 229940058352 levulinate Drugs 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229940116318 copper carbonate Drugs 0.000 title claims abstract description 19
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 title claims abstract description 19
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 15
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 title claims abstract description 10
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 65
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 63
- 239000003054 catalyst Substances 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- -1 hydroxyl Aluminium oxide Chemical compound 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 239000000047 product Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 235000019421 lipase Nutrition 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of in-situ reducing basic copper carbonate/method of aluminum oxyhydroxide catalysis levulic acid or levulinate to gamma-valerolactone, reaction process are as follows: by levulic acid or its ester, secondary alcohol and basic copper carbonate/aluminum oxyhydroxide (Cu2(OH)2CO3/ AlOOH) it is fitted into autoclave, it is uniformly mixed, is reacted 1~24 hour at 140~220 DEG C after sealing, obtain gamma-valerolactone solution after cooling.The reaction had preferable yield within 5 hours short time, and experimentation is easy to operate, low in cost, and reaction temperature is lower, had good IP prospecting.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of in-situ reducing basic copper carbonate/aluminum oxyhydroxides
Be catalyzed levulic acid or levulinate to gamma-valerolactone method.
Background technique
Since natural resources is limited and to the increasing of demand for energy, biomass is selectively converted to fuel and chemistry
Product are of great significance in the human society of high speed development.In the distinct methods of biomass conversion, catalysis route is especially heavy
It wants, many biomass can produce derivatization product and fuel by carefully designing catalyst system.Gamma-valerolactone is considered as
Sustainable production one of fuel and the most promising platform chemicals of high valuable chemicals, can be by hydrogenolysis from wooden
The levulic acid of cellulose or its ester obtain.
The hydrogenolysis has two different paths.First paths are, in H2In the presence of using a series of metals (such as
Pd, Ru, Rh, Pt, Re, Ni, Co, Mo and Cu) as catalyst progress hydrogenolysis；Second paths are, by using alcohol or
Formic acid and transition metal replace H2And noble metal can reduce reaction condition respectively as reaction hydrogen source and catalyst, realize
Hydrogenolysis.Recently, in the second approach, catalytic transfer hydrogenation (CTH) reacts the alternative as hydrogen hydrogenation reaction,
Have been considered as the high effective way of synthesis γ-GVL.The catalyst of this kind of reaction has a metal, metal complex, metal oxide or
Hydroxide, various zeolites etc..And in these catalyst, the metal oxide-loaded loaded catalyst of base metal is one
Class efficiently, the cheap, catalyst that easily prepares.
Currently, (such as: Cu/ZrO for this kind of catalyst2、Cu-Ni/Al2O3Deng), it is required to by high-temperature hydrogen reduction,
It is not only complicated for operation in this way to participate in reaction, and the high requirements on the equipment.And then some researchers discovery passes through methanol
It reforms, CuO can be reduced to Cu to be catalyzed the synthesis of γ-GVL.But the reforming temperature of methanol is higher and CuO is not easy to be reduced,
Limit its application on catalysis levulic acid and its Lipase absobed γ-GVL.
CN 104693159A discloses a kind of catalyst that liquid-phase hydrogenatin prepares the method for gamma-valerolactone and its uses.It should
The loaded catalyst that method uses, active metal are precious metal palladium or palladium-nickel alloy, and catalyst is with high costs, and are needed certain
Additional hydrogen pressure be just able to achieve higher hydrogenation selectivity.
CN 104829559A discloses a kind of method for preparing gamma-valerolactone by methyl ester levulinate.In levulic acid first
The Copper-Chromium Oxide Catalysts without weighted BMO spaces are added in the mixed liquor of ester and methanol, pass through in-situ reducing copper oxide catalyzation
The reaction.The catalyst includes the chromium harmful to human body and environment, for environmental requirement, needs to consider to the catalyst
The synthetical recovery of middle chromium, and the temperature reacted is higher.
CN 107253937A discloses a kind of synthetic method of gamma-valerolactone.This method uses copper-based bimetallic catalyst
(Zr, Al, Mg, Ca, Zn, Ba or Ni) participates in the synthesis of gamma-valerolactone by in-situ reducing copper oxide.This method reaction
Temperature is higher (180 DEG C -280 DEG C), increases production cost.
Summary of the invention
The object of the invention is that provide a kind of by in-situ reducing basic copper carbonate/hydroxyl to solve the above-mentioned problems
Base aluminium oxide (Cu2(OH)2CO3/ AlOOH) Lai Cuihua levulic acid or levulinate to gamma-valerolactone method.
The present invention through the following technical solutions to achieve the above objectives:
The technical scheme adopted by the invention is that passing through low temperature secondary alcohol in-situ reducing Cu2(OH)2CO3/ AlOOH turns to be catalyzed
Hydrogenation levulic acid or its ester are moved to gamma-valerolactone, specific experiment follows the steps below:
By levulic acid or its ester, secondary alcohol and Cu2(OH)2CO3/ AlOOH is fitted into autoclave, is uniformly mixed, sealing
It is reacted 1~24 hour at 140~220 DEG C afterwards, obtains gamma-valerolactone solution after cooling.
Further, 5h is reacted under 180 DEG C of stirrings after sealing.
Further, the levulic acid or its ester: secondary alcohol: Cu2(OH)2CO3/ AlOOH is according to (0.1-1mmol): (10-
30mL): the ratio mixing of (0.01-0.4g).
Further, the levulic acid or its ester: secondary alcohol: Cu2(OH)2CO3The preferred proportion of/AlOOH are as follows:
0.67mmol:20mL:0.1g.
Further, the levulic acid or its ester are levulic acid, methyl ester levulinate, ethyl levulinate or acetyl
Butyl propionate.
Further, the secondary alcohol is isopropanol, sec-butyl alcohol and cyclohexanol.
Further, the Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 1.208-4.832g Cu
(NO3)2·3H2O and 1.500-9.378gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；With
Afterwards, with 1mol L-1Na2CO3Solution tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four
Five times, it is placed in 80 DEG C of oven dryings；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain Cu2(OH)2CO3/
AlOOH。
The beneficial effects of the present invention are:
The present invention is that a kind of in-situ reducing basic copper carbonate/aluminum oxyhydroxide catalysis levulic acid or levulinate arrive
The method of gamma-valerolactone, compared with prior art, the present invention has the advantage that
1, the present invention applies Cu2(OH)2CO3/ AlOOH compound synthesizes Cu/AlOOH catalysis by secondary alcohol in-situ reducing
Agent, and then catalytic transfer hydrogenation levulic acid or its Lipase absobed gamma-valerolactone.
2, catalyst of the invention is cheap and easy to get, stable in catalytic performance, and reusability is good, and entirely reaction does not need
Under hydrogen environment plus hydrogen, a series of process temperature all controls at 200 DEG C hereinafter, have relatively industrial operational safety by force,
With extraordinary industrial applications potentiality.
3, the present invention uses secondary alcohol simultaneously as hydrogen donor and reaction media, does not need external hydrogen source and other solvents, instead
It answers system simple, is conducive to the separation of target product.
4, the present invention synthesizes gamma-valerolactone by catalytic transfer hydrogenation levulic acid or its ester.
5, catalyst of the invention composition active metal and carrier are cheap and easy to get, good economy performance.
6, the Cu/AlOOH catalyst of in-situ reducing is the particle of 30-40nm, has fabulous catalytic activity.
Detailed description of the invention
Fig. 1 is the gas-chromatography comparative diagram of product gamma-valerolactone and gamma-valerolactone standard items in the embodiment of the present invention 1.Its
In, A is gamma-valerolactone standard sample；B is the gas chromatogram of product；
Retention time 6.90min is gamma-valerolactone；
Retention time 6.50min is methyl ester levulinate；
Retention time 8.84min is 1,4- pentanediol；
Fig. 2 is transmission electron microscope (TEM) figure of in-situ reducing Cu/AlOOH in the embodiment of the present invention 1
Wherein Fig. 2A can be seen that the particle of catalyst in 30-40nm or so.Fig. 2 B can be seen that Cu (111) crystal face and
(031) crystal face of AlOOH.
Fig. 3 is the X-ray powder diffraction (XRD) of the Cu/AlOOH in situ in the present invention with different Cu/Al molar ratios
Figure.
Wherein, diffraction maximum is the characteristic peak of Cu, respectively 2 θ=43.2 °, 50.4 ° and 74.1 °.Since AlOOH is lower
Crystallinity, so in addition to Cu/Al molar ratio be 0 when, the XRD of other ratios does not see the characteristic peak of AlOOH.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
One kind passing through in-situ reducing Cu2(OH)2CO3/ AlOOH comes in catalytic transfer hydrogenation levulic acid or its ester to γ-penta
The method of ester, specifically follows the steps below:
By a certain amount of levulic acid or its ester, secondary alcohol and a certain amount of Cu2(OH)2CO3/ AlOOH catalyst is packed into high pressure
In reaction kettle, it is uniformly mixed, is reacted at 140~220 DEG C at 1~24 hour, preferably 180 DEG C after sealing and react 5h, it is cooling
After obtain gamma-valerolactone solution.
Wherein, levulic acid or its ester: secondary alcohol: Cu2(OH)2CO3/ AlOOH catalyst is according to (0.1-1mmol): (10-
30mL): the ratio mixing of (0.01-0.4g).
Preferably, levulic acid or its ester: secondary alcohol: Cu2(OH)2CO3/ AlOOH catalyst is according to (0.67mmol):
(20mL): the ratio mixing of (0.1g).
Preferably, secondary alcohol is isopropanol, sec-butyl alcohol and cyclohexanol
Preferably, levulic acid or its ester are levulic acid, methyl ester levulinate, ethyl levulinate or levulic acid fourth
Ester.
Wherein, Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 1.208-4.832g Cu (NO3)2·3H2O
And 1.500-9.378gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol is used
L-1Na2CO3Solution tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, is placed in
80 DEG C of oven dryings；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain Cu2(OH)2CO3/AlOOH。
Preferred Cu2(OH)2CO3/ AlOOH is that Cu/Al molar ratio is 3/1.
Principal product after reaction is gamma-valerolactone, and main by-product is Isosorbide-5-Nitrae-pentanediol.
Embodiment 1
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 5h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
As shown in Figure 1, being detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS) to acquired solution.
According to concentration-peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 90.51%.
Fig. 2 can be obtained, and the Cu/AlOOH of in-situ reducing is the lattice that nano particle has just looked at out Cu and AlOOH, can in conjunction with Fig. 3
It obtains, Cu2(OH)2CO3/ AlOOH produces Cu/AlOOH by in-situ reducing.
Embodiment 2
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 1h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 34.10%.
Embodiment 3
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react at 180 DEG C for 24 hours, after reaction kettle is cooling,
It is to be measured.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 54.27%.
Embodiment 4
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react at 140 DEG C for 24 hours, after reaction kettle is cooling,
It is to be measured.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 90.76%.
Embodiment 5
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react at 220 DEG C for 24 hours, after reaction kettle is cooling,
It is to be measured.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 18.96%.
Embodiment 6
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 12h at 160 DEG C, after reaction kettle is cooling,
It is to be measured.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 90.34%.
Embodiment 7
By 0.67mmol levulic acid, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put into appearance
Product is after closed reactor, to be stirred to react 5h at 180 DEG C in the autoclave of 35mL, to be measured after reaction kettle is cooling.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 17.8%.
Embodiment 8
By 0.67mmol ethyl levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 5h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 90.12%.
Embodiment 9
By 0.67mmol Butyl acetylpropanoate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml isopropanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 5h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 91.14%.
Embodiment 10
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml sec-butyl alcohol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 5h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 89.37%.
Embodiment 11
By 0.67mmol methyl ester levulinate, 0.1g Cu2(OH)2CO3/ AlOOH (Cu/Al=3/1), 20ml cyclohexanol are put
Enter in the autoclave that volume is 35mL, after closed reactor, is stirred to react 5h at 180 DEG C, after reaction kettle is cooling, to
It surveys.
Wherein Cu2(OH)2CO3/ AlOOH catalyst the preparation method comprises the following steps: by 3.624g Cu (NO3)2·3H2O and
1.875gAl2(NO3)3·9H2O is dissolved in 40mL deionized water, stirs a few minutes at room temperature；Then, 1mol/LNa is used2CO3It is molten
Liquid tune PH to 8-9 is stirred ten minutes, is stood overnight；It then filters, is washed with deionized four or five times, it is dry to be placed in 80 DEG C of baking ovens
It is dry；Then grinding, is placed in 200 DEG C of Muffle kiln roastings.Finally obtain the Cu that Cu/Al molar ratio is 3/12(OH)2CO3/AlOOH。
Acquired solution is detected using gas chromatograph-mass spectrometer (GC-MS) (TRACE DSQ GC-MS).According to concentration-
Peak area standard curve and peak areas, the yield that can calculate gamma-valerolactone in product is 40.92%.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of in-situ reducing basic copper carbonate/aluminum oxyhydroxide is catalyzed levulic acid or levulinate to gamma-valerolactone
Method, it is characterised in that: by levulic acid or levulinate, secondary alcohol and basic copper carbonate/aluminum oxyhydroxide (Cu2(OH)2CO3/ AlOOH) catalyst is fitted into autoclave, and it is uniformly mixed, is reacted 1~24 hour at 140~220 DEG C after sealing,
Product gamma-valerolactone is obtained after cooling.
2. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that react 5h under 180 DEG C of stirrings after sealing.
3. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that the levulic acid or levulinate: secondary alcohol: basic copper carbonate/hydroxyl
Aluminium oxide (Cu2(OH)2CO3/ AlOOH) according to (0.1-1mmol): (10-30mL): the ratio mixing of (0.01-0.4g).
4. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that the levulic acid or levulinate: secondary alcohol: basic copper carbonate/hydroxyl
Aluminium oxide (Cu2(OH)2CO3/ AlOOH) preferred proportion are as follows: 0.67mmol:20mL:0.1g.
5. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that the levulinate are as follows: methyl ester levulinate, ethyl levulinate or second
One of acyl butyl propionate.
6. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that the secondary alcohol is isopropanol, sec-butyl alcohol and cyclohexanol.
7. in-situ reducing basic copper carbonate according to claim 1/aluminum oxyhydroxide catalysis levulic acid or levulic acid
Method of the ester to gamma-valerolactone, which is characterized in that the basic copper carbonate/aluminum oxyhydroxide (Cu2(OH)2CO3/ AlOOH) it urges
Agent the preparation method comprises the following steps: by 1.208-4.832g Cu (NO3)2·3H2O and 1.500-9.378gAl2(NO3)3·9H2O is dissolved in
In 40mL deionized water, a few minutes are stirred at room temperature；Then, with 1mol L-1Na2CO3Solution tune PH to 8-9 is stirred ten minutes,
It stands overnight；It then filters, is washed with deionized four or five times, is placed in 80 DEG C of oven dryings；Then grinding, is placed in 200 DEG C of horses
Not kiln roasting.Finally obtain catalyst basic copper carbonate/aluminum oxyhydroxide (Cu2(OH)2CO3/AlOOH)。
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| CN201810791154.5A CN109694363B (en) | 2018-07-18 | 2018-07-18 | Method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide |
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| Title |
|---|
| AMOL M. HENGNE等: "Cu–ZrO nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to γ-valerolactone", 《GREEN CHEM.》 * |
| SHYAM SUNDER R. GUPTA等: "Selective hydrogenation of levulinic acid into γ-valerolactone over Cu/Ni hydrotalcite-derived catalyst", 《CATALYSIS TODAY》 * |
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