CN108047173A - A kind of method for preparing gamma-valerolactone - Google Patents
A kind of method for preparing gamma-valerolactone Download PDFInfo
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- CN108047173A CN108047173A CN201711358080.8A CN201711358080A CN108047173A CN 108047173 A CN108047173 A CN 108047173A CN 201711358080 A CN201711358080 A CN 201711358080A CN 108047173 A CN108047173 A CN 108047173A
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- catalyst
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- valerolactone
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 26
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 91
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 45
- 238000002360 preparation method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229910015711 MoOx Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 2
- 230000005574 cross-species transmission Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This divisional application is related to a kind of method for preparing γ valerolactones, and particularly levulic acid is in CuAg/Al2O3Selective hydrogenation generates γ valerolactones under the action of catalyst.CuAg/Al2O3Catalyst needs not move through reduction pretreatment, in-situ reducing can generate catalytic activity under 180 DEG C, 1.4MPa temperate conditions under the promotion of Ag, make the yields of γ valerolactones close to 100%, CuAg/Al2O3Catalyst saves reduction pretreatment step, significantly reduce the operation and maintenance cost of catalytic reaction, and the catalyst can inhibit Cu precipitations under 180 DEG C, 1.4MPa temperate conditions, be conducive to product separating-purifying, still there is stability active and very high well by recycled for multiple times, there is industrial application value.
Description
The application is Application No. 2017108277374, the applying date is September in 2017 14, a kind of entitled " system
The divisional application of the method for standby gamma-valerolactone ".
Technical field
The present invention relates to a kind of CuAg/Al2O3Catalyst, the preparation method of the catalyst and the catalyst prepare γ-
Application in valerolactone.
Background technology
The increasingly depleted and global warming of fossil resource have triggered deep thinking of the people to novel renewable energy.
And biomass is widely present as one of new energy, is a kind of renewable biomass, biomass not only may be used on earth
To provide carbonylation product for human development, the principle of Green Chemistry is also complied with.Wherein levulic acid (LA) is one kind by biology
The good platform chemicals that matter obtains are chosen as 12 big biomass in 2000 by American National Ministry of Energy regenerative resource laboratory
One of raw material.Under catalyst action, LA carbonyl hydrogens and then esterification can obtain gamma-valerolactone (GVL).GVL is acknowledged as
It is most to be potential by what biomass synthesized, most stable of platform chemicals.GVL is widely used, except can make solvent, food additives
Outside, research recently finds GVL are converted into C using means such as " catalytic decarbonations " additive with ethanol petrol fuel8-
C18Liquid hydrocarbon fuel.In addition, the excellent macromolecule polymeric material of a variety of thermal stabilities can also be synthesized by GVL, including
The composite material of nylon-type, polyacrylate has important application value.Promoting the key that this reacts industrialization is out
Send effective catalyst.
Homogeneous catalyst in a mild condition selective hydrogenation prepare shown in the reaction of GVL it is good activity and selection
Property.However, in general there are the shortcomings of perishable and more difficult recycling for these homogeneous catalysts.At present, used in the field
Heterogeneous catalysis mainly includes nickel-base catalyst (Ni/Al2O3, Ni-MoOx/C), copper-based catalysts (Cu/Cr2O3、Cu/SiO2)
Wait non-precious metal catalysts and noble metal catalyst (Ru/C, Pd/C, Pt/C).Although some noble metal catalyst energy so far
Preferable catalytic effect is enough obtained, but since its is expensive, some researchers are focused on non-precious metal catalyst.
Ni–MoOx/C[1]And Ni/Al2O3 [2]Higher GVL yields are although taken Deng some nickel-base catalysts, but catalyst is shown
Poor stability, when reusing, the conversion ratio of LA is compared compared with the first round significant reduction.Hengne[3]It employs
The Cu/Al reduced under 350 DEG C of atmosphere of hydrogen2O3And Cu/ZrO2Catalyst is in 3.45MPaH2LA selective hydrogenations are catalyzed under pressure
GVL is prepared, the yield for obtaining GVL is 100%, and it is a kind of highly active catalytic component for being catalyzed the reaction to illustrate copper.It is but copper-based
There is also some problems for catalyst.For example, the precipitation of active ingredient copper is very serious.Copper is lost in the carboxylate radical for being primarily due to LA
It is reacted with Cu.If carboxyl is masked before LA hydrogenation reactions, i.e., with alcohol first with LA reactions generation ester or using alcohol
Make carboxyl esterification as solvent, it can a degree of precipitation for inhibiting copper component.But there is alcohol participation reaction speed can be reduced,
The selectivity of GVL is significantly reduced[3]。Putrakumar B[4]Using Cu/Al2O3Reaction and Yan K at 265 DEG C[5]It adopts
With Cu-Fe catalyst in 7MPaH2Reaction under pressure can effectively inhibit the precipitation of active ingredient copper in catalyst.However,
The condition of these reactions is all harsher, and the reaction under high-temperature and high-pressure conditions will also result in high energy consumption, past when reaction temperature is higher
Toward carbon distribution is formed, cause catalyst serious inactivation.And this kind of copper-based catalysts are generally required before the reaction in 300-400 DEG C of H2
Prereduction under atmosphere, catalyst after reduction also easy Oxidative inactivation[6].If catalyst can exempt high temperature reduction pretreatment,
With regard to operation and maintenance cost can be saved.
The content of the invention
The shortcomings that in order to overcome the above-mentioned prior art and deficiency, the present invention will prepare GVL for LA selective hydrogenations and provide one
Kind new catalyst.The catalyst is using cheap precious metals ag and base metal Cu as active component, with γ-Al2O3To carry
Body.CuAg/Al2O3Ag is by triggering Hydrogen spillover effect that the reduction temperature of Cu can be promoted to reduce in catalyst, therefore the catalyst
High temperature pre-reduction treatment is needed not move through, it during the reaction being capable of autoreduction generation catalytic activity；Simultaneously under the promotion of Ag,
The precipitation of copper is effectively prevented under mild hydrogenation conditions by means of Hydrogen spillover effect.The catalyst is in 1.4MPa hydrogen pressures
Under power and 180 DEG C or so of temperate condition, it is possible to which, by LA Efficient Conversions into GVL, yield is close to 100%, and Cu will not be precipitated；
Also turn out that the catalyst has very high stability by the circulation experiment of 9 times.
The object of the present invention is to provide a kind of methods that catalytic hydrogenation levulic acid prepares gamma-valerolactone, i.e. levulic acid
Or its solution changes into gamma-valerolactone with hydrogen under catalytic action, the method for preparing catalyst for reacting used is：Select Cu and
Ag is as active component, γ-Al2O3As carrier, CuAg/Al is made by infusion process or deposition-precipitation method2O3Catalyst, institute
The infusion process stated is one kind in equi-volume impregnating, excessive infusion process or multiple maceration.More preferable equi-volume impregnating.
Using CuAg/Al2O3The method that catalyst to catalyzing hydrogenating levulic acid prepares gamma-valerolactone, specially：To reaction
Levulic acid, reaction dissolvent and CuAg/Al are added in kettle2O3Catalyst is filled with hydrogen into reaction kettle, and heating reaction kettle reacts,
Reaction temperature is 160-220 DEG C, and Hydrogen Vapor Pressure is 0.5~4.5MPa；The preferred CuAg/Al2O3The preparation method of catalyst
Including preparation process in detail below：
(1) dissolve：It is 0.4~4mmolCuAg/g (γ-Al by Cu and Ag total load amounts2O3) weigh the nitrate of Cu and Ag
And it is dissolved in deionized water, wherein Cu：The mol ratio of Ag is 1：20~10：1；
(2) impregnate：Carrier γ-Al are added in solution made from step (1)2O3, make carrier γ-Al2O3Solution is complete
It absorbs, obtains dipping object；
(3) it is dry：The dipping object that step (2) obtains is stood 1 at room temperature~for 24 hours, be then placed in drying baker in 105~
Dry 10 at 150 DEG C~for 24 hours；
(4) roast：Dried dipping object is put into heating furnace under air atmosphere with the heating speed of 1~20 DEG C/min
Rate is raised to 400~550 DEG C from room temperature, at this temperature 3~10h of constant temperature, and CuAg/Al is made2O3Catalyst.
Further, the reaction dissolvent is one kind in tetrahydrofuran and dioxane, preferentially using tetrahydrofuran.
Compared with prior art, the beneficial effects of the present invention are：
(1)CuAg/Al2O3Catalyst needs not move through reduction pretreatment, it can be in 180 DEG C, 1.4MPa under the promotion of Ag
In-situ reducing generates catalytic activity under temperate condition, and the yield of gamma-valerolactone is close to 100%.Catalyst saves reduction pretreatment
Step significantly reduces the operation and maintenance cost of catalytic reaction.
(2)CuAg/Al2O3Catalyst can inhibit Cu precipitations under 180 DEG C, 1.4MPa temperate conditions.Inhibit metal
Precipitation not only improves catalyst stability, and is conducive to product separating-purifying.
(3)CuAg/Al2O3Catalyst can obtain very high activity and selectivity under 180 DEG C, 1.4MPa temperate conditions,
And still there is good activity by recycled for multiple times, catalyst stability is fine.
Description of the drawings
Fig. 1 is CuAg/Al2O3Circular response in THF solution；
Fig. 2 is CuAg/Al2O3XPS phenetic analysis；
Fig. 3 is CuAg/Al2O3And Cu/Al2O3TPR table sign analysis.
Specific embodiment
The present invention is described in detail below by the drawings and specific embodiments, but is not limited the scope of the invention.Such as without special
Illustrate, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be chemically public
Department's purchase.Preferably, drying baker is vacuum drying chamber, heating furnace is Muffle furnace.
The intermittent reaction of embodiment 1-4 differential responses temperature
1. catalyst preparation：CuAg/Al is prepared using equi-volume impregnating2O3Catalyst concretely comprises the following steps：
(1) Vehicle element：Take a certain amount of γ-Al2O3Through temperature programming to 550 DEG C in Muffle furnace, at 550 DEG C
Constant temperature calcining 3h；
(2)γ-Al2O3The measure of water absorption：Accurately weigh 1.0000g γ-Al2O3Deionized water is added dropwise dropwise, it is agitated
Carrier of being subject to afterwards is wet glutinous, if sticky shape, is slowly siphoned away moisture with filter paper, the volume of deionized water added by record, is
Saturated water adsorptive value is about that 0.8ml water is optimal, i.e. γ-Al2O3Water absorption be 0.8ml/g；
(3) solution is configured：1449.6mg Cu (NO are weighed respectively3)2·3H2O and 1018.98mg AgNO33ml is dissolved in go
In ionized water, copper nitrate and silver nitrate solution are configured to；
(4) impregnate：Weigh the γ-Al after roasting in 5g steps (1)2O3Carrier is separately added into 2ml steps in 100ml beakers
Suddenly the copper nitrate and silver nitrate solution configured in (2), quickly stirring 20min makes carrier then be stood at room temperature in wet glutinous shape
2-5h；
(5) it is dry：Sample after being stood in step (4) is placed in 105 DEG C of dry 12h in vacuum drying chamber, it is long with agate
Time grinds, it is made to become powder；
(6) roast：Powdered samples prepared by step (5) are put into crucible, is placed in Muffle furnace and is arrived through temperature programming
450 DEG C, the constant temperature calcining 3h at 450 DEG C, sample sealed storage is taken out when temperature is down to 100 DEG C.
2. reaction test：Using the property of intermittent reaction test copper-silver bimetallic catalyst levulic acid hydrogenation reaction
Can, it concretely comprises the following steps：
(1) 10ml reaction kettles are taken, add in 300.0mg levulic acids, 6ml tetrahydrofurans 150mgCu-Ag/Al thereto2O3
Catalyst (Cu and Ag molar ratios nCu：nAg=1：1, carrying capacity 1.6mmol/g), reaction kettle is tightened into simultaneously check device air-tightness, really
1.4MPa hydrogen is filled in the air tight backward kettle of protection device, heats reaction kettle, and starts stirring, mixing speed 400rpm rises
Start timing when height is to assigned temperature, react 2h.
(2) after reaction, liquid product is collected, is analyzed with gas-chromatography.Catalyst is recycled by filtering
Wherein：C-LA (conversion ratio of levulic acid)=(amount of substance after the amount-LA reactions of LA initial substances)/LA startings
Amount × 100% of substance
Amount × 100% of amount/LA initial substances of Y-GVL (yield of gamma-valerolactone)=GVL generation substances
S-GVL (selectivity of gamma-valerolactone)=Y-GVL (yield of gamma-valerolactone)/C-GVL (turns of gamma-valerolactone
Rate) × 100%
Chromatographiccondition is：Using hydrogen flame detector (FID), hydrogen is as carrier gas, internal standard method, methyl iso-butyl ketone (MIBK)
(MIBK) it is internal standard compound.
3. reaction result is shown in Table 1.
The result of 1 differential responses temperature of table
From embodiment 1-4 as it can be seen that 210 DEG C, LA can be converted completely during 2h.
The intermittent reaction of 5,6,7 different catalysts dosage of embodiment
1. catalyst preparation：With the catalyst preparation process in embodiment 1.
2. reaction test：With reaction test process in embodiment 1, the reaction time 4h will be changed to, reaction temperature will be fixed as
180 DEG C, the dosage of catalyst is shown in Table 2.
3. reaction result is shown in Table 2.
The result of 2 different catalysts dosage of table
Change catalyst amount, be selectively kept at more than 95%；When catalyst amount increases, reaction speed is accelerated.
The intermittent reaction of 7,8,9 differential responses time of embodiment
1. catalyst preparation：With the catalyst preparation process in embodiment 1.
2. reaction test：With reaction test process in embodiment 1, reaction temperature is fixed as 180 DEG C, the reaction time is shown in Table
3。
3. reaction result is shown in Table 3.
The result of 3 differential responses time of table
Be appropriately extended the reaction time, be conducive to LA and fully convert, when reacted between be 4h when, LA can be converted completely.
The intermittent reaction of 10,11,12 different hydrogen pressure of embodiment
1. catalyst preparation：With the catalyst preparation process in embodiment 1.
2. reaction test：With reaction test process in embodiment 1, the reaction time 0.5h will be changed to, reaction temperature will be fixed
For 180 DEG C, reaction Hydrogen Vapor Pressure is shown in Table 4.
3. reaction result is shown in Table 4.
The result of 4 different hydrogen pressure of table
It is appropriate to increase Hydrogen Vapor Pressure, be conducive to LA and fully convert, when Hydrogen Vapor Pressure is 2.5MPa, LA can be converted completely.
The intermittent reaction of copper silver different proportion in 13,14,15,16 catalyst of embodiment
1. catalyst preparation：The CuAg/Al of different proportion is prepared using equi-volume impregnating2O3Catalyst, specific steps
For：
(1) Vehicle element：With embodiment 1；
(2)γ-Al2O3The measure of water absorption：With embodiment 1；
(3) solution is configured：9664mg Cu (NO are weighed respectively3)2·3H2O and 6793.2mgAgNO3It is dissolved in 20ml deionizations
In water, copper nitrate and silver nitrate solution are configured to；
(4) impregnate：Take three 100ml beakers, number 13,15,16.4ml silver nitrate solutions are added in into 13 beaker of number,
3ml copper nitrate solutions and 1ml silver nitrate solutions are added in the beaker of number 15,4ml copper nitrates are added in into the beaker of number 16
Solution weighs the γ-Al in three parts (1)2O3Carrier, every part of 5g are put in three beakers, and quickly stirring 20min makes carrier in wet glutinous
Shape then stands 2-5h at room temperature.N has been made respectivelyCu：nAgFor 0:1、3:1、1:0 catalyst precursor；1:1 catalysis
Agent presoma is prepared with embodiment 1；
(5) it is dry：With embodiment 1；
(6) roast：It will be with embodiment 1.
2. reaction test：With reaction test process in embodiment 1, the reaction time 3h will be changed to, reaction temperature will be fixed as
180 DEG C, nCu：nAgIt is shown in Table 5.
3. reaction result is shown in Table 5.
The result of copper silver different proportion in 5 catalyst of table
Work as n from table 5Cu：nAg=1:Reaction effect is best when 1, this illustrates the silver-colored needs one of the active ingredient copper of the catalyst
The progress of the suitable efficient catalytic hydrogenation reaction of proportioning ability, in order to verify result above, we will distinguish in the reaction time again
1h, 2h and 4h are fixed as, above reaction has been carried out in the case where other conditions are constant, has drawn identical result.
The result that 1,17,18 levulic acid of embodiment reacts in different solvents
1. catalyst preparation：With the catalyst preparation process in embodiment 1.
2. reaction test：With reaction test process in embodiment 1, reaction temperature is fixed as 180 DEG C, solvent for use is shown in Table
6。
3. reaction result is shown in Table 6.
The result that 6 levulic acid of table reacts in different solvents
Reaction dissolvent has a significant impact reaction effect, and in the three kinds of solvents tested, tetrahydrofuran has optimal molten
Agentization acts on.
The intermittent reaction of the catalyst levulic acid of the different carrying capacity of embodiment 1,19,20
1. catalyst preparation：The CuAg/Al of different proportion is prepared using equi-volume impregnating2O3Catalyst, specific steps
For：
(1) Vehicle element：With embodiment 1；
(2)γ-Al2O3The measure of water absorption：With embodiment 1；
(3) solution is configured：362.4mg Cu (NO are weighed respectively3)2·3H2O and 254.745mgAgNO3Be dissolved in 3ml go from
In sub- water, I solution of copper nitrate I and silver nitrate is configured to；3624mgCu (NO are weighed respectively3)2·3H2O and 2547.45mgAgNO3
It is dissolved in 3ml deionized waters, is configured to II solution of copper nitrate II and silver nitrate；
(4) impregnate：Take 2 100ml beakers, number 19,20.Respectively added in into 19 beaker of number 1 solution of 2ml silver nitrates and
1 solution of copper nitrate respectively adds in II solution of II solution of 2ml silver nitrates and copper nitrate into the beaker of number 20, weighs in two parts (1)
γ-Al2O3Carrier, every part of 5g, is put in beaker respectively, and quickly stirring 20min makes carrier in wet glutinous shape, then quiet at room temperature
Put 2-5h.The catalyst precursor that carrying capacity is 0.4mmol/g and 4.0mmol/g has been made respectively；Before the catalyst of 1.6mmol/g
The preparation of body is driven with embodiment 1；
(5) it is dry：With embodiment 1；
(6) roast：It will be with embodiment 1.
2. reaction test：With reaction test process in embodiment 1, reaction temperature is fixed as 180 DEG C, catalyst loading is shown in
Table 7.
3. reaction result is shown in Table 7.
The result of 7 different catalysts carrying capacity of table
It is appropriate to increase copper silver carrying capacity in catalyst, be conducive to LA and fully convert, but when carrying capacity is excessive, the conversion ratio of LA
It reduces instead.
Test is precipitated in embodiment 21-24 metals
1. catalyst preparation：CuAg/Al2O3It prepares with the catalyst preparation process in embodiment 1, Cu/Al2O3It prepares same
Catalyst preparation process in embodiment 16；Using CuNO3·3H2O and NaOH direct precipitation methods prepare Kocide SD powder；It will
Obtained Kocide SD powder obtains cupric oxide powder in the 500 degree of roastings of groom's stove, by cupric oxide powder in 350 DEG C of H2Under atmosphere
Reductase 12 h obtains Ni metal powder；
2. reaction test：With reaction test process in embodiment 1, the reaction time 4h will be changed to, reaction temperature will be fixed as
180 DEG C, metal amount of precipitation is shown in Table 8；
3. reaction result is shown in Table 8.
Test is precipitated in 8 metal of table
Levulic acid is only combined with the copper of oxidation state metallic copper on catalyst is caused largely to be precipitated, without with elemental copper knot
It closes；The addition of Ag promotes the reduction of Cu in catalyst so that copper is also at reduction-state at reaction conditions, inhibits so as to reach
The effect that Cu is precipitated.
Embodiment 25CuAg/Al2O3The circular response of catalyst
1. catalyst preparation：CuAg/Al2O3It prepares with the catalyst preparation process in embodiment 1, after being roasted in air
Directly use.
2. reaction test：With reaction test process in embodiment 1, the reaction time 4h will be changed to, reaction temperature will be fixed as
180℃.The first round after reaction, with dropper suctions out supernatant in reaction tube, and catalyst is stayed after washing 2 times with THF and done down
One wheel reaction.
3. reaction result is shown in Fig. 1.
As shown in Figure 1, CuAg/Al2O3Catalyst still has good stability by nine repetition reactions, and LA's turns
Rate is still up to 100%.
26 catalyst characterization of embodiment
CuAg/Al shown in Fig. 22O3XPS characterization results before and after catalyst reacts under the conditions of 180 DEG C/1.4MPa.Fresh
Contain copper oxide in catalyst, and there is no cupric in post catalyst reaction, illustrate that Cu is by in-situ reducing during the reaction.
So the catalyst is without reduction pretreatment, during the reaction can in-situ reducing generate catalytic activity.In reduction-state
Cu will not be precipitated, so CuAg/Al2O3Catalyst has the ability that Cu is precipitated of resisting.
Cu/Al shown in Fig. 32O3The reduction temperature of middle Cu is near 260 DEG C, significantly larger than 180 DEG C of reaction temperatures, and CuAg/
Al2O3The reduction temperature of middle Cu is near 140 DEG C, hence it is evident that less than 180 DEG C reaction temperatures, so CuAg/Al2O3It can be 180
℃、1.4MPaH2Reaction condition under autoreduction.
Bibliography
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Valerolactone by Ni and MoOx co-loaded carbon catalysts [J] .Green Chemistry,
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[2] Hengst K, Schubert M, Carvalho H W P, et al.Synthesis of γ-
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[3] Hengne A M, Rode C V.Cu-ZrO2nanocomposite catalyst for selective
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Claims (3)
- A kind of 1. method for preparing gamma-valerolactone, which is characterized in that into reaction kettle add in levulic acid, reaction dissolvent and CuAg/Al2O3Catalyst is filled with hydrogen into reaction kettle, and heating reaction kettle reaction, reaction temperature is 160-220 DEG C, hydrogen pressure Power is 0.5~4.5MPa, after reaction, collects liquid product.
- 2. according to the method described in claim 1, it is characterized in that, the reaction dissolvent is in tetrahydrofuran and dioxane One kind.
- 3. according to the method described in claim 1, it is characterized in that, the reaction dissolvent is tetrahydrofuran.
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| US20120197029A1 (en) * | 2009-09-11 | 2012-08-02 | Korea Research Institute Of Chemical Technology | Method for producing cyclicised compounds from organic acids having from 4 to 6 carbon atoms |
| CN106256811A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | The compositions that the method for synthesis aromatic hydrocarbons and the method obtain |
| CN106256809A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | The compositions that the method for biomass production aromatic hydrocarbons and the method obtain |
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| IN2012DE00662A (en) * | 2012-03-07 | 2015-08-21 | Council Scient Ind Res | |
| CN106238047B (en) * | 2016-01-29 | 2019-02-22 | 中国科学院兰州化学物理研究所苏州研究院 | Valerate bio-fuel production catalyst and the method for inhibiting catalyst carbon deposit |
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| US20120197029A1 (en) * | 2009-09-11 | 2012-08-02 | Korea Research Institute Of Chemical Technology | Method for producing cyclicised compounds from organic acids having from 4 to 6 carbon atoms |
| CN106256811A (en) * | 2015-06-19 | 2016-12-28 | 中国石油化工股份有限公司 | The compositions that the method for synthesis aromatic hydrocarbons and the method obtain |
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