CN105330523A - Method for preparing cyclopentanone by taking biomass resource as raw material - Google Patents
Method for preparing cyclopentanone by taking biomass resource as raw material Download PDFInfo
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- CN105330523A CN105330523A CN201510687358.0A CN201510687358A CN105330523A CN 105330523 A CN105330523 A CN 105330523A CN 201510687358 A CN201510687358 A CN 201510687358A CN 105330523 A CN105330523 A CN 105330523A
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Abstract
The invention belongs to the technical field of biomass conversion utilization, and concretely relates to a method for preparing cyclopentanone by taking biomass resource as a raw material. The method comprises taking furfural coming from biomass as the raw material, taking a hydrogen-containing gas as a reducing agent, and in the presence of a metal supported type catalyst, performing hydrogenation rearrangement reaction in a high-pressure reaction kettle or a fixed bed reactor, so as to obtain cyclopentanone in one step, wherein the carrier of the metal supported type catalyst is selected from Nb2O5, H-ZSM-5 molecular sieve, HY molecular sieve, Fe2O3, ZrO2, Al2O3, SiO2, CeO2, MgO, active carbon, and TiO2 in various crystal forms, the active composition is selected from Au, Pt, Ru, Rh, Pd, Ir, Ni and Cu, and the active composition load capacity is 0.1-5% of the catalyst. The method is mild in reaction technological conditions, and cheap and easily-available in raw materials, is capable of realizing quantitative conversion of furfural to cyclopentanone, and belongs to an environment-friendly green chemical technology.
Description
Technical field
The invention belongs to Wood Adhesives from Biomass and utilize technical field, be specifically related to a kind of method preparing cyclopentanone.
Background technology
Due to the increase of energy demand in the exhaustion of traditional energy and global range, the development of substitute energy has been a great concern at present.With reproducible biomass resource for raw material obtains energy chemistry product, reduce chemical to the dependence of the fossil resources such as oil, there is important scientific meaning and application prospect.Carbohydrate is the chief component of biomass resource, efficiently can obtain biological based platform compound furfural (FFA) processed through hydrolysis, dehydration.In recent years, the catalyzed conversion of FFA has caused the broad interest of domestic and international investigator, and makes great progress.Be raw material with furfural, through over hydrogenation, oxidation, nitrated, halogenation, the reactions such as condensation, can obtain multiple important Chemicals.Such as, the hydrogenation reaction of furfural can generate furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methyl furan, 2-methyltetrahydrofuran etc.; The oxidizing reaction of furfural can obtain furancarboxylic acid, maleic anhydride; The nitration reaction of furfural can produce 5-Nitrofulral diacetate; Furfural can generate furans, tetrahydrofuran (THF) through decarbonylation reaction; And produce furfuryl resin etc. by furfural polycondensation.Therefore, with furfural be the deep processing series product of raw material in pharmacy industry, organic synthesis, macromolecular material chemical industry all has vital role.But still have some problems demand to solve in the trans-utilization field of furfural, one is that preparation longer heterogeneous catalyst of a kind of life-span carrys out quantitatively obtained a certain product efficiently, two is to develop the variation route that a series of furfural prepares derived product.
Cyclopentanone is a kind of important Organic Chemicals, is mainly used in the industries such as medicine, spices and rubber synthesis.Such as may be used for the products such as synthetic perfume methyl dihydrojasmonate, white orchid ketone, 2 n hexyl cyclopentanone; As excellent solvent, cyclopentanone also has in electron trade to be applied very widely.The preparation method of cyclopentanone mainly contains two kinds of methods, i.e. hexanodioic acid decarboxylation cyclisation method and cyclopentene oxidizing (Fig. 1).Hexanodioic acid decarboxylation cyclisation method is the main production technology (as Chinese patent CN1594259, European patent EP 306873) of current industrial employing, but the production of oxalic acid is depended on the raw material that this route prepares cyclopentanone, relate to step many, and relate to decarboxylation procedure in process of production, Theoretical Mass yield is lower, and Atom economy is not high.Cyclopentene oxidizing is another technological line (as patent JP04312549, WO2003078372, WO2006032532) preparing cyclopentanone, general employing Wacker type oxide catalyst, or adopts N
2o is as oxygenant, and direct and cyclopentenes reaction generates cyclopentanone.But in Wacker process, generally there is a large amount of chlorion, not only corrosion reacting kettle but also easily increase chloro-product; And with N
2o generally carries out as the oxidation style of oxygenant under high temperature (280 DEG C) high pressure (30MPa), severe reaction conditions.Therefore develop preparing new raw material, variation route, particularly utilizing inexpensive abundant biomass resource of cyclopentanone, have great importance.
Furfural (FFA) is the material being derived from biomass, the alternative petroleum compound set up it and produced and use of FFA, and up to the present, has carried out the research to this furfural.Furfural is industrially using the agriculture and forestry organic waste material of cheapness (as corn cob, bagasse, cotton seed hulls etc.) as raw material scale operation.China is big producing country and the big export country of furfural, and within 2010, Chinese furfural output reaches more than 30 ten thousand tons, accounts for more than 80% of worldwide production total amount.Furfural and cyclopentanone all have five carbon atoms, therefore, furfural are converted into cyclopentanone, have important using value.Therefore, hydrogenation of furfural is reset and is produced the focus (Fig. 2) that cyclopentanone becomes biomass research gradually in recent years.Such as, with Ru-Ce-SiO at Chinese patent CN103159606A reports 100-180 DEG C
2for catalyzer, it is 72% that hydrogenation of furfural resets the yield obtaining cyclopentanone; Chinese patent CN102807483B reports furfural conversion under copper-based catalysts effect and produces cyclopentanone; Chinese patent CN104069886A reports a kind of catalyzer of Y zeolite load, and furfural aqueous solution is converted into the yield 96% of cyclopentanone.It should be noted that each relating to that furfural produces the above-mentioned file of cyclopentanone admits efficiency, selectivity and the commercial competitiveness needing to improve this method.In fact, chemical industry exacerbates the production improvement of cyclopentanone or the demand of alternative business method to using the evolutionary development of renewable raw materials.
Summary of the invention
The object of this invention is to provide a kind of environmental protection and efficiency of pcr product high take biomass resource as the method that cyclopentanone prepared by raw material.
The method preparing cyclopentanone provided by the invention, to be derived from the furfural of biomass as raw material, under metal load type catalyst exists, with hydrogen-containing gas (hydrogen or synthetic gas) for reductive agent, through hydrogenation-rearrangement reaction in autoclave or fixed-bed reactor, a step obtains cyclopentanone.
The inventive method does not rely on fossil resource completely, and step is less, green economy, and the transformation efficiency of furfural and the selectivity of cyclopentanone are all close to a hundred per cent.Up to the present, though there are some to be converted into the report of cyclopentanone about furfural, but the yield of product is all very low.Therefore, raw material route of the present invention is a technological line with original innovation.
Provided by the inventionly prepare in the method for cyclopentanone, furfural is converted into cyclopentanone will consider the step such as shortening and isomerization, therefore needs to design the catalyst system with difference in functionality, as support of the catalyst, active ingredient etc.The catalyzer of the present invention's design is metal load type catalyst; The carrier that catalyzer uses is selected from Nb
2o
5, H-ZSM-5 molecular sieve, HY molecular sieve, Fe
2o
3, ZrO
2, Al
2o
3, SiO
2, CeO
2, MgO, gac, and the TiO of various crystal formation
2; Catalyst activity component is selected from Au, Pt, Ru, Rh, Pd, Ir, Ni, Cu, in one; Activity component load quantity is the 0.1-5% of catalyzer total amount.
The preparation method of above-mentioned metal load type catalyst provided by the present invention, concrete steps are:
(1) at 6080 DEG C, be 0.252.5mmolL to 100400mL, concentration
-1hAuCl
40.11.0mmolL is added in solution
-1precipitation agent, the pH to 8.09.0 of regulator solution;
(2) oxide carrier is added in the solution that step (1) obtains, stir 26h, be cooled to room temperature;
(3) by the solution suction filtration that step (2) obtains, and wash without chlorion to solution, then by throw out vacuum-drying 1224h under 2030 DEG C (preferably 25 DEG C);
(4) by dried solids in step (3) at 5 volume %H
2in/Ar at 200400 DEG C reduction treatment 16h, namely obtain nano catalyst of the present invention.
Wherein, step (1) described precipitation agent is selected from NaOH, KOH, Na
2cO
3, one in urea.
The catalyzer that the invention provides other metal active centres loads except Au all adopts pickling process to prepare.Preparation process is:
In the aqueous solution of metal-salt, add carrier, stir 4-8 hour, and then stir evaporate to dryness under 60-100 DEG C of condition, 200-600 DEG C of reduction 1-5 hour in hydrogen atmosphere before using.
Provided by the inventionly prepare in the method for cyclopentanone, reaction take water as reaction medium, and furfural aqueous solution concentration is 1-30%, and reaction pressure is 0.5-8MPa, and temperature of reaction is 80-180 DEG C.Preferred concentration is 5-10%, and preferred pressure is 140-160 DEG C.
Provided by the inventionly prepare in the method for cyclopentanone, the concrete operations carrying out reacting in autoclave are: in certain density furfural aqueous solution, add a certain amount of catalyzer, rise to appointment temperature of reaction after gas displacement; Then, be filled with hydrogen or synthetic gas to specifying reaction pressure, stirring reaction 0.1-12 hour, namely obtains cyclopentanone and other converted products.
Provided by the inventionly prepare in the method for cyclopentanone, the concrete operations carrying out reacting in fixed-bed reactor are: by catalyst filling to the constant temperature zone in fixed-bed reactor, by certain density furfuryl aldehyde solution, the fixed-bed reactor that catalyzer is housed are entered with hydrogen or synthetic gas, react, obtaining the mixture flow of cyclopentanone, water and hydrogen, obtaining pure cyclopentanone through being separated.
Provided by the inventionly prepare in the method for cyclopentanone, in described liquid-phase reaction system, also can add suitable solubility promoter.
Described solubility promoter is preferably one or more in common organic solvents, comprises: ethanol, methyl alcohol, acetone, butanols, dioxane.More preferably solubility promoter is ethanol.
Provided by the inventionly prepare in the method for cyclopentanone, described hydrogen-containing gas is hydrogen or H arbitrarily
2the synthetic gas of/CO ratio.
Route provided by the invention has following characteristics:
(1) the method Raw of cyclopentanone is prepared (as hexanodioic acid with tradition, cyclopentenes etc.) finally derive from the fossil resource such as coal, oil difference, in method provided by the invention, raw materials used furfural is prepared by acidolysis by agricultural waste (corn cob, cotton seed hulls, bagasse etc.), and this production process achieves industrialization.Namely raw material furfural is renewable, does not rely on fossil resource.Therefore adopting furfural to be the method that cyclopentanone prepared by raw material, is a continuable variation route;
(2) in method provided by the invention, furfural is converted into cyclopentanone and carries out in water medium.Water is the inexpensive abundant green solvent of nature, and the present invention adopts water consumption substitution organic solvent, has both been conducive to reducing production cost, is also conducive to environment protection;
(3) raw material furfural and product cyclopentanone are carbon five compound, do not have the loss of carbon in reaction process, have higher Atom economy.Conversion from furfural to cyclopentanone both can a step complete in a kettle., also can realize in fixed-bed reactor, not need isolation of intermediate products, and the yield of cyclopentanone can reach 99%.Compared with hexanodioic acid preparation method, greatly reduce from final raw material to the reactions steps of cyclopentanone, this had both been conducive to reducing costs, and was also conducive to the yield improving cyclopentanone.
In a word, whole production process environmental protection, has higher economic and social benefit, is a new way preparing cyclopentanone, has higher industrial prospect.
Accompanying drawing explanation
Fig. 1 is the route that fossil resources produces cyclopentanone.
Fig. 2 is the route that biomass resource produces cyclopentanone.
Fig. 3 is Au/TiO in embodiment 5
2the reaction mechanism figure of catalyst system.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1, ferric oxide load gold catalyst is prepared by coprecipitation method.
By 0.468gHAuCl
44H
2o, 12.65gFe (NO
3)
39H
2o, 0.5L water drops in 1L beaker, and to instill concentration under 80 DEG C of agitation conditions be the sodium hydroxide solution of 0.2M is about 8 to pH, continues stirring 30 minutes, by sedimentation and filtration, is washed with distilled water to without Cl
-, vacuum-drying 12 hours, finally retort furnace roasting 4 hours at 300 DEG C.After cooling, obtained catalyzer, is expressed as Au/Fe
2o
3.
Embodiment 2, titanium oxide, aluminum oxide, magnesium oxide, cerium oxide, niobium oxides load gold catalyst are prepared by sodium hydroxide deposition-precipitation.
By 0.104gHAuCl
44H
2o, 0.5L water drops in 1L beaker, and to instill concentration under 80 DEG C of agitation conditions be the sodium hydroxide solution of 0.2M is about 7 to pH, drops into 5gTiO
2or Al
2o
3or CeO
2, continue stirring at 80 DEG C 2 hours, by sedimentation and filtration, be washed with distilled water to without Cl-, vacuum-drying 12 hours, finally retort furnace roasting 4 hours at 300 DEG C.After cooling, obtained catalyzer, is expressed as Au/TiO
2, Au/Al
2o
3, Au/MgO, Au/CeO
2or Au/Nb
2o
5.
Embodiment 3, zirconium white, silicon oxide, H-ZSM-5 molecular sieve, the molecular sieve carried Au catalyst of HY are prepared by ammoniacal liquor deposition-precipitation.
By 0.104gHAuCl
44H
2o, 0.5L water drops in 1L beaker, drops into 5gZrO
2or SiO
2, to instill concentration under agitation condition be the ammonia soln of 0.26M is about 9 to pH, continues stirring 8 hours, by sedimentation and filtration, be washed with distilled water to without Cl under room temperature
-, vacuum-drying 12 hours, finally retort furnace roasting 4 hours at 300 DEG C.After cooling, obtained catalyzer, is expressed as Au/ZrO
2, Au/SiO
2, Au/H-ZSM-5 or Au/HY.
Embodiment 4, other load type metal catalysts preparation except Au.
Take 0.664gH
2ptCl
69H
2o, 0.420gPdCl
2, 0.508gRhCl
3, 0.646gRuCl
33H
2o, 0.670gH
2irCl
66H
2o drops in 5 100mL beakers respectively, then adds 5gTiO respectively
2with 20mL water, stir careful evaporate to dryness in 80 DEG C of water-baths, the sample of gained dries 12 hours in 100 DEG C of baking ovens, is proceeded to by solid at 350 DEG C of not kiln roastings 2 hours of getting down from horse in crucible, then at 5%H
2in/Ar air-flow at 300 DEG C after reductase 12 hour.After cooling, obtained catalyzer, is expressed as Pt/TiO
2, Pd/TiO
2, Rh/TiO
2, Ru/TiO
2, Ir/TiO
2.
Embodiment 5, weighs catalyzer 0.1g, 0.5g furfural in embodiment 1-4 respectively, drops into and fills in the 50mL stainless steel autoclave of 10mL water, then use air in hydrogen exchange autoclave, be filled with 4MPa hydrogen, temperature in the kettle is risen to 160 DEG C, react 1 hour.Product gas chromatogram fixative measures, and internal standard substance is durol.Furfural transformation efficiency, cyclopentanone selectivity is in table 1.Wherein Au/TiO
2the reaction mechanism of catalyst system is shown in accompanying drawing 3.
Table 1
。
Embodiment 6, adopts the Au/TiO in embodiment 5
2catalyzer.Catalyst preparing is both embodiment 2, changes the concentration of temperature of reaction, reaction pressure and reactant furfural, the results are shown in Table 2.
Table 2
。
Embodiment 7, weighs catalyst A u/TiO in embodiment 1
2quality 0.1g, furfural 0.5g, drop into and fill in the 50mL stainless steel autoclave of 10mL water, then use air in hydrogen exchange autoclave, be filled with 4MPa synthetic gas (H
2/ CO=1,2,3,4,5), temperature in the kettle is risen to 160 DEG C, reacts 1 hour.Product gas chromatogram fixative measures, and internal standard substance is durol.Furfural transformation efficiency is 100%, and cyclopentanone selectivity is 99%.
Embodiment 8, weighs catalyst A u/TiO in embodiment 1
2quality 0.1g, furfural 0.5g, and 10mL contains the aqueous solution (water/ethanol=1,2,3 of a certain amount of ethanol, 4,5), drop in 50mL stainless steel autoclave, then use air in hydrogen exchange autoclave, be filled with 4MPa hydrogen, temperature in the kettle risen to 160 DEG C, react 1 hour.Product gas chromatogram fixative measures, and internal standard substance is durol.
Embodiment 9, weighs catalyst A u/TiO in embodiment 1
2quality 0.1g, furfural 0.5g, and 10mL contains the aqueous solution (water/acetone=1,2,3 of a certain amount of acetone, 4,5), drop in 50mL stainless steel autoclave, then use air in hydrogen exchange autoclave, be filled with 4MPa hydrogen, temperature in the kettle risen to 160 DEG C, react 1 hour.Product gas chromatogram fixative measures, and internal standard substance is durol.
Embodiment 10, joins in the autoclave of 10L, by 192g(2 mole by 1 premium on currency) furfural adds in reactor, then adds the 1%Au/TiO in 10g embodiment 5
2, sealed reactor, with air in the complete replacement reaction kettle of hydrogen, after inflation/deflation 3 times, again passes into hydrogen or synthetic gas to 4MPa, is heated to temperature of reaction 160 DEG C, reacts 10 hours.Abundant reaction, cools after question response completes, and by reacting liquid filtering, filter cake is catalyzer, and recyclable continuation is applied mechanically, and impouring 5L ethyl acetate in filtrate, abundant extracting and separating, gets organic phase atmospheric distillation, obtain cyclopentanone.Show through gas chromatography combined with mass spectrometry analyser result, the transformation efficiency of furfural is 100%, and cyclopentanone yield is 99%.
Embodiment 11, in fixed-bed reactor, furfural is converted into the operation method of cyclopentanone is that, with 5% furfural aqueous solution for raw material, the catalyzer loaded in fixed-bed reactor is the 1%Au/TiO in 1g embodiment 5
2, temperature of reaction selects 160 DEG C, reaction pressure 4MPa, and hydrogen/furfural mole number is 150/1, and the mass space velocity of furfural is 0.5h
-1, the transformation efficiency of furfural and the selectivity of product are by gas chromatographic detection, and after reacting 2,6,20,50,100h respectively, experimental result is in table 3.
Table 3
。
Embodiment 12, is mixed to get reaction stoste by 0.5g acetyl furan, 10mL water.Reaction stoste is joined in the autoclave of 50mL, and adds the 1%Au/TiO in 0.1g embodiment 5
2.After the air in hydrogen exchange autoclave, pressure in still is risen to 4MPa, reactor heating to 160 DEG C, reaction 4h.The transformation efficiency of reactant and the selectivity of product are by gas chromatographic detection, and the transformation efficiency of acetyl furan is the selectivity of 98%, 2-methyl-cyclopentanone is 97%.
Embodiment 13, is mixed to get reaction stoste by 0.5g5-methyl furfural, 10mL water.Reaction stoste is joined in the autoclave of 50mL, and adds the 1%Au/TiO in 0.1g embodiment 5
2.After the air in hydrogen exchange autoclave, pressure in still is risen to 4MPa, reactor heating to 160 DEG C, reaction 4h.The transformation efficiency of reactant and the selectivity of product are by gas chromatographic detection, and the transformation efficiency of acetyl furan is the selectivity of 98%, 3-methyl-cyclopentanone is 97%.
Embodiment 14, is mixed to get reaction stoste by 0.5g propionyl furans, 10mL water.Reaction stoste is joined in the autoclave of 50mL, and adds the 1%Au/TiO in 0.1g embodiment 5
2.After the air in hydrogen exchange autoclave, pressure in still is risen to 4MPa, reactor heating to 160 DEG C, reaction 4h.The transformation efficiency of reactant and the selectivity of product are by gas chromatographic detection, and the transformation efficiency of acetyl furan is the selectivity of 98%, 2-ethylcyclopentanone is 97%.
Embodiment 15, is mixed to get reaction stoste by 0.5g5-ethyl furfural, 10mL water.Reaction stoste is joined in the autoclave of 50mL, and adds the 1%Au/TiO in 0.1g embodiment 5
2.After the air in hydrogen exchange autoclave, pressure in still is risen to 4MPa, reactor heating to 160 DEG C, reaction 4h.The transformation efficiency of reactant and the selectivity of product are by gas chromatographic detection, and the transformation efficiency of acetyl furan is the selectivity of 98%, 3-ethylcyclopentanone is 97%.
Claims (8)
1. one kind is the method that cyclopentanone prepared by raw material with biomass resource, it is characterized in that, to be derived from the furfural of biomass as raw material, under metal load type catalyst exists, take hydrogen-containing gas as reductive agent, through hydrogenation-rearrangement reaction in autoclave or fixed-bed reactor, a step obtains cyclopentanone.
2. method according to claim 1, is characterized in that, described metal load type catalyst, and its carrier is selected from Nb
2o
5, H-ZSM-5 molecular sieve, HY molecular sieve, Fe
2o
3, ZrO
2, Al
2o
3, SiO
2, CeO
2, MgO, gac, and the TiO of various crystal formation
2; Active ingredient is selected from Au, Pt, Ru, Rh, Pd, Ir, Ni, Cu, in one; Activity component load quantity is the 0.1-5% of catalyzer total amount.
3. method according to claim 2, is characterized in that, described hydrogenation-rearrangement reaction is reaction medium with water, and furfural aqueous solution concentration is 1-30%, and reaction pressure is 0.5-8MPa, and temperature of reaction is 80-180 DEG C.
4. method according to claim 3, is characterized in that, the concrete operations carrying out reacting in autoclave are: in furfural aqueous solution, add a certain amount of catalyzer, rise to appointment temperature of reaction after gas displacement; Then, be filled with hydrogen or synthetic gas to specifying reaction pressure, stirring reaction 0.1-12 hour, namely obtains cyclopentanone and other converted products.
5. method according to claim 3, it is characterized in that, the concrete operations carrying out reacting in fixed-bed reactor are: by catalyst filling to the constant temperature zone in fixed-bed reactor, by furfural aqueous solution, the fixed-bed reactor that catalyzer is housed are entered with hydrogen or synthetic gas, reacting, obtain the mixture flow of cyclopentanone, water and hydrogen, obtaining pure cyclopentanone through being separated.
6. according to the method one of claim 1-5 Suo Shu, it is characterized in that, adding in described reaction system has solubility promoter.
7. method according to claim 6, is characterized in that, described solubility promoter is one or more in organic solvent ethanol, methyl alcohol, acetone, butanols, dioxane.
8. according to the method one of claim 1-5 Suo Shu, it is characterized in that, described hydrogen-containing gas is hydrogen or any H
2the synthetic gas of/CO ratio.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6092234A (en) * | 1983-10-26 | 1985-05-23 | Sumitomo Chem Co Ltd | Production of cyclopentanone |
| US7425657B1 (en) * | 2007-06-06 | 2008-09-16 | Battelle Memorial Institute | Palladium catalyzed hydrogenation of bio-oils and organic compounds |
| CN102807483A (en) * | 2012-08-17 | 2012-12-05 | 中国科学技术大学 | Method for preparing cyclopentanone and/or cyclopentanol by furfural or furfuryl alcohol |
| CN103159606A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Method for preparing cyclopentanone by using furaldehyde as raw material |
| CN104069886A (en) * | 2014-07-11 | 2014-10-01 | 东南大学 | Preparation method and use of catalyst for preparation of cyclopentanone through hydrogenation of water phase furfural |
-
2015
- 2015-10-22 CN CN201510687358.0A patent/CN105330523A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6092234A (en) * | 1983-10-26 | 1985-05-23 | Sumitomo Chem Co Ltd | Production of cyclopentanone |
| US7425657B1 (en) * | 2007-06-06 | 2008-09-16 | Battelle Memorial Institute | Palladium catalyzed hydrogenation of bio-oils and organic compounds |
| CN103159606A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Method for preparing cyclopentanone by using furaldehyde as raw material |
| CN102807483A (en) * | 2012-08-17 | 2012-12-05 | 中国科学技术大学 | Method for preparing cyclopentanone and/or cyclopentanol by furfural or furfuryl alcohol |
| CN104069886A (en) * | 2014-07-11 | 2014-10-01 | 东南大学 | Preparation method and use of catalyst for preparation of cyclopentanone through hydrogenation of water phase furfural |
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