CN102658131A - Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst - Google Patents
Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst Download PDFInfo
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Abstract
The invention provides a ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and a preparation method for the ruthenium-based catalyst. The ruthenium-based catalyst comprises an active ingredient and a catalyst carrier, wherein the active ingredient is ruthenium and accounts for 1 to 10 weight percent and the rest is the catalyst carrier; or the ruthenium-based catalyst comprises an active ingredient, a cocatalyst and a catalyst carrier, wherein the cocatalyst is a group VIII element or a group IB element and accounts for not more than 10 weight percent, the active ingredient is ruthenium and accounts for 1 to 5 weight percent, and the rest is the catalyst carrier. An acetylpropionic acid solution can be completely converted under the action of the ruthenium-based catalyst at the temperature of between 70 and 120DEG C under the pressure of 1 to 5MPa, and the selectivity of the gamma-valerolactone is up to 100 percent. The invention has the advantages that the catalyst is prepared by a green synthesis process, the process is simple and easy to operate, the product selectivity is high, the production process is high in safety, environmental pollution is avoided, and the catalyst has potential industrial application value.
Description
Technical field
The invention belongs to living beings transformation technology field, relate to a kind of preparation method and technical process thereof that is used for the supported ruthenium catalyst of biomass-based levulic acid system gamma-valerolactone.
Background technology
Along with the worsening shortages of fossil energy in the global range and the crisis of ecological deterioration, make development of new and eco-friendly regenerative resource and chemicals become the hot fields of current scientific research.Living beings receive increasing concern as a kind of renewable resource of green.Living beings are a kind of renewable resources that are converted into liquid fuel and carbon back chemicals, and enormous amount is cheap, biodegradable, and is with its conversion, significant in the environmental friendliness medium.In addition, biomass resource still is a kind of resource of neutral carbon, and more and more serious environmental problems such as " greenhouse effects " has immeasurable meaning for solving now.
In biomass energy, gamma-valerolactone is acknowledged as a kind of good energy substance that is used for global accumulating, compares with traditional liquid fuel, and gamma-valerolactone has the following advantages:
1, hypotoxicity: be present in the fruit at nature, be widely used in field of food industry, its LD
50Be 8800mg/kg, toxicity is less than ethanol.
2, high storing and transporting security property: higher boiling (207 ℃), low melting point (31 ℃), flash-point (96 ℃), low volatility (80 ℃ of 3.5KPaat), special odor are convenient to find to leak, and are beneficial to the long-distance transport of gamma-valerolactone, and dissolve each other with water and to be beneficial to biodegradation.
3, being suitable as vehicle fuel uses: No. 95 gasoline property that add the 10v/v% gamma-valerolactone are with to add same volume of ethanol gasoline property closely similar, and gamma-valerolactone can not generate azeotropic mixture with water, separate the energy consumption of distilling well below ethanol.
The levulic acid hydro-conversion is that gamma-valerolactone is one of committed step of living beings conversion.Patent WO 02074760 and US0055270 are illustrated in 4.83～5.52MPa Hydrogen Vapor Pressure; Under 140～160 ℃ the reaction condition; Levulic acid can reduce under the effect of loaded noble metal catalyst and generate gamma-valerolactone; But under the condition of high temperature, high pressure, accomplish, reaction condition is very harsh.
Patent CN 101376650A is to be hydrogen source with formic acid, and as reducing agent, reaction temperature is 100～200 ℃; Using the homogeneous phase ruthenium catalyst, is to exist with liquid form, is unfavorable for catalyst recovery; And exist the reaction time to reach 12 hours, shortcoming such as the yield of gamma-valerolactone is on the low side.Therefore use Green Chemical Technology, choose suitable catalyst, developing levulic acid, efficiently to make the technical process of gamma-valerolactone be inevitable choice.
Summary of the invention
The invention provides the ruthenium-based catalyst that a kind of solvent-free microwave auxiliary heat solution preparation is used for levulic acid system gamma-valerolactone; Be with precious metals complex and catalyst carrier ground and mixed; Through the auxiliary pyrolysis of microwave in the inert atmosphere, form stable carried noble metal nanocatalyst.The solvent-free microwave assistant heating changes reaction mechanism, has reduced reaction activity, has improved solid-phase reaction velocity.The key for preparing equal dispersible granule is to make reaction system to produce crystal seed explosively, and makes all crystal seeds grow into homogeneous granules synchronously.Heating using microwave makes in the system temperature basically identical everywhere, helps the formation of dispersed system.
The present invention proposes a kind of method for preparing gamma-valerolactone with levulic acid; To overcome the defective on the prior art, compared with present technology, adopt catalyst provided by the invention to be used for the levulic acid hydrogenation reduction; The levulic acid conversion ratio is high, and the selectivity of gamma-valerolactone and yield are high.
Technical scheme of the present invention is following:
A kind ofly being used for the ruthenium-based catalyst that levulic acid prepares gamma-valerolactone, comprising active component and catalyst carrier, is the ruthenium-based catalyst of active component with the ruthenium, and mass percent is 1～10wt%; Remainder is catalyst carrier or ruthenium-based catalyst, comprises active component, co-catalyst and catalyst carrier, and co-catalyst is group VIII element or I B family element, and its mass percent is for being not more than 10wt%; With the ruthenium is active component, and mass percent is 1～5wt%; Remainder is a catalyst carrier.
Ruthenium-based catalytic agent carrier of the present invention is raw material of wood-charcoal material, oxide or molecular sieve, and wherein the raw material of wood-charcoal material comprises active carbon, carbon black, CNT or charcoal nanofiber; Oxide carrier comprises aluminium oxide, silica, titanium oxide or their binary mixed oxide; Described molecular sieve carrier is a MCM series, ZSM is serial, SBA is serial or faujasite.
The preparation method of ruthenium-based catalyst of the present invention is a solvent-free microwave auxiliary heat solution; Concrete steps are: with the metal precursor (carbonyl-complexes or acetylacetonate compound) and the abundant ground and mixed of carrier of ruthenium and co-catalyst, pack the mixture after grinding in fixed bed or the fluidized-bed reactor into; Fixed bed reactors are as for the bottom, with reducing gas purging and maintenance reducing atmosphere with reactant; Fluidized-bed reactor is that the uniform sample of ground and mixed is placed on the sieve plate, purges from bottom to top with reducing gas, makes mix powder fluidisation in pipe; Under reducing atmosphere, adopt microwave-heating, drop to room temperature in inertia or reducing atmosphere then, promptly get the supported ruthenium catalyst of the levulic acid system of being applied to gamma-valerolactone.
The preparation method of ruthenium-based catalyst of the present invention also can be traditional infusion process, and the metal precursor of ruthenium and co-catalyst is dissolved in the solution, and carrier is mixed with above-mentioned solution, stirs the vacuum dried overnight.With the hydrogen heating reduction, argon gas atmosphere is cooled to room temperature with the gained sample, gets final product to such an extent that be applied to the supported ruthenium catalyst of levulic acid system gamma-valerolactone.
Ruthenium-based catalyst of the present invention, in the levulic acid material liquid, the levulic acid mass percent is 1～30%; Charge into 1～5MPa hydrogen; Add 1～5% the ruthenium-based catalyst press the levulic acid mass percent, with the autoclave sealing, controlling reaction temperature is 70～120 ℃; Reacted 1～10 hour, and collected product liquid.
Activity of such catalysts provided by the invention can be used following method test:
In 50mL stainless steel autoclave (as shown in Figure 1), investigate catalyst activity.The ruthenium-based catalyst of levulic acid aqueous feed solution and 1 unit is put into still.Catalyst needs the preliminary treatment reduction: at H
2Heating reduction obtains the catalyst of fresh attitude to remove surface passivation layer under the atmosphere.Autoclave sealing back is with air in the hydrogen exchange still three times, in still, fills hydrogen to certain pressure then and tests leakage.Levulic acid prepares the reaction of gamma-valerolactone, and the levulic acid mass percent is 1～30%, and is preferred 10～20%, and temperature is 70～120 ℃, and preferred 80～100 ℃, Hydrogen Vapor Pressure 1～5MPa, preferred 2～4MPa, and begin to stir, speed is 600r/min.Product adopts gas-chromatography to analyze, and measures the conversion ratio of levulic acid, the productive rate and the selectivity of product.
The present invention overcomes the defective on the prior art, is green synthesis process, and it is low to have a cost, and technology is simple, easy operating, and product selectivity is high, and the production process security performance is good, and the advantage of non-environmental-pollution has potential industrial application value.
Description of drawings
The employed autoclave sketch map of Fig. 1 levulic acid system gamma-valerolactone
The specific embodiment
Below in conjunction with instance the present invention is done further description, but invention is not limited.
Embodiment 1～4: Preparation of Catalyst
The auxiliary pyrolysis of microwave prepares 5wt%Ru/AC, 5wt%Ru/CNT, 5wt%Ru/FCNT and 5wt%Ru/ γ-Al
20
3Catalyst.Take by weighing 0.0105g (5wt%) ten dicarbapentaborane, three rutheniums and 0.1g carrier (CNT after cocoanut active charcoal, CNT, the oxidation processes), mix, in the fluidised reaction tube of in agate mortar, packing into behind the grinding 20min; Argon purge 2h, microwave 800W heats 5min, and the argon gas flow velocity is in the reaction: 50mL/min; Be cooled to room temperature in the argon gas atmosphere; About 12h can obtain supported ruthenium catalyst, lists in that sequence number is 1～4 in the table 1.
Embodiment 5: Preparation of Catalyst
The auxiliary pyrolysis preparation of microwave (2wt%Ru+2wt%Pt)/CNT catalyst.Take by weighing 0.0084g (2wt%) ten dicarbapentaborane three rutheniums, 0.0081g (2wt%) acetylacetone,2,4-pentanedione platinum and the untreated CNT of 0.2g, mix, in the fluidised reaction tube of in agate mortar, packing into behind the grinding 20min; Hydrogen purge 2h, microwave 800W heats 5min, and the hydrogen in reaction flow velocity is: 50mL/min; Be cooled to room temperature in the argon gas atmosphere; About 12h can obtain supported ruthenium platinum bimetallic catalyst, lists in that sequence number is 5 in the table 1.
Embodiment 6: Preparation of Catalyst
The auxiliary pyrolysis preparation of microwave (2wt%Ru+2wt%Pd)/AC catalyst.Take by weighing 0.0168g (2wt%) ten dicarbapentaborane three rutheniums, 0.0229g (2wt%) palladium acetylacetonate and 0.4g cocoanut active charcoal, mix, in the fluidised reaction tube of in agate mortar, packing into behind the grinding 20min; Hydrogen purge 2h, microwave 800W heats 3min, and the hydrogen in reaction flow velocity is: 50mL/min; Be cooled to room temperature in the argon gas atmosphere; About 12h can obtain supported ruthenium platinum bimetallic catalyst, lists in that sequence number is 6 in the table 1.
Embodiment 7: Preparation of Catalyst
Tradition immersion process for preparing 5wt%Ru/ γ-Al
2O
3Catalyst.Take by weighing 0.1897gRuCl
33H
2O is dissolved in the 10mL deionized water, and the 1.5g activated alumina is mixed with above-mentioned solution, stirs 100 ℃ of dried overnight of vacuum.The gained sample with the heating rate to 400 of 5 ℃/min ℃, was kept 4 hours, and argon gas atmosphere is cooled to room temperature, get final product Ru/ γ-Al
2O
3Catalyst lists in that sequence number is 7 in the table 1.
Catalyst among table 1. embodiment 1～6
| Embodiment | Sample number into spectrum | Catalyst is formed | The preparation method |
| 1 | 1 | 5％Ru/AC | Novel microwave auxiliary heat solution |
| 2 | 2 | 5％Ru/CNT | Novel microwave auxiliary heat solution |
| 3 | 3 | 5％Ru/FCNT | Novel microwave auxiliary heat solution |
| 4 | 4 | 5％Ru/γ-Al 2O 3 | Novel microwave auxiliary heat solution |
| 5 | 5 | (2％Ru+2％Pt)/CNT | Novel microwave auxiliary heat solution |
| 6 | 6 | (2％Ru+2％Pd)/AC | Novel microwave auxiliary heat solution |
| 7 | 7 | Ru/γ-Al 2O 3 | The tradition infusion process |
Embodiment 8～14: different catalysts prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g 1～No. 6, under hydrogen atmosphere, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL, the levulic acid aqueous solution and the above-mentioned preprocessed catalyst of 0.1g/mL (mass fraction 10%), sealing charges into hydrogen to 2MPa, and 600r/min stirs, and is warming up to 100 ℃, keeps 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 1～7 in the table 2.
Embodiment 15～19: the differential responses solvent prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g No. 1, under hydrogen 50mL/min purges, carry out temperature programming, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL; Levulic acid cyclohexane solution of (0.1g/mL mass fraction 10%) (methyl phenyl ethers anisole solution, methanol solution, ethanolic solution or acetone soln) and above-mentioned preprocessed catalyst; Sealing charges into hydrogen to 2MPa, and 600r/min stirs; Be warming up to 100 ℃, kept 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 8～12 in the table 2.
Embodiment 20～22: the differential responses temperature prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g No. 1, under hydrogen 50mL/min purges, carry out temperature programming, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL, the levulic acid aqueous solution and the above-mentioned preprocessed catalyst of 0.1g/mL (mass fraction 10%), sealing charges into hydrogen to 2MPa, and 600r/min stirs, and is warming up to 70,80 or 90 ℃, keeps 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 13～15 in the table 2.
Embodiment 23～24: differential responses pressure prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g No. 1, under hydrogen atmosphere, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL, the levulic acid aqueous solution and the above-mentioned preprocessed catalyst of 0.1g/mL (mass fraction 10%), sealing charges into hydrogen to 1MPa or 3MPa, and 600r/min stirs, and is warming up to 90 ℃, keeps 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 16～17 in the table 2.
Embodiment 25～26: the differential responses substrate concentration prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g No. 1, under hydrogen atmosphere, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL, the levulic acid aqueous solution and the above-mentioned preprocessed catalyst of 0.15g/mL (mass fraction 15%) or 0.2g/mL (mass fraction 20%), sealing; Charge into hydrogen to 2MPa; 600r/min stirs, and is warming up to 90 ℃, keeps 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 18～19 in the table 2.
Embodiment 27: high reactant concentration high pressure prepares the reaction test of gamma-valerolactone to levulic acid
Get catalyst 0.1000g No. 1, under hydrogen atmosphere, be warming up to 250 ℃, kept 2 hours with 5 ℃/min.In the 50mL autoclave, add 25mL, the levulic acid aqueous solution and the above-mentioned preprocessed catalyst of 0.2g/mL (mass fraction 20%), sealing charges into hydrogen to 4MPa, and 600r/min stirs, and is warming up to 90 ℃, keeps 2 hours.Carry out the intermittent sampling analysis in the course of reaction.Concrete testing result lists in that sequence number is 18～19 in the table 2.
Testing result compares the (reaction time: 2h) among each embodiment of table 2.
Through above-mentioned each embodiment interpretation of result, prove the good catalytic performance of ruthenium-based catalyst prepared among the present invention for the reaction of levulic acid hydrogenation system gamma-valerolactone, reaction can be at 80 ℃; Carry out under the 2MPa temperate condition; And with water is reaction dissolvent, reduces production costs, and greatly reduces environmental pollution; Green friendly, have potential industrial application value.
Claims (7)
1. one kind is used for the ruthenium-based catalyst that levulic acid prepares gamma-valerolactone, comprises active component and catalyst carrier, it is characterized in that: be the ruthenium-based catalyst of active component with the ruthenium, mass percent is 1～10wt%; Remainder is a catalyst carrier.
2. ruthenium-based catalyst as claimed in claim 1 comprises active component, co-catalyst and catalyst carrier, it is characterized in that: co-catalyst is group VIII element or I B family element, and its mass percent is for being not more than 10wt%; With the ruthenium is active component, and mass percent is 1～5wt%; Remainder is a catalyst carrier.
3. according to claim 1 or claim 2 ruthenium-based catalyst, it is characterized in that: catalyst carrier is raw material of wood-charcoal material, oxide or molecular sieve.
4. ruthenium-based catalyst as claimed in claim 3, its catalyst carrier is characterised in that:
Described raw material of wood-charcoal material comprises active carbon, carbon black, CNT or charcoal nanofiber;
Described oxide comprises aluminium oxide, silica, titanium oxide or their binary mixed oxide;
Described molecular sieve is a MCM series, ZSM is serial, SBA is serial or faujasite.
5. according to claim 1 or claim 2 ruthenium-based catalyst, it is characterized in that: ruthenium-based catalyst is prepared by solvent-free microwave auxiliary heat solution.
6. claim 1,2 or 4 described ruthenium-based catalysts are used for levulic acid and prepare gamma-valerolactone, it is characterized in that: will contain mass percent is in the material liquid adding autoclave of 1～30% levulic acid; Charge into 1～5MPa hydrogen; Add 1～5% the ruthenium-based catalyst press the levulic acid mass percent, with the autoclave sealing, controlling reaction temperature is 70～120 ℃; Reacted 1～10 hour, and collected product liquid.
7. claim 3 or 5 described ruthenium-based catalysts are used for levulic acid and prepare gamma-valerolactone, it is characterized in that: will contain mass percent is in the material liquid adding autoclave of 1～30% levulic acid; Charge into 1～5MPa hydrogen; Add 1～5% the ruthenium-based catalyst press the levulic acid mass percent, with the autoclave sealing, controlling reaction temperature is 70～120 ℃; Reacted 1～10 hour, and collected product liquid.
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| CN105289592A (en) * | 2015-11-19 | 2016-02-03 | 中科合成油技术有限公司 | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation |
| CN106582666A (en) * | 2016-12-21 | 2017-04-26 | 大连理工大学 | Gamma-valerolactone hydrogenation catalyst, preparation method thereof and method for preparation of 1,4-pentanediol and 2-methyltetrahydrofuran |
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| CN109569589A (en) * | 2018-12-10 | 2019-04-05 | 郑州师范学院 | A kind of levulic acid adds hydrogen gamma-valerolactone M-B@Al2O3Catalyst and its preparation method and application |
| CN109569589B (en) * | 2018-12-10 | 2021-10-26 | 郑州师范学院 | Method for preparing gamma-valerolactone M-B @ Al by hydrogenation of levulinic acid2O3Catalyst, preparation method and application thereof |
| CN109999799A (en) * | 2019-05-28 | 2019-07-12 | 云南大学 | Preparation, performance test methods and the application of the ruthenium catalyst of loaded nano containing zirconium |
| CN109999799B (en) * | 2019-05-28 | 2020-09-18 | 云南大学 | Preparation method, performance test method and application of zirconium-containing supported nano ruthenium catalyst |
| CN114163404A (en) * | 2021-12-24 | 2022-03-11 | 兰州大学 | Method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
| CN115282957A (en) * | 2022-08-17 | 2022-11-04 | 青岛科技大学 | Method for catalyzing levulinic acid hydrogenation reaction by alkali lignin-based carbon-loaded ruthenium |
| WO2024160745A1 (en) | 2023-02-01 | 2024-08-08 | Eco-Oil Miljöbränslen I Sverige AB | Process for continuous hydrogenation of aqueous levulinic acid to gamma-valerolactone and its tandem conversion to high octane gasoline range hydrocarbons |
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