CN101805316A - Method for preparing Gamma-valerolactone by using supported iridium catalyst - Google Patents
Method for preparing Gamma-valerolactone by using supported iridium catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical engineering energy sources, in particular to a method for preparing Gamma-valerolactone by using a supported iridium catalyst. The catalyst used in the invention is prepared by adopting a deposition precipitation method, a sol gel method and a common dipping method, and the supported iridium catalyst with a nanometer size is prepared by taking an oxide, a hydroxide, active carbon and insoluble salt as carriers, depositing iridium on the carriers, baking and deoxidizing. The supported iridium catalyst has the characteristics of high activity, little iridium grains and good stability. By adopting the method, hydrogenation reduction of levulinic acid can be realized under a mild condition to prepare Gamma-valerolactone, thereby the defect that the traditional method for producing Gamma-valerolactone needs a high-temperature and high-pressure process is overcome, and the security and the economy of a production system are improved. The catalyst can be easily recovered and recycled, and keep higher activity after repeated use, thereby having higher industrial application value.
Description
Technical field
The invention belongs to the chemical industry energy technology field, being specially adapted to biomass is the field of raw material production vehicle fuel and high added value chemical, is specifically related to a kind of method for preparing γ-Wu Neizhi with supported iridium catalyst catalytic reduction levulinic acid.
Background technology
Energy dilemma is the huge challenge that the middle of this century is about to face.Coal resources still can be exploited 100 years, oil 30～40 years, Sweet natural gas 50～60 years.Ecological crisis is the huge challenge that current society has faced.Can alternate be the reproducible energy and new forms of energy subsequently, relatively more real be renewable energy source at present.In renewable energy source, comprise wind energy, sun power, bioenergy, water power.What really can carry out extensive industrialization development in 30 or five ten years at current and expected future is biomass energy, and it is the most potential energy.The joint investigation in 2005 of the USDOE and the Ministry of Agriculture is reported, farming, forestry layout is not being done under the cataclysmal prerequisite 30% of the alternative U.S crude consumption of the annual 1300000000 tons of cellulose biomass producing of the U.S..
γ-Wu Neizhi is a kind of very high biomass-based hardware and software platform compound of potential using value that has, and it not only can be produced vehicle fuel and can also be used to the very high chemical of production added value.In itself, owing to be that natural product has unique fruit aroma, therefore obtained using widely, when the amount with 0.0005-0.002% joins the plumpness that can increase cigarette in the cigarette shreds, mellow and full sense, fluency in foodstuffs industry; In addition, since its have low melting point (31 ℃), high boiling point (207 ℃), lightning (96 ℃) and make it that good application future arranged aspect the solvent with characteristics that water dissolves each other; Moreover quite similar with the character of the alcoholic acid gasoline that adds equivalent amount when joining a certain amount of γ-Wu Neizhi in the gasoline, and γ-Wu Neizhi can not form azeotrope with water, and energy consumption is well below ethanol during distillation; Dumesic research group (science, 2010,327,1110) finds can directly prepare the alkene that contains 8 carbon by γ-Wu Neizhi and substitute transport fuel gasoline by open loop, decarboxylation, oligomerisation recently, has solved present problem of energy crisis.
The production process of γ-Wu Neizhi is a raw material with biomass-based levulinic acid mainly at present, and catalyst system therefor is a ruthenium-based catalyst, obtains by heterogeneous and homogeneous hydrogenation, and is as shown below:
Patent WO 02074760 and US0055270 show levulinic acid under the effect of loaded noble metal catalyst, when hydrogen pressure is 700～800psi, can reduce the generation γ-Wu Neizhi when temperature of reaction is 140～160 ℃, and productive rate reaches about 97%.Patent US Patent 0254384 points out in supercritical co that with the carried noble metal for catalyzer hydrogen is reductive agent, the productive rate of this reaction can reach more than 99%.Patent CN 101376650 reported with formic acid be hydrogen source when temperature of reaction is 100～200 ℃, prepare γ-Wu Neizhi by the ruthenium-based catalyst homogeneous hydrogenation, productive rate can reach 99.44%.In sum, the problem that exists severe reaction conditions (high temperature, high pressure) or catalyzer to be difficult to reclaim when preparing γ-Wu Neizhi with current technology, finally cause the production cost height, of poor benefits, security is low.
Summary of the invention
The present invention proposes a kind ofly to prepare the method for γ-Wu Neizhi with supported iridium catalyst, to overcome the drawback of prior art, meets the requirement of Green Chemistry, and better industrial application prospect is arranged.
The used catalyzer of the present invention is the loaded nano iridium catalyst, and the nanometer iridium uniform particles of metallic state is distributed on the carrier, and nanometer iridium particle grain size is a nano level, and with carrier very strong interaction is arranged.This catalyzer can realize that under relatively mild condition the levulinic acid catalytic reduction prepares γ-Wu Neizhi, catalyzer still can reach more than 99% through the productive rate of reusing back γ-Wu Neizhi more than 5 times, has embodied the high efficiency and the anti-usability of supported iridium catalyst.
In autoclave, add solvent and a certain amount of reactant levulinic acid, the iridium catalyst that adds the 0.05-1.0mol% that presses the levulinic acid molar weight then, after mixing, autoclave is sealed, charge into the hydrogen of 0.1～5.0MPa, control reaction temperature is 25～200 ℃, reacts 1～20 hour, promptly obtains the target product γ-Wu Neizhi.Product analysis is analyzed by gas chromatography-mass spectrum.
The used supported iridium catalyst of the present invention adopts deposition-precipitation method, sol-gel method and common immersion process for preparing.After the metal iridium of nominal price is deposited to carrier surface, promptly obtain the load iridium catalyst 200 to 500 ℃ of reduction by sodium borohydride reduction or by hydrogen.
Described iridium is catalyst based to be various loaded catalysts, comprising: Ir/TiO
2, Ir/SiO
2, Ir/MgO, Ir/ZnO, Ir/Al
2O
3, Ir/CeO
2, Ir/BaSO
4, Ir/C etc.
The solvent of reaction can be an organic solvent commonly used such as dioxane, ether, ethanol, methyl alcohol, acetone, toluene, also can be ionic liquid and water, even under solvent-free condition, also can carry out, select the unimportant of what solvent, key is that selected solvent can not produce toxic action to catalyzer.
The recovery set of catalyzer is as follows with step: reacted mixed solution is taken out, and centrifugation goes out catalyzer, after washing, alcohol are washed several times, and drying.Dried catalyzer is directly tested next time, use 5 to 10 times repeatedly after, catalyzer has still kept original catalytic activity, has shown better industrial application prospect.
The present invention has following advantage:
1, the catalytic activity height of catalyzer, selectivity is good.
2, catalyzer can adopt the method for simple filtration to separate from reaction system after reaction, through recovering original catalytic activity after the washing drying, can be repeatedly used, and has shown high prospects for commercial application.
When 3, utilizing this catalyzer to carry out the levulinic acid hydrogenation, the reaction conditions gentleness, temperature of reaction and pressure use hydrogen to realize the greenization of reaction as hydrogen source far below other heterogeneous catalyst.
4, compare with homogeneous catalyst, heterogeneous catalyst has the characteristics of being convenient to recycle, and just can finalize the design to heterogeneous catalyst by the method that adds sizing agent and setting agent, and the heterogeneous catalyst after the moulding is convenient to directly carry out industry and is used.
The invention solves the existing process that γ-Wu Neizhi needs High Temperature High Pressure of producing, improved the security and and the economy of production system.Under the effect of supported iridium catalyst, be lower than 100 ℃ in temperature, pressure is lower than under the condition of 1.0MPa just can realize the levulinic acid hydrogenation.Used catalyzer just can directly use by simple process, has realized recycling of catalyzer.Because raw material levulinic acid of the present invention can be by comprising agricultural and forestry waste such as stalk, rice husk, corn stalk, grass, wood chip, bark or bagasse, the farm crop of carbohydrate containing such as potato, cassava, Ipomoea batatas, potato, sugarcane or beet, and the biomass of carbohydrate such as Mierocrystalline cellulose, starch, maltose, sucrose, fructose or glucose are raw material, utilize prior art to obtain through hydrolysis, the abundant raw material cost price is low cheap.Because the present invention has realized the upgrading of levulinic acid, therefore be to realize that further biomass fuel substitutes fossil oil, for biorefining provides intermediate raw material, and indicated a kind of good developing direction for production high added value chemical.
Embodiment
Describe the present invention below by embodiment, but content of the present invention is not limited thereto.
Embodiment 1～4:
The H that in the 50ml beaker, adds 5ml 10g/L
2IrCl
6Solution (in iridium) adds the 1g titania support after ultrasonic 30 minutes, room temperature dipping 2 hours, drying, after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour the target catalyzer.Reaction conditions: in autoclave, add the 10mL dioxane and make solvent, 0.5g levulinic acid and 0.05g catalyzer, autoclave is sealed, charge into the hydrogen of 1.0MPa, 80 ℃ were reacted 1,2,3,4 hour, finished the reaction postcooling to room temperature, slowly were decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Experimental result sees Table that sequence number is 1～4 in 1.
Embodiment 5～11:
The H that in the 50mL beaker, adds 5ml 10g/L
2IrCl
6Solution (in iridium) adds the 1g titania support after ultrasonic 30 minutes, room temperature dipping 2 hours, drying, after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour the target catalyzer.Reaction conditions: in autoclave, add the 10mL dioxane and make solvent, 0.5g levulinic acid and 0.05g catalyzer, autoclave is sealed, charge into the hydrogen of 1.0MPa, 80 ℃ were reacted 3 hours, finished the reaction postcooling to room temperature, slowly were decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Support of the catalyst can also be Al
2O
3, MgO, SiO
2, ZnO, CeO
2, gac, BaSO
4, concrete support of the catalyst and experimental result see Table that sequence number is 5～11 in 1.
Embodiment 12～17:
The H that in the 50mL beaker, adds 5ml 10g/L
2IrCl
6Solution (in iridium) adds the 1g titania support after ultrasonic 30 minutes, room temperature dipping 2 hours, drying, after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour the target catalyzer.Reaction conditions: add the 10mL solvent in autoclave, 0.5g levulinic acid and 0.05g catalyzer seal autoclave, charge into the hydrogen of 1.0MPa, 80 ℃ were reacted 3 hours, finished the reaction postcooling to room temperature, slowly be decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Reaction solvent can be commonly used organic solvent and water such as ether, ethanol, methyl alcohol, acetone, toluene, and experimental result sees Table that sequence number is 12～17 in 1.
Embodiment 18～20:
The H that in the 50mL beaker, adds 5ml 10g/L
2IrCl
6Solution (in iridium) adds the 1g titania support after ultrasonic 30 minutes, room temperature dipping 2 hours, drying, after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour the target catalyzer.Reaction conditions: in autoclave, add the 10ml dioxane and make solvent, 0.5g levulinic acid and 0.05g catalyzer, autoclave is sealed, charge into the hydrogen of 2.0MPa, 0.8MPa, 0.5MPa, 80 ℃ were reacted 3 hours, finished the reaction postcooling to room temperature, slowly were decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Experimental result sees Table that sequence number is 18～20 in 1.
Embodiment 21～25:
The H that in the 50mL beaker, adds 5mL 10g/L
2IrCl
6Solution (in iridium) adds the 1g titania support after ultrasonic 30 minutes, room temperature dipping 2 hours, drying, after the roasting under 400 ℃ of air atmospheres in 300 ℃ of hydrogen gas stream reductase 12 hour the target catalyzer.Reaction conditions: in autoclave, add the 10mL dioxane and make solvent, 0.5g levulinic acid and 0.05g catalyzer, autoclave is sealed, charge into the hydrogen of 0.1MPa, 50 ℃, 100 ℃, 120 ℃, 150 ℃, 200 ℃ were reacted 3 hours, finished the reaction postcooling to room temperature, slowly were decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Experimental result sees Table that sequence number is 21～25 in 1.
Embodiment 26:
The HirCl that adds 12.6mL 0.024mol/L in the 40mL deionized water
6Solution, 3.67 gram urea, stirring and dissolving joins 2g titanium dioxide (P25) in this solution, and 80 ℃ of water-bath induction stirring 2 hours, suction filtration, washing, drying, 400 ℃ of hydrogen reducings obtained the target catalyzer.Reaction conditions: in autoclave, add the 10mL dioxane and make solvent, 0.5g levulinic acid and 0.05g catalyzer, autoclave is sealed, charge into the hydrogen of 0.1MPa, 80 ℃ were reacted 3 hours, finished the reaction postcooling to room temperature, slowly were decompressed to barometric point, open autoclave and take a sample, send GC-MS to detect.Experimental result sees Table that sequence number is 26 in 1.
The productive rate of γ-Wu Neizhi all detects by gas chromatography-mass spectrum logotype instrument (GC-MS) in all enforcements of the present invention.Undertaken qualitatively by the retention time of mass spectrum and pure sample product, undertaken quantitatively by marker method.All results and detailed reaction conditions are listed in the table 1.
Detected result among each embodiment of table 1 relatively
By above-mentioned experiment, proved that supported iridium catalyst is showing excellent catalysis characteristics aspect the levulinic acid shortening, catalyzer can be reused, reaction can be carried out being lower than under 100 ℃, this is reflected under the situation of water as solvent and also can carries out smoothly, has demonstrated very high industrial application value.
Claims (6)
1. method for preparing γ-Wu Neizhi with supported iridium catalyst, it is characterized in that: in autoclave, add solvent and a certain amount of reactant levulinic acid, the iridium catalyst that adds the 0.05-1.0mol% that presses the levulinic acid molar weight then, after mixing, with the autoclave sealing, charge into the hydrogen of 0.1～5.0MPa, control reaction temperature is 25～200 ℃, reacted 1～20 hour, and promptly obtained the target product γ-Wu Neizhi.
2. preparation γ-Wu Neizhi method according to claim 1, it is characterized in that preparing the used method of supported iridium catalyst has deposition-precipitation method, sol-gel method or common pickling process; Used iridium source is chloro-iridic acid, iridic chloride and iridous chloride.
3. preparation γ-Wu Neizhi method according to claim 2 is characterized in that used supported iridium catalyst carrier TiO
2, Al
2O
3, MgO, SiO
2, ZnO, CeO
2, gac or BaSO
4
4. preparation γ-Wu Neizhi method according to claim 2 is characterized in that the charge capacity of iridium in the supported iridium catalyst being calculated as 0.5～20wt% with metal iridium.
5. according to the described preparation γ-Wu Neizhi of claim 1 method, it is characterized in that the solvent that reacts is dioxane, ether, ethanol, methyl alcohol, acetone, toluene, ionic liquid or water.
6. preparation γ-Wu Neizhi method according to claim 1 is characterized in that reaction pressure is 0.1～10.0MPa, and temperature of reaction is 250～200 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| CN102617519A (en) * | 2012-03-05 | 2012-08-01 | 中国石油大学(华东) | Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation |
| CN102658131A (en) * | 2012-04-26 | 2012-09-12 | 大连理工大学 | Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst |
| CN103497168A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Method for preparing gamma-valerolactone by transferring and hydrogenating levulinic acid and ester thereof |
| CN104496945A (en) * | 2015-01-08 | 2015-04-08 | 山西大学 | Preparation method of gamma-valerolactone |
| CN106866589A (en) * | 2017-01-17 | 2017-06-20 | 浙江大学 | A kind of preparation method of γ valerolactones |
| CN107073462A (en) * | 2014-11-19 | 2017-08-18 | 索尔维特殊聚合物意大利有限公司 | Use the one kettle way method of heterogeneous catalysis |
| US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
| US9914714B2 (en) | 2015-12-23 | 2018-03-13 | Neste Oy J | Selective process for conversion of levulinic acid to gammavalerolactone |
| CN112898244A (en) * | 2019-12-03 | 2021-06-04 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN113398925A (en) * | 2021-07-07 | 2021-09-17 | 南京工业大学 | Iridium-loaded heterogeneous catalyst and preparation method and application thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| CN102558108B (en) * | 2011-12-22 | 2014-07-16 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| CN102617519A (en) * | 2012-03-05 | 2012-08-01 | 中国石油大学(华东) | Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation |
| CN102617519B (en) * | 2012-03-05 | 2014-08-13 | 中国石油大学(华东) | Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation |
| CN102658131A (en) * | 2012-04-26 | 2012-09-12 | 大连理工大学 | Ruthenium-based catalyst for preparing gamma-valerolactone from acetylpropionic acid, and preparation method for ruthenium-based catalyst |
| CN103497168A (en) * | 2013-10-18 | 2014-01-08 | 厦门大学 | Method for preparing gamma-valerolactone by transferring and hydrogenating levulinic acid and ester thereof |
| CN103497168B (en) * | 2013-10-18 | 2016-05-18 | 厦门大学 | A kind of levulic acid and ester class transfer hydrogenation thereof are prepared the method for gamma-valerolactone |
| CN107073462A (en) * | 2014-11-19 | 2017-08-18 | 索尔维特殊聚合物意大利有限公司 | Use the one kettle way method of heterogeneous catalysis |
| CN104496945B (en) * | 2015-01-08 | 2016-06-22 | 山西大学 | A kind of preparation method of gamma-valerolactone |
| CN104496945A (en) * | 2015-01-08 | 2015-04-08 | 山西大学 | Preparation method of gamma-valerolactone |
| US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
| US9914714B2 (en) | 2015-12-23 | 2018-03-13 | Neste Oy J | Selective process for conversion of levulinic acid to gammavalerolactone |
| CN106866589A (en) * | 2017-01-17 | 2017-06-20 | 浙江大学 | A kind of preparation method of γ valerolactones |
| CN106866589B (en) * | 2017-01-17 | 2019-02-26 | 浙江大学 | A kind of preparation method of gamma-valerolactone |
| CN112898244A (en) * | 2019-12-03 | 2021-06-04 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN112898244B (en) * | 2019-12-03 | 2022-12-13 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN113398925A (en) * | 2021-07-07 | 2021-09-17 | 南京工业大学 | Iridium-loaded heterogeneous catalyst and preparation method and application thereof |
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Application publication date: 20100818 |