CN105233878A - Synthesis method for metal-loaded-type MIL-101 bio-oil hydrogenation catalyst - Google Patents
Synthesis method for metal-loaded-type MIL-101 bio-oil hydrogenation catalyst Download PDFInfo
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- CN105233878A CN105233878A CN201510765730.5A CN201510765730A CN105233878A CN 105233878 A CN105233878 A CN 105233878A CN 201510765730 A CN201510765730 A CN 201510765730A CN 105233878 A CN105233878 A CN 105233878A
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Abstract
The invention provides a synthesis method for a metal-loaded-type MIL-101 bio-oil hydrogenation catalyst, and belongs to the technical field of catalyst synthesis. The synthesis method comprises the steps that firstly, an MIL-101 carrier is synthesized; secondly, a metal-loaded-type MIL-101 hydrogenation catalyst is obtained by steeping transition metal salt and rare earth metal salt; finally, the catalyst and bio-oil are put into a batch reactor, a hydrodeoxygenation reaction is performed for 1-10 h at the hydrogen pressure of 2-4 MPa at the temperature of 100 DEG C-250 DEG C, and a bio-oil hydrodeoxygenation product is obtained. The metal-loaded-type MIL-101 bio-oil hydrogenation catalyst obtained through the method is high in metal content and conversion rate to bio-oil, good in product selectivity, long in life and capable of being circularly used for multiple times.
Description
Technical field
The present invention relates to a kind of synthetic method of metal load type MIL-101 bio oil hydrogenation catalyst, belong to catalyst synthesis technology field.
Background technology
MIL-101 is part and trivalent metal core Cr by terephthalic acid (TPA)
3o (CO
2)
6super tetrahedral secondary structure unit is synthesized by hydrothermal synthesis method, obtains and has three-dimensional open-framework complex.The framework material of this macropore range has specific area greatly, the feature (thermal stable temperature is close to 250 DEG C) of chemical stability and Heat stability is good, and permanent placement can not change the skeleton structure of MIL-101 in atmosphere.
Current MIL-101 is mainly used as adsorption and separation material, simultaneously due to its highdensity transition metal sites and huge specific area, MIL material is had a wide range of applications at catalytic field.Such as, in patent CN104722338A, inventor uses butyl titanate to carry out modification to the MIL-101 (Cr) after degassed, and obtain a kind of titanium modification MIL-101 (Cr) catalyst, its specific area is 1400 ~ 2000m
2/ g, the reactivity of oxidation sweetening is 70 ~ 80%.Liu Hongli (HongliLiu, YalingLiu, YingweiLi, etal.Metal-OrganicFrameworkSupportedGoldNanoparticlesasa HighlyActiveHeterogeneousCatalystforAerobicOxidationofAl cohols [J] .TheJournalofPhysicalChemistryC, 2010, 114 (31): 13362-13369) etc. people adopts PVP to make protectant sol-gal process (CD/PVP) to have prepared Au/MIL-101, this catalyst can efficient catalytic 1-benzyl carbinol under the condition of not adding alkali, the TOF of its selective oxidation is up to 29300h
-1, its TOF value is higher than the most active Au catalyst of bibliographical information under identical reaction conditions, in addition, he is also by simple infusion process load P d, prepare that not only to have Lewis acid but also have the difunctional Pd/MIL-101 catalyst of hydrogenation activity, realize the aqueous phase phenol hydrogenation of phenol under normal temperature and pressure conditions to react a step and quantitatively prepare cyclohexanone, after 11h is anti-, cyclohexanone reaches the yield of >99.9%, and catalyst has good stability, after reusing 5 times, catalytic activity does not change.
Although the MIL-101 catalyst material of carried noble metal has been reported, but expensive its industrial applications that makes of noble metal is restricted, the present invention relates to a kind of synthetic method of metal load type MIL-101 bio oil hydrogenation catalyst, the metal of load is cheap and easy to get, and prepares multi-chemical to biological oil hydrodeoxygenation and have application prospect widely.
Summary of the invention
The synthetic method of a kind of metal load type MIL-101 bio oil hydrogenation catalyst that the present invention proposes, preparing on the basis of MIL-101 material at present, first synthesizing MIL-101 carrier, then obtaining bio oil hydrogenation catalyst by impregnated transition metal and rare earth metal.On the one hand, MIL-101 supported synthesis methods simple and effective, reaction condition is gentle; On the other hand, the tenor of metal load type MIL-101 hydrogenation catalyst is high, is conducive to absorption and the reaction of bio oil, and therefore catalytic effect is remarkable, and bio oil conversion ratio is high, good product selectivity.
The synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 2 ~ 4%, the chromic nitrate slowly added under constantly stirring, mass concentration is 5 ~ 8%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.1 ~ 1%, continues stirring 10 ~ 40min, crystallization 5 ~ 10h at 180 ~ 250 DEG C, naturally cool to room temperature, after filtration, obtain green crystal.
(2) reflux the ethanol of the green crystal volumetric concentration 50 ~ 95% in step (1) under 60 ~ 90 DEG C of conditions washing 3 ~ 5 times, then centrifugal treating is carried out, the speed of centrifugation is 4000 ~ 6000rpm, time is 5 ~ 15min, finally sediment is put dry 1 ~ 5h in an oven, temperature is 100 ~ 200 DEG C, obtains MIL-101 carrier.
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 2 ~ 8h, load capacity is 1 ~ 30%, then the dry 5 ~ 10h of baking oven is put into, temperature is 100 ~ 200 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
Wherein, transition metal salt described is in step (3) one or both in nickel inorganic salts, molybdenum inorganic salts, tungsten inorganic salts, cobalt inorganic salts, and rare earth metal salt is any one in lanthanum inorganic salts, cerium inorganic salts.
Metal load type MIL-101 hydrogenation catalyst can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 2 ~ 4MPa, carry out hydrogenation deoxidation reaction 1 ~ 10h under temperature 100 ~ 250 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product.
Bio oil recited above is one or more in phenol, paracresol, o-methoxyphenol, levulic acid, cyclopentanone, methyl acetate and vanillic aldehyde.
The invention has the advantages that:
1, the synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, the cheaper starting materials preparing MIL-101 carrier in the method used is easy to get, and preparation technology is efficient, is easy to suitability for industrialized production.
2, the synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, the MIL-101 carrier that the method obtains has size uniformity, regular appearance, and specific area is large, the advantages such as hydrothermally stable is good.
3, the synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, by the multimetal reforming catalyst obtained at MIL-101 supported on carriers transition metal and rare earth metal, tenor is high, and reactivity is high, catalyst life is long, can repeatedly recycle.
4, the synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, the metal load type MIL-101 hydrogenation catalyst that the method obtains, high to the conversion ratio of bio oil, hydrogenation deoxidation Be very effective, good product selectivity.
Accompanying drawing explanation
Fig. 1: the flow chart of the synthetic method of a kind of metal load type MIL-101 bio oil hydrogenation catalyst that the present invention proposes.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments in detail technical characterstic of the present invention is described in detail.
The synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, as shown in Figure 1, specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 2 ~ 4%, the chromic nitrate slowly added under constantly stirring, mass concentration is 5 ~ 8%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.1 ~ 1%, continues stirring 10 ~ 40min, crystallization 5 ~ 10h at 180 ~ 250 DEG C, naturally cool to room temperature, after filtration, obtain green crystal.
(2) reflux the ethanol of the green crystal volumetric concentration 50 ~ 95% in step (1) under 60 ~ 90 DEG C of conditions washing 3 ~ 5 times, then centrifugal treating is carried out, the speed of centrifugation is 4000 ~ 6000rpm, time is 5 ~ 15min, finally sediment is put dry 1 ~ 5h in an oven, temperature is 100 ~ 200 DEG C, obtains MIL-101 carrier.
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 2 ~ 8h, load capacity is 1 ~ 30%, then the dry 5 ~ 10h of baking oven is put into, temperature is 100 ~ 200 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
Wherein, transition metal salt described is in step (3) one or both in nickel inorganic salts, molybdenum inorganic salts, tungsten inorganic salts, cobalt inorganic salts, and rare earth metal salt is any one in lanthanum inorganic salts, cerium inorganic salts.
Metal load type MIL-101 hydrogenation catalyst can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 2 ~ 4MPa, carry out hydrogenation deoxidation reaction 1 ~ 10h under temperature 100 ~ 250 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product.
Bio oil recited above is one or more in phenol, paracresol, o-methoxyphenol, levulic acid, cyclopentanone, methyl acetate and vanillic aldehyde.
embodiment 1:
The synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 3%, the chromic nitrate slowly added under constantly stirring, mass concentration is 7%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.8%, continues to stir 30min, crystallization 8h at 220 DEG C, naturally cool to room temperature, after filtration, obtain green crystal.
(2) reflux the ethanol of the green crystal volumetric concentration 95% in step (1) under 70 DEG C of conditions washing 5 times, then centrifugal treating is carried out, the speed of centrifugation is 5000rpm, time is 10min, finally sediment is put dry 3h in an oven, temperature is 150 DEG C, obtains MIL-101 carrier.
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 6h, and load capacity is 10%, then puts into the dry 7h of baking oven, temperature is 150 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
Wherein, transition metal salt described is in step (3) nickel inorganic salts and tungsten inorganic salts, and rare earth metal salt is lanthanum inorganic salts.
Metal load type MIL-101 hydrogenation catalyst can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 3MPa, carry out hydrogenation deoxidation reaction 6h under temperature 150 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product.
Bio oil recited above is phenol.
Result shows, the specific area of this catalyst reaches 2586m
2/ g, the conversion ratio of phenol is 91%, and the selective of product cyclohexanone is 79%.
embodiment 2:
The synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 2%, the chromic nitrate slowly added under constantly stirring, mass concentration is 6%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.5%, continues to stir 15min, crystallization 5h at 250 DEG C, naturally cool to room temperature, after filtration, obtain green crystal.
(2) reflux the ethanol of the green crystal volumetric concentration 70% in step (1) under 85 DEG C of conditions washing 4 times, then centrifugal treating is carried out, the speed of centrifugation is 6000rpm, time is 5min, finally sediment is put dry 2h in an oven, temperature is 200 DEG C, obtains MIL-101 carrier.
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 4h, and load capacity is 5%, then puts into the dry 10h of baking oven, temperature is 100 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
Wherein, transition metal salt described is in step (3) molybdenum inorganic salts and cobalt inorganic salts, and rare earth metal salt is cerium inorganic salts.
Metal load type MIL-101 hydrogenation catalyst can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 2MPa, carry out hydrogenation deoxidation reaction 4h under temperature 200 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product.
Bio oil recited above is o-methoxyphenol.
Result shows, the specific area of this catalyst reaches 3011m
2/ g, the conversion ratio of o-methoxyphenol is 95%, and the selective of product hexahydrotoluene is 83%.
embodiment 3:
The synthetic method of a kind of metal load type MIL-101 of the present invention bio oil hydrogenation catalyst, specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 4%, the chromic nitrate slowly added under constantly stirring, mass concentration is 5%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.3%, continues to stir 25min, crystallization 10h at 180 DEG C, naturally cool to room temperature, after filtration, obtain green crystal.
(2) reflux the ethanol of the green crystal volumetric concentration 50% in step (1) under 90 DEG C of conditions washing 3 times, then centrifugal treating is carried out, the speed of centrifugation is 4000rpm, time is 15min, finally sediment is put dry 5h in an oven, temperature is 105 DEG C, obtains MIL-101 carrier.
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 2h, and load capacity is 25%, then puts into the dry 5h of baking oven, temperature is 100 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
Wherein, transition metal salt described is in step (3) nickel inorganic salts and molybdenum inorganic salts, and rare earth metal salt is lanthanum inorganic salts.
Metal load type MIL-101 hydrogenation catalyst can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 4MPa, carry out hydrogenation deoxidation reaction 8h under temperature 100 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product.
Bio oil recited above is vanillic aldehyde.
Result shows, the specific area of this catalyst reaches 2194m
2/ g, the conversion ratio of vanillic aldehyde is 93%, and the selective of product 2-methoxyl group-4-methylphenol is 88%.
Claims (3)
1. a synthetic method for metal load type MIL-101 bio oil hydrogenation catalyst, is characterized in that the method specifically comprises the following steps:
(1) taking terephthalic acid (TPA) is dissolved in deionized water, be configured to the solution that mass concentration is 2 ~ 4%, the chromic nitrate slowly added under constantly stirring, mass concentration is 5 ~ 8%, then the hydrofluoric acid dropwise dripped in mixed liquor to volumetric concentration is 0.1 ~ 1%, continues stirring 10 ~ 40min, crystallization 5 ~ 10h at 180 ~ 250 DEG C, naturally cool to room temperature, after filtration, obtain green crystal;
(2) reflux the ethanol of the green crystal volumetric concentration 50 ~ 95% in step (1) under 60 ~ 90 DEG C of conditions washing 3 ~ 5 times, then centrifugal treating is carried out, the speed of centrifugation is 4000 ~ 6000rpm, time is 5 ~ 15min, finally sediment is put dry 1 ~ 5h in an oven, temperature is 100 ~ 200 DEG C, obtains MIL-101 carrier;
(3) by transition metal salt and rare earth metal salt with on the MIL-101 carrier be immersed in after water-soluble solution described in step (2), dip time is 2 ~ 8h, load capacity is 1 ~ 30%, then the dry 5 ~ 10h of baking oven is put into, temperature is 100 ~ 200 DEG C, obtains metal load type MIL-101 hydrogenation catalyst.
2. the synthetic method of metal load type MIL-101 bio oil hydrogenation catalyst according to claim 1, it is characterized in that: described transition metal salt is one or both in nickel inorganic salts, molybdenum inorganic salts, tungsten inorganic salts, cobalt inorganic salts, rare earth metal salt is any one in lanthanum inorganic salts, cerium inorganic salts.
3. metal load type MIL-101 bio oil hydrogenation catalyst according to claim 1, can be used for the hydrogenation deoxidation of oxygenatedchemicals in bio oil, its method is: MIL-101 hydrogenation catalyst and bio oil are put into batch reactor, at Hydrogen Vapor Pressure 2 ~ 4MPa, carry out hydrogenation deoxidation reaction 1 ~ 10h under temperature 100 ~ 250 DEG C of conditions, finally obtain biological oil hydrodeoxygenation product; Described bio oil composition is one or more in phenol, paracresol, o-methoxyphenol, levulic acid, cyclopentanone, methyl acetate and vanillic aldehyde.
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Cited By (5)
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|---|---|---|---|---|
| CN108565420A (en) * | 2018-04-08 | 2018-09-21 | 湖北大学 | Co is carried on the material, preparation method and application of MIL-101 |
| CN109529934A (en) * | 2018-12-06 | 2019-03-29 | 怀化学院 | MIL-101 loaded catalyst and the preparation method and application thereof |
| CN110975938A (en) * | 2019-12-18 | 2020-04-10 | 华能国际电力股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN113457740A (en) * | 2021-05-31 | 2021-10-01 | 鹤壁腾飞清洁能源有限公司 | Catalyst for preparing ethanol by catalytic hydrogenation of methyl acetate and preparation method thereof |
| CN114460150A (en) * | 2022-02-09 | 2022-05-10 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | Unmarked DNA photoelectrochemical detection method based on MOFs composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565420A (en) * | 2018-04-08 | 2018-09-21 | 湖北大学 | Co is carried on the material, preparation method and application of MIL-101 |
| CN109529934A (en) * | 2018-12-06 | 2019-03-29 | 怀化学院 | MIL-101 loaded catalyst and the preparation method and application thereof |
| CN110975938A (en) * | 2019-12-18 | 2020-04-10 | 华能国际电力股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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| CN113457740A (en) * | 2021-05-31 | 2021-10-01 | 鹤壁腾飞清洁能源有限公司 | Catalyst for preparing ethanol by catalytic hydrogenation of methyl acetate and preparation method thereof |
| CN114460150A (en) * | 2022-02-09 | 2022-05-10 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | Unmarked DNA photoelectrochemical detection method based on MOFs composite material |
| CN114460150B (en) * | 2022-02-09 | 2023-04-11 | 福州市第二医院（福建省福州中西医结合医院、福州市职业病医院） | Unmarked DNA photoelectrochemical detection method based on MOFs composite material |
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Application publication date: 20160113 |