CN101733097B - Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application - Google Patents
Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application Download PDFInfo
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- CN101733097B CN101733097B CN2009101753375A CN200910175337A CN101733097B CN 101733097 B CN101733097 B CN 101733097B CN 2009101753375 A CN2009101753375 A CN 2009101753375A CN 200910175337 A CN200910175337 A CN 200910175337A CN 101733097 B CN101733097 B CN 101733097B
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Abstract
The invention relates to a catalyst for preparing gamma-valerolactone by alpha-angelica lactone, which is characterized by comprising the following components by weight percent calculated by oxide: 0.5-15% of active component, 0.05-20% of catalyst accelerator and the balance of carrier. The invention has the advantages of low cost, simple process, easy operation, high product yield and good safety in the production process.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application by alpha-angelica lactone hydrogenation preparing gamma-valerolactone.
Background technology
Gamma-valerolactone (C
5H
8O
2, Mw=100.10), chemical name is 4-hydroxyl-3-penetenoic acid lactone or 5-methyl-2 (3H)-furanone, can be used as flavoring essence, organic synthesis intermediate, macromolecule polyester monomer, vehicle fuel, adhesive etc. and be applied to numerous industries.In China, these article only have small lot batch manufacture, and price is very expensive, have had a strong impact on the utilization and extention of these article.
The preparation method of gamma-valerolactone mainly is to be raw material with the levulic acid at present, makes through lactonizing behind the first heterogeneous catalysis hydrogenation.Liu Daojun etc. (fragrance flavor and cosmetic, 1999,4,1-4) adopting levulic acid is raw material, through alkali lye neutralization, catalytic hydrogenation with add three processes of acid lactoneization and make gamma-valerolactone, complex technical process, side reaction is many, and yield is low.Tang Tianshu (fragrance flavor and cosmetic, 1996,4,5-7) reported that a kind of is raw material with the levulic acid; Through the method for the synthetic gamma-valerolactone of esterification, microorganism carbonyl reduction and lactonization reaction, process is complicated, the strain improvement difficulty; Reaction time is long, and accessory substance is many, and yield only reaches 61.1%.Patent WO 02074760 shows that levulic acid can generate gamma-valerolactone with the hydrogen reaction of 700～800psi under the noble metal catalyst effect, and yield can reach 96%, but adopts noble metal to cause the technology cost expensive, is difficult to large-scale production.Patent US0254384 points out that in supercritical CO 2 medium the highest yield of this reaction can reach 99%, but technology need consume great amount of carbon dioxide, and can produce a small amount of 2-methyltetrahydrofuran (reaction process is prone to down generate peroxide, has hidden peril of explosion).
Alpha-angelica lactone (C
5H
6O
2) as a kind of important chemical intermediate, can make through intramolecular dehydration by biomass-based platform greenization compound levulic acid.Patent 200910073688.5 is described the preparation process of alpha-angelica lactone in detail.With the alpha-angelica lactone is raw material, can make gamma-valerolactone through a step catalysis cyclic olefinic bond hydrogenation, and the catalyst cost is low, and technology is simple, easy operating, and product yield is high.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, easy operating, and product yield is high, catalyst and preparation method and application by alpha-angelica lactone hydrogenation preparing gamma-valerolactone that the production process security is good.
Catalyst of the present invention is an active component with rhodium, platinum or palladium, is co-catalyst with at least a in manganese, barium, zirconium, magnesium, the calcium, and carrier is aluminium oxide, silica, sial composite oxides or active carbon.
Catalyst of the present invention is formed: count in oxide, the active component weight content is 0.5%～15%, is preferably 2%～10%.The co-catalyst weight content is 0.05%～20%, is preferably 1%～15%, and remainder is a carrier.
Catalyst of the present invention adopts the equi-volume impregnating preparation, and concrete preparation process is following:
(1), the soluble-salt of rhodium, platinum or palladium and the soluble-salt of co-catalyst are made into mixed solution by the catalyst composition;
(2), the mixed solution incipient impregnation that (1) is prepared is to carrier;
(3), with (2) gained catalyst at 90～120 ℃ of down dry 2～24h, at 350～600 ℃ of following roasting 2～24h, promptly get required catalyst.
The soluble-salt of described rhodium, platinum or palladium is nitrate, chlorate, chloroplatinic acid etc.The soluble-salt of co-catalyst manganese, barium, zirconium, magnesium or calcium is nitrate or chlorate.
The invention also discloses the process conditions by alpha-angelica lactone hydrogenation preparing gamma-valerolactone: reaction temperature is 100～300 ℃, preferred 140～200 ℃; Pressure is 1～10MPa, preferred 3～6MPa; Liquid hourly space velocity (LHSV) is 1～8h
-1, preferred 2～5h
-1Raw material is alpha-angelica lactone and hydrogen, and wherein hydrogen to oil volume ratio is 100～1000, preferred 200～500.The mode of reaction can be batch (-type) or continous way, preferred continous way.
Advantage of the present invention is following:
Technology is simple, easy operating, and product yield is high, and the production process security is good.The alpha-angelica lactone conversion ratio can be up to 99.8%, and the gamma-valerolactone selectivity is up to 99.7%.
The specific embodiment
Further specify the present invention with following embodiment, but invention is not limited.
Embodiment 1～3:
Preparation of Catalyst:
The nitrate of active component and manganese nitrate (or barium nitrate, zirconium nitrate) formed by catalyst be made into mixed solution (composition of catalyst sees table one for details); At room temperature incipient impregnation is to the sial complex carrier; Dry 24h in 90 ℃ of baking ovens; At 350 ℃ of roasting 24h, promptly get embodiment 1～3 and change agent.The reaction condition and the result of alpha-angelica lactone hydrogenation preparing gamma-valerolactone see table one.
Embodiment 4～9:
Preparation of Catalyst:
The chlorate of active component and manganese chloride (or barium chloride, zirconium oxychloride) formed by catalyst be made into mixed solution (composition of catalyst sees table one for details); At room temperature incipient impregnation is to alumina support; Dry 2h in 120 ℃ of baking ovens, 600 ℃ of roasting 2h promptly get embodiment 4～9 and change agent.The reaction condition and the result of alpha-angelica lactone hydrogenation preparing gamma-valerolactone see table one.
Embodiment 10～12:
Preparation of Catalyst:
The chlorate of active component and manganese chloride (or barium chloride, zirconium oxychloride) formed by catalyst be made into mixed solution (composition of catalyst sees table one for details); At room temperature incipient impregnation is to silica support; Dry 12h in 100 ℃ of baking ovens; 400 ℃ of roasting 16h promptly get embodiment 10～12 and change agent.The reaction condition and the result of alpha-angelica lactone hydrogenation preparing gamma-valerolactone see table one.
Embodiment 13～16:
The chlorate of active component and the chlorate of co-catalyst are made into mixed solution (composition of catalyst sees table one for details) by the catalyst composition; At room temperature incipient impregnation is to absorbent charcoal carrier; Dry 9h in 110 ℃ of baking ovens, 400 ℃ of roasting 6h promptly get embodiment 13～16 and change agent.The reaction condition and the result of alpha-angelica lactone hydrogenation preparing gamma-valerolactone see table one.
The comparative example 1,2:
Prepared 5%Pt/Al with equi-volume impregnating
2O3, the 5%Rh/C catalyst, concrete preparation method is with embodiment 1～16, and reaction condition sees table one for details.
| Embodiment | Catalyst is formed | Reaction temperature/℃ | Reaction pressure/MPa | Air speed/h -1 | Hydrogen to oil volume ratio | Alpha-angelica lactone conversion ratio/% | Gamma-valerolactone selectivity/% |
| 1 | 15％Rh-0.05％MnO 2/Al 2O 3-SiO 2 | 100 | 10 | 1 | 200 | 56.2 | 98.6 |
| 2 | 1％Pt-2％MnO 2/Al 2O 3-SiO 2 | 300 | 10 | 8 | 100 | 59.6 | 65.6 |
| 3 | 10％Pd-2％MnO 2/Al 2O 3-SiO 2 | 200 | 10 | 6 | 200 | 94.5 | 92.4 |
| 4 | 10％Rh-15％MnO 2/Al 2O 3 | 180 | 5 | 5 | 200 | 93.2 | 98.5 |
| 5 | 10％Pt-10％MnO 2/Al 2O 3 | 150 | 1 | 1 | 200 | 95.1 | 98.5 |
| 6 | 10％Pd-5％MnO 2/Al 2O 3 | 250 | 5 | 3 | 300 | 98.5 | 99.4 |
| 7 | 5％Rh-2％CaO/Al 2O 3 | 150 | 5 | 5 | 300 | 95.5 | 92.8 |
| 8 | 5％Pt-2％CaO/Al 2O 3 | 150 | 7 | 3 | 300 | 94.6 | 99.5 |
| 9 | 5％Pd-2％CaO/Al 2O 3 | 150 | 7 | 3 | 600 | 94.4 | 95.8 |
| 10 | 5％Rh-2％BaO/SiO 2 | 300 | 1 | 2 | 300 | 97.6 | 96.5 |
| 11 | 5％Pt-2％BaO/SiO 2 | 300 | 1 | 8 | 300 | 95.3 | 95.2 |
| 12 | 5％Pd-2％BaO/SiO 2 | 300 | 1 | 8 | 300 | 95.4 | 99.1 |
| 13 | 5％Rh-2％ZrO 22％BaO/C | 150 | 8 | 4 | 600 | 99.7 | 99.5 |
| 14 | 5％Pt-2％ZrO 2-2％BaO-2％BaO/C | 150 | 6 | 4 | 800 | 98.1 | 96.5 |
| 15 | 5％Pd-2％MgO-2％BaO-2％CaO/C | 250 | 5 | 4 | 1000 | 97.3 | 97.9 |
| 16 | 5％Rh-1％MnO 2-1％MgO-2％ZrO 2/C | 150 | 5 | 4 | 100 | 99.8 | 99.7 |
| Contrast 1 | 5％Pt/Al 2O 3 | 150 | 5 | 4 | 300 | 87.5 | 88.6 |
| Contrast 2 | 5％Rh/C | 150 | 5 | 4 | 300 | 91.3 | 86.7 |
Claims (3)
1. the Application of Catalyst of a preparing gamma-valerolactone by alpha-angelica lactone is characterized in that comprising the steps:
Reaction temperature is 100～300 ℃, and pressure is 1～10MPa, and liquid hourly space velocity (LHSV) is 1～8h
-1, raw material is alpha-angelica lactone and hydrogen, and wherein hydrogen to oil volume ratio is 100～1000, and the mode of reaction is batch (-type) or continous way;
Described catalyst is formed: count in oxide, the active component weight content is 0.5%～15%, and the co-catalyst weight content is 0.05%～20%, and remainder is a carrier; Described active component is rhodium, platinum or palladium, and described co-catalyst is at least a in manganese, barium, magnesium, the calcium, and described carrier is silica or active carbon.
2. the Application of Catalyst of a kind of preparing gamma-valerolactone by alpha-angelica lactone as claimed in claim 1 is characterized in that described active component weight content is 2%～10%, and the co-catalyst weight content is 1%～15%.
3. the Application of Catalyst of a kind of preparing gamma-valerolactone by alpha-angelica lactone as claimed in claim 1 is characterized in that reaction temperature is 140～200 ℃, and pressure is 3～6MPa, and liquid hourly space velocity (LHSV) is 2～5h
-1, hydrogen to oil volume ratio is 200～500.
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|---|---|---|---|
| CN2009101753375A CN101733097B (en) | 2009-12-07 | 2009-12-07 | Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101753375A CN101733097B (en) | 2009-12-07 | 2009-12-07 | Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application |
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| CN101733097B true CN101733097B (en) | 2012-11-14 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2786852A (en) * | 1953-08-19 | 1957-03-26 | Quaker Oats Co | Process of preparing gammavalerolactone |
| CN85100761A (en) * | 1985-04-01 | 1986-09-24 | 中国科学院山西煤炭化学研究所 | Fibrous catalyst for selective hydrogenation of dienes and method for making thereof |
| CN1704160A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Catalyst for hydrogen oxidation reaction in ethylbenzene dehydrogenation process |
-
2009
- 2009-12-07 CN CN2009101753375A patent/CN101733097B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2786852A (en) * | 1953-08-19 | 1957-03-26 | Quaker Oats Co | Process of preparing gammavalerolactone |
| CN85100761A (en) * | 1985-04-01 | 1986-09-24 | 中国科学院山西煤炭化学研究所 | Fibrous catalyst for selective hydrogenation of dienes and method for making thereof |
| CN1704160A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Catalyst for hydrogen oxidation reaction in ethylbenzene dehydrogenation process |
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