CN103980241A - Delta-valerolactone production method - Google Patents
Delta-valerolactone production method Download PDFInfo
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- CN103980241A CN103980241A CN201410162813.0A CN201410162813A CN103980241A CN 103980241 A CN103980241 A CN 103980241A CN 201410162813 A CN201410162813 A CN 201410162813A CN 103980241 A CN103980241 A CN 103980241A
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- valerolactone
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- pentanediol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
The invention relates to a delta-valerolactone production method, which is a chemical product production technology, the production method overcomes the disadvantages of other technologies. The production method comprises the following steps: 1) a 1,5-pentanediol raw material is introduced in a drying tower for dehydrating, wherein water content is ensured lower than 1wt%, the water content is lower than 0.5wt% under optimization condition, further optimization is carried out, the water content is lower than 0.1wt%, after further optimization, the water content is lower than 0.05wt% which is 500wppm; through researches, this step is very important to decide whether the high quality product can be obtained or not; 3)dried 1, 5-pentanediol and hydrogen are mixed and then introduced in a carburetor, wherein the mol ratio of hydrogen to 1,5-pentanediol is 10-5: 1; and 3)vaporized hydrogen and 1,5-pentanediol are introduced in a dehydrogenation reactor, under the condition that normal pressure is 0.1MPa and the temperature is 230-270 DEG C, 1,5-pentanediol is conversed to delta-valerolactone under the effect of a dehydrogenation catalyst, wherein delta-valerolactone yield exceeds 98%, and the water content in the crude product is lower than 0.5wt%.
Description
Technical field: the production method that the present invention relates to a kind of Chemicals production technology, especially δ-valerolactone.
Background technology: δ-valerolactone, has another name called 1,5-valerolactone, delta-valerolactone, tetrahydrochysene-2H-2-pyrone, tetrahydrochysene coumalin, tetrahydrochysene cumalin; English name is Delta-Valerolactone, and abbreviation title is generally δ-VL or DVL, and molecular formula is C5H8O2.Due to its good application flexibility, lower bio-toxicity, more derivative compound, be easy to polymerization and significantly increase the features such as viscosity such as coating, δ-valerolactone is of many uses in polyester, urethane, special solvent, coating etc.
The open a kind of use 1 of CN 101157677,5-pentanediol generates the method for δ-valerolactone, and described method is to make solvent with tributyl phosphate, by 1,5-pentanediol, under load type nano gold catalyst effect, generates δ-valerolactone with high-pressure air generation oxidizing reaction.The method need to be used a large amount of solvents, and because δ-valerolactone and 1,5-PD belong to inflammable articles, and what therefore easily meet accident on firely waits dangerously, and metering be than generating water, and separating difficulty increases.
US20110237806 is open a kind of with 1,5-pentanediol is the method that raw material dehydrogenation generates δ-valerolactone, the method is used copper-based catalysts, in its disclosed embodiment, the 1,5-PD using consists of 97%, undeclared water-content, its δ-valerolactone selectivity is 96% left and right, and outlet water-content does not also illustrate.In this invention, be not that qualified product, catalyst life problem carried out description to the refinement treatment of thick product.
The present invention develops a kind of generation method capable of being industrialized high 1,5-PD yield is converted into the δ-valerolactone of high-quality.Main novelty is improved and is: the first, design the Production Flow Chart with raw material drying, and the second, invent the cycle catalyzer that special high yield and overlength are used.
Summary of the invention: the object of this invention is to provide the production method of a kind of δ-valerolactone capable of being industrialized, it has overcome the shortcoming of other technology, and the object of the present invention is achieved like this, and it is the δ-valerolactone that high 1,5-PD yield is converted into high-quality.Main novelty is improved and is: the first, design the Production Flow Chart with raw material drying, and the second, invent the cycle catalyzer that special high yield and overlength are used.
1,5-PD of the present invention is with raw material, and main reaction equation is as follows:
Processing method of the present invention is: the first step, and 1,5-PD raw material is entered in drying tower and dewatered, ensure that water-content is lower than 1wt%, under optimal conditions, lower than 0.5wt%, further optimize, lower than 0.1wt%, further optimize situation, lower than 0.05wt%, i.e. 500wppm.Contriver, through hard research, finds that can this step most important for the product that obtain high-quality; Second step enters in vaporizer after dried 1,5-PD is mixed with hydrogen, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; The 3rd step is by the hydrogen and 1 after vaporization, 5-pentanediol enters in dehydrogenation reactor, under normal pressure ~ 0.1MPa, 230 ~ 270 DEG C of conditions, under the effect of dehydrogenation catalyst by 1,5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield exceedes 98%, exports in thick product water-content lower than 0.5wt%.
Described dehydrogenation catalyst at least comprises: copper 15 ~ 35wt%, silver 0.2 ~ 2.0wt%, rare earth element 1 ~ 5wt%, carrier 20 ~ 60wt%.
Contriver screens rear discovery and in copper-based catalysts, contains in right amount when silver-colored, and activity, selectivity and the work-ing life of catalyzer are greatly improved, particularly work-ing life, prolongation that can be at double.
Meaning of the present invention is: the first, design the Production Flow Chart with raw material drying, and the second, invent the cycle catalyzer that special high yield and overlength are used.
Embodiment: embodiment 1, processing method of the present invention are: the first step; by 1; 5-pentanediol raw material enters in drying tower and dewaters, and ensures that water-content is lower than 1wt%, under optimal conditions; lower than 0.5wt%; further optimize, lower than 0.1wt%, further optimize situation; lower than 0.05wt%, i.e. 500wppm; Second step enters in vaporizer after dried 1,5-PD is mixed with hydrogen, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; The 3rd step is by 1 after vaporization, 5-pentanediol and hydrogen enter in dehydrogenation reactor, under normal pressure ~ 0.1MPa, 230 ~ 270 DEG C of conditions, under the effect of dehydrogenation catalyst by 1,5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield exceedes 98%, exports in thick product water-content lower than 0.5wt%.
Embodiment 2, described dehydrogenation catalyst at least comprise: copper 15 ~ 35wt%, silver 0.2 ~ 2.0wt%, rare earth element 1 ~ 5wt%, carrier 20 ~ 60wt%.
Embodiment 3, in the tubular reactor of 10L loaded catalyst, (chief component is zirconium ~ 30wt%, copper ~ 28wt% to described MQ-DVL-1 catalyzer, silver 0.4wt%, surplus is oxygen and graphite), first catalyzer is reduced 48 hours in hydrogen and nitrogen mixture atmosphere, reduction temperature is the highest 300 DEG C;
1 of molecular sieve drying will be used subsequently, 5-pentanediol 4L/h, water-content 400wppm enters vaporizer after passing into and mixing with hydrogen 115L/h in mixing tank, fully after vaporization, enter in dehydrogenation reactor, desorption temperature is controlled at 250 ~ 260 DEG C, and pressure is normal pressure, export pentanediol content in thick product and be less than 0.5wt%, DVL selectivity is more than 99mol%, and water-content, lower than 0.1wt%, does not detect 5-hydrogenation of hydroxypentylaldehyd; After catalyzer continuous and steady operation 3000 hours, reactivity worth is still stable, and outlet composition is basically identical with the initial stage.
Embodiment 4, the thick product of gained is obtained to qualified product after two atmospheric tower rectifying, DVL content is greater than 99.8wt%, and the total recovery from 1,5-PD to DVL is more than 95%.
Claims (7)
1. a production method for δ-valerolactone, is characterized in that, uses 1; 5-pentanediol, as raw material, generates δ-valerolactone under the effect of dehydrogenation catalyst, and concrete steps are as follows: the first step; 1,5-PD raw material is entered in drying tower and dewatered, ensure that water-content is lower than 1wt%; under optimal conditions, lower than 0.5wt%, further optimize; lower than 0.1wt%; further optimize situation, lower than 0.05wt%, i.e. 500wppm; Second step, enters in vaporizer after hydrogen is mixed with dried 1,5-PD, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; The 3rd step is by the hydrogen and 1 after vaporization, 5-pentanediol enters in dehydrogenation reactor, under normal pressure ~ 0.1MPa, 230 ~ 270 DEG C of conditions, under the effect of dehydrogenation catalyst by 1,5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield exceedes 98%, exports in thick product water-content lower than 0.5wt%; Described dehydrogenation catalyst at least comprises: copper 15 ~ 35wt%, silver 0.2 ~ 2.0wt%, rare earth element 1 ~ 5wt%, carrier 20 ~ 60wt%.
2. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, described support of the catalyst is selected from titanium oxide, zirconium white, calcium oxide, aluminum oxide and silicon oxide one or more.
3. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, described support of the catalyst is selected from one or more in titanium oxide, zirconium white and calcium oxide.
4. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, the rare earth element in described catalyzer is selected from the one in La and Ce, and content is 1.5 ~ 3wt%.
5. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, described raw material 1,5-PD content water-content after super-dry is no more than 500wppm.
6. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, described thick products export water-content control is no more than 0.3wt%.
7. the production method of a kind of δ-valerolactone as claimed in claim 1, is characterized in that, in described catalyzer, silver content is 0.5 ~ 1.0wt%.
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| CN201410162813.0A CN103980241B (en) | 2014-04-23 | 2014-04-23 | A kind of production method of δ-valerolactone |
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| CN201410162813.0A CN103980241B (en) | 2014-04-23 | 2014-04-23 | A kind of production method of δ-valerolactone |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010009964A1 (en) * | 2000-01-14 | 2001-07-26 | Dairen Chemical Corporation | Catalyst for preparing lactone and a method for preparing lactone |
| CN101977684A (en) * | 2008-03-19 | 2011-02-16 | 巴斯夫欧洲公司 | Use of a supported catalyst containing precious metal for oxidative dehydrogenation |
| US20110237806A1 (en) * | 2008-12-05 | 2011-09-29 | Basf Se | Process for preparing delta-valerolactone in the gas phase |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010009964A1 (en) * | 2000-01-14 | 2001-07-26 | Dairen Chemical Corporation | Catalyst for preparing lactone and a method for preparing lactone |
| CN101977684A (en) * | 2008-03-19 | 2011-02-16 | 巴斯夫欧洲公司 | Use of a supported catalyst containing precious metal for oxidative dehydrogenation |
| US20110237806A1 (en) * | 2008-12-05 | 2011-09-29 | Basf Se | Process for preparing delta-valerolactone in the gas phase |
Non-Patent Citations (3)
| Title |
|---|
| FUMIYA SATO ET AL.: "Dehydration of 1,5-pentanediol over rare earth oxides", 《APPLIED CATALYSIS A: GENERAL》 * |
| K. INUI ET AL.: "Dehydrogenative Esterification over Copper-based Catalyst", 《STUDIES IN SURFACE SCIENCE AND CATALYSIS》 * |
| 程丹等: "δ-环戊内酯的合成及应用", 《安徽化工》 * |
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Inventor after: Song Guoquan Inventor after: Xiao Qiang Inventor after: Yang Li Inventor after: Yan Guangxue Inventor after: Wu Zhengling Inventor after: Wu Yanbin Inventor before: Xiao Qiang Inventor before: Song Guoquan Inventor before: Yang Li Inventor before: Yan Guangxue |