CN103980241B - A kind of production method of δ-valerolactone - Google Patents
A kind of production method of δ-valerolactone Download PDFInfo
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- CN103980241B CN103980241B CN201410162813.0A CN201410162813A CN103980241B CN 103980241 B CN103980241 B CN 103980241B CN 201410162813 A CN201410162813 A CN 201410162813A CN 103980241 B CN103980241 B CN 103980241B
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- valerolactone
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- production method
- pentanediol
- hydrogen
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- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000009834 vaporization Methods 0.000 claims abstract description 5
- 230000008016 vaporization Effects 0.000 claims abstract description 5
- 239000006200 vaporizer Substances 0.000 claims abstract description 5
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 2
- 239000000292 calcium oxide Substances 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000003672 processing method Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The production method of δ-valerolactone is an a kind of Chemicals production technology, and which overcome the shortcoming of other technology, its processing method is: 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 optimization, lower than 0.1wt%, further optimizes 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 being mixed with hydrogen by dried 1,5-PD, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; 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, by 1 under the effect of dehydrogenation catalyst, 5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield is more than 98%, to export in thick product water-content lower than 0.5wt%.
Description
Technical field: the present invention relates to a kind of Chemicals production technology, especially the production method of 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 makes 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 needs to use a large amount of solvent, and belongs to inflammable articles due to δ-valerolactone and 1,5-PD, and what therefore easily meet accident on firely waits dangerous, and metering is than generating water, separating difficulty increase.
US20110237806 is open a kind of with 1,5-pentanediol is the method that raw material dehydrogenation generates δ-valerolactone, the method uses copper-based catalysts, in embodiment disclosed in it, the 1,5-PD used consists of 97%, undeclared water-content, its δ-valerolactone selectivity is about 96%, and outlet water-content does not also illustrate.In the invention, not to the refinement treatment of thick product be qualified product, catalyst life problem carried out description.
The present invention develops the δ-valerolactone that 1,5-PD height yield is converted into high-quality by a kind of generation method capable of being industrialized.Main novelty is improved and is: the first, devises the Production Flow Chart with raw material drying, the second, has invented the cycle catalytic agent of special high yield and overlength use.
Summary of the invention: the production method that the object of this invention is to provide a kind of δ-valerolactone capable of being industrialized, which overcome the shortcoming of other technology, the object of the present invention is achieved like this, and it is δ-valerolactone 1,5-PD height yield being converted into high-quality.Main novelty is improved and is: the first, devises the Production Flow Chart with raw material drying, the second, has invented the cycle catalytic agent of special high yield and overlength use.
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, is entered in drying tower by 1,5-PD raw material and dewaters, and ensures that water-content is lower than 1wt%, under optimal conditions, lower than 0.5wt%, optimize further, 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 being mixed with hydrogen by dried 1,5-PD, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; 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, by 1 under the effect of dehydrogenation catalyst, 5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield is more than 98%, to export 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 screen rear discovery in copper-based catalysts containing appropriate silver-colored time, activity, the selectivity of catalyzer and be greatly improved work-ing life, particularly work-ing life, can prolongation at double.
Meaning of the present invention is: the first, devises the Production Flow Chart with raw material drying, the second, has invented the cycle catalytic agent of special high yield and overlength use.
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 optimization, lower than 0.1wt%, further optimizes situation; lower than 0.05wt%, i.e. 500wppm; Second step enters in vaporizer after being mixed with hydrogen by dried 1,5-PD, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; 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, by 1 under the effect of dehydrogenation catalyst, 5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield is more than 98%, to export 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, described MQ-DVL-1 catalyzer (mainly consists of zirconium ~ 30wt%, copper ~ 28wt%, silver 0.4wt%, surplus is oxygen and graphite), first reduced 48 hours in hydrogen and nitrogen mixture atmosphere by catalyzer, reduction temperature is the highest 300 DEG C;
To 1 of molecular sieve drying be used subsequently, 5-pentanediol 4L/h, water-content 400wppm enters vaporizer after passing into and mixing with hydrogen 115L/h in mixing tank, enter after abundant vaporization in dehydrogenation reactor, desorption temperature controls 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 at more than 99mol%, and water-content, lower than 0.1wt%, does not detect 5-hydrogenation of hydroxypentylaldehyd; Catalyzer continuous and steady operation is after 3000 hours, and reactivity worth is still stablized, and outlet composition is basically identical with the initial stage.
Embodiment 4, the thick product of gained is obtained qualified product after two atmospheric tower rectifying, DVL content is greater than 99.8wt%, from 1,5-PD to the total recovery of DVL more than 95%.
Claims (7)
1. a production method for δ-valerolactone, is characterized in that, uses 1,5-pentanediol is as raw material, and under the effect of dehydrogenation catalyst, generate δ-valerolactone, concrete steps are as follows: the first step, 1,5-PD raw material is entered in drying tower and dewaters, ensure that water-content is lower than 0.1wt%; Second step, enters in vaporizer after being mixed by hydrogen with dried 1,5-PD, and the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; 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, by 1 under the effect of dehydrogenation catalyst, 5-pentanediol is converted into δ-valerolactone, wherein δ-valerolactone yield is more than 98%, to export 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 to be 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 be selected from titanium oxide, zirconium white and calcium oxide one or more.
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 controls to be 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN103980241A CN103980241A (en) | 2014-08-13 |
| CN103980241B true CN103980241B (en) | 2015-10-21 |
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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 |
-
2014
- 2014-04-23 CN CN201410162813.0A patent/CN103980241B/en active Active
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 |
|---|
| Dehydration of 1,5-pentanediol over rare earth oxides;Fumiya Sato et al.;《Applied Catalysis A: General》;20120114;第419-420卷;第41-48页 * |
| Dehydrogenative Esterification over Copper-based Catalyst;K. Inui et al.;《Studies in Surface Science and Catalysis》;Elsevier B.V.;20071231;第172卷;第547-548页 * |
| δ-环戊内酯的合成及应用;程丹等;《安徽化工》;20070815;第33卷(第4期);第6-9页 * |
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| CN103980241A (en) | 2014-08-13 |
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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 |
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Address after: 457000 Meiqi Chemical Co., Ltd., West Section of Shengli Road, Puyang City, Henan Province Patentee after: New Maiqi Materials Co.,Ltd. Country or region after: China Address before: 457000 Meiqi Chemical Co., Ltd., West Section of Shengli Road, Puyang City, Henan Province Patentee before: MYJ CHEMICAL CO.,LTD. Country or region before: China |