CN102249886A - Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework - Google Patents
Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework Download PDFInfo
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- CN102249886A CN102249886A CN2011101304833A CN201110130483A CN102249886A CN 102249886 A CN102249886 A CN 102249886A CN 2011101304833 A CN2011101304833 A CN 2011101304833A CN 201110130483 A CN201110130483 A CN 201110130483A CN 102249886 A CN102249886 A CN 102249886A
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- Prior art keywords
- beta
- methylnaphthalene
- mcm
- molecular sieve
- iron
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- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 11
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 230000018199 S phase Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by an MCM-41 molecular sieve with an iron-containing framework. Specifically, an MCM-41 molecular sieve with an iron-containing framework is employed as a catalyst to oxidize beta-methylnaphthalene for preparing beta-methyl naphthoquinone, with a beta-methylnaphthalene conversion rate of 65% and a beta-methyl naphthoquinone selectivity of 37%. The method of the invention can substantially improve the conversion rate in beta-methyl naphthoquinone production through beta-methylnaphthalene oxidation, and greatly shorten the reaction time. Wherein, the catalyst is repeatedly usable.
Description
Technical field
The present invention relates to the preparation method of Beta-methyl naphthoquinones, and relate to the ferruginous MCM-41 molecular sieve catalyst of a kind of skeleton.
Background technology
The Beta-methyl naphthoquinones is that synthetic K is the important intermediate of VITAMIN, has been widely used at aspects such as medicine and fodder additivess.Because Beta-methyl naphthoquinones of many uses, the synthetic method of this compound that also a lot of bibliographical informations arranged at present.
People such as Nakaoji K have reported in its patent (Nakaoji Kozo, Nakaoji Shigeru. JP:10245358,1998.) and have utilized dichromic acid that the Beta-methyl naphthoquinones aqueous solution is handled about 2.7h down at 90 ℃ that productive rate can reach 64.7%.This technology can produce a large amount of chromate waste waters in process of production, handles numerous and diverse difficulty, and environmental pollution is very serious.People (Yamaguchi S, Inoue M. such as Yamaguchi S
J.Chem Pharm Bull. 1986,34,445) reported and in the Glacial acetic acid medium, used the hydrogen peroxide oxidation beta-methylnaphthalene to generate the method for Beta-methyl naphthoquinones.This method product sepn process complexity, and acetic acid has highly corrosive, requires very high to production unit.Among the patent US4.632.782, generate quinone with blended sulfuric acid trivalent, tetravalent cerium salt oxidation naphthalene.But because the power consumption during the very expensive and oxidation of cerium salt is too big, Financial cost is too high, is extensive use of bigger difficulty.People such as Zhu Aishi (Zhu Aishi, Sun Jun.
Chinese Journal of Pharmaceuticals. 1999,30,324) be oxygenant with organo-peroxide (as Peracetic Acid), glacial acetic acid is a reaction medium, it is 98% Beta-methyl naphthoquinones product that reaction obtains massfraction, but because some organo-peroxide is expensive, so the production cost of this method is higher.
People (Oscar A. Anunziata, Liliana B. Pierella. such as Oscar A. Anunziata
J. Mol. Catal. A-Chem.1999,149:255) reported the application of Beta type zeolite catalyst in the preparation of Beta-methyl naphthoquinones that contains elemental iron or titanium.This method is a catalyzer (Beta type zeolite: the large pore molecular sieve with three-dimensional twelve-ring craspedodrome pore passage structure with the Beta type zeolite that contains ferro element, aperture size surpasses 50nm), with the acetonitrile is solvent, generate the Beta-methyl naphthoquinones with the hydrogen peroxide oxidation beta-methylnaphthalene, react that transformation efficiency is 24% after 4 hours, selectivity of product is 39%.
The MCM-41 molecular sieve appears at people (C.T. Kresge, M.E. Leonowicz. such as Kresge the earliest as a kind of ordered mesoporous material of six side's phases
Nature1992,359:710) in the report, it is a kind of novel nano structural material, and the duct is six side's phase ordered arrangement and aperture size between 2-10nm.Transition metal atoms (as Fe) is introduced in the framework of molecular sieve, made it homodisperse and become the active centre of catalyzed reaction, become the current research focus.People such as Jian Panming are in its patent (Jian Panming, Pan Duoli, Fu Qiang, Guiyang, the village etc.CN200810194551.0) reported the preparation method of doping MCM-41 molecular sieve in, Co, Cu, Fe or Ni have been introduced in the MCM-41 framework of molecular sieve.
Summary of the invention
The present invention with the ferruginous MCM-41 molecular sieve of skeleton (write a Chinese character in simplified form: it is as follows Fe-MCM-41) to be that the catalyst oxidation beta-methylnaphthalene prepares the step of Beta-methyl naphthoquinones:
A. beta-methylnaphthalene, acetonitrile and Fe-MCM-41 are put into container, stir down temperature is raised to 100 ℃; The mass ratio of beta-methylnaphthalene and acetonitrile is 1: 1-40; The mass ratio of beta-methylnaphthalene and Fe-MCM-41 is 1: 0.05-0.2
B. in container, slowly add hydrogen peroxide, under 100 ℃, stirring reaction 1-4 hours; The mass ratio of hydrogen peroxide and beta-methylnaphthalene is 1:0.05-0.5
C. reaction finishes after-filtration, separates, and obtains product Beta-methyl naphthoquinones
The invention is characterized in that with the ferruginous MCM-41 molecular sieve of skeleton (Fe-MCM-41) be catalyzer, the quality percentage composition of iron is 4%-30% in the molecular sieve.
Gas chromatographic analysis shows: the beta-methylnaphthalene transformation efficiency reaches 65%, and the selectivity of Beta-methyl naphthoquinones reaches 37%.This method has significantly improved the beta-methylnaphthalene oxidation and has prepared the transformation efficiency of Beta-methyl naphthoquinones and significantly shortened the reaction times, and catalyzer is reusable.
Embodiment
Following examples only are used for the present invention is specifically described.But protection scope of the present invention is not limited in following examples.(following is the quality percentage composition) embodiment 1: with Fe-MCM-41 catalyzer (iron level 4%) 0.05g, beta-methylnaphthalene 0.5g, acetonitrile 14g pack in the reactor, mixing and stirring, lasting agitation condition is warmed up to 100 ℃, slowly adds the 3g hydrogen peroxide, adds in 15 minutes.React after 1 hour, mixture is filtered, separate, obtain product Beta-methyl naphthoquinones.Gas chromatographic analysis: the beta-methylnaphthalene transformation efficiency is 61%, and Beta-methyl naphthoquinones selectivity is 35%.
Embodiment 2: with Fe-MCM-41 catalyzer (iron level 25%) 0.1g, beta-methylnaphthalene 0.5g, acetonitrile 14g pack in the reactor, mixing and stirring, and lasting agitation condition is warmed up to 100 ℃, slowly adds 3 g hydrogen peroxide, adds in 15 minutes.React after 1 hour, mixture is filtered, separate, obtain product Beta-methyl naphthoquinones.Gas chromatographic analysis: the beta-methylnaphthalene transformation efficiency is 71%, and Beta-methyl naphthoquinones selectivity is 31%.
Embodiment 3: with Fe-MCM-41 catalyzer (iron level 8%) 0.05g, beta-methylnaphthalene 0.5g, acetonitrile 14g pack in the reactor, mixing and stirring, and lasting agitation condition is warmed up to 100 ℃, slowly adds 3 g hydrogen peroxide, adds in 15 minutes.React after 1 hour, mixture is filtered, separate, obtain product Beta-methyl naphthoquinones.Gas chromatographic analysis: the beta-methylnaphthalene transformation efficiency is 65%, and Beta-methyl naphthoquinones selectivity is 36%.
Embodiment 4: with Fe-MCM-41 catalyzer (iron level 8%) 0.05g, beta-methylnaphthalene 0.5g, acetonitrile 14g pack in the reactor, mixing and stirring, and lasting agitation condition is warmed up to 100 ℃, slowly adds the 7g hydrogen peroxide, adds in 30 minutes.React after 1 hour, mixture is filtered, separate, obtain product Beta-methyl naphthoquinones.Gas chromatographic analysis: the beta-methylnaphthalene transformation efficiency is 64%, and Beta-methyl naphthoquinones selectivity is 20%.
Claims (2)
1. the ferruginous MCM-41 molecular sieve catalytic of a skeleton oxidation beta-methylnaphthalene prepares the method for Beta-methyl naphthoquinones,
It is characterized in that step is as follows:
A. beta-methylnaphthalene, acetonitrile and Fe-MCM-41 are put into container, stir down temperature is raised to 100 ℃
B. in container, slowly add hydrogen peroxide, under 100 ℃, stirring reaction 1-4 hours
C. reaction finishes after-filtration, separates, and obtains product Beta-methyl naphthoquinones.
2. according to the described method of claim 1, the mass ratio that it is characterized in that beta-methylnaphthalene and acetonitrile is 1: 1-40; The mass ratio of beta-methylnaphthalene and Fe-MCM-41 is 1: 0.05-0.2; The mass ratio of hydrogen peroxide and beta-methylnaphthalene is 1:0.05-0.5; The quality percentage composition of iron is 4%-30% among the Fe-MCM-41.
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| CN2011101304833A CN102249886A (en) | 2011-05-19 | 2011-05-19 | Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework |
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| CN2011101304833A CN102249886A (en) | 2011-05-19 | 2011-05-19 | Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516054A (en) * | 2011-12-15 | 2012-06-27 | 东南大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone |
| CN110845318A (en) * | 2019-11-27 | 2020-02-28 | 郑州大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone by catalyzing 2-methylnaphthalene |
| CN110845317A (en) * | 2019-11-27 | 2020-02-28 | 郑州大学 | Method for preparing 2-methyl-1, 4-naphthoquinone by catalytic oxidation of 2-methylnaphthalene with functionalized carbon material |
| CN113171798A (en) * | 2021-05-07 | 2021-07-27 | 南京工业大学 | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone through catalysis |
| CN115974670A (en) * | 2023-01-10 | 2023-04-18 | 南京工业大学 | Method for synthesizing 2-methyl-1,4-naphthoquinone by oxidizing cobalt phthalonitrile polymerization catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516054A (en) * | 2011-12-15 | 2012-06-27 | 东南大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone |
| CN110845318A (en) * | 2019-11-27 | 2020-02-28 | 郑州大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone by catalyzing 2-methylnaphthalene |
| CN110845317A (en) * | 2019-11-27 | 2020-02-28 | 郑州大学 | Method for preparing 2-methyl-1, 4-naphthoquinone by catalytic oxidation of 2-methylnaphthalene with functionalized carbon material |
| CN110845318B (en) * | 2019-11-27 | 2022-08-26 | 郑州大学 | Method for synthesizing 2-methyl-1, 4-naphthoquinone by catalyzing 2-methylnaphthalene |
| CN113171798A (en) * | 2021-05-07 | 2021-07-27 | 南京工业大学 | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone through catalysis |
| CN113171798B (en) * | 2021-05-07 | 2023-07-07 | 南京工业大学 | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis |
| CN115974670A (en) * | 2023-01-10 | 2023-04-18 | 南京工业大学 | Method for synthesizing 2-methyl-1,4-naphthoquinone by oxidizing cobalt phthalonitrile polymerization catalyst |
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Application publication date: 20111123 |