CN100368087C - Nonmetal composite catalytic system consisting of organic matter and use thereof - Google Patents
Nonmetal composite catalytic system consisting of organic matter and use thereof Download PDFInfo
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- CN100368087C CN100368087C CNB2004100335853A CN200410033585A CN100368087C CN 100368087 C CN100368087 C CN 100368087C CN B2004100335853 A CNB2004100335853 A CN B2004100335853A CN 200410033585 A CN200410033585 A CN 200410033585A CN 100368087 C CN100368087 C CN 100368087C
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Abstract
The present invention relates to a nonmetal composite catalytic system for hydrocarbon catalytic selective oxidation. A bicomponent nonmetal catalytic system prepared from organic matter quinone compounds and N-hydroxyphthalimide is used for hydrocarbon selective oxidation and prepares oxygen-containing compounds of alcohol, aldehyde, ketone, acid, hydrogen alkylperoxide, etc. in the mode of the air or the oxygen as an oxygen source. The used quinone compounds comprise organic compounds of benzoquinone, naphthoquinone, anthraquinone, etc. and substituted derivatives thereof. The catalytic system has the characteristics of wide application range of substrate hydrocarbon compounds, mild reaction condition, few by-products, etc.
Description
Technical field
The present invention relates to a kind of nonmetal composite catalyst system, the i.e. a kind of nonmetal composite catalyst system of forming by two kinds of organic matters, specifically, form by quinones or the diphenols organic matter and the N-hydroxyphthalimide that under the oxygen condition, can generate quinones.
The invention still further relates to the method that above-mentioned catalyst is used for the reaction of hydro carbons catalytic selective oxidation, under the effect of this catalyst system and catalyzing, with the hydro carbons is reactant, uses the air or oxygen selective oxidation, generates oxygenatedchemicals such as alcohol, aldehyde, ketone, acid and alkyl peroxide.
Background technology
Organic oxygen-containing compound comprises alcohol, aldehyde, ketone, acid and alkyl peroxide etc., and they all are the meticulous very widely organic products of purposes.The compound of these kinds has multiple production method, wherein, by petrochemicals hydro carbons inexpensive, wide material sources is raw material, under the effect of catalyst, with air or oxygen is oxidant, the direct method of selecting oxygenation to be combined to organic oxygen-containing compound to hydro carbons is the route of succinct economy.This method has obtained many application on industrial production, but the catalyst that uses all is metallic catalyst or metal-organic complex catalyst basically.These methods often exist the reaction temperature height, and feed stock conversion is lower, and selectivity of product is lower, and accessory substance waits not enough more.
European patent (EP858835) has been reported the composite catalyst system that a class is made up of the metallic compound and the N-hydroxyphthalimide of 4-11 family; Under the effect of this catalyst system and catalyzing, hydro carbons can be used molecular oxygen oxidation, generates oxygenatedchemicals; For example, by Mn (acac)
2, RuCl
3, Co (acac)
2Under the composite catalyst system effect of forming with the N-hydroxyphthalimide, reaction 6 hours in acetate under 100 ℃, 90% cyclohexane is oxidized, wherein 76% generates adipic acid.Similarly patent also has world patent (WO9728897,2000048972), Japan Patent (JP11349493,11279112) etc.
The above-mentioned this composite catalyst system of being made up of N-hydroxyphthalimide and metallic compound all needs to use one or more metallic compounds to be used as one or more components.
Summary of the invention
The purpose of this invention is to provide the nonmetal composite catalyst system that a kind of organic matter is formed.
Another object of the present invention is to utilize above-mentioned catalyst system and catalyzing, is that reactant prepares organic oxygen-containing compound with the hydro carbons.
For achieving the above object, technological thought of the present invention is:
With the N-hydroxyphthalimide is a kind of fixedly component, and the quinones organic compound is second component, is combined into nonmetal composite catalyst system.The mass ratio of quinones and N-hydroxyphthalimide can be 0.01-10, and preferable mass ratio is 0.05-5, and best mass ratio is 0.1-1.
Described second component comprises quinones and can generate the organic matter of quinones under the oxygen condition; Wherein, quinones comprises benzoquinones class, naphthoquinones class and anthraquinone class organic compound; The organic matter that can generate quinones under the oxygen condition is meant benzenediol class, naphthalenediol class and oxanthranol class.
Described quinones and diphenols compound can be not contain substituent parent compound, also can be to contain one or more substituent naphthoquinone derivatives; Described substituting group comprises-R ,-OH ,-NH
2,-OR ,-COOH ,-COOR ,-F ,-Cl ,-Br ,-SO
3H ,-NO
2,-CN etc.; Substituent position can be various possible positions.
The present invention is used for hydrocarbon oxidization with above-mentioned catalyst system and catalyzing and prepares organic oxygen-containing compound, and the key step of its method is:
Catalyst system and catalyzing and reactant hydro carbons are placed in the reactor, stir, 25-120 ℃, oxygen source pressure 0.2-1.0MPa reacted 1-20 hour.
The mass concentration scope of nonmetal composite catalyst system can 0.1-20%; When use amount was high, oxidation effectiveness was better, but can increase cost, and therefore, preferable concentration is 0.5-15%, and best concentration is 1-10%.
Described hydro carbons comprises cycloalkane and contains the unsaturated hydrocarbons compounds of α-H.
Described oxygen source is an air or oxygen.
The present invention has following advantage: the reaction condition gentleness, do not use metallic compound, and the over oxidation accessory substance is few, and applied widely.
The specific embodiment
Below by embodiment method provided by the invention is described in detail, but do not limit the present invention in any form.The formation of its component of catalyst system and catalyzing that adopts such as: the present invention, though and to be used to react the kind of raw material hydro carbons of usefulness very extensive, as long as technical scheme according to the invention, all can be used for realizing the present invention.In view of the above, for simplicity's sake, the present invention is not enumerated out one by one in an embodiment.Those skilled in the art are according to technical scheme of the present invention and in conjunction with the embodiments, are readily appreciated that and implement.
Embodiment 1: the ethylbenzene air oxidation
In 250 milliliters there-necked flask, drop into 100 milliliters of ethylbenzene, 1.6 gram N-hydroxyphthalimides and 15.7 gram 1-fluoro-9, the 10-anthraquinone; Stir down heat temperature raising to 80 ℃, with the wireway that inserts in the reactant liquor, bubbling air continuously, air mass flow is 50 ml/min, discharges from serpentine condenser more than air, react 15 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of ethylbenzene is 45.1%, and the selectivity of acetophenone is 60.3%, and the selectivity of 1-benzyl carbinol is 15.5%, and the selectivity of 1-phenethyl hydrogen peroxide is 24.1%.
Embodiment 2: the ethylbenzene dioxygen oxidation
In 250 milliliters autoclave pressure, drop into 50 milliliters of ethylbenzene, 2.0 gram N-hydroxyphthalimides and 1.0 gram 2-ethyls-9, the 10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 80 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.5MPa, react 5 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of ethylbenzene is 38.3%, and the selectivity of acetophenone is 52.3%, and the selectivity of 1-benzyl carbinol is 11.5%, and the selectivity of 1-phenethyl hydrogen peroxide is 36.1%.
Embodiment 3: the ethylbenzene dioxygen oxidation
Press the identical method of embodiment 2 to ethylbenzene oxidation, the different quinones that only is to use, reaction result sees Table 1.Ketone was represented acetophenone during table 1 product distributed, and alcohol is represented the 1-benzyl carbinol, crossed representative 1-phenethyl hydrogen peroxide.
Table 1: various quinones obtain the reaction result that the diphenols compound is used for ethylbenzene oxidation
| Numbering | Quinones or diphenols compounds | Conversion ratio (%) | Product distribution (%) | ||
| Ketone | Alcohol | Cross | |||
| 1 | 2,3-dimethoxy 1,4-benzoquinone | 20.3 | 33.1 | 12.6 | 54.0 |
| 2 | Hydroquinones | 13.1 | 30.5 | 13.1 | 56.2 |
| 3 | 1, the 4-naphthoquinones | 45.5 | 40.7 | 15.0 | 44.0 |
| 5 | 1,4-naphthoquinones-2-carboxylate methyl ester | 50.4 | 48.8 | 5.0 | 46.1 |
| 6 | 1, the 4-dihydroxy naphthlene | 21.8 | 41.3 | 14.7 | 44.0 |
| 7 | 9, the 10-anthraquinone | 42.5 | 30.0 | 15.8 | 54.2 |
| 9 | 2-fluoro-9, the 10-anthraquinone | 59.5 | 47.7 | 5.4 | 46.8 |
| 11 | 1,4-diaminourea-2,3-two chloro-9,10-anthraquinone | 65.8 | 72.8 | 13.8 | 13.5 |
| 12 | 1,4-diaminourea-2,3-dicyano-9,10-anthraquinone | 63.3 | 70.6 | 10.5 | 18.8 |
Embodiment 4: cyclohexane oxidation
In 250 milliliters autoclave pressure, drop into 100 milliliters of cyclohexanes, 7.2 gram N-hydroxyphthalimides and 0.7 gram 1-amino-4-bromo-9, the 10-anthraquinone-2-sulfonic acid; The envelope still stirs down heat temperature raising when temperature in the kettle is 90 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.3MPa, react 10 hours, with gas chromatograph assay products composition.The result is, conversion of cyclohexane is 11.3%, and the selectivity of cyclohexanone is 52.3%, and the selectivity of cyclohexanol is 31.5%, and the selectivity of cyclohexyl hydroperoxide is 16.1%.
Embodiment 5: cyclohexene oxide
In 250 milliliters autoclave pressure, drop into 100 milliliters of cyclohexene, 40 milligrams of N-hydroxyphthalimides and 40 milligram 1,4-naphthoquinones-1-carboxylic acid; The envelope still stirs down heat temperature raising when temperature in the kettle is 100 ℃, and aerating oxygen oxygen to the still is pressed and reached 1.0MPa, react 20 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of cyclohexene is 93.3%, and the selectivity of hexamethylene-2-ketenes is 82.3%, and the selectivity of hexamethylene-2-enol is 5.5%, and the selectivity of cyclohexyl hydroperoxide is 6.1%.
Embodiment 6: the cyclopentene oxidation
In 250 milliliters autoclave pressure, drop into 50 milliliters of cyclopentene, 400 milligrams of N-hydroxyphthalimides and 4 milligram 9,10-dihydroxy-anthracene; The envelope still stirs down heat temperature raising when temperature in the kettle is 60 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.3MPa, react 4 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of cyclopentene is 97.0%, and the selectivity of ring penta-2-ketenes is 76.3%, and the selectivity of ring penta-2-enol is 8.5%, and the selectivity of cyclohexyl hydroperoxide is 3.1%.
Embodiment 7: toluene oxidation
In 250 milliliters autoclave pressure, drop into 50 milliliters of toluene, 5.0 gram N-hydroxyphthalimides and 1.0 gram 1-nitros-9, the 10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 30 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.3MPa, react 17 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of toluene is 45.0%, and benzoic selectivity is 63.3%, and the selectivity of benzaldehyde is 18.5%, and the selectivity of phenmethylol is 10.5%, and the selectivity of benzyl hydrogen peroxide is 7.7%.
Embodiment 8: the adamantane oxidation
In 250 milliliters autoclave pressure, drop into 50 gram adamantane, 1.4 gram N-hydroxyphthalimides and 1.0 gram 2-(N-methylamino) 1,4-benzoquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 50 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.2MPa, react 12 hours, with gas chromatograph assay products composition.The result is, the conversion ratio of adamantane is 55.5%, and the selectivity of adamantane-1-alcohol is 54.3%, and the selectivity of adamantane-2-alcohol is 5.5%, and the selectivity of adamantane ketone is 6.5%, and the selectivity of adamantane hydrogen peroxide is 33.7%.
Embodiment 9: to the fluorine ethylbenzene oxidation
In 250 milliliters autoclave pressure, drop into 50 milliliters to fluorine ethylbenzene, 3.0 gram N-hydroxyphthalimides and 2.0 gram 1-amino-2-bromo-4-hydroxyls-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 70 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.5MPa, react 2 hours, with gas chromatograph assay products composition.The result is, is 88.3% to the conversion ratio of fluorine ethylbenzene, and the selectivity of acetophenone is 92.3%, and the selectivity of 1-benzyl carbinol is 3.5%, and the selectivity of 1-phenethyl hydrogen peroxide is 3.8%.
Embodiment 10:6-methoxyl group-1,2,3,4-naphthane oxidation oxidation
In 250 milliliters autoclave pressure, drop into 50 milliliters of 6-methoxyl groups-1,2,3,4-naphthane, 3.0 gram N-hydroxyphthalimides and 2.0 grams 1,5-dihydroxy-9,10-anthraquinone; The envelope still stirs down heat temperature raising when temperature in the kettle is 120 ℃, and aerating oxygen oxygen to the still is pressed and reached 0.5MPa, react 3 hours, with gas chromatograph assay products composition.The result is, 6-methoxyl group-1,2,3, the conversion ratio of 4-naphthane are 90.3%, 6-methoxyl group-1,2,3, and the selectivity of 4-naphthane-1-ketone is 95.2%, 6-methoxyl group-1-hydroxyl-1,2,3, the selectivity of 4-naphthane is 3.5%.
Claims (6)
1. the nonmetal composite catalyst formed of an organic matter, form by quinone or two phenolic compounds and N-hydroxyphthalimide, the mass ratio of quinone or two phenolic compounds and N-hydroxyphthalimide is 0.01-10, wherein, quinone comprises: benzoquinones, naphthoquinones, anthraquinone or one or more substituent benzoquinones, naphthoquinones or anthraquinone are arranged, described substituent position is meant any commutable position in benzoquinones, naphthoquinones or the anthraquinone, and described substituting group comprises :-OH ,-NH
2,-COOH ,-F ,-Cl ,-Br ,-SO
3H ,-NO
2,-CN; Two phenolic compounds comprise: benzenediol, naphthalenediol and oxanthranol.
2. according to the described catalyst of claim 1, it is characterized in that the mass ratio of quinone or two phenolic compounds and N-hydroxyphthalimide is 0.05-5.
3. according to the described catalyst of claim 1, it is characterized in that the mass ratio of quinone or two phenolic compounds and N-hydroxyphthalimide is 0.1-1.
4. be used for the method that oxidation reactions of hydrocarbons prepares organic oxygen-containing compound according to claim 1,2 or 3 described catalyst, key step is:
0.1-20% by reactant hydrocarbon mass concentration places in the reactor with catalyst, stirs, and 25-120 ℃, oxygen source pressure 0.2-1.0MPa reacted 1-20 hour.
5. in accordance with the method for claim 4, it is characterized in that described hydrocarbon comprises cycloalkane and contains the unsaturated hydrocarbon compound of α-H.
6. in accordance with the method for claim 4, it is characterized in that described oxygen source is an air or oxygen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100490976C (en) * | 2006-02-15 | 2009-05-27 | 中国科学院大连化学物理研究所 | Bionic composite catalyst system for selective oxidation of arene |
| CN101613252B (en) * | 2008-06-25 | 2012-11-07 | 中国科学院大连化学物理研究所 | Method for synthesizing oxygen-containing compounds by selective oxidization of hydrocarbons in the presence of metal and quinine catalyst |
| CN106554365B (en) * | 2016-11-12 | 2019-01-08 | 嘉兴敏实机械有限公司 | A kind of preparation process and its application of entecavir midbodies |
| CN107011133B (en) * | 2017-05-25 | 2020-01-03 | 中国科学技术大学 | Method for directly oxidizing benzylic C-H bond into ketone |
| WO2021035382A1 (en) * | 2019-08-23 | 2021-03-04 | 辽宁凯莱英医药化学有限公司 | Method forcontinuous synthesis of 2-cyclopentene-1-one |
| CN110407678A (en) * | 2019-08-23 | 2019-11-05 | 辽宁凯莱英医药化学有限公司 | 2- cyclopentene-1-one is continuously synthesizing to method |
| CN114054085B (en) * | 2020-08-03 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst composition and method for synthesizing isophthalic acid by oxidizing metaxylene |
| CN112574102B (en) * | 2020-12-24 | 2022-05-13 | 安道麦安邦(江苏)有限公司 | Novel method for synthesizing pymetrozine intermediate nicotinaldehyde |
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| US6037477A (en) * | 1997-05-13 | 2000-03-14 | Daicel Chemical Industries, Ltd. | Oxidation process of ethers |
| CN1087726C (en) * | 1997-03-11 | 2002-07-17 | 大赛璐化学工业株式会社 | Oxidation process for branched chain aliphatic hydrocarbon and process for preparing oxide thereof |
| US6642419B1 (en) * | 1999-02-19 | 2003-11-04 | Daicel Chemical Industries, Ltd. | Oxidation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087726C (en) * | 1997-03-11 | 2002-07-17 | 大赛璐化学工业株式会社 | Oxidation process for branched chain aliphatic hydrocarbon and process for preparing oxide thereof |
| US6037477A (en) * | 1997-05-13 | 2000-03-14 | Daicel Chemical Industries, Ltd. | Oxidation process of ethers |
| US6642419B1 (en) * | 1999-02-19 | 2003-11-04 | Daicel Chemical Industries, Ltd. | Oxidation method |
Non-Patent Citations (1)
| Title |
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| 烃类氧化新的N-羟基邻苯二甲酰亚胺基催化氧化体系. 章永洁等.化学工业与工程，第21卷第1期. 2004 * |
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