CN101455889A - Halogeno-benzene liquid-phase hydrogenation and dehalogenation method - Google Patents
Halogeno-benzene liquid-phase hydrogenation and dehalogenation method Download PDFInfo
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- CN101455889A CN101455889A CNA2007103059774A CN200710305977A CN101455889A CN 101455889 A CN101455889 A CN 101455889A CN A2007103059774 A CNA2007103059774 A CN A2007103059774A CN 200710305977 A CN200710305977 A CN 200710305977A CN 101455889 A CN101455889 A CN 101455889A
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Abstract
The invention discloses a halogeno benzene liquid-phase hydrogenation and dehalogenation method. The method utilizes palladium loaded by a carbon nanotube as a catalyst and hydrazine hydrate as a hydrogen donor to realize hydrogenation and dehalogenation of halogeno benzene under the condition of liquid-phase reaction at normal pressure. The reaction conditions of the method are mild; the conversion rate of a substrate can reach as high as 99 percent; the selectivity of corresponding dehalogenation products is 100 percent; the palladium loading is low; and the catalyst can be recycled.
Description
Technical field
The present invention relates to a kind of method of halogeno-benzene liquid-phase hydrogenation and dehalogenation.
Background technology
The fragrance halogenated organic compounds be the most general also be one of the most stable toxic pollutant.The processing of these class debirs is critical environmental problems.The processing of traditional halogenated organic compound comprises direct decomposition and oxidation, and this process needs very high temperature usually, discharges a large amount of toxic gases simultaneously.The method of catalytic hydrogenation dehalogenation is because can avoid the formation of toxic compounds and relatively low reaction temperature to be subjected to people's attention just day by day.In hydrodehalogenation reaction catalyzed, catalyst is being played the part of crucial role.Precious metals pd is considered to the most effective hydrodehalogenation catalyst usually.People have investigated the performance of various Pd catalyst, for example: homogeneous phase Pd complex compound, Pd/C, Pd/ZrO
2And the Pd catalyst of other metal oxides or polyvinyl resin load.These catalyst all are proved to be effective hydrodehalogenation catalyst.Yet traditional heterogeneous hydrodehalogenation catalyst also needs to overcome following obstacle: 1. the high activity of catalyst depends on higher Pd load capacity to a great extent, is generally 5-10wt%, and therefore, the cost of catalyst is higher.2. the halogen acids that produces in the course of reaction causes catalyst stability to descend to poisoning of active component.3. the loss of Pd causes catalyst separation and reclaims difficulty in the liquid phase.Many researchers think that the method that overcomes these obstacles is to seek the carrier of new type.
Summary of the invention
The object of the invention is at prior art, seeks a kind of catalyst and realizes the halogeno-benzene liquid-phase hydrogenation and dehalogenation method.
Invention thought of the present invention is to utilize carbon nanotube loaded palladium as catalyst (Pd/CNTs), is hydrogen donor with the hydrazine hydrate, realizes the hydrodehalogenation to halogeno-benzene under the normal pressure liquid-phase reaction condition.
A kind of method of halogeno-benzene liquid-phase hydrogenation and dehalogenation is characterized in that this method with halogeno-benzene, hydrazine hydrate and reaction dissolvent mixing, adds carbon nanotube loaded palladium catalyst then, and under normal pressure, 20-80 ℃ of reaction realizes the liquid-phase hydrogenation and dehalogenation of halogeno-benzene; Wherein reaction dissolvent is selected from methyl alcohol, ethanol, isopropyl alcohol, oxolane, normal octane or water.
The load capacity of palladium catalyst of the present invention is 1-5wt%.
Halogeno-benzene as reaction substrate can be selected from a halo, dihalo and contain other substituent halogeno-benzene, be specially chlorobenzene, bromobenzene, iodobenzene, o-dichlorohenzene, paracide, m-dibromobenzene, paradibromobenzene, parachlorophenol, paranitrochlorobenzene, to the nitro bromobenzene, the stupid or parachloroacetophenone to nitro iodine.
The mol ratio of halogeno-benzene of the present invention and hydrazine hydrate is 1:1.75-1:40.
The mol ratio of halogeno-benzene of the present invention and reaction dissolvent is 1:4.9-1:99.
The mass ratio of catalyst of the present invention and halogeno-benzene is 1:3.15-1:24.
The Pd/CNTs catalyst adopts conventional immersion process for preparing, specifically is the CNT behind the purifying is joined in the aqueous solution of palladium bichloride, in ultrasonic wave, handled 0.5-4 hour, and 100 ℃ of dried overnight then, 300 ℃ of roastings obtain.
Reaction condition gentleness of the present invention, the conversion ratio of substrate can be up to more than 99%, and corresponding dehalogenation product selectivity is 100%, and the load capacity of palladium is lower, and catalyst can be recycled.
The present invention has the following advantages: the Pd load capacity that (1) is lower, reduced the cost of catalyst; (2) higher hydrodehalogenation activity and selectivity; (3) with hydrazine hydrate as hydrogen donor, more safer than hydrogen, simpler; (4) Wen He reaction condition; (5) catalyst can recycle and reuse.
The specific embodiment
Embodiment 1:
The CNT of getting behind the 1g purifying joins 16.5ml, the PdCl of 0.01137mol/l
2In the aqueous solution, handled 4 hours in ultrasonic wave, then 100 ℃ of following dried overnight, 300 ℃ of roastings obtained the Pd/CNTs catalyst that load capacity is 2wt% in 3 hours.
Above-mentioned catalyst is used for the debromination of bromobenzene, and with the 5mmol bromobenzene, 4ml methyl alcohol and 2ml (85wt%) hydrazine hydrate mixes, and adds 50mg Pd/CNTs catalyst, and 60 ℃ were reacted 6 hours.The dehalogenation result is the bromobenzene conversion ratio〉99%, the selectivity of product benzene is 100%.
Embodiment 2-14: describe with table 1.
Table 1: experiment condition is: catalyst, 50mg; Bromobenzene, 5mmol; Solvent, 4ml; Reacted 6 hours.
| Embodiment | Reaction temperature (℃) | Solvent | Hydrazine hydrate amount (ml) | Pd load capacity (%) | Bromobenzene conversion ratio (%) | The selectivity of benzene (%) |
| 2 | 60 | Methyl alcohol | 0.5 | 2 | >99 | 100 |
| 3 | 60 | Ethanol | 2 | 2 | >99 | 100 |
| 4 | 60 | Methyl alcohol | 4 | 2 | 98 | 100 |
| 5 | 60 | Isopropyl alcohol | 1 | 2 | >99 | 100 |
| 6 | 60 | Methyl alcohol | 2 | 1 | 51 | 100 |
| 7 | 60 | Water | 2 | 2 | 85 | 100 |
| 8 | 60 | Methyl alcohol | 1 | 2 | >99 | 100 |
| 9 | 20 | Methyl alcohol | 2 | 2 | 80 | 100 |
| 10 | 60 | Normal octane | 3 | 2 | 98 | 100 |
| 11 | 40 | Methyl alcohol | 2 | 2 | 91 | 100 |
| 12 | 80 | Methyl alcohol | 2 | 2 | >99 | 100 |
| 13 | 60 | Methyl alcohol | 2 | 5 | >99 | 100 |
| 14 | 60 | Oxolane | 2 | 2 | 74 | 100 |
Embodiment 15-25: describe with table 2.
Table 2: experiment condition is: 2wt%Pd/CNTs, 50mg; Substrate, 5mmol; Hydrazine hydrate, 2ml (85wt%); Methyl alcohol, 4ml; 60 ℃ of reaction 6h.
Substrate: 1mmol.
Claims (6)
1, a kind of method of halogeno-benzene liquid-phase hydrogenation and dehalogenation is characterized in that this method with halogeno-benzene, hydrazine hydrate and reaction dissolvent mixing, adds carbon nanotube loaded palladium catalyst then, and under normal pressure, 20-80 ℃ of reaction realizes the liquid-phase hydrogenation and dehalogenation of halogeno-benzene; Wherein reaction dissolvent is selected from methyl alcohol, ethanol, isopropyl alcohol, oxolane, normal octane or water.
2, the method for claim 1, the load capacity that it is characterized in that palladium catalyst is 1-5wt%.
3, the method for claim 1 is characterized in that halogeno-benzene is selected from chlorobenzene, bromobenzene, and iodobenzene, o-dichlorohenzene, paracide, m-dibromobenzene, paradibromobenzene, parachlorophenol, paranitrochlorobenzene, to the nitro bromobenzene, the stupid or parachloroacetophenone to nitro iodine.
4, the method for claim 1, the mol ratio that it is characterized in that halogeno-benzene and hydrazine hydrate is 1:1.75-1:40.
5, the method for claim 1, the mol ratio that it is characterized in that halogeno-benzene and reaction dissolvent is 1:4.9-1:99.
6, the method for claim 1, the mass ratio that it is characterized in that catalyst and halogeno-benzene is 1:3.15-1:24.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103059774A CN101455889A (en) | 2007-12-13 | 2007-12-13 | Halogeno-benzene liquid-phase hydrogenation and dehalogenation method |
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| CNA2007103059774A CN101455889A (en) | 2007-12-13 | 2007-12-13 | Halogeno-benzene liquid-phase hydrogenation and dehalogenation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503706A (en) * | 2015-12-28 | 2016-04-20 | 衢州学院 | Dehalogenation degradation method for halogenated pyridine compound |
| CN108465190A (en) * | 2018-05-07 | 2018-08-31 | 南京大学 | A kind of method that iodo x-ray contrast agent liquid phase catalytic hydrogenation takes off iodine |
| CN110721742A (en) * | 2019-10-09 | 2020-01-24 | 中国科学院福建物质结构研究所 | Construction of porous organic framework and application of porous organic framework in hydrodehalogenation reaction |
-
2007
- 2007-12-13 CN CNA2007103059774A patent/CN101455889A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503706A (en) * | 2015-12-28 | 2016-04-20 | 衢州学院 | Dehalogenation degradation method for halogenated pyridine compound |
| CN108465190A (en) * | 2018-05-07 | 2018-08-31 | 南京大学 | A kind of method that iodo x-ray contrast agent liquid phase catalytic hydrogenation takes off iodine |
| CN110721742A (en) * | 2019-10-09 | 2020-01-24 | 中国科学院福建物质结构研究所 | Construction of porous organic framework and application of porous organic framework in hydrodehalogenation reaction |
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Open date: 20090617 |