CN103506133A - Anti-dehalogenation Pd-Fe/C catalyst for preparing halogen aniline and preparation method of same - Google Patents
Anti-dehalogenation Pd-Fe/C catalyst for preparing halogen aniline and preparation method of same Download PDFInfo
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- CN103506133A CN103506133A CN201310431573.5A CN201310431573A CN103506133A CN 103506133 A CN103506133 A CN 103506133A CN 201310431573 A CN201310431573 A CN 201310431573A CN 103506133 A CN103506133 A CN 103506133A
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Abstract
The invention provides an anti-dehalogenation Pd-Fe/C catalyst for preparing halogen aniline and a preparation method of the catalyst. The Pd-Fe/C catalyst is prepared through the dipping reduction method by adopting Fe as doping element and active carbons as carrier, wherein the atom ratios of Pd to Fe are respectively 1: 1, 2: 1 and 1: 2; the catalyst is used for preparing the halogen aniline through hydrogenation of halogen nitrobenzene; the selectivity is high up to 98.9%; the dehalogenation condition is greatly modified; and the catalyst can be continuously used more than 20 times. The catalyst of the invention has high selectivity; and the adopted preparation method has the advantages of mild reaction conditions, low catalyst dosage, high catalytic hydrogenation activity and reuse capacity, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of catalyst, relate in particular to the loading type Pd-Fe/C Catalysts and its preparation method for halo aniline for halogenated nitrobenzene Hydrogenation.
Background technology
Halo aniline, if chloroaniline, fluoroaniline, fluorochlorobenzene amine are Elementary Chemical Industry raw materials, its application is very extensive, both can be used as pesticide intermediate, also can be used as medicine intermediate, and can be used as fine chemistry industry, the basic material of the deep processed products such as electronic material.
General with hydrogenation catalysts such as skeleton Ni, Pd/C, but easy dehalogenation causes catalyst poisoning, reduces reaction yield.Generally dehalogenation inhibitor can be in reaction, added, but product quality can be affected.Also can make in advance catalyst poisoning, reduce the activity of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of reaction condition is gentle, catalyst amount is few, catalytic hydrogenation activity is high halogenated nitrobenzene Hydrogenation for the preparation method of halogeno-benzene amine catalyst.
For solving the problems of the technologies described above, the invention provides a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline, adopt Fe as doped chemical, active carbon is carrier, in catalyst, the mol ratio of Pd:Fe atom is 1:l, 2:1 and 1:2, and described Pd-Fe/C catalyst for halo aniline, selectively can reach 98.9% for halogenated nitrobenzene Hydrogenation, dehalogenation situation is greatly improved, and catalyst can be applied mechanically more than 20 times continuously.
The present invention also provides a kind of preparation method of the anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline: adopt Fe as doped chemical, take active carbon as carrier, by dipping method of reducing, prepare, concrete preparation method is as follows:
Take pretreated active carbon; add isopropyl alcohol and deionized water; after ultrasonic being uniformly dispersed; with mixing containing FeCl3 with containing two solution of PdCl2 of dissolve complete, inert gas shielding, the formalin that drips 0.1-0.5mol/L under ultrasonic and 60～80 ℃ of constant temperature is made reducing agent; in this process, to solution, add NaOH solution to make its pH value remain on 8; after formaldehyde drips completely, then continuing to react 2～6h so that it reacts thoroughly. suction filtration after reacting completely, washing is to neutrality and without Cl
-, finally in vacuum drying chamber, at 40～50 ℃, be dried 24～48h, obtain for halogenated nitrobenzene Hydrogenation for halogeno-benzene amine catalyst Pd-Fe/C catalyst.
Described carrier pretreatment be by active carbon with rare nitric acid at 60 ℃～70 ℃ stirring and refluxing 10～12h, suction filtration, is washed till neutrality by deionized water, standby after 80 ℃～120 ℃ oven dry dewater.
Described activated carbon dosage, by the Pd-Fe/C calculated finally making: (Pd+Fe)/C (M/M)=40～45%.
The weight of described isopropyl alcohol is 50～100 times of ferric trichloride weight, and the 50-150 of the weight that the weight of deionized water is ferric trichloride doubly.
Described containing FeCl
3with containing PdCl
2two solution usage be 10～20 times of ferric trichloride consumption, FeCl in solution
3and PdCl
2mass ratio 1:0.55,1:1.09 and 1:2.19.
Described inert gas is nitrogen or helium.
The molal weight of described formalin is counted 5～10 times of ferric trichloride molal weight with pure formaldehyde amount.
The activity rating reaction of catalyst is carried out in batch reactor.In reaction pressure, be 1～1.5 MPa, temperature is 60～90 ℃, reacts 8～12h, and halogenated nitrobenzene is reaction raw materials, and absolute methanol is solvent.Gas-chromatography is carried out sample analysis.
The prepared catalyst of the present invention is compared with traditional Pd/C catalyst, has the following advantages: (1) reaction selectivity is high, reaches 98.9%; (2) reaction condition is gentle, can make reaction temperature be down to 60～70 ℃, pressure 1～1.5 MPa; (3) catalyst amount is less, and catalytic hydrogenation activity is high and reusable, and catalyst can be applied mechanically more than 20 times continuously, is suitable for industrial production.
The specific embodiment
By the following examples the present invention is described in further details, but does not form any restriction to the scope of the present invention.
Embodiment 1
The preparation of Pd-Fe/C (Pd:Fe is 2:1) catalyst: take the pretreated active carbon of 0.2g; add 8ml isopropyl alcohol and 10ml deionized water; after ultrasonic being uniformly dispersed; with mixing containing FeCl3 0.08g with containing two solution of PdCl2 0.176g of dissolve complete; nitrogen protection; the formalin 25ml that drips 0.3mol/L under ultrasonic and 60 ℃ of constant temperature makees reducing agent; in this process, to solution, add NaOH solution to make its pH value remain on 8; after formaldehyde drips completely; continuing again to react 2h so that its reaction is thorough. suction filtration after reacting completely, washing is to neutrality and without Cl
-, finally in vacuum drying chamber, at 40 ℃, be dried 24h, obtain Pd-Fe/C (Pd:Fe is 2:1) catalyst.Pd-Fe/C (Pd:Fe is 1:1), the preparation method of Pd-Fe/C (Pd:Fe is 1:2) catalyst is the same.
Embodiment 2
According to embodiment 1, we test different halogenated nitrobenzenes, and contrast hydroconversion condition and result are as follows
In sum, Pd-Fe/C catalyst prepared by the present invention not only can well transform halogenated nitrobenzene, and dehalogenation when can better restrain hydrogenation.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified or is equal to replacement technical scheme of the present invention; and not departing from aim and the scope of technical scheme, it all should be encompassed in claim scope of the present invention.
Claims (8)
1. for the preparation of an anti-dehalogenation Pd-Fe/C catalyst for halo aniline, it is characterized in that: described catalyst is usingd Fe as mixing element, and active carbon is carrier, in catalyst, Pd:Fe atomic molar is than being 1:l, 2:1 and 1:2.
2. for the preparation of a preparation method for the anti-dehalogenation Pd-Fe/C catalyst of halo aniline, it is characterized in that: adopt Fe as doped chemical, take active carbon as carrier, by dipping method of reducing, prepare, concrete preparation method is as follows:
Take pretreated active carbon, add isopropyl alcohol and deionized water, after ultrasonic being uniformly dispersed, with the FeCl that contains of dissolve complete
3with containing PdCl
2two solution mix; inert gas shielding; the formalin that drips 0.1-0.5mol/L under ultrasonic and 60～80 ℃ of constant temperature is made reducing agent; in this process, to solution, add NaOH solution to make its pH value remain on 8; after formaldehyde drips completely; continue again to react 2～6h so that its reaction is thorough, suction filtration after reacting completely, washing is to neutrality and without Cl
-, finally in vacuum drying chamber, at 40～50 ℃, be dried 24～48h, obtain for halogenated nitrobenzene Hydrogenation for halogeno-benzene amine catalyst Pd-Fe/C catalyst.
3. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, it is characterized in that: described carrier pretreatment for by active carbon with rare nitric acid at 60 ℃～70 ℃ stirring and refluxing 10～12h, suction filtration, by deionized water, be washed till neutrality, standby after 80 ℃～120 ℃ oven dry dewater.
4. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, it is characterized in that: described activated carbon dosage, by the Pd-Fe/C calculated finally making: (Pd+Fe)/C (M/M)=40～45%.
5. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, it is characterized in that: the weight of described isopropyl alcohol is 50～100 times of ferric trichloride weight, the 50-150 of the weight that the weight of deionized water is ferric trichloride doubly.
6. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, it is characterized in that: the weight of described isopropyl alcohol is 50～100 times of ferric trichloride weight, the 50-150 of the weight that the weight of deionized water is ferric trichloride doubly.
7. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, is characterized in that: described inert gas is nitrogen or helium.
8. the preparation method of a kind of anti-dehalogenation Pd-Fe/C catalyst for the preparation of halo aniline according to claim 2, is characterized in that: the molal weight of described formalin is counted 5～10 times of ferric trichloride molal weight with pure formaldehyde amount.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
| CN109621992A (en) * | 2019-02-11 | 2019-04-16 | 陈欣 | A method of catalysis preparation treatment breast cancer medicines lapatinib intermediate |
| CN110624571A (en) * | 2019-09-27 | 2019-12-31 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
| CN111151267A (en) * | 2020-01-15 | 2020-05-15 | 辽宁科技大学 | Recoverable hydrogenation catalyst with magnetic porous carbon material loaded with zero-valent Fe-Pd, and preparation method and application thereof |
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| WO2004063170A1 (en) * | 2003-01-09 | 2004-07-29 | University Of Delhi | A process for the synthesis of bisbenzimidazoles and its derivations |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004063170A1 (en) * | 2003-01-09 | 2004-07-29 | University Of Delhi | A process for the synthesis of bisbenzimidazoles and its derivations |
| CN102786424A (en) * | 2012-08-22 | 2012-11-21 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| MENGYIN LIAO ET AL.: "Pd decorated Fe/C nanocatalyst for formic acid electrooxidation", 《ELECTROCHIMICA ACTA》, vol. 111, 28 August 2013 (2013-08-28), pages 504 - 509, XP028768597, DOI: doi:10.1016/j.electacta.2013.08.102 * |
| 江红等: "掺杂Fe元素对Pd/C催化剂性能的影响", 《无机材料学报》, vol. 23, no. 4, 31 July 2008 (2008-07-31), pages 847 - 850 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
| CN109621992A (en) * | 2019-02-11 | 2019-04-16 | 陈欣 | A method of catalysis preparation treatment breast cancer medicines lapatinib intermediate |
| CN110624571A (en) * | 2019-09-27 | 2019-12-31 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
| CN110624571B (en) * | 2019-09-27 | 2022-07-05 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
| CN111151267A (en) * | 2020-01-15 | 2020-05-15 | 辽宁科技大学 | Recoverable hydrogenation catalyst with magnetic porous carbon material loaded with zero-valent Fe-Pd, and preparation method and application thereof |
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