CN103285856B - A kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline and preparation method thereof - Google Patents
A kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline and preparation method thereof Download PDFInfo
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- CN103285856B CN103285856B CN201310228856.XA CN201310228856A CN103285856B CN 103285856 B CN103285856 B CN 103285856B CN 201310228856 A CN201310228856 A CN 201310228856A CN 103285856 B CN103285856 B CN 103285856B
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Abstract
The invention discloses a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline and preparation method thereof, relate to a kind of catalyst, the preparation method of the halonitro prepared from benzene and hydrogen halogeno-benzene amine catalyst that a kind of reaction condition is gentle, catalyst amount is few, catalytic hydrogenation activity is high is provided.Described catalyst comprises hydrogenation component and carrier, described hydrogenation component is metal Ru, add appropriate vanadium pentoxide, carrier is the one in aluminium oxide, active carbon, CNT or silica, and the load capacity of hydrogenation component is 1.0wt% ~ 4.0wt% by weight percentage.With infusion process with containing the solution impregnating carrier of Ru presoma, then drying, roasting, reduction obtain for the supported ruthenium catalyst of halonitro prepared from benzene and hydrogen for halo aniline.Prepared catalyst halogenated nitrobenzene conversion ratio is 100%, and dehalogenation is less than 0.1%, is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of catalyst, be specifically related to a kind of for the supported ruthenium catalyst and preparation method thereof of halonitro prepared from benzene and hydrogen for halo aniline.
Background technology
Halo aniline, if chloroaniline, fluoroaniline, fluoroaluminate glasses are Elementary Chemical Industry raw materials, its application is widely, both can as pesticide intermediate, also can as medicine intermediate, and can as fine chemistry industry, the basic material of the deep processed products such as electronic material.The main method of current reduction is generally iron powder reducing, hydrogenating reduction is main.The catalyst that wherein hydrogenation is conventional is Raney's nickel, palladium carbon catalyst, platinum carbon, must add different suppression agent during its reduction.
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 halonitro prepared from benzene and hydrogen for the preparation method of halogeno-benzene amine catalyst.
For solving the problems of the technologies described above, the present invention is achieved through the following technical solutions:
A kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline, comprise hydrogenation component and carrier, described hydrogenation component is metal Ru, and carrier is the one in aluminium oxide, active carbon, CNT or silica, and the load capacity of hydrogenation component is 1.0wt% ~ 4.0wt% by weight percentage.Carrier is all commercially available prod, and specific area requires 150m
2/ more than g.
Described carrier preferably aluminium oxide.
For the preparation of a preparation method for the anti-dehalogenation ruthenium-based catalyst of halo aniline, comprise the steps:
1) pretreatment of carrier:
When carrier is active carbon, by active carbon dust technology at 60 DEG C ~ 70 DEG C stirring and refluxing 10 ~ 12h, suction filtration, is washed till neutrality by deionized water, for subsequent use after 80 DEG C ~ 120 DEG C oven dry dewater;
When carrier is silica, silica dust technology is at room temperature flooded 20 ~ 24h, is washed till neutrality by deionized water, for subsequent use after 450 DEG C ~ 500 DEG C roasting 1 ~ 2h;
When carrier is CNT, by CNT dust technology at 70 DEG C ~ 140 DEG C stirring and refluxing 6 ~ 24h, suction filtration, is washed till neutrality by deionized water, and gained filter cake is dried overnight at 80 DEG C ~ 120 DEG C, for subsequent use after grinding;
2) equi-volume impregnating is adopted, by catalyst proportion, carrier be impregnated in 12 ~ 24h in ruthenium precursor salt compound water solution or ethanolic solution under room temperature, then dry 4 ~ 12h at 80 DEG C ~ 150 DEG C, roasting 2 ~ 6h in air at 300 DEG C ~ 500 DEG C, described ruthenium precursor salt compound is Ru (NO) (NO
3)
3or RuCl
3;
3) by roasting catalyst at 300 DEG C ~ 500 DEG C in hydrogen reductase 12 ~ 6h, obtain for halogenated nitrobenzene Hydrogenation for halogeno-benzene amine catalyst.
The activity rating reaction of catalyst is carried out in batch reactor.Be 1.50MPa in reaction pressure, temperature is 90 DEG C, and reaction 8h, halogenated nitrobenzene is reaction raw materials, and absolute methanol is solvent.Gas-chromatography carries out sample analysis.
Beneficial effect of the present invention: the catalyst prepared by the present invention, compared with traditional Raney's nickel catalyst, has the following advantages:
(1) preparation method is simple;
(2) reaction condition is gentle, reaction temperature can be made to be down to 90 DEG C, pressure 1.5MPa;
(3) catalyst amount is less, and catalytic hydrogenation activity is high and reusable, is suitable for industrial production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is elaborated.
embodiment 1
1) by 0.0626 gram of Ru (NO) (NO
3)
3be dissolved in 1.2mL ethanol, after stirring and dissolving, obtain Ru (NO) (NO
3)
3ethanolic solution;
2) by 1 gram of active aluminum oxide carrier, (alumina support is commercially available prod, specific area 150m
2/ more than g) and 0.01 gram of vanadium pentoxide be impregnated into above-mentioned Ru (NO) (NO
3)
3in ethanolic solution, at room temperature fully flood 20h, then dry 10h at 80 DEG C, finally in Muffle furnace with 300 DEG C of roasting 4h;
3) by the catalyst for preparing reductase 12 h under 400 DEG C of conditions in hydrogen, obtain the supported ruthenium catalyst that Ru load capacity is 2%, be labeled as 2%Ru/Al
2o
3.
The activity rating reaction of catalyst is carried out in batch reactor, appreciation condition: catalyst amount is 0.01g, chloro-4 fluoronitrobenzenes of 3-are 5 grams, absolute ethyl alcohol 20ml, reaction pressure is 1.5MPa, and temperature is 85 DEG C, reaction 6h, catalyst hydrogenation activity is under the reaction conditions the chloro-4 fluoronitrobenzene conversion ratios (%) of 3-is 100%, and dehalogenation is 0.008%.Same appreciation condition, changes by catalyst as business Raney's nickel catalyst into, and the chloro-4 fluoronitrobenzene conversion ratios of reaction result 3-are 99.5%, dehalogenation reaction thing summation 5.3%; Catalyst is changed into the platinum carbon of 1%, the chloro-4 fluoronitrobenzene conversion ratios of reaction result 3-are 100%, dehalogenation reaction thing summation 2.3%.As can be seen from reaction evaluating result, the catalyst adopting the present invention to prepare has the good Hydrogenation of chloro-4 fluoronitrobenzene of 3-and suppresses dehalogenation performance.
embodiment 2
According to embodiment 1, different halogenated nitrobenzenes is tested, contrast hydroconversion condition and result as follows:
Above-described embodiment is only in order to illustrate technical scheme of the present invention but not to limit design of the present invention and protection domain; those of ordinary skill of the present invention is modified to technical scheme of the present invention or equivalent replacement; and not departing from aim and the scope of technical scheme, it all should be encompassed in right of the present invention.
Claims (7)
1. the anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline, it is characterized in that: described catalyst comprises hydrogenation component and carrier, described hydrogenation component is metal Ru, add appropriate vanadic anhydride, carrier is the one in aluminium oxide, active carbon, CNT or silica, and the load capacity of hydrogenation component is 1.0wt% ~ 4.0wt% by weight percentage.
2. a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 1, is characterized in that: described carrier is Al
2o
3.
3. a preparation method for the anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 1 and 2, is characterized in that: the preparation method of described catalyst is as follows:
1) Vehicle element;
2) equi-volume impregnating is adopted, by catalyst proportion, carrier and vanadic anhydride be impregnated in 12 ~ 24h in ruthenium precursor salt compound water solution or ethanolic solution under room temperature, then dry 4 ~ 12h, roasting 2 ~ 6h in air at 300 DEG C ~ 500 DEG C at 80 DEG C ~ 150 DEG C;
3) by roasting catalyst at 300 DEG C ~ 500 DEG C in hydrogen reductase 12 ~ 6h, the ruthenium-based catalyst of halo aniline must be prepared.
4. the preparation method of a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 3, it is characterized in that: the Vehicle element described in step 1) is at 60 DEG C ~ 70 DEG C stirring and refluxing 10 ~ 12h by active carbon dust technology, suction filtration, neutrality is washed till by deionized water, for subsequent use after 80 DEG C ~ 120 DEG C oven dry dewater.
5. the preparation method of a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 3, it is characterized in that: the Vehicle element described in step 1) is at room temperature to flood 20 ~ 24h by silica dust technology, neutrality is washed till by deionized water, for subsequent use after roasting 1 ~ 2h at 450 DEG C ~ 500 DEG C.
6. the preparation method of a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 3, it is characterized in that: the Vehicle element described in step 1) is at 70 DEG C ~ 140 DEG C stirring and refluxing 6 ~ 24h by CNT dust technology, suction filtration, neutrality is washed till by deionized water, gained filter cake is dried overnight at 80 DEG C ~ 120 DEG C, for subsequent use after grinding.
7. the preparation method of a kind of anti-dehalogenation ruthenium-based catalyst for the preparation of halo aniline according to claim 3, is characterized in that: step 2) described in ruthenium precursor salt compound be Ru (NO) (NO
3)
3or RuCl
3.
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| CN103464149B (en) * | 2013-09-30 | 2016-05-04 | 郑州大学 | Ru/MWCNTs Catalysts and its preparation method |
| CN104292113A (en) * | 2014-03-04 | 2015-01-21 | 多氟多化工股份有限公司 | Preparation method of 3-chloro-4-fluoroaniline |
| CN105801429B (en) * | 2014-12-31 | 2019-09-24 | 安徽新北卡化学有限公司 | A kind of preparation method of the chloro- 2,4 difluorobenzene amine of 3,5- bis- |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
| CN114618504A (en) * | 2022-04-14 | 2022-06-14 | 大连理工大学 | Nickel-oxide composite catalyst for preparing iodoarylamine from iodoaromatic nitro compound at high selectivity and application of nickel-oxide composite catalyst |
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| CN103111293A (en) * | 2013-02-07 | 2013-05-22 | 厦门大学 | Catalyst for preparing p-acetaminocyclohexanol and preparation method thereof |
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| WO1996036597A1 (en) * | 1995-05-19 | 1996-11-21 | Novartis Ag | Process for the catalytic hydrogenation of aromatic nitro compounds |
| CN101569859A (en) * | 2009-05-21 | 2009-11-04 | 江苏康恒化工有限公司 | Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst |
| CN103111293A (en) * | 2013-02-07 | 2013-05-22 | 厦门大学 | Catalyst for preparing p-acetaminocyclohexanol and preparation method thereof |
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