CN101569859A - Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst - Google Patents
Method for preparing halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing a halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst, which comprises the following steps: evenly mixing surfactant aqueous solution with pre-dissolved ruthenium salt solution; adding a reducer to deoxidize the mixture so as to form surfactant stable nano-ruthenium colloidal solution; adding a carrier to the ruthenium colloidal solution for adsorption, and filtering the mixture after the adsorption; and washing the catalyst until the filtrate is neutral to obtain the highly-dispersed supported nano-ruthenium catalyst. The method has the advantages of simplicity, low cost, good repeatability and environmental protection, and the prepared catalyst has high dispersion degree and long service life.
Description
Technical field:
The present invention relates to a kind of catalyst.
Background technology:
Halo aniline is the important organic intermediate of a class, is widely used in the synthetic of fine chemical products such as dyestuff, medicine, agricultural chemicals, spices.Industrial, chloro aminobenzen is generally made by the chloronitrobenzene reduction, and the method that present halogenated nitrobenzene compound is reduced to the chloro aromatic amine compound mainly contains following several: chemical reduction method, electrolytic reduction, carbon monoxide reducing process, catalytic hydrogenating reduction method.Chemical reduction method is organized production as waiting with iron powder, akali sulphide, hydrazine hydrate, boron hydride, and technological process is long, the three wastes are many, big for environment pollution.Electrolytic reduction is not because the industrialization report is seen in the consideration of aspects such as electrode material, electrolysis installation, cost so far at home.The carbon monoxide reducing process has more research in the laboratory, but yet there are no the industrialization report.The hydrogenating reduction method has good product quality, produce that the three wastes are few, post processing reaches advantages such as good reaction selectivity easily, uses very extensive on laboratory research and industrial production.Along with the enhancing of development of science and technology and environmental consciousness, the catalytic hydrogenating reduction technology more and more comes into one's own and develops.Below mainly introduce the progress that the catalytic hydrogenation legal system is equipped with chloro aminobenzen.
In process, usually be accompanied by the hydrogenolysis of carbon-halogen bond, generate aniline the catalytic hydrogenation of halogenated nitrobenzene.Therefore, adopt the key issue of catalytic hydrogenation method synthesizing halogen aniline is how to control the selectivity of reaction, prevent the generation of dechlorination, and hydrogenation selectivity is improved, the crucial selection that is catalyst system again.The present invention proposes halogenated nitrobenzene selective hydrogenation high-activity nano Ru Preparation of catalysts method
Nano metal has and is different from metallic atom and the body special physics and the chemical property of metal mutually, thereby is widely used in fields such as catalysis industry.The character of metal micelle is not only relevant with the size of particle, also is subjected to the influence of its shape reunion situation and oxidation state.Therefore the preparation of the controlled colloidal particle of particle diameter and shape is a challenging subject in the nanometer material science always.In recent years, the metallic colloid that adopts distinct methods to prepare high dispersive, narrow distribution also and then with it loads to the appropriate carriers surface, has become the target that many catalysis workers make great efforts.
Surfactant can be by the change concentration of metal ions as protectant chemical reduction method, the kind of reducing agent and consumption, and surfactant or high molecular concentration, preparation parameters such as temperature and PH are controlled particle diameter, and the preparation method is simple, good reproducibility.Macromolecule commonly used is polyvinylpyrrolidone (PVP), polymine (PEI), polyvinyl alcohol (PVA).PVP is the stable metal colloid effectively, but reaction there is certain inhibitory action, as the coordination that the C=O among Ru atom and the PVP produces, PVP has not just played stabilization to metallic colloid, also the effective absorption of reactant and the desorption of product has been played reaction.Therefore, be badly in need of new surfactant of exploitation or natural and synthetic high polymer stabilizing agent as metallic colloid.
Summary of the invention:
The object of the present invention is to provide that a kind of decentralization height, preparation method are simple, the preparation method of free of contamination halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst.
Technical solution of the present invention is:
A kind of preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst is characterized in that: comprise the following steps: successively
(1) aqueous surfactant solution is even with the ruthenium salt solution mix of dissolving in advance, add the reducing agent reduction then, form surfactant stabilized nano ruthenium colloidal solution;
(2) the ruthenium colloidal solution that step (1) made adds carrier absorption, after adsorption process finishes, filters, and it is neutral that washing catalyst to filtrate is, obtain high degree of dispersion, the loaded nano ruthenium catalyst.
In the step (1) surfactant concentration be critical micelle concentration 1-500 doubly, the concentration of reducing agent is 0.001～1mol/L, reduction temperature is 10-90 ℃, the recovery time is 0.1-12 hour.
Described reducing agent is one or several the mixture in methyl alcohol, formaldehyde, hydrazine hydrate, sodium borohydride, lithium aluminium hydride reduction, the natrium citricum.
Described surfactant is a nonionic surface active agent, is one or more the mixture in sapn type, brij type, hydrogenated rosin glyceride, AEO methyl-monosilane, tween type, polyethylene glycols, APG, the polyvinylpyrrolidone.
Described nail salt is one or more the mixture in ruthenium bromide, ruthenium hydrochloride amine, ruthenium hydrochloride sodium, ruthenic chloride, ruthenium hydrochloride potassium, nitric acid ruthenium, triphenyl phosphorus hydrogenized carbonyl ruthenium, acetic acid ruthenium, carbonyl ruthenic chloride, the triphenyl phosphorus ruthenic chloride.
Described carrier is activated carbon, alundum (Al, silica, zirconium dioxide, tin ash, iron oxide or titanium dioxide; And before using, the carrier except that active carbon must handle the back oven dry through alkali lye.
The used alkali lye of described vehicle treated is one or more the alcoholic solution or the aqueous solution in NaOH, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium butoxide, butanols potassium, the butanols lithium.
Reduction temperature is 20-40 ℃.
The present invention can obtain high degree of dispersion, the loaded nano ruthenium catalyst, the load time of carrier is 3 minutes-3 hours, the load capacity of ruthenium is 0.2wt%-20wt%.Beneficial effect of the present invention also is:
1. surfactant is one or more mixture.
2. the metal Ru colloid decentralized photo of surfactant protection is a water, does not need other organic solvent, has avoided organic contamination, has reduced production cost simultaneously.
3. the metallic colloid of surfactant protection is easy to be adsorbed onto on the carrier, and load factor is up to more than 99.7%, and the nano-ruthenium catalyst stable in properties after the load is difficult for running off, the catalytic activity height, and the life-span is long.
4. method for preparing catalyst is simple, and repeatability is excellent, and the nano-metal particle high degree of dispersion is on carrier, and particle diameter distributes and is mainly the 2-4 nanometer.
5. filtrate filtered can be recycled.
The invention will be further described below in conjunction with embodiment.
The specific embodiment:
Handle through alkali lye earlier before carrier uses among the embodiment 1～4, method is:
The sodium hydrate aqueous solution of preparation 4% is an amount of, and is all moistening with the aluminium oxide that the method for spraying will be handled, 120-125 ℃ of oven dry.
Embodiment 1:
With 0.1g Ru (NO
3)
3Be dissolved in the 50mL water, the hydrochloric acid with 30% is transferred PH=1.0-1.1, and 5g/L PVP solution 3.9mL is added Ru (NO
3)
3In the aqueous solution, stir 1h, dropwise add 4.5g/L NaBH, aqueous solution 40mL obtains the metal Ru colloid that PVP protects after reduction is finished.Add alundum (Al 2g then, stir 2h after, filtration washing makes the ruthenium load capacity and is 3% Ru/AL
2O
3Catalyst.
Embodiment 2:
With 0.1gRuCl
3H
2O is dissolved in the 50mL water, and the hydrochloric acid with 30% is transferred PH=1.0-1.1, dropwise adds 4.5g/L NaBH with stirring 1h in the 5g/L PVP solution 5mL adding RuCl aqueous solution.Aqueous solution 40mL obtains the metal Ru colloid that PVP protects after reduction is finished.Add alundum (Al 2g then, stir 2h after, filtration washing makes the ruthenium load capacity and is 3% Ru/Ru/AL
2O
3Catalyst.
Embodiment 3:
0.2589g acetic acid ruthenium added to be dissolved with in 0.2732g Span20 and the 0.1943gTween20400mL water dissolve hydrochloric acid accent PH=1.0-1.1 with 30%.Dropwise add under the vigorous stirring and contain 0.1374gNaBH.Aqueous solution 200mL, reduction obtains the metal Ru colloid of Span20 and Tween20 protection after finishing.Add alundum (Al 2g in colloidal solution, stir the back and filter washing, THF (oxolane) rinse makes the ruthenium load capacity and is 5% Ru/AL
2O
3Catalyst.
Embodiment 4:
With 0.2589gRuCl
3H
2The O adding is dissolved with the 0.2732g Span20 and the 0.1943gBrij35400mL aqueous solution; hydrochloric acid with 30% is transferred PH=1.0-1.1; dropwise add the aqueous solution 200mL that contains 0.1374gNaBH under the vigorous stirring, obtain the metal Ru colloid of Brij35 and Span20 protection after reduction is finished.Add alundum (Al 2g in colloidal solution, filter washing after stirring 1.5h, the THF rinse makes the ruthenium load capacity and is 5% Ru/AL
2O
3Catalyst.
Embodiment 5:
In being the still formula high-pressure reactor of 100mL, puts into volume 11 grams 3,5-dichloronitrobenzene, 30mL methyl alcohol, 1.5g the catalyst that embodiment 2 makes, airtight back hydrogen exchange 3 times is put into slowly heat temperature raising to 80 ℃ of oil bath, pressurization reaches 6.0MPa, behind the 30min, and sample analysis.3,5-dichloronitrobenzene conversion ratio 100%, 3,5-dichloroaniline selectivity 100%
Embodiment 6:
In being the still formula high-pressure reactor of 100mL, volume puts into the 6g p-Nitrobromobenzene, 20mL water, the catalyst that 0.5g embodiment 1 makes, nitrogen replacement 3 times of airtight post-reactor, hydrogen exchange 3 times is warming up to 100 ℃, add hydrogen to 2MPa, behind the 30min, reaction is finished.Sample analysis, p-Nitrobromobenzene conversion ratio 100%, para-bromoaniline selectivity 100%.
Embodiment 7:
In being the still formula high-pressure reactor of 100mL, volume puts into the 6g m-chloro-nitrobenzene, 20mL methyl alcohol, the catalyst that 0.5g embodiment 2 makes, nitrogen replacement 3 times of airtight post-reactor, hydrogen exchange 3 times is warming up to 90 ℃, add hydrogen to 1.5MPa, behind the 30min, reaction is finished.Sample analysis, m-chloro-nitrobenzene conversion ratio 100%, m-chloroaniline selectivity 100%.
Embodiment 8:
In being the still formula high-pressure reactor of 100mL, volume puts into the 6g o-chloronitrobenzene, 20mL methyl alcohol, the catalyst that 0.5g embodiment 1 makes, nitrogen replacement 3 times of airtight post-reactor, hydrogen exchange 3 times is warming up to 90 ℃, add hydrogen to 2MPa, behind the 40min, reaction is finished.Sample analysis, o-chloronitrobenzene conversion ratio 100%, o-chloraniline selectivity 100%.
Embodiment 9:
In being the still formula high-pressure reactor of 100mL, volume puts into the 6g parachloronitrobenzene, 20mL water, 0.5g the catalyst that embodiment 3 makes, nitrogen replacement 3 times of airtight post-reactor, hydrogen exchange 3 times, charge into 0.5MPa hydrogen then, put into slowly heat temperature raising to 80 ℃ of oil bath, adjust hydrogen valve, make system pressure reach 2MPa, behind the 40min, reaction is finished.Analyze parachloronitrobenzene conversion ratio 100%, parachloroanilinum selectivity 100%.
Embodiment 10:
Reducing agent is one or several the mixture in methyl alcohol, formaldehyde, hydrazine hydrate, lithium aluminium hydride reduction, the natrium citricum.Surfactant is one or more the mixture in sapn type, hydrogenated rosin glyceride, AEO methyl-monosilane, polyethylene glycols, the APG.Nail salt is one or more the mixture in ruthenium bromide, ruthenium hydrochloride amine, ruthenium hydrochloride sodium, ruthenium hydrochloride potassium, triphenyl phosphorus hydrogenized carbonyl ruthenium, carbonyl ruthenic chloride, the triphenyl phosphorus ruthenic chloride.Carrier is activated carbon, silica, zirconium dioxide, tin ash, iron oxide or titanium dioxide; And before using, the carrier except that active carbon must handle the back oven dry through alkali lye.The used alkali lye of vehicle treated is one or more the alcoholic solution or the aqueous solution in potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium butoxide, butanols potassium, the butanols lithium.All the other are with embodiment 1 or 2.
Claims (8)
1, a kind of preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst is characterized in that: comprise the following steps: successively
(1) aqueous surfactant solution is even with the ruthenium salt solution mix of dissolving in advance, add the reducing agent reduction then, form surfactant stabilized nano ruthenium colloidal solution;
(2) the ruthenium colloidal solution that step (1) made adds carrier absorption, after adsorption process finishes, filters, and it is neutral that washing catalyst to filtrate is, obtain high degree of dispersion, the loaded nano ruthenium catalyst.
2, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 1, it is characterized in that: the 1-500 that the middle surfactant concentration of step (1) is a critical micelle concentration doubly, the concentration of reducing agent is 0.001～1mol/L, reduction temperature is 10-90 ℃, and the recovery time is 0.1-12 hour.
3, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 1 is characterized in that: described reducing agent is one or several the mixture in methyl alcohol, formaldehyde, hydrazine hydrate, sodium borohydride, lithium aluminium hydride reduction, the natrium citricum.
4, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 1, it is characterized in that: described surfactant is a nonionic surface active agent, is one or more the mixture in sapn type, brij type, hydrogenated rosin glyceride, AEO methyl-monosilane, tween type, polyethylene glycols, APG, the polyvinylpyrrolidone.
5, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 1 is characterized in that: described nail salt is one or more the mixture in ruthenium bromide, ruthenium hydrochloride amine, ruthenium hydrochloride sodium, ruthenic chloride, ruthenium hydrochloride potassium, nitric acid ruthenium, triphenyl phosphorus hydrogenized carbonyl ruthenium, acetic acid ruthenium, carbonyl ruthenic chloride, the triphenyl phosphorus ruthenic chloride.
6, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 1 is characterized in that: described carrier is activated carbon, alundum (Al, silica, zirconium dioxide, tin ash, iron oxide or titanium dioxide; And before using, the carrier except that active carbon must handle the back oven dry through alkali lye.
7, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 6 is characterized in that: the used alkali lye of described vehicle treated is one or more the alcoholic solution or the aqueous solution in NaOH, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, lithium methoxide, sodium butoxide, butanols potassium, the butanols lithium.
8, the preparation method of halogenated nitrobenzene selective hydrogenation high-activity nano-ruthenium catalyst according to claim 2 is characterized in that: reduction temperature is 20-40 ℃.
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| CN103242116A (en) * | 2012-02-10 | 2013-08-14 | 淮海工学院 | Novel method for preparing arylamine through reducing aromatic nitro compound |
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| CN105771976A (en) * | 2016-03-16 | 2016-07-20 | 西安凯立新材料股份有限公司 | Ruthenium precursor for preparing ruthenium carbon catalyst and preparation method of catalyst |
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| CN109647517A (en) * | 2017-10-11 | 2019-04-19 | 中国科学院大连化学物理研究所 | One kind being used for nitro benzene and its derivative hydrogenation catalyst preparation method |
| CN109847762A (en) * | 2019-01-18 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst, preparation method and application for the reaction of hydrogenation synthesis para-aminophenol |
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