CN104437459A - Activated carbon supported bismuth oxide and preparation method and application thereof - Google Patents
Activated carbon supported bismuth oxide and preparation method and application thereof Download PDFInfo
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- CN104437459A CN104437459A CN201410660299.3A CN201410660299A CN104437459A CN 104437459 A CN104437459 A CN 104437459A CN 201410660299 A CN201410660299 A CN 201410660299A CN 104437459 A CN104437459 A CN 104437459A
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- activated carbon
- bismuth oxide
- carbon supported
- preparation
- supported bismuth
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Abstract
The invention discloses activated carbon supported bismuth oxide and a preparation method and an application of the activated carbon supported bismuth oxide to preparation of arylamine through reduction of an aromatic nitro compound. The activated carbon supported bismuth oxide takes activated carbon as a supporter and adopts bismuth oxide as an active ingredient; the preparation method specially comprises the following steps: dissolving Bi(NO3)3.5H2O with a 30% of HNO3 solution under a stirring condition and diluting distilled water to obtain a Bi(NO3)3 solution; adding with activated carbon, dropwise adding a NaOH solution slowly under a stirring condition and regulating the pH value to be alkaline; transferring into a hydrothermal reaction kettle for hydrothermal reaction, washing a product after finishing the reaction, and performing vacuum drying to obtain the activated carbon supported bismuth oxide catalyst. The operation is simple and safe when the activated carbon supported bismuth oxide is applied to the preparation of aromatic amine, appropriate amount of common solvent is adopted as a reducing medium, and the solvent can be recycled; and the reduction reaction can be carried out smoothly under normal pressure, a high-pressure reactor is not required, no waste gas and waste residue are generated, the post-treatment is simple, and the solvent is spun to be dried, thus, the product is obtained.
Description
Technical field
The invention belongs to organic reaction catalyst field, be specifically related to a kind of activated carbon supported bismuth oxide, preparation and the application on preparing arylamine by reducing aromatic nitro compound thereof.
Background technology
Aromatic amino compound is a kind of very important Organic Ingredients, is widely used in dyestuff, medicine, agricultural chemicals, additive, surfactant, textile auxiliary, chelating agent and the production such as polymerization, fire retardant.The preparation of aromatic amine mainly contains the reduction etc. containing the preparation of amino compound condensation, nitro compound.Wherein condensation reaction comprises the exchange reaction, aldol condensation etc. of halogen and metal.Because condensation reaction needs to add amino protecting group in the reaction, its yield is lower, is generally used for the synthesis of predetermined substance.Aromatic nitro compound is reduced to the common method that corresponding amino-compound is fine chemistry industry manufacture arylamine.Nitroreduction prepares arylamine because it is easy and simple to handle, raw material is cheaply easy to get and extensive use.
Reducing aromatic nitro compound is that the method for arylamine mainly contains electrolytic reduction, CO/H
2o reduction system method, catalytic hydrogenation method and hydrazine hydrate method.Electrolytic reduction equipment investment is comparatively large, and energy consumption is relatively high, and industrial industry is produced also exists certain technical problem; CO/H
2it is good that O reduction system has equipment interoperability, and reaction easily controls, and raw material such as to be easy to get at the advantage, but this method is high to catalyst requirement, there is noble metal catalyst and reclaim problem, and reaction mostly needs HTHP; Catalytic hydrogenation method good product quality, the three wastes are few, and post processing is simple, and alternative control, industrial production has good application prospect, but equipment investment is large, and production cost is high, is generally used for large-scale production.
Hydrazine hydrate method nitro compound reducing arylamine, has that equipment investment is little, reaction condition is gentle, reduction yield is high, can carry out partial reduction, do not produce the features such as waste gas waste residue.The catalyst being comparatively early used for Reduction of Nitro Aromatic Compounds with Hydrazine Hydrate has Pb/C and Raney Ni, and Pb/C price is high, and Raney Ni not easily preserves.What research in recent years was more is iron (III) compound catalyst, and iron (III), although compound catalyst is inexpensive, declines rapidly higher than iron (III) catalyst activity when 70 DEG C in temperature.Most compounds of bismuth have the characteristic of nontoxic, easy process and humidity.Therefore, along with the raising of environmental requirement, bismuth and chemical compound lot thereof are widely used in organic synthesis.
Document 1 (Cai Keying, Yue Wei, Zhou Yingmei, Wei Xianyong. the Reduction of Nitro Aromatic Compounds with Hydrazine Hydrate arylamine [J] of bismuth nitrate and activated carbon catalysis. chemical reagent, 2009,31 (11), 945-947.) using bismuth nitrate and active carbon as catalyst, Compounds with Hydrazine Hydrate Catalyzed reduction nitrobenzene, investigated the impact on reaction of bismuth nitrate consumption (bismuth nitrate 0.04-0.08g/1mmol nitrobenzene) and activated carbon dosage (active carbon 0.00-0.20g/1mmol nitrobenzene), the yield wherein obtaining product is 20-99%.
Document 2 (Cai Keying, Liu Changning, Zhou Yingmei, Yue Wei. activated carbon loaded bismuthyl hydroxide reduction of Aromatic Nitro Compounds with Hydrazine Hydrate Catalyzed [J]. applied chemistry, 2009,26 (9), 1080-1083.) BiO (the OH)/C catalyst that adopted infusion process to prepare, investigated the impact of BiO (OH) load capacity (5%, 10%, 15%) on reaction, the yield wherein obtaining product is 44-99%.
Following defect is there is in above-mentioned research work on catalyst preparing and application:
(1) recycling rate of waterused of catalyst is lower, repeats for several times, and due to the loss of bismuth (III), the catalytic activity of catalyst declines, as document 1;
(2), in catalyst preparation process, owing to only changing the concentration of ammoniacal liquor, and Bi (NO is not changed accordingly
3)
35H
2the amount of O, causes part Bi (NO
3)
35H
2the non-complete reaction of O, does not meet the requirement of green syt, as document 2.
Summary of the invention
The object of the present invention is to provide that a kind of activity is high, the catalyst of the activated carbon supported bismuth oxide of excellent catalytic effect; The preparation method simultaneously providing this catalyst and the application prepared at catalysis reducing aromatic nitro compound on aromatic amine.
The technical solution realizing the object of the invention is:
A kind of activated carbon supported bismuth oxide, it is characterized in that, be take active carbon as carrier, bismuth oxide is active component, and concrete grammar is as follows:
The first step: by Bi (NO
3)
35H
2o with 30% HNO
3solution stirring and dissolving, and with distilled water diluting, obtain Bi (NO
3)
3solution;
Second step: active carbon is put into the Bi (NO that the first step obtains
3)
3in solution, under agitation, slowly drip NaOH solution wherein, adjust pH to alkalescence;
3rd step: proceeded in hydrothermal reaction kettle by second step product and carry out hydro-thermal reaction, after reaction terminates, obtains the catalyst of activated carbon supported bismuth oxide after product washing, vacuum drying.
Bi (NO in the first step
3)
35H
2the amount of O is 0.001mol ~ 0.005mol, distilled water diluting to 50 ~ 100ml.
In second step, the quality of active carbon is 4 ~ 10g.
In second step, mixing time 12 ~ 24h, adjusts pH=10 ~ 14.
In 3rd step, hydrothermal temperature 100-200 DEG C, hydro-thermal reaction time 12 ~ 24h.
In 3rd step, baking temperature is 50 ~ 100 DEG C.
The application of activated carbon supported bismuth oxide of the present invention on preparing arylamine by reducing aromatic nitro compound, prepares aromatic amine compounds for catalysis nitroaromatic.Such as: 3-Aminotrifluorotoluene, open-chain crown ether, m-bromoaniline.
Compared with prior art, its remarkable advantage is in the present invention:
(1) compared with bismuth nitrate, bismuth oxide (active component) is more stable, not easily runs off, thus improves the recycling rate of waterused of catalyst, for subsequent reactions provides convenient;
(2) with bismuthyl hydroxide, in preparation process, raw material is converted into bismuth oxide completely, thus decreases the raw material required for catalyst preparing, cost-saving, is suitable for industrial production.
(3) the activated carbon supported bismuth oxide catalyst that the present invention relates to, can be applied in catalysis reducing aromatic nitro compound and prepare in the reaction of aromatic amine, for organic synthesis provides new opportunity.
Accompanying drawing explanation
Accompanying drawing is the XRD figure of active carbon and activated carbon supported bismuth oxide.
Detailed description of the invention
In order to understand the present invention better, illustrate technical scheme of the present invention below by specific embodiment.
One, the preparation of activated carbon supported bismuth oxide
Embodiment 1
The first step: take 0.485g (0.001mol) Bi (NO
3)
35H
2o, puts into small beaker, is the HNO of 30% by 10mL volume fraction
3dissolve, then adding distil water is diluted to 50mL, obtains Bi (NO
3)
3solution.
Second step: accurate weighing 4.0g active carbon, adds to the Bi (NO prepared
3)
3in solution, stir 12h, obtain the Bi (NO flooded
3)
3/ C solution.Under magnetic stirring, slowly drip the NaOH solution of 30%, adjust pH=11-12.3rd step: proceed in hydrothermal reaction kettle by second step product, sealing, is warming up to 180 DEG C, and insulation 12h, then naturally cools to room temperature.The sediment obtained is washed with distilled water to neutrality, vacuum drying 4h at 60 DEG C.The material obtained is the catalyst of activated carbon supported bismuth oxide.
Be illustrated in figure 1 the XRD figure of activated carbon supported bismuth oxide prepared by the present invention, as can be seen from Figure in 2 θ=28 °, 32 °, 47 ° and about 56 ° there is spectrum peak, the diffraction maximum of the bismuth oxide checked according to characteristic diffraction peak data and powder diffraction card (PDF) contrasts and can confirm, what prepare is bismuth oxide.Illustrate that end product is activated carbon supported bismuth oxide.
Embodiment 2
The first step: take 0.970g (0.002mol) Bi (NO
3)
35H
2o, puts into small beaker, is the HNO of 30% by 10mL volume fraction
3dissolve, then adding distil water is diluted to 100mL, obtains Bi (NO
3)
3solution.
Second step: accurate weighing 6.0g active carbon, adds to the Bi (NO prepared
3)
3in solution, stir 18h, obtain the Bi (NO flooded
3)
3/ C solution.Under magnetic stirring, slowly drip the NaOH solution of 30%, adjust pH=10-11.3rd step: proceed in hydrothermal reaction kettle by second step product, sealing, is warming up to 100 DEG C, and insulation 12h, then naturally cools to room temperature.The sediment obtained is washed with distilled water to neutrality, vacuum drying 4h at 80 DEG C.
Embodiment 3
The first step: take 1.455g (0.003mol) Bi (NO
3)
35H
2o, puts into small beaker, is the HNO of 30% by 10mL volume fraction
3dissolve, then adding distil water is diluted to 80mL, obtains Bi (NO
3)
3solution.
Second step: accurate weighing 8.0g active carbon, adds to the Bi (NO prepared
3)
3in solution, stir 24h, obtain the Bi (NO flooded
3)
3/ C solution.Under magnetic stirring, slowly drip the NaOH solution of 30%, adjust pH=12-13.3rd step: proceed in hydrothermal reaction kettle by second step product, sealing, is warming up to 200 DEG C, and insulation 24h, then naturally cools to room temperature.The sediment obtained is washed with distilled water to neutrality, vacuum drying 4h at 60 DEG C.
Embodiment 4
The first step: take 1.940g (0.002mol) Bi (NO
3)
35H
2o, puts into small beaker, is the HNO of 30% by 10mL volume fraction
3dissolve, then adding distil water is diluted to 60mL, obtains Bi (NO
3)
3solution.
Second step: accurate weighing 4.0g active carbon, adds to the Bi (NO prepared
3)
3in solution, stir 12h, obtain the Bi (NO flooded
3)
3/ C solution.Under magnetic stirring, slowly drip the NaOH solution of 30%, adjust pH=13-14.3rd step: proceed in hydrothermal reaction kettle by second step product, sealing, is warming up to 150 DEG C, and insulation 12h, then naturally cools to room temperature.The sediment obtained is washed with distilled water to neutrality, vacuum drying 4h at 80 DEG C.
Two, the application of activated carbon supported bismuth oxide on preparing arylamine by reducing aromatic nitro compound
The synthesis of embodiment 5 3-Aminotrifluorotoluene
In the there-necked flask of 100ml, add 25g ethanol, 3.8g m-nitryl benzotrifluoride and 1g example 1 catalyst, start magnetic agitation, is heated to boiling, drips the hydrazine hydrate of 3.2g 80% in 10min, reaction 2h.After having reacted, cooling, filtration, filtrate is revolved and is steamed removing ethanol, obtains product, yield 99%.
The synthesis of embodiment 6 open-chain crown ether
In the there-necked flask of 100ml, add 25g toluene, 4.1g para-nitrotoluene and 1.5g example 2 catalyst, start magnetic agitation, be heated to 70 DEG C, drip the hydrazine hydrate of 3.75g 80% in 10min, reaction 3h.After having reacted, cooling, filtration, filtrate is revolved and is steamed removing toluene, obtains product, yield 98%.
The synthesis of embodiment 7 m-bromoaniline
In the there-necked flask of 100ml, add 25g isopropyl alcohol, 5g m-bromoaniline and 0.8g example 4 catalyst, start magnetic agitation, be heated to 60 DEG C, drip the hydrazine hydrate of 4.2g 80% in 10min, reaction 5h.After having reacted, cooling, filtration, filtrate is revolved and is steamed removing isopropyl alcohol, obtains product, yield 98%.
Catalyst activity charcoal load bismuth oxide of the present invention has good catalytic activity in hydrazine hydrate legal system is for 3-Aminotrifluorotoluene, open-chain crown ether, m-bromoaniline, but be not limited to the preparation of this several aromatic amine, potential catalytic activity is also also existed to the preparation of other aromatic amine compounds.
Claims (10)
1. an activated carbon supported bismuth oxide, is characterized in that, be take active carbon as carrier, bismuth oxide is active component, and concrete grammar is as follows: by Bi (NO
3)
35H
2o with 30% HNO
3solution stirring and dissolving, and with distilled water diluting, obtain Bi (NO
3)
3solution; Drop into active carbon again, under stirring condition, slowly drip NaOH solution wherein, adjust pH to alkalescence; Proceed in hydrothermal reaction kettle and carry out hydro-thermal reaction, after reaction terminates, after product washing, vacuum drying, obtain the catalyst of activated carbon supported bismuth oxide.
2. activated carbon supported bismuth oxide according to claim 1, is characterized in that, described Bi (NO
3)
35H
2the amount of O is 0.001mol ~ 0.005mol, distilled water diluting to 50 ~ 100ml; The quality of active carbon is 4 ~ 10g, mixing time 12 ~ 24h, and adjust pH=10 ~ 14, hydro-thermal reaction time 12 ~ 24h, baking temperature is 50 ~ 100 DEG C.
3. a preparation method for activated carbon supported bismuth oxide, is characterized in that, described catalyst is prepared by following methods:
The first step: by Bi (NO
3)
35H
2o with 30% HNO
3solution stirring and dissolving, and with distilled water diluting, obtain Bi (NO
3)
3solution;
Second step: active carbon is put into the Bi (NO that the first step obtains
3)
3in solution, under agitation, slowly drip NaOH solution wherein, adjust pH to alkalescence;
3rd step: proceeded in hydrothermal reaction kettle by second step product and carry out hydro-thermal reaction, after reaction terminates, obtains the catalyst of activated carbon supported bismuth oxide after product washing, vacuum drying.
4. the preparation method of activated carbon supported bismuth oxide according to claim 3, is characterized in that, Bi (NO in the first step
3)
35H
2the amount of O is 0.001mol ~ 0.005mol, distilled water diluting to 50 ~ 100ml.
5. the preparation method of activated carbon supported bismuth oxide according to claim 3, is characterized in that, in second step, the quality of active carbon is 4 ~ 10g.
6. the preparation method of activated carbon supported bismuth oxide according to claim 3, is characterized in that, in second step, mixing time 12 ~ 24h, adjusts pH=10 ~ 14.
7. the preparation method of activated carbon supported bismuth oxide according to claim 3, is characterized in that, in the 3rd step, and hydrothermal temperature 100-200 DEG C, hydro-thermal reaction time 12 ~ 24h.
8. the preparation method of activated carbon supported bismuth oxide according to claim 3, is characterized in that, in the 3rd step, baking temperature is 50 ~ 100 DEG C.
9., based on the application of activated carbon supported bismuth oxide according to claim 1 on preparing arylamine by reducing aromatic nitro compound, it is characterized in that: prepare aromatic amine compounds for catalysis nitroaromatic.
10. application according to claim 9, is characterized in that, prepared arylamine is 3-Aminotrifluorotoluene, open-chain crown ether, m-bromoaniline.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944075A (en) * | 2017-04-20 | 2017-07-14 | 东北大学 | A kind of method that nitro reducing catalyst is prepared by reduced iron powder waste residue |
| CN108962622A (en) * | 2018-07-16 | 2018-12-07 | 晋江瑞碧科技有限公司 | A kind of preparation method of Carbon anode electrode plate |
| CN110152649A (en) * | 2019-06-14 | 2019-08-23 | 昆明理工大学 | A kind of preparation method and application of pros' phase bismuth oxide active carbon photochemical catalyst |
| CN110496596A (en) * | 2018-05-18 | 2019-11-26 | 南京理工大学 | Charcoal-montmorillonite composite material and its preparation method and application |
| CN110773205A (en) * | 2019-11-12 | 2020-02-11 | 河北地质大学 | Bi 4NbO 8Method for producing Cl |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944075A (en) * | 2017-04-20 | 2017-07-14 | 东北大学 | A kind of method that nitro reducing catalyst is prepared by reduced iron powder waste residue |
| CN106944075B (en) * | 2017-04-20 | 2019-05-03 | 东北大学 | A method of nitro reducing catalyst is prepared by reduced iron powder waste residue |
| CN110496596A (en) * | 2018-05-18 | 2019-11-26 | 南京理工大学 | Charcoal-montmorillonite composite material and its preparation method and application |
| CN108962622A (en) * | 2018-07-16 | 2018-12-07 | 晋江瑞碧科技有限公司 | A kind of preparation method of Carbon anode electrode plate |
| CN110152649A (en) * | 2019-06-14 | 2019-08-23 | 昆明理工大学 | A kind of preparation method and application of pros' phase bismuth oxide active carbon photochemical catalyst |
| CN110152649B (en) * | 2019-06-14 | 2021-09-14 | 昆明理工大学 | Preparation method and application of tetragonal phase bismuth oxide activated carbon photocatalyst |
| CN110773205A (en) * | 2019-11-12 | 2020-02-11 | 河北地质大学 | Bi 4NbO 8Method for producing Cl |
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