CN110723800A - Application of copper/graphene catalyst in water treatment - Google Patents
Application of copper/graphene catalyst in water treatment Download PDFInfo
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- CN110723800A CN110723800A CN201911011094.1A CN201911011094A CN110723800A CN 110723800 A CN110723800 A CN 110723800A CN 201911011094 A CN201911011094 A CN 201911011094A CN 110723800 A CN110723800 A CN 110723800A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention belongs to the technical field of environmental pollution treatment, and relates to an application of a copper/graphene catalyst in water treatment. According to the method, graphene and copper sulfate are used as raw materials, ascorbic acid is used as a reducing agent, and the copper/graphene catalyst is prepared. The catalyst can realize the controllable generation of copper nanoparticles, can be stably dispersed on the surface of graphene, thereby producing good catalytic performance, particularly catalytic reduction of nitroaromatic compounds, has the degradation rate of 95% on nitroaromatic hydrocarbons and the selectivity of 98% on arylamine, and still maintains the degradation rate of the nitroaromatic hydrocarbons to be more than 93% after four times of cyclic use, shows good catalytic activity and stability, and is a high-efficiency green recyclable catalyst.
Description
Technical Field
The invention relates to the technical field of environmental pollution treatment, in particular to application of a copper/graphene catalyst in water treatment, and especially relates to application of the copper/graphene catalyst in water treatment of a compound containing nitroaromatic.
Background
Nitro polycyclic aromatic hydrocarbons are a class of organic pollutants found in the environment in the end of the 70's 20 th century, mainly derived from organic matter, incomplete combustion of biomass, parent polycyclic aromatic hydrocarbons in the atmosphere and atmospheric media (NO)2、NO3 -、HNO3Etc.) are generated by a photochemical reaction. The nitro polycyclic aromatic hydrocarbon has direct mutagenicity and carcinogenicity, and although the concentration of the nitro polycyclic aromatic hydrocarbon in the atmosphere is far lower than that of Polycyclic Aromatic Hydrocarbon (PAHs), the variation activity of the nitro polycyclic aromatic hydrocarbon is tens to thousands of times higher than that of parent PAHs. Thus when the particles carrying NPAHs enterAfter entering the human body, the health of the human body can be seriously threatened. According to the particle size of the particulate matter, different parts of the human body can be reached, for example, PM10 can reach the bronchus of a human body, and PM2.5 can reach the lung of the human body.
At present, nitro reduction method is generally adopted for processing nitro compound, and nitro compound with strong toxicity can be reduced into arylamine compound. In the conventional technology for reducing nitroaromatics, metals such as Pd, Ni, and Cu are generally used as catalysts for improving efficiency, and various nano-catalysts on which graphene such as Pd, Ni, and Cu is used as a carrier have been developed. The graphene nano catalyst can not only prevent the agglomeration of nano particles, but also stabilize the nano particles, achieve the effect of recycling for many times, and show good reaction activity. However, because Pd and Ni catalysts are more toxic and expensive, and do not require the use of more toxic phosphorus-containing ligands for unstable and highly toxic organophosphine ligands, compared to Cu catalysts, the development of a water treatment application for reducing nitroaromatic compounds using Cu/graphene as a catalyst has great economic and practical value.
Disclosure of Invention
The invention aims to provide an application of a copper/graphene catalyst in water treatment, and particularly relates to an application of the copper/graphene catalyst in water treatment of a nitro-aromatic compound. According to the method, graphene and copper sulfate are used as raw materials, divalent copper in the copper sulfate is reduced into zero-valent copper nanoparticles by ascorbic acid, and the zero-valent copper nanoparticles are dispersed on the surface of the graphene, so that the copper/graphene catalyst is prepared. And applying the prepared copper/graphene catalyst to catalytic reduction of nitroaromatic compounds in water treatment.
In order to achieve the purpose, the invention adopts the following technical scheme:
putting a nitroaromatic compound and a copper/graphene catalyst into a reaction device, adding a mixed solvent of water and ethanol in a certain proportion, uniformly stirring, raising the temperature to a certain temperature, adding sodium borohydride, keeping the reaction for 2-4 h, stopping heating after the reaction is finished, and naturally cooling to room temperature.
Furthermore, the feeding ratio of the nitro compound, the copper/graphene and the sodium borohydride is (1-5): 5-10): 1-5 by weight ratio.
Further, the nitroaromatic compounds include nitrobenzene, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, p-methylnitrobenzene, 2-nitrobiphenyl, p-nitrobenzoic acid, p-nitrobenzaldehyde and p-nitrochlorobenzene.
Further, the temperature is raised to 40 ℃ to 70 ℃, preferably 50 ℃.
Further, sodium borohydride is metered in batchwise or continuously.
Further, the copper/graphene is prepared by the following method:
firstly, preparing graphene oxide by adopting an improved Hummers method, then adding the graphene oxide into N-methylpyrrolidone for ultrasonic dispersion, adjusting the pH value to 10 by using a NaOH solution, sequentially adding ascorbic acid and copper sulfate pentahydrate, raising the temperature to a certain temperature, keeping the reaction for 2-3 h, cooling the reaction product after the reaction is finished, adding water, standing the reaction product to remove supernatant, sequentially washing the reaction product with distilled water and absolute ethyl alcohol for three times, centrifuging the reaction product, collecting precipitate, and drying the precipitate in vacuum to obtain black copper/graphene solid.
The invention has the following positive effects:
1. the developed water treatment method adopts the copper/graphene catalyst to carry out catalytic reduction on the nitroaromatic compound in the sodium borohydride, and compared with the prior art which adopts a hydrogen hydrogenation reduction method, the water treatment method has higher safety, and the hydrogen has the characteristic of being easier to explode.
2. The developed water treatment method adopts a copper/graphene catalyst to carry out catalytic reduction in sodium borohydride, the conversion rate of the nitroaromatic compound exceeds 95%, and the selectivity of the arylamine compound reaches 98%; after the copper/graphene catalyst is repeatedly used for four times, the conversion rate of the nitroaromatic compound still exceeds 93%, the selectivity of the arylamine compound still reaches 96%, and the catalytic effect is not obviously reduced.
3. The developed preparation method of the copper/graphene catalyst adopts ascorbic acid as a reducing agent, so that the reduction effect is thorough, the toxicity is low, the price is low, and the prepared copper/graphite is very stable in property and is not easy to oxidize.
4. The similar catalyst is mainly a noble metal supported catalyst such as Au, Pd and Pt, and the Cu nanoparticle supported graphene catalyst is used for catalytic reduction of nitroarene, and has catalytic activity and selectivity similar to those of the noble metal, but the copper/graphene catalyst is low in price and less in toxicity.
Detailed Description
The present invention is further described in the following examples, which should not be construed as limiting the scope of the invention, but rather as providing the following examples which are set forth to illustrate and not limit the scope of the invention.
Example 1
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
100mg of nitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 200ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 40 ℃, sodium borohydride with the total amount of 100mg is added in 3 times in sequence, and the reaction is kept for 2 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 2
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
200mg of nitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 4 times in sequence, and the reaction is kept for 3 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 3
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
300mg of nitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 400ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 60 ℃, sodium borohydride with the total amount of 100mg is added in 5 times in sequence, and the reaction is kept for 4 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 4
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
200mg of nitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 6 times in sequence, and the reaction is kept for 2 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 5
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
200mg of p-chloronitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 6 times in sequence, and the reaction is kept for 2 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 6
The embodiment provides a water treatment application of a copper/graphene catalyst, and a treatment method of the copper/graphene catalyst comprises the following steps:
200mg of o-nitrophenol and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 6 times, and the reaction is kept for 2 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 7
This example provides a water treatment application of a copper/graphene catalyst, and when the catalyst is recycled four times, the treatment method is as follows:
200mg of nitrobenzene and 500mg of copper/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 4 times in sequence, and the reaction is kept for 3 hours. And after the reaction is finished, stopping heating, naturally cooling to room temperature, filtering and collecting reactants to obtain the copper/graphene catalyst, and repeating the reaction for four times.
Comparative example 1
This example provides a water treatment application of copper catalyst, the treatment method is as follows:
200mg of nitrobenzene and 500mg of copper catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is stirred uniformly, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 4 times, and the reaction is kept for 3 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Comparative example 2
The embodiment provides a water treatment application of a palladium-nickel/graphene catalyst, and a treatment method of the palladium-nickel/graphene catalyst comprises the following steps:
200mg of nitrobenzene and 500mg of palladium-nickel/graphene catalyst are placed in a reaction device, 100ml of water and 300ml of ethanol are added, the mixture is uniformly stirred, after the temperature is raised to 50 ℃, sodium borohydride with the total amount of 100mg is added in 4 times in sequence, and the reaction is kept for 3 hours. After the reaction is finished, stopping heating, and naturally cooling to room temperature.
Example 8
In this example, the arylamine yield, arylamine selectivity and mass spectrum data after the conversion of the nitroaromatic compound were tested in examples 1 to 7 using copper/graphene and comparative example 1 using copper as a catalyst and comparative example 2 using palladium nickel/graphene, and the specific contents are as follows:
when the reaction solution is obtained in the examples 1 to 7 and the comparative examples 1 to 2, the final reaction solution is filtered to obtain a filtrate, the filtrate is extracted by ethyl acetate, the organic phase is quantified by gas chromatography, qualitative analysis is carried out by gas phase-mass spectrometry, and the detection results are shown in the following table 1
TABLE 1
| Examples | m/z (relative abundance,%) | Yield of aromatic amine | Selectivity for aromatic amines |
| Example 1 | 93(M+,100)；66(43)；52(8)；39(19) | 96.5 | 99.2 |
| Example 2 | 93(M+,100)；66(43)；52(8)；39(19) | 98.3 | 98.9 |
| Example 3 | 93(M+,100)；66(43)；52(8)；39(19) | 97.2 | 98.6 |
| Example 4 | 93(M+,100)；66(43)；52(8)；39(19) | 95.9 | 98.4 |
| Example 5 | 127(M+,100)；100(12)；92(22)；65(30) | 97.8 | 98.1 |
| Example 6 | 109(M+,100)；81(14)；80(27)；53(10) | 98.1 | 98.4 |
| Example 7 | 93(M+,100)；66(43)；52(8)；39(19) | 93.6 | 96.3 |
| Comparative example 1 | 93(M+,100)；66(43)；52(8)；39(19) | 76.4 | 79.1 |
| Comparative example 2 | 93(M+,100)；66(43)；52(8)；39(19) | 96.8 | 98.8 |
From the above data, the following conclusions can be drawn:
(1) the corresponding arylamine compounds were generated in the examples 1 to 7 and the comparative examples 1 to 2.
(2) From example 7, it can be seen that after the reaction is completed, the copper/graphene catalyst is recovered by filtration, and after the catalyst is repeatedly used for four times, the yield of the arylamine is more than 93%, and the selectivity of the arylamine is more than 96%, which indicates that the catalytic efficiency is not significantly reduced.
(3) Compared with the comparative example 1, when the copper/graphene composite catalyst is used for replacing the copper catalyst, the yield and the selectivity of the arylamine are higher, the yield of the arylamine is more than 95%, and the selectivity of the arylamine is more than 98%.
(4) Compared with the comparative example 2, when the copper/graphene composite catalyst is used for replacing the palladium-nickel/graphene alloy composite catalyst, the yield and the selectivity of the arylamine are similar.
Therefore, when the copper/graphene catalyst is applied to water treatment of the nitro-aromatic compound, the method has the advantages of high catalytic efficiency, low copper toxicity, relatively low price and simplicity and safety in the whole water treatment method.
Claims (8)
1. The application of the copper/graphene catalyst in water treatment is characterized in that: the copper/graphene catalyst is applied to water treatment of the nitro-containing aromatic compound.
2. The use of the copper/graphene catalyst of claim 1 in water treatment, comprising the steps of:
putting a nitroaromatic compound and a copper/graphene catalyst into a reaction device, adding a mixed solvent of water and ethanol in a certain proportion, uniformly stirring, raising the temperature to a certain temperature, adding sodium borohydride, keeping the reaction for 2-4 h, stopping heating after the reaction is finished, and naturally cooling to room temperature.
3. The use of a copper/graphene catalyst according to claim 2 in water treatment, wherein: the material ratio of the nitro compound, the copper/graphene and the sodium borohydride is (1-5) to (5-10) to (1-5) by weight.
4. The use of a copper/graphene catalyst according to claim 2 in water treatment, wherein: the nitroaromatic compounds include nitrobenzene, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, p-methylnitrobenzene, 2-nitrobiphenyl, p-nitrobenzoic acid, p-nitrobenzaldehyde and p-nitrochlorobenzene.
5. The use of a copper/graphene catalyst according to claim 2 in water treatment, wherein: the temperature is raised to 40-70 ℃.
6. The use of a copper/graphene catalyst according to claim 5 in water treatment, wherein: preferably 50 deg.c.
7. The use of a copper/graphene catalyst according to claim 2 in water treatment, wherein: the sodium borohydride is metered in batchwise or continuously.
8. The use of a copper/graphene catalyst according to claim 2 in water treatment, wherein: the copper/graphene is prepared by the following method:
firstly, preparing graphene oxide by adopting an improved Hummers method, then adding the graphene oxide into N-methylpyrrolidone for ultrasonic dispersion, adjusting the pH value to 10 by using a NaOH solution, sequentially adding ascorbic acid and copper sulfate pentahydrate, raising the temperature to a certain temperature, keeping the reaction for 2-3 h, cooling the reaction product after the reaction is finished, adding water, standing the reaction product to remove supernatant, sequentially washing the reaction product with distilled water and absolute ethyl alcohol for three times, centrifuging the reaction product, collecting precipitate, and drying the precipitate in vacuum to obtain black copper/graphene solid.
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