CN1332891C - Hydrogen peroxide catalytic decomposing method of phenol compound - Google Patents

Abstract

The invention discloses a hydrogen peroxide catalytic decomposition method for phenolic compounds, which belongs to the technical field of environmental treatment. Using vanadate or heteropolyvanadate as a catalyst, hydrogen peroxide as an oxidant, and phenolic compounds are added to a water-acetonitrile (4:1 v/v) solution, and the catalytic decomposition reaction is carried out under heating and stirring conditions. Make the decomposition conversion rate of phenolic compounds reach more than 97%. The invention can decompose the refractory phenolic compound into CO ₂ and corresponding inorganic anion and nitromethane or acetic acid with high efficiency and rapid catalysis in neutral water-acetonitrile solution.

Description

A kind of hydrogen peroxide catalytic decomposition method of phenolic compound

technical field

The invention belongs to the technical field of environmental treatment, and in particular relates to a hydrogen peroxide catalytic decomposition method of phenolic compounds.

Background technique

The environmental problems caused by the rapid development of the chemical industry have become one of the focuses that the world pays close attention to. Phenolic compounds in industrial wastewater are the main pollutants, such as chlorophenols, which are widely used as insecticides, disinfectants, wood preservatives; industrial processes such as insecticides, dyes, explosives, in the preparation of textiles and paper Nitrophenols are widely used in The phenolic compounds in these discharged industrial wastewaters still pollute the environment greatly even at very low concentrations, and these compounds are difficult to treat with biodegradable methods due to their stability. The chemical methods currently used mainly include chemical oxidation and photocatalytic decomposition. Miguel L. Rodriguez, Vitaliy I. Timokhin, etc. reported in the literature "Advances in Environmental Research 7 (2003) 583-595" that the chemical oxidation method cannot completely decompose phenol. And C.-H.Yoon, S.-H.Cho, S.-H.Kim and S.-R.Ha, etc. reported in the literature "WaterScience and Technology Vol43, No.2, pp.229-236" , The wet air oxidation method must be carried out under high temperature and high pressure, the catalyst is easily deactivated, and the treatment cost is high. PVKamat, reported in "Chem.Rev.3 (1993) 267", the photocatalytic decomposition method is mainly to decompose phenolic compounds into biodegradable organic small compounds under the irradiation of ultraviolet and visible light in the presence of hydrogen peroxide or ozone or titanium dioxide. molecules, CO ₂ and the corresponding mineralized inorganic anions. In the literature "A. Mylonas, E. Papaconstantinou, J. Photochemistry and Photobiology A: Chemistry 94 (1996) 77-82", "A. Hiskia, E. Androulaki et al. Res. Chem. Intermed. Vol.26, No. .3, pp.235-251(2000)" and "P.Kormali, D.Dimoticali, E.Papaconstantinou, et al.AppliedCatalysis B:Enviromental 48(2004) 175-183)", Keggin-type phosphotungstic acid Found to be a photocatalyst as effective as titanium dioxide for decomposing chlorophenols into carbon dioxide and hydrochloric acid. However, this photocatalytic reaction is carried out under acidic conditions (pH ~ 2), and the catalytic degradation of the more recalcitrant nitrophenol has not been reported.

Contents of the invention

The object of this invention is to provide a kind of hydrogen peroxide catalytic decomposition method of phenolic compound, it is characterized in that with vanadate or heteropolyvanadate as catalyst, hydrogen peroxide aqueous solution is oxygenant, in water-acetonitrile mixed solution, Heating, stirring, carrying out the catalytic decomposition reaction of phenolic compound, this system catalytic degradation reaction comprises the following steps:

1) (20-70) μ mol vanadate or (2-6) μ mol heteropolyvanadate catalyst is dissolved in (1-8) ml, 30% (v/v) hydrogen peroxide, press water-acetonitrile ( 4:1 v/v) and acetonitrile to make 10ml homogeneous aqueous solution;

2) Dissolving the phenolic compound in the water-acetonitrile solution (4:1v/v) containing the catalyst and hydrogen peroxide in step (1), heating at 30-70°C, and reacting for 10-120 minutes under stirring, the phenolic compound The compounds decompose into CO ₂ , H ₂ O and the corresponding inorganic anions and nitromethane or acetic acid.

The vanadate is KVO ₃ , NaVO ₃ , or NH ₄ VO ₃ .

The heteropolyvanadate is K ₇ NiV ₁₃ O ₃₈ and K ₇ MnV ₁₃ O ₃₈ .

The beneficial effects of the present invention are: compared with the prior art, the present invention enables the refractory phenolic compounds such as nitrophenol to be rapidly and efficiently decomposed into _CO2 and corresponding inorganic anions and nitromethane or acetic acid under neutral conditions. The decomposition conversion rate of various phenols can reach more than 97%.

Detailed ways

The invention is a new hydrogen peroxide catalytic degradation method for phenolic compounds. Using vanadate or heteropolyvanadate as a catalyst, hydrogen peroxide as an oxidant, the catalytic decomposition reaction of phenolic aromatic compounds is carried out under the condition of heating and stirring in a water-acetonitrile (4:1v/v) mixed solvent. The catalytic decomposition reaction includes the following steps:

1) Dissolve the preferred 40 μmol of vanadate or 3 μmol of heteropolyvanadate catalyst in (1-8) ml, 30% (v/v) hydrogen peroxide, and mix with acetonitrile according to water-acetonitrile (4: 1v/v) into 10ml homogeneous aqueous solution;

2) Dissolving the phenolic compound in the water-acetonitrile solution containing the catalyst and hydrogen peroxide in (1), heating at 30-70°C, and reacting for 10-120 minutes under stirring, the phenolic compound is degraded into CO ₂ , H ₂ O and corresponding inorganic salts and a small amount of phenolic organic degradation small molecules (such as nitromethane or acetic acid).

The aforementioned vanadate is KVO ₃ , NaVO ₃ , or NH ₄ VO ₃ ; the heteropolyvanadate is K ₇ NiV ₁₃ O ₃₈ or K ₇ MnV ₁₃ O ₃₈ .

The following examples are given to further illustrate the present invention.

Example 1:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve in 8 ml of 30% hydrogen peroxide and 2 ml of acetonitrile to prepare a homogeneous solution. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 99.2%.

Example 2:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 50°C for catalytic degradation reaction. The reaction time is 40 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 98.7%.

Example 3:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 30°C for catalytic degradation reaction. The reaction time is 10 hours, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 99.5%.

Example 4:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 1 ml of 30% (v/v) hydrogen peroxide, and prepare a homogeneous solution with 2 ml of acetonitrile and 7 ml of water. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 60 minutes, and the result of the reaction is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 53%.

Example 5:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 2 ml of 30% (v/v) hydrogen peroxide, and prepare a homogeneous solution with 2 ml of acetonitrile and 6 ml of water. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 60 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 66.5%.

Embodiment 6:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 3 ml of 30% (v/v) hydrogen peroxide, and prepare a homogeneous solution with 2 ml of acetonitrile and 5 ml of water. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 30 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 88%.

Embodiment 7:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 4 ml of 30% (v/v) hydrogen peroxide, and prepare a homogeneous solution with 2 ml of acetonitrile and 4 ml of water. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 30 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 91%.

Embodiment 8:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 6 ml of 30% (v/v) hydrogen peroxide, and prepare a homogeneous solution with 2 ml of acetonitrile and 2 ml of water. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 30 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 94%.

Embodiment 9:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-necked round bottom flask, 0.57g (4mmol) of o-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is that o-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of o-nitrophenol reaches 97.5%.

Example 10:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.57g (4mmol) m-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the result of the reaction is that m-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of m-nitrophenol reaches 99%.

Example 11:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.38g (4mmol) of p-phenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 60 minutes, and the reaction result is: phenol is decomposed into CO ₂ and water and a small amount of acetone, and the decomposition conversion rate of phenol reaches 97.5%.

Example 12:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.51g (4mmol) of p-chlorophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is that p-chlorophenol is decomposed into CO ₂ and Cl ^- , and the conversion rate of p-chlorophenol reaches 98.5%.

Example 13:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-necked round bottom flask, 0.51g (4mmol) o-chlorophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is that o-chlorophenol is decomposed into CO ₂ and Cl ^- , and the decomposition conversion rate of o-chlorophenol reaches 98%.

Example 14:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.51g (4mmol) m-chlorophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is that m-chlorophenol is decomposed into CO ₂ and Cl ^- , and the conversion rate of m-chlorophenol reaches 99%.

Example 15:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.43g (4mmol) p-cresol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 120 minutes, and the reaction result is: p-cresol is decomposed into CO _and water, and the decomposition conversion rate of p-cresol reaches 99.1%.

Example 16:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-neck round bottom flask, 0.5g (4mmol) p-hydroxyanisole was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 60 minutes, and the reaction result is that p-hydroxyanisole is decomposed into _CO and water, and the decomposition conversion rate of p-hydroxyanisole reaches 99.2%.

Example 17:

Weigh 5.3 mg (3 μmol) of KVO ₃ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and mix with 2 ml of acetonitrile to form a homogeneous solution. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is: p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and acetic acid, and the decomposition conversion rate of p-nitrophenol reaches 99.5%.

Example 18:

Weigh 5.7 mg (3 μmol) of K ₇ MnV ₁₃ O ₃₈ catalyst, dissolve it in 8 ml of 30% (v/v) hydrogen peroxide and prepare a homogeneous solution with 2 ml of acetonitrile. In a 50ml two-necked round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for catalytic degradation reaction. The reaction time is 15 minutes, and the reaction result is that p-nitrophenol is decomposed into CO ₂ , NO ₃ ^- and a small amount of NO ₂ ^- and nitromethane, and the decomposition conversion rate of p-nitrophenol reaches 99%.

Comparative example 1:

Under the condition of no catalyst, 0.57g (4mmol) of p-nitrobenzene was dissolved in 8ml of 30% (v/v) hydrogen peroxide and 2ml of acetonitrile to form a homogeneous solution. In a 50ml two-neck round bottom flask, stir, and heat to reflux to 70°C for reaction. The reaction time is 120 minutes, and the result of the reaction is that the decomposition conversion rate of p-nitrophenol is only 15%.

Comparative example 2:

Weigh 5.7 mg (3 μmol) of K ₇ NiV ₁₃ O ₃₈ catalyst, dissolve in 8 ml of water and 2 ml of acetonitrile to prepare a homogeneous solution. In a 50ml two-neck round bottom flask, 0.57g (4mmol) p-nitrophenol was dissolved in the above homogeneous solution, stirred, and heated to reflux to 70°C for reaction. The reaction time was 120 minutes, and the reaction result was that p-nitrophenol hardly decomposed.

Through the comparison of the above examples, it can be concluded that the present invention can efficiently and rapidly decompose phenolic compounds into _CO2 and corresponding inorganic anions and a small amount of phenolic organic degradation small molecules under neutral conditions.

Claims (2)

1. a hydrogen peroxide catalytic decomposition method of phenolic compound, it is characterized in that: the method is catalyzer with heteropolyvanadate, is oxygenant with hydrogen peroxide, in the water-acetonitrile of 4: 1 (v/v) In the solution, the catalytic decomposition reaction of the phenolic compound is carried out under heating and stirring conditions, and the catalytic decomposition reaction comprises the following steps: 1) Dissolve 2-6 μmol of heteropolyvanadate catalyst in 1-8ml, 30% (v/v) hydrogen peroxide, and form 10ml of homogeneous aqueous solution according to water-acetonitrile (4:1v/v) and acetonitrile; 2) Dissolve the phenolic compound in the 4:1 (v/v) water-acetonitrile solution containing the catalyst and hydrogen peroxide in step (1), heat at 30-70°C, and react under stirring for 10-120 minutes, the phenol The compounds decompose into CO ₂ , H ₂ O and corresponding inorganic anions and nitromethane or acetic acid. 2. The hydrogen peroxide catalytic decomposition method of phenolic compounds according to claim 1, characterized in that: the heteropolyvanadate is K ₇ NiV ₁₃ O ₃₈ and K ₇ MnV ₁₃ O ₃₈ .