WO2006081774A1

WO2006081774A1 - METHOD FOR CATALYTIC DEGRADING p-NITROBENZENE SUBSTANCE WITH NANO-Cu2O BY MECHANISM

Info

Publication number: WO2006081774A1
Application number: PCT/CN2006/000199
Authority: WO
Inventors: Aiqian Zhang; Nan Meng; Shuokui Han; Yun Chen
Original assignee: Nanjing University
Priority date: 2005-02-05
Filing date: 2006-02-05
Publication date: 2006-08-10
Also published as: CN1657427A; CN100344547C

Abstract

The invention relates to a degradation method for p-nitrobenzene substance in water, which discloses a method for catalytic degrading the p-nitrobenzene substance with nano-Cu2O by mechanism. The process includes the following steps: (1) loading wastewater containing the p-nitrobenzene substance with a reactor; (2) adding nano-Cu2O to the reactor in the ratio of 0.50 g/L ~ 4 g/L; (3) providing a friction between a friction device and the bottom of the reactor by an additional power. According to the invention, the degradation efficiencies of the p-nitrobenzene substance solution of 20-100 mg/L may exceed 70 %.

Description

Method for mechanically catalyzing the degradation of p-nitrobenzene by nano-sized cuprous oxide

The invention relates to a method for degrading p-nitrobenzene in water, and more particularly to a method for mechanically degrading p-nitrobenzene by nano-sized cuprous oxide.

Second, the background technology

P-nitrobenzene is a typical toxic organic pollutant in the surface water environment. Because it is low in water and difficult to degrade, it is difficult to remove it from water. At present, the main methods for treating nitrobenzene in water are physical methods, chemical methods and biological methods.

The physical method is mainly removed by adsorption and sedimentation. "Chinese chlor-alkali" 2003 "Break adsorption treatment of p-nitrophenol industrial wastewater" used CHA-111 adsorption resin for the treatment and recovery of p-nitrophenol-containing wastewater, the adsorption rate of more than 90%. "Chemical World" 2004 06 "Research on the adsorption of p-nitrophenol in modified honeycomb cinder" by using triethanolamine (TEA) and cetyltrimethylammonium bromide (CTMAB) to modify honeycomb cinder, respectively. The performance of cinder adsorption of p-nitrophenol in water. The results show that the treatment of p-nitrophenol-containing wastewater with modified cinder is effective. Environmental Science and Technology, 2000, No. 03, “Research on the adsorption of p-nitrophenol by modified fly ash”, studied the adsorption of harmful p-nitrophenol in aqueous solution by using fly ash (FA) and impregnated fly ash (IFA). . C. Rajagopal et al. used granular activated carbon (GAC) as adsorbent to treat nitrobenzene wastewater, and established a kinetic model for predictive absorption. The treatment of adsorptive removal process for treatment of explosives contaminated qd waste water using activated Carbon [J] . Journal of Hazardous Materials, 2001, 87 (1- 3) : 73- 98). However, these treatment methods do not decompose and remove p-nitrobenzene substances. Although recycling is used twice, the cost is high and it is easy to cause secondary pollution.

The chemical methods mainly include photo-assisted Fenton reaction, heterogeneous photocatalysis, photoelectrocatalysis, and electrochemical methods. "Journal of Guangdong University of Technology" 2001, 04, "Electrochemical oxidation of refractory organic matter p-nitrophenol", discloses the use of electrochemical oxidation to degrade p-nitrophenol; Zhou Minghua et al. Degradation of Nitrophenol in Three Homogeneous Photochemical Advanced Oxidation Processes Combined with UV/O ₂ , UV/Fe ^{3 +} and UV/Fe ³⁺ I 3⁄40 ₂ and Electrocatalytic Degradation (Photoelectric Integrated Degradation Based on Homogeneous Photochemical Oxidation Studies on p-nitrophenol, Chinese Journal of Catalysis, 2002, 04); Zhao Deming et al. The effect of sound wave (US/F, entw) on the degradation of p-nitrophenol in water (Fenton reagent enhanced Laisheng wave treatment of p-nitrophenol in water, Journal of Zhejiang University of Technology, 2004, 03); A. Di Paola, etc. Titanium is used as a catalyst to degrade quinone phenol by Heterogeneous photocatalytic degradation of nitrophenols (Journal of Photochemistry and Photobiology A: Chemistry 155 (2003) 207 - 214 ); Mehmeta. Outran et al. Completion Destruction of p-Nitrophenol in Aqueous Medium by Electro - Fenton Method, Environ. Sci. Technol. 2000, 34, 3474-3479 ) ₀ iguel Rodriguez et al., under UV irradiation, H ₂ 0 ₂ and Fe ³⁺ photodegradation of nitrobenzene degradation (Influence of H202 and Fe (III) in the photodegradation [J] . Journal of Photochemistry and Photobiology A: Chemistry, 2000, 133 : 123-127). Most of the chemical methods can completely mineralize the nitrobenzenes, but these methods require the use of electrical energy, and there is a problem of high energy consumption and low efficiency.

The biological method is mainly to degrade p-nitrophenol by microorganisms. Liu Zhi et al. Degradation of p-nitrophenol by methyl parathion-degrading bacterium DLL-E4 (Pseudomonas put i da) (Degradation of p-nitrophenol by methyl sulfonium-degrading bacteria DLL E ⁴ , China Environmental Science 2003 04)) Gao Shixiang et al. investigated the effect of cyclodextrin on the degradation of p-nitrophenol during the degradation process by studying the microbial degradation process of p-nitrophenol (β-cyclodextrin versus p-nitrophenol) Effects of Degradation, Environmental Chemistry, 2003, 05); Orashnsky Frieda et al. used adsorption-biodegradation process to treat nitrobenzene wastewater. Activated carbon with strong adsorption capacity can adsorb most of the toxic pollutants in wastewater, and then biodegrade the nitrate at low concentration. Evaluation of toxic organics removal by simultaneous adsorption and biodegradation [C] . proceedings of Industrial Waste Conferece, 1997 159-171 ). Wu Jianfeng et al reported that a bacterial CNB1 strain of Comaraonas capable of degrading p-chloronitrobenzene was isolated from activated sludge treated with chloronitrobenzene production plant wastewater, and the bacteria were degraded. The characteristics of chloronitrobenzene were studied (Isolation, identification and degradation characteristics of Comacon^ CNB1 degrading p-chloronitrobenzene, Journal of Microbiology 2004, Vol. 44, No. 1). However, the biological treatment method is not efficient, and the culture of the strain is difficult, and the reaction environment is high and difficult to achieve.

A method for treating p-nitrophenol production wastewater is disclosed in a method for treating and recycling a wastewater of p-nitrophenol production (Patent Application No. 200410014570. 2), and the process is as follows: Pretreatment, adsorption of nitroxide in the wastewater, back-blowing using sodium chloride, desorption and adsorption of p-nitroxon 3⁄4 phenol. The method can recover p-nitrophenol, and the caustic soda and hydrochloric acid required for the production of p-nitrophenol can be recycled. The shortcoming of this method is that the process is complicated and the working conditions are more limited.

Cuprous oxide is a P-type semiconductor. It is an important inorganic chemical raw material and has a wide range of applications in the fields of antifouling paints, pigments and welding industries. Due to its small forbidden band width, only 2.0-2.2 eV, it is easy to generate photo-generated carriers under the illumination of sunlight, and has excellent stability. It is widely used in petrochemical catalysis and photovoltaic cells. Applications. In 1998, Michikazu Hara and others first reported that cuprous oxide can decompose water under visible light, which is believed to have the potential to convert solar energy into 3⁄4 energy (Michikazu Hara et al , Cu ₂ 0 as a photocatalyst for overall water splitting under visible) Light Irradiation, Chem. Commun., 1998). T. Mahalingam et al. reported the preparation of cuprous oxide films as electrodes for photoelectrochemical solar cells (T. Mahal ingam et. al, Characterization of pulse plated Cu20 thin films, Surface and Coatings Technology 168 (2003) 111-114).

Mechanical catalysis is a catalytic method in which mechanical energy is converted into chemical energy by a catalyst to promote the reaction. The principle is to rapidly rub the catalyst at the bottom of the vessel by a stir bar of different materials to generate electrons and promote the reaction. Go Hitoki et al. first reported the use of oxides such as cuprous oxide as a catalyst to catalyze the decomposition of water by mechanical friction to produce hydrogen, and proposed a new way to generate clean energy (Go Hitoki, Catalysis Today 63 (2000) 175 - 181 , Mechano-catalytic overall water splitting on some mixed oxides). Subsequently, the research group successively published related articles on mechanical catalysis, but both applied to decompose water to achieve energy conversion, and did not apply to the field of decomposition of organic pollutants.

The results of the literature search indicated that no report on the mechanical catalyzed degradation of p-nitrobenzene in water by cuprous oxide was found before the completion of the present invention. Third, the invention content

1. Technical problems to be solved

P-nitrobenzene is a typical toxic organic pollutant in surface water environment. Because it is low in water and difficult to degrade, it is difficult to remove it from water. The object of the present invention is to provide a method for effectively degrading p-nitrobenzene in water, and mechanically catalyzing the degradation of p-nitrobenzene in water by using nano-sized cuprous oxide, which can effectively remove p-nitrobenzene in water. Class of substances. , Technical solutions

The technical solutions adopted are as follows;

A method for mechanically catalyzing the degradation of p-nitrobenzene by nano-sized cuprous oxide, the steps of which include -

(1) placing the wastewater of p-nitrobenzene in a reactor;

(2) adding nano-sized cuprous oxide in a ratio of 0.50 g / L ~ 4 g / L;

(3) The friction device is rubbed against the bottom surface of the reactor by external force.

The nano-sized cuprous oxide has a particle size ranging from 50 to 500 nm. During the reaction, due to the friction, the particle size of the relatively large particle size of cuprous oxide will become smaller, and the final particle size of cuprous oxide will be between 50 and 200 nra. Cuprous oxide acts only as a catalyst during the reaction.

When the concentration of p-nitrobenzene waste water is 20~: I00mg/L, the degradation effect is better than other concentrations; the optimum treatment wastewater concentration is 60~100mg/L. When the concentration is too high, the effect of degradation is lowered, and when the concentration is too low, the treatment cost is relatively high.

Nano-sized cuprous oxide can be prepared by a glucose reduction method and an improved electrolysis method. The specific operation of preparing the nano-sized cuprous oxide by the glucose reduction method is as follows: 1000 ml of distilled water is added, and 0.3 mL of a film solution of 0.1 mL of a 13 ml/0 film solution is added, and the mixture is placed in a microwave oven. Power irradiation rapidly warmed the mixed solution to 95 °C. The mixture was quickly cooled to room temperature with an ice water bath, and the obtained cuprous oxide sol was poured into a 250 ml centrifuge tube, centrifuged at 4500 r/min for 30 min, taken out, and the supernatant was transferred to a 150 ml beaker for use. The above preparation steps were repeated using the supernatant, centrifuged at high speed, and then the supernatant was discarded. Add a small amount of distilled water, centrifuge for 15 minutes, then aspirate the supernatant and centrifuge with water. Wash it as many times as this. Then a small amount of ethanol was added and volatilized to a thousand in a nitrogen atmosphere. Finally, a small amount of diethyl ether was added dropwise, and after the ether was evaporated, a yellow powder was obtained, which was placed in a desiccator and sealed for use.

Improved electrolytic method for preparing nano-sized cuprous oxide. 250 _{g of} NaCl, 0.5 _{g of} NaOH, 0.1 _{g of} N3⁄4Cr ₂ 0 _{7 was} dissolved in 1000 ml of water, and an O. lg stabilizer was added, and the dissolution was ultrasonically promoted as an electrolyte. The copper piece is polished and ultrasonically cleaned as an electrode. The electrolytic cell was placed in an ultrasonic oscillator, copper was used as an electrode, and electrolyzed at a current of 20 raA/cra2 for 8 minutes. The product was centrifuged, washed three times with distilled water, washed three times with acetone, and dried at room temperature to obtain yellow-green oxidation. Cuprous particles, placed in a desiccator for sealing.

The addition ratio of nano-sized cuprous oxide is 3 to 4 g/L.

The friction device is made of polytetrafluoroethylene material, and the contact surface of the reactor with the friction is ordinary glass, quartz glass, pyrex glass. Increasing the frictional contact area and friction rate helps to increase the reaction rate. Machinery The power of friction can be electromagnetic stirring, electric stirring, in order to save energy and environmental protection, solar energy, wind energy, etc. can be used as power. The friction between the friction device and the bottom surface of the reactor can be achieved by means of rotation, reciprocation or the like. The effect of friction rate on the degradation effect is not obvious. After reaching a certain rate, increasing the friction rate does not improve the conversion rate from mechanical energy to chemical energy. Increasing the contact area of mechanical friction can significantly improve the degradation efficiency. The longer the mechanical friction, the better the degradation effect, but the excessively long time degradation effect is not obvious, and the energy consumption is increased. Under the same conditions, keep the reaction temperature at 30-50 °C, and adjust the pH 5-9 to achieve better degradation.

3, beneficial effects

By using the method of the invention, the catalytic degradation rate of p-nitrobenzenes in the wastewater of 20-100 mg/L can reach more than 70%, the method is simple and easy, and the material is easy to obtain. The cost is low. If natural energy is used as mechanical friction power, such as solar energy, wind energy, etc., it is more economical and environmentally friendly, and has industrial application prospects. Fourth, the specific implementation

The invention is further illustrated by the following examples

Example 1

The tempering temperature is 0. 10g / L of the p-nitrophenol solution 200ml was placed in the reactor, adding 0. 80g of improved copper oxide prepared by the hydrolysis method, the solution 11 was 5. 5, maintaining the reaction temperature for the winter water temperature (10 ° C). Add a magnetic body with a length of 56 mm and a bottom area of 2. 24X 10 - ⁴ m ² , which is electromagnetically stirred to cause friction with the bottom surface. What is the friction area? 4 ⁶ > 10 - ³ m ² , the friction rate is 600 rpm, and the sample is sampled at 2 ml for high-speed centrifugation. The supernatant is taken for liquid chromatography.

The degradation rate of p-nitrophenol after the 12-hour reaction was 82.46%. Example 2:

The solution of 0. 10g / L of p-nitrophenol solution 200ml was placed in the reactor, adding 0. 80g modified copper oxide prepared by the hydrolysis method, the pH of the solution was 5.6, maintaining the reaction temperature for the winter water temperature (10' C). A magnet having a length of 36 mm and a bottom area of 1.44X l (T ⁴ m ² ) is electromagnetically agitated to cause friction with the bottom surface, and the friction area is 1. 02 X 10" ³ ra ² , and the friction rate is 600 rpm. /min, time-sampling 2ml idling centrifugation, taking the house supernatant for liquid chromatography. It was determined that the degradation rate of p-nitrophenol after the i2 hour reaction reached 81.69%. Example 3:

200 ml of a p-nitrophenol solution having a concentration of 0.10 g/L was placed in a reactor, and 0.90 g of cuprous oxide prepared by an improved hydrolysis method was added, and the pH of the solution was 6.0, and the reaction temperature was maintained at a winter water temperature (10 ° C). Add a length of 28mm, the bottom area of the magnetic sub 1.12X, electromagnetic stirring a manner so as friction with the bottom surface, area of Friction 6.15 ^10-4! ^, The friction rate was 600 rpm, and 2 ml of high-speed centrifugation was sampled at regular intervals, and the supernatant was taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 80.0% after 12 hours of reaction. Example 4 _:

200 ml of a p-nitrophenol solution having a concentration of 0.080 g/L was placed in a reactor, and 0.50 g of cuprous oxide prepared by an improved hydrolysis method was added. The solution pH was 8 to 9, and the reaction temperature was maintained at a winter water temperature (10 Torr). Electromagnetic stirring was used to rub against the bottom surface, the friction area was 1.02×10 m ² , the friction rate was 600 rpm, and the sample was sampled at 2 ml for high-speed centrifugation. The supernatant was taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 74.2% after 7 hours of reaction and reached 86.5 after 10 hours.

%. Example 5

200 ml of a p-nitrophenol solution having a concentration of 0.060 g/L was placed in a reactor, and 0.40 g of cuprous oxide prepared by an improved hydrolysis method was added, and the solution 11 was 5.6, and the reaction temperature was maintained at a winter water temperature (10 ° C).电磁 Electromagnetic stirring was used to rub against the bottom surface. The friction area was 1.0 ² Xl (Tm ² , the friction rate was 600 rpm, and the sample was sampled at 2 ml for high-speed centrifugation. The supernatant was taken for liquid chromatography.

It was determined that the degradation rate of nitrophenol was 71.4% after 5 hours of reaction and 79.0% after 10 hours. Example 6:

200 ml of a p-nitrophenol solution having a concentration of 0.050 g/L was placed in a reactor, and 0.80 g of cuprous oxide prepared by an improved hydrolysis method was added. The pH of the solution was 7 to 8, and the reaction temperature was maintained at a winter water temperature (10 Torr). 电磁 Use electromagnetic stirring to rub against the bottom surface. The friction area is L02Xl (T ³ m ² , friction rate is 600 rpm, timed sampling? ml high-speed centrifugation, and the supernatant is taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 71.99% after 12 hours of reaction. Example 7

200ml of p-nitrophenol solution with a concentration of 0.020g / L was placed in the reactor, and Q.60g modified cuprous oxide prepared by hydrolysis method was added. The pH of the solution was 6~6.5, and the reaction temperature was kept at winter water temperature (10 °C). ). Bian way electromagnetic stirring so that the bottom surface friction, a friction area 1.02X10- ³ m ^2, friction speed of 600 rev / min, the sampling timing of 2ml high-speed centrifugation, the supernatant was measured by liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 71.3% after 7 hours of reaction and reached 85.1 after 10 hours.

%. Example 8

200ml of p-nitrophenol solution with a concentration of 0.10g / L was placed in the reactor, 0.10g of cuprous oxide prepared by improved hydrolysis method was added, the pH of the solution was 5~6, and the reaction temperature was maintained at winter water temperature (10 °C). . Electromagnetic stirring manner with the bottom surface of the friction, a friction area 1.02X10- ³ m ^2, friction speed of 600 rev / min, the sampling timing of 2ml high-speed centrifugation, the supernatant was measured by liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 72.2% after 4 hours of reaction, and the degradation rate reached 88.7% after 8 hours, and 92.9% after 10 hours. Example 9:

200 ml of a p-nitrophenol solution having a concentration of 0.10 g/L was placed in a reactor, and 0.60 g of cuprous oxide prepared by an improved hydrolysis method was added, and the solution 11 was 5.6, and the reaction temperature was maintained at a winter water temperature (10 Torr).电磁 Electromagnetic stirring is used to rub against the bottom surface. The friction area is 1.02Χ1 (Γ ³ m ² , the friction rate is 600 rpm, the timed sampling is 2 ml idling centrifugal separation, and the supernatant is taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 70% after 5 hours of reaction, and the degradation rate reached 82.9% after 8 hours, and reached 88.9% after 10 hours. Example 10: Put a concentration of 0. lQg / L of p-nitrophenol solution 200ml in the reactor, add 0.80g modified copper oxide prepared by the hydrolysis method, the solution! "1 is 5.6, keep the temperature inside the reactor at room temperature in summer (30 °C). Use electromagnetic stirring to rub against the bottom surface. The friction area is 1.02X10— ^:i m ² , the friction rate is 600 rpm, and the sample is sampled at 2 ml for high-speed centrifugation. The supernatant is taken for liquid phase. Chromatographic determination. After 2 hours of reaction, the degradation rate of p-nitrophenol reached 70.4%, and the degradation rate reached 91.9% after 4 hours.

Example 11

200 nil of a p-nitrophenol solution having a concentration of 0.06 g/L was placed in the reactor, and the cuprous oxide prepared by the Q.6Qg modified hydrolysis method was added, and the solution was 5.6, and the temperature in the reactor was maintained at 40 Torr. Electromagnetic stirring manner with the bottom surface of the friction, a friction area 1.02X10- ³ m ^2, friction speed of 600 rev / min, the sampling timing of 2ml high-speed centrifugation, the supernatant was measured by liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 77.9% after 2 hours of reaction, and the degradation rate reached 86.7% after 3 hours. Example 12:

200 ml of a p-nitrophenol solution having a concentration of 0, 10 g/L was placed in a reactor, and 0.70 g of cuprous oxide prepared by an improved hydrolysis method was added, and the solution 11 was 5.6, keeping the temperature in the reactor at 50 °C. Electromagnetic stirring manner with the bottom surface of the friction, a friction area 1.02X10- ³ m ^2, friction speed of 600 rev / min, the sampling timing of 2ml high-speed centrifugation, the supernatant was measured by liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 80.3% after 2 hours of reaction, and the degradation rate reached 90% after 4 hours. Example 13

200 ml of a p-nitrophenol solution having a concentration of 0.08 g/L was placed in a reactor, 0.50 g of cuprous oxide prepared by the improved hydrolysis method was added, and the pH of the reaction solution was adjusted to 7.0, and the reaction temperature was maintained at a winter water temperature (10). ° C) o electromagnetic stirring manner with the bottom surface of the friction, a friction area 1.02X10- ³ m ^2, friction speed of 600 rev / min, the sampling timing of 2ml high-speed centrifugation, the supernatant was measured by liquid chromatography .

It was determined that the degradation rate of p-nitrophenol after the reaction for 5 hours reached 73.7%, and the degradation rate after 10 hours was Up to 84.8% Example 14:

200 ml of a p-nitrophenol solution having a concentration of 0.03 g/L was placed in a reactor, 0.30 g of cuprous oxide prepared by an improved hydrolysis method was added, and the pH of the reaction solution was adjusted to 9.0, and the reaction temperature was maintained at a winter water temperature (10). °C). Bian way electromagnetic stirring so that the bottom surface friction, a friction area 1.02X10- ³ m ^2, friction was tied 600 rev / min, the sampling timing of the high ¾1 K. centrifugation, the supernatant was measured by liquid chromatography.

After the reaction, the degradation rate of p-nitrophenol after 3 hours of reaction is reached? ² .0%, the degradation rate can reach 91.9% after 10 hours. Example 15;

A p-nitrophenol solution 20 (1⁄21) having a concentration of 0.07 g/L was placed in the reactor, 0.60 g of cuprous oxide prepared by an improved hydrolysis method was added, and the solution pH was 6.2, and the reaction temperature was maintained at a winter water temperature (10 ° C). c electromagnetic stirring manner with the bottom surface of the friction, a friction area 1.02X10- ³ m ^2, friction rate of 600 rev / min, to a certain time in the reaction (5 or 6 hours), addition of NaCl, in the solution The concentration of Na ions reached 0.01 mol/L, and 2 ml of high-speed centrifugation was sampled at a time, and the supernatant was taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol reached 72.2% after 4 hours of reaction, and the degradation rate reached 88.7% after 8 hours, and 92.9% after 10 hours. The effect is the same as without NaCl addition. Example 16:

The basic operation was the same as in Example 15, except that CaCl ₂ was used instead of NaCl at a concentration of 0.01-0.05 mol/L, and the effects were basically the same. Example 17

200 ml of a p-nitrophenol solution having a concentration of 0.10 g/L was placed in a reactor, and 0.80 g of cuprous oxide prepared by a modified glucose reduction method (particle size: 75-100 nm) was added, and the solution 11 was 5.6, and the reaction temperature was maintained in winter. Water temperature (10 ° C). Electromagnetic stirring is used to cause friction with the bottom surface, and the friction area is 1. 02 X 10" ³ m ² , the friction rate is 600 rpm, sample 2 ml high-speed centrifugation at regular intervals, and take the supernatant to perform liquid chromatography.

It was determined that the degradation rate of p-nitrophenol after the reaction for 10 hours can reach 80%. Example 18

Put the concentration of 0. 10g / L of p-nitrophenol solution 200ral in the reactor, adding 0. 80g low-current electrolysis (particle size 200_500nm) prepared cuprous oxide, the solution pH is 5 ~ 6, keep the reaction temperature For the winter water temperature U0 °C>. Electromagnetic stirring was used to make friction with the bottom surface. The friction area was 1.02X 10" ³ m ² , the friction rate was 60P rpm, and the sample was sampled at 2 ml for high-speed centrifugation. The supernatant was taken for liquid chromatography.

It was determined that the degradation rate of p-nitrophenol after the 8-hour reaction can reach 80%.

The cuprous oxide prepared in the above examples was replaced by cuprous oxide prepared by other methods, and the particle size ranged from 50 to 500 nm, and other reaction conditions were unchanged, and similar results were obtained. Example 19

The temperature of the winter water temperature is maintained at a temperature of 8.0 g. °C). Using electromagnetic stirring to cause friction with the bottom surface, the friction area is 1. 02 X 10 - ³ m ² , the friction rate is

600 rpm, timed sampling 2 ml high speed centrifugation, the supernatant was taken for liquid chromatography.

It was determined that the degradation rate of chloronitrobenzene reached 80% after 8 hours of reaction. Example 20

A concentration of 0. 050g / L solution of p-chloronitrobenzene 200ml placed in a reactor, added 0. 80g improved cuprous oxide prepared by hydrolysis, _P H is adjusted 5.0, maintaining the reaction temperature for the winter temperature ( 10 ° C). The electric friction is used to cause friction with the bottom surface, and the friction area is 1. 02 X 10 - ³ m ² , and the friction rate is

It was determined that the degradation rate of chloronitrobenzene reached 75% after 8 hours of reaction. Example 21:

O. 80g改。 The concentration of 0. 050g / L of p-chloronitrobenzene solution 200ml was placed in the reactor, adding 0. 80g modified The cuprous oxide prepared by the hydrolysis method is adjusted to pJ ^{3⁄4 4} .Q, and the reaction temperature is maintained as the winter water temperature (10 Ό). Using electric mixing method; ^ friction with the bottom surface, the friction area is 1.02X10 - ³ m ² , and the friction rate is

It was determined that the degradation rate of chloronitrobenzene reached 70% after 8 hours of reaction. Example 22

50 ml of a p-bromonitrobenzene solution having a concentration of 0.050 g/L was placed in a reactor, and a cuprous oxide prepared by 0.65 g of sodium borohydride method was added, and the solution was 5.6, and the reaction temperature was maintained at a winter water temperature (10 ° C). ). Using electric mixer manner so that the bottom surface friction, a friction area 1.02X10- ³ m ^2, friction rate

It was determined that the degradation rate of bromonitrobenzene reached 90% after 5 hours of reaction. Example 23

Put a concentration of 0.050g / L of p-bromonitrobenzene solution 5 (1⁄21 in the reactor, add 0.45g of cuprous hydride prepared by sodium borohydride method, the solution pH is 6.0, keep the reaction temperature is winter water temperature (10 ° C). Using electric stirring to make friction with the bottom surface, the friction area is 1.02 X 10— ³ m ² , and the friction rate is

600 rpm, timed sampling 2 ml idling centrifugal separation, the supernatant was taken for liquid chromatography.

It was determined that the degradation rate of bromonitrobenzene reached 90% after 5 hours of reaction.

Claims

Rights request

A method for mechanically catalyzing the degradation of p-nitrophenylhydrazine by nano-recorded cuprous oxide, the steps of which include: a) placing a wastewater of p-nitrobenzene in a reactor;

b) adding nano-sized cuprous oxide in a ratio of 0.50 g / L ~ 4 g / L;

c) Using external force to rub the friction device against the bottom surface of the reactor.

2. The method for mechanically catalyzing degradation of p-nitrobenzenes by nano-sized cuprous oxide according to claim 1, wherein the nano-sized cuprous oxide particles in the step (2) have a particle size range of 50~ 500 nanometers.

3. The method for mechanically catalyzing degradation of p-nitrobenzenes by nano-sized cuprous oxide according to claim 2, characterized in that the concentration of the p-nitrobenzene waste water in the step (1) is 20~

The method for mechanically catalyzing degradation of p-nitrobenzenes by nano-sized cuprous oxide according to claim 3, wherein the p-nitrobenzene substance in the step (1) is p-nitrophenol, p-Chloronitrobenzene, p-nitrochlorobenzene, p-nitrobromobenzene.

The method for mechanically catalyzing the degradation of p-nitrobenzene by nano-sized cuprous oxide according to claim 4, wherein the nano-sized cuprous oxide is prepared by a glucose reduction method.

6. The method of mechanically catalyzing the degradation of p-nitrobenzene species by nano-sized cuprous oxide according to claim 4, characterized in that the nano-sized cuprous oxide is prepared by a modified electrolysis method.

7. The method for mechanically catalyzing the degradation of p-nitrobenzene by nano-sized cuprous oxide according to claims 1 to 6, characterized in that the friction device of the friction device described in step (3) rubs against the bottom surface of the reactor It is a friction method driven by electromagnetic friction, electric friction and other energy.

8. The method for mechanically catalyzing the degradation of p-nitrobenzenes by nano-sized cuprous oxide according to claims 1 to 6, characterized in that the proportion of nano-sized cuprous oxide in the step (2) is 3 to 4 g/ L.

9. The method for mechanically catalyzing the degradation of p-nitrobenzene by nano-sized cuprous oxide according to claims 1 to 6, characterized in that the concentration of the p-nitrobenzene waste water in the step (1) is 60~100mg/L.