CN103551164B - Nitrogenous sulphur oxygen helerocyclics is had to eelctro-catalyst and the preparation method of efficient catalytic degradation function - Google Patents

Abstract

The invention discloses an electrocatalyst with high-efficiency catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds and a preparation method. Add AgNO3 to isopropanol to obtain solution _A , add treated _Al2O3 to solution _A , filter to obtain particle B and microemulsion X, and obtain particle D after washing with ethanol; add particle D to X Particle F was obtained after medium filtration. Solutions B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , C, D, E, F were prepared using Ce(NO ₃ ) ₂ , CoCl ₂ , NiCl ₂ . Particle F is treated with solutions B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ in sequence to obtain particle I. Particle I was added to solution C, filtered, washed with ethanol and dried to obtain Particle K. Particle K was added to solution D, filtered, washed with ethanol and dried to obtain particle M. M was added to solution E, filtered, washed with ethanol and dried to obtain particle O. Add particle O to solution F, filter, wash with ethanol, dry and calcinate at 550°C for 4 hours, and then an electrocatalyst with efficient catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds is obtained.

Description

Electrocatalyst with high-efficiency catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds and preparation method

technical field

The invention belongs to the technical field of chemically modified electrodes for treating wastewater by an electrocatalytic oxidation method, and in particular relates to an electrocatalyst and a preparation method having a high-efficiency catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds.

Background technique

Electrocatalytic oxidation technology degrades organic pollutants in wastewater by generating strong oxidizing active groups such as hydroxyl radicals. It has no secondary pollution, low cost, strong applicability, and high efficiency in treating high-concentration, biodegradable wastewater. Advanced features, in which three-dimensional electrocatalytic oxidation technology, by adding a catalytically active particle electrode between the anode and cathode of the two-dimensional electrode, the surface of the filled granular electrode is charged in a certain way, and the effective area of the two-dimensional electrode is improved. Small, poor mass transfer effect, low current efficiency and other defects, it is suitable for various concentrations of wastewater, even for wastewater with low pollutant concentration, it has a good treatment effect, and it is a kind of electrocatalytic oxidation water treatment that has been studied more at present. technology. The application of the three-dimensional electrode method to wastewater treatment is not only closely related to the performance of the main electrode, but also closely related to the performance of the particle electrode. Therefore, how to improve the catalytic performance of the particle electrode has become a research hotspot in recent years.

The commonly used particle electrode materials mainly include metal conductors, metal oxides, glass or plastic balls coated with metal layers, graphite particles, activated alumina particles, carbon fiber materials, and activated carbon particles. The large resistance and low conductivity of traditional electrodes make it low current efficiency, insufficient stability, short life, high electrode material cost in wastewater treatment, and the electrode preparation process is complicated, which limits the development of particle electrode materials. Therefore, the new The research on particle electrode materials still needs to be further strengthened. In recent years, the preparation of supported particle electrodes by impregnation-thermal decomposition has attracted more and more attention from scholars, but there are disadvantages such as poor reusability and low electrode efficiency, and there is still a lack of research on the preparation process of particle electrodes.

Contents of the invention

The object of the present invention is to provide a kind of electrocatalyst and preparation method that have efficient catalytic degradation function to nitrogen-containing sulfur oxygen heterocyclic compound, described electrocatalyst is the support Ag doping NiO _- CeO2 active alumina containing CoO intermediate layer particle electrodes. The concrete steps of its preparation method are as follows:

(1) Wash 300g of γ-A1 ₂ O ₃ balls with a particle size of 3-5mm with 500ml of deionized water, repeat the washing 3 times, then soak in 200ml of absolute ethanol for 10h, and wash once with 500ml of deionized water Afterwards, drying at 80°C for 10 hours to obtain granular substance A;

( ₂ ) Add 50ml of AgNO with a concentration of 0.5mol/L into 150ml of isopropanol to obtain solution A;

(3) Add the granular substance A obtained in step (1) to the solution A obtained in step (2), and shake it in a shaker for 3h, filter to obtain granular substance B and microemulsion X, and use 100mL of 95% mass concentration Wash the granular substance B with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance C;

(4) The granular substance C obtained in step (3) is placed in a muffle furnace and roasted at 500° C. for 4 hours to obtain the granular substance D;

(5) Add the granular substance D obtained in step (4) to the microemulsion X obtained in step (3), and shake it in a shaker for 3h, filter and remove the liquid to obtain granular substance E, and use 100mL of ethanol with a mass concentration of 95% Washing the granular substance E, repeating the washing twice, then drying at 80°C for 10 hours, and then roasting in a muffle furnace at 500°C for 4 hours to obtain granular substance F;

(6) 10ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 100ml concentration is 0.5mol/L CoCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 10ml concentration is 0.5mol /L NiCl ₂ solution, shake well and divide into 5 equal parts to obtain solution B ₁ , solution B ₂ , solution B ₃ , solution B ₄ , and solution B ₅ ;

(7) Add the granular substance F obtained in step (5) to the solution B ₁ obtained in step (6), shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G1, and use 100mL of ethanol with a mass concentration of 95% washing the granular substance G1, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H1;

(8) Add the granular substance H1 obtained in step ( ₇ ) into the solution B2 obtained in step (6), and shake it in a shaker for 3 hours, remove the liquid by filtration to obtain granular substance G2, and use 100mL of ethanol with a mass concentration of 95%. washing the granular substance G2, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₂ ;

(9) Add the granular substance _H2 obtained in step (8) to the solution _B3 obtained in step (6), shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G3, and use 100mL of 95% mass concentration washing the granular substance G3 with ethanol, repeating the washing twice, and then drying at 80° C. for 10 hours to obtain the granular substance H ₃ ;

(10) Add the granular substance H3 obtained in step ( ₉ ) to the solution B4 obtained in step ( ₆ ), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G4, and use 100mL of washing the granular substance G4 with ethanol, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₄ ;

( ₁₁ ) Add the granular substance H4 obtained in step (10) to the solution B5 obtained in step ( ₆ ), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G5, and use 100mL of Wash the granular substance G5 with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance _H5 ; place _H5 in a muffle furnace and roast at 550°C for 4 hours to obtain granular substance I;

(12) 20ml concentration of 0.5mol/L Ce(NO ₃ ) ₂ solution and 80ml concentration of 0.5mol/L CoCl ₂ solution were added to 120ml isopropanol and 5ml concentrated hydrochloric acid, and then 20ml concentration of 0.5mol was added /L of _NiCl solution to obtain solution C;

(13) Add the granular substance I obtained in step (11) to the solution C obtained in step (12), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance J, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance J, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance K;

(14) 40ml concentration of 0.5mol/L Ce(NO ₃ ) ₂ solution and 40ml concentration of 0.5mol/L CoCl ₂ solution were added to 120ml isopropanol and 5ml concentrated hydrochloric acid, and then 40ml concentration of 0.5mol was added /L of _NiCl solution to obtain solution D;

(15) Add the granular substance K obtained in step (13) to the solution D obtained in step (14), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance L, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance L was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance M;

(16) Add 45ml of Ce(NO ₃ ) ₂ solution with a concentration of 0.5mol/L and 15ml of a _CoCl solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 60ml with a concentration of 0.5mol /L of _NiCl solution to obtain solution E;

(17) Add the particulate matter M obtained in step (15) to the solution E obtained in step (16), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate matter N, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance N, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance O;

(18) 15ml concentration of 0.5mol/L Ce(NO ₃ ) ₂ solution and 5ml concentration of 0.5mol/L CoCl ₂ solution were added to 120ml isopropanol and 5ml concentrated hydrochloric acid, and then 100ml concentration of 0.5mol was added /L of _NiCl solution to obtain solution F;

(19) Add the particulate substance O obtained in step (17) to the solution F obtained in step (18), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate substance P, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance P was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance Q, which was placed in a muffle furnace and roasted at 550°C for 4 hours, and the obtained granular substance was nitrogen-containing sulfur-oxygen Electrocatalysts with highly efficient catalytic degradation functions for heterocyclic compounds.

The beneficial effect of the invention is that the prepared electrocatalyst with efficient catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds has the characteristics of high current efficiency, strong stability, long electrode life and the like.

Detailed ways

The invention provides an electrocatalyst with high-efficiency catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds and a preparation method thereof,

The following is an example to illustrate its implementation process.

Example 1.

Wash 300g of γ-Al ₂ O ₃ spheres with a particle size of 3-5mm with 500ml of deionized water, repeat the washing 3 times, then soak in 200ml of absolute ethanol for 10h, wash once with 500ml of deionized water, and then Dry at 80° C. for 10 h to obtain granular substance A.

Add 50ml of AgNO3 with a concentration of 0.5mol/ _L into 150ml of isopropanol to obtain solution A. Add granular substance A to solution A, shake in a shaker for 3 h, filter to obtain granular substance B and microemulsion X, wash granular substance B with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then wash at 80 Dry at ℃ for 10 hours to obtain granular substance C; put granular substance C in a muffle furnace and roast at 500°C for 4 hours to obtain granular substance D; add granular substance D to microemulsion X, and Shake for 3 hours, filter and remove the liquid to obtain particulate matter E, wash E with 100mL of ethanol with a mass concentration of 95%, repeat the washing twice, then dry at 80°C for 10h, and then bake in a muffle furnace at 500°C 4h, the particulate matter F was obtained.

Add 10ml of Ce(NO ₃ ) ₂ solution with a concentration of 0.5mol/L and 100ml of a CoCl ₂ solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 10ml of 0.5mol/L with a concentration of Divide the NiCl ₂ solution into 5 equal parts after shaking to obtain solution B ₁ , solution B ₂ , solution B ₃ , solution B ₄ , and solution B ₅ ;

Add the particulate matter F to the solution B1, and shake it in _a shaker for 3h, remove the liquid by filtration to obtain the particulate matter G1, wash the granular matter G1 with 100mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then wash at 80°C Dry under conditions for 10 hours to obtain granular substance H1 _; add granular substance H1 to solution B2 and shake in _a shaker for ₃ hours, filter and remove the liquid to obtain granular substance G2, and wash the particles with 100 mL of ethanol with a mass concentration of 95% Substance G2, repeated washing twice, and then dried at 80°C for 10 hours to obtain granular substance _H2 ; adding granular substance _H2 to solution _B3 , shaking in a shaker for 3 hours, filtering to remove the liquid to obtain granular substance G3 , wash the granular substance G3 with 100mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then dry it at 80°C for 10h to obtain the granular substance _{H3 ;} add the granular substance _H3 to the solution B4, and shake Shake in the bed for 3 hours, remove the liquid by filtration to obtain granular substance G4, wash the granular substance G4 with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance H4 _; H4 was added to solution B5 and shaken in a shaker for ₃ hours, and the liquid was removed by filtration to obtain particulate matter G5. _The particulate matter G5 was washed with 100 mL of ethanol with a mass concentration of 95%, and the washing was repeated twice. Dry for 10 hours to obtain granular substance H ₅ ; place H ₅ in a muffle furnace for calcination at 550° C. for 4 hours to obtain granular substance I.

Add 20ml of Ce(NO ₃ ) ₂ solution with a concentration of 0.5mol/L and 80ml of a CoCl ₂ solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 20ml of 0.5mol/L NiCl ₂ solution to obtain solution C.

Add granular substance I to solution C, and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance J, wash granular substance J with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store the granular substance at 80°C Under drying for 10 h, granular material K was obtained.

40ml concentration of 0.5mol/L Ce(NO ₃ ) ₂ solution and 40ml concentration of 0.5mol/L CoCl ₂ solution were added to 120ml isopropanol and 5ml concentrated hydrochloric acid, and then 40ml concentration of 0.5mol/L NiCl ₂ solution to obtain solution D.

Add granular substance K to solution D, and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance L, wash granular substance L with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Under drying for 10h, the granular material M was obtained.

Add 45ml of 0.5mol/L Ce(NO ₃ ) ₂ solution and 15ml of 0.5mol/L CoCl ₂ solution into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, then add 60ml of 0.5mol/L NiCl ₂ solution to obtain solution E.

Add the particulate matter M to the solution E, and shake it in a shaker for 3 hours; remove the liquid by filtration to obtain the particulate matter N, wash the granular matter N with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Under drying for 10h, granular material O was obtained.

Add 15ml of 0.5mol/L Ce(NO ₃ ) ₂ solution and 5ml of 0.5mol/L CoCl ₂ solution into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 100ml of 0.5mol/L NiCl ₂ solution to obtain solution F.

Add the particulate matter O to the solution F and shake it in a shaker for 3 hours; remove the liquid by filtration to obtain the particulate matter P, wash the particulate matter P with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Drying for 10 hours under low temperature to obtain granular material Q, put Q in a muffle furnace and roast at 550°C for 4 hours, and the obtained granular material is an electrocatalyst with efficient catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds.

The following is the electrocatalyst with efficient catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds prepared by the method of the present invention, and the degradation test of coal chemical industry wastewater in a three-dimensional electrode reactor is carried out to further illustrate the present invention.

The electrocatalyst with high-efficiency catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds prepared by the method of the present invention is packed in a three-dimensional electrode reactor, and a degradation test is carried out on coal chemical industry wastewater. The results show that the electrode can efficiently treat coking wastewater. COD, when the influent COD is 512mg/L, the electrocatalyst with efficient catalytic degradation function for nitrogen-containing sulfur-oxygen heterocyclic compounds prepared by the method of the present invention is the third pole, and the pH is 4.5, and the voltage is 12V. Under the condition that the treatment time is 60min, the COD in the effluent after treatment is reduced to 43mg/L, and the treatment efficiency reaches 91.60%.

Claims (1)

1. nitrogenous sulphur oxygen helerocyclics is had to a preparation method for the eelctro-catalyst of efficient catalytic degradation function, it is characterized in that, the concrete steps of the method are as follows:

(1) by 300g particle diameter be the γ-Al of 3-5mm ₂o ₃ball 500mL deionized water washing, repeated washing 3 times, then puts into 200mL absolute ethyl alcohol and soaks 10h, and after 500mL washed with de-ionized water 1 time, dry 10h under 80 DEG C of conditions, obtains particulate matter A;

(2) be the AgNO of 0.5mol/L by 50mL concentration ₃add in 150mL isopropyl alcohol, obtain solution A;

(3) the particulate matter A that step (1) obtains is added in the solution A that step (2) obtains, and 3h is shaken in shaking table, filtration obtains particulate matter B and microemulsion X, with the ethanol washing granule substance B that 100mL mass concentration is 95%, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter C;

(4) the particulate matter C that step (3) obtains is placed in Muffle furnace roasting 4h under 500 DEG C of conditions, obtains particulate matter D;

(5) the particulate matter D that step (4) obtains is added in the microemulsion X that step (3) obtains, and 3h is shaken in shaking table, cross and filter liquid and obtain particulate matter E, with the ethanol washing granule material E that 100mL mass concentration is 95%, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, is then placed in Muffle furnace roasting 4h under 500 DEG C of conditions, obtains particulate matter F;

(6) by 10mL concentration be the Ce (NO of 0.5mol/L ₃) ₂solution and 100mL concentration are the CoCl of 0.5mol/L ₂solution joins in 120mL isopropyl alcohol and 5mL concentrated hydrochloric acid, and then adds the NiCl that 10mL concentration is 0.5mol/L ₂solution, is divided into equivalent 5 parts, obtains solution B after shaking up ₁, solution B ₂, solution B ₃, solution B ₄, solution B ₅;

(7) the particulate matter F that step (5) obtains is added the solution B that step (6) obtains ₁in, and 3h is shaken in shaking table, filtering liquid obtains particulate matter G1 excessively, and be the ethanol washing granule material G1 of 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter H ₁;

(8) by particulate matter H that step (7) obtains ₁add the solution B that step (6) obtains ₂in, and 3h is shaken in shaking table, filtering liquid obtains particulate matter G2 excessively, and be the ethanol washing granule material G2 of 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter H ₂;

(9) by particulate matter H that step (8) obtains ₂add the solution B that step (6) obtains ₃in, and 3h is shaken in shaking table, filtering liquid obtains particulate matter G3 excessively, and be the ethanol washing granule material G3 of 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter H ₃;

(10) by particulate matter H that step (9) obtains ₃add the solution B that step (6) obtains ₄in, and 3h is shaken in shaking table, filtering liquid obtains particulate matter G4 excessively, and be the ethanol washing granule material G4 of 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter H ₄;

(11) by particulate matter H that step (10) obtains ₄add the solution B that step (6) obtains ₅in, and 3h is shaken in shaking table, filtering liquid obtains particulate matter G5 excessively, and be the ethanol washing granule material G5 of 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtains particulate matter H ₅; By H ₅be placed in Muffle furnace roasting 4h under 550 DEG C of conditions, obtain particulate matter I;

(12) by 20mL concentration be the Ce (NO of 0.5mol/L ₃) ₂solution and 80mL concentration are the CoCl of 0.5mol/L ₂solution joins in 120mL isopropyl alcohol and 5mL concentrated hydrochloric acid, and then adds the NiCl that 20mL concentration is 0.5mol/L ₂solution, obtains solution C;

(13) the particulate matter I that step (11) obtains is added in the solution C that step (12) obtains, and shake 3h in shaking table; Crossing and filter liquid and obtain particulate matter J, is the ethanol washing granule material J of 95% by 100mL mass concentration, repeated washing 2 times, and then dry 10h under 80 DEG C of conditions, obtains particulate matter K;

(14) by 40mL concentration be the Ce (NO of 0.5mol/L ₃) ₂solution and 40mL concentration are the CoCl of 0.5mol/L ₂solution joins in 120mL isopropyl alcohol and 5mL concentrated hydrochloric acid, and then adds the NiCl that 40mL concentration is 0.5mol/L ₂solution, obtains solution D;

(15) the particulate matter K that step (13) obtains is added in the solution D that step (14) obtains, and shake 3h in shaking table; Crossing and filter liquid and obtain particulate matter L, is the ethanol washing granule material L of 95% by 100mL mass concentration, repeated washing 2 times, and then dry 10h under 80 DEG C of conditions, obtains particulate matter M;

(16) by 45mL concentration be the Ce (NO of 0.5mol/L ₃) ₂solution and 15mL concentration are the CoCl of 0.5mol/L ₂solution joins in 120mL isopropyl alcohol and 5mL concentrated hydrochloric acid, and then adds the NiCl that 60mL concentration is 0.5mol/L ₂solution, obtains solution E;

(17) the particulate matter M that step (15) obtains is added in the solution E that step (16) obtains, and shake 3h in shaking table; Crossing and filter liquid and obtain particulate matter N, is the ethanol washing granule material N of 95% by 100mL mass concentration, repeated washing 2 times, and then dry 10h under 80 DEG C of conditions, obtains particulate matter O;

(18) by 15mL concentration be the Ce (NO of 0.5mol/L ₃) ₂solution and 5mL concentration are the CoCl of 0.5mol/L ₂solution joins in 120mL isopropyl alcohol and 5mL concentrated hydrochloric acid, and then adds the NiCl that 100mL concentration is 0.5mol/L ₂solution, obtains solution F;

(19) the particulate matter O that step (17) obtains is added in the solution F that step (18) obtains, and shake 3h in shaking table; Cross and filter liquid and obtain particulate matter P, with the ethanol washing granule Substance P that 100mL mass concentration is 95%, repeated washing 2 times, then dry 10h under 80 DEG C of conditions, obtain particulate matter Q, Q is placed in Muffle furnace roasting 4h under 550 DEG C of conditions, the particulate matter obtained is the eelctro-catalyst nitrogenous sulphur oxygen helerocyclics to efficient catalytic degradation function.