A water treatment oxidation device and its application

Abstract

The present invention relates to a water treatment high-efficiency oxidation device and its application, belonging to the technical field of wastewater treatment. The device comprises a water inlet regulating box and a reactor; the water inlet regulating box comprises a first water inlet pump, a first water inlet, a feeding port, a first agitator, a pH meter and a first water outlet; the reactor comprises a second water inlet pump, a second water inlet, an insulating and heat-insulating inner shell, a reactor outer shell, a conductive carbon material, an insulating clamp, a power supply, a second agitator, a thermometer, a sampling port and a second water outlet. The present invention utilizes the Joule heat generated by the conductive carbon material to achieve rapid heating of the sewage, so that the PS is activated to generate strong oxidizing free radicals, thereby improving the PS activation efficiency and facilitating the rapid removal of pollutants.

Description

Technical Field

[0001] The invention relates to a water treatment oxidation device and application thereof, belonging to the technical field of wastewater treatment. Background Art

[0002] The discharge volume of difficult-to-treat wastewater such as chemical wastewater, pharmaceutical wastewater, printing and dyeing wastewater, coking wastewater, and phenolic wastewater is increasing, and the types of new difficult-to-degrade pollutants contained in difficult-to-treat wastewater are also increasing, and the concentration is increasing. These difficult-to-degrade pollutants are generally difficult to biodegrade, and will enter natural water bodies with the effluent of sewage treatment plants, and accumulate in plankton, plants, and aquatic organisms, and be transmitted through the food chain, causing serious water environment pollution and health hazards.

[0003] Based on sulfate free radical (SO4˙ - ) is considered a promising pollutant degradation technology. ˉ It is produced by activating persulfate (PS). Commonly used PS mainly include monopersulfate (PMS) and peroxydisulfate (PDS). PMS / PDS can be activated by light, heat, alkali and catalyst. Catalyst activation has the highest activation efficiency, but the use of catalyst materials will increase the cost of sewage treatment, and there is a possibility of secondary pollution of the effluent due to leaching of metal ions. Alkaline catalysis generally requires the addition of alkaline substances to adjust the pH value of the solution. After the reaction, the pH of the effluent needs to be adjusted, which also increases the treatment cost. Thermal activation is the use of energy generated by heating to activate PS. It is a simple and effective method for PS activation. The peroxide bond (O–O) bond energy in PS is 140~213.3kJ, so theoretically, a heating temperature greater than 40°C can cause O–O to break and produce SO4˙ - and hydroxyl radicals (·OH), degrading pollutants in water. At present, the main heating methods for thermal activation of PS include water bath heating, microwave heating, photothermal conversion heating, etc. Among them, the heating rate of water bath heating is slow, microwave heating generally requires high energy consumption, and the heating effect of photothermal conversion is poor. With the assistance of light-absorbing materials, water can only be heated to 40-50°C. Joule heat is the heat generated when electric current passes through a conductor. Currently, Joule heat heating has been used for rapid adsorption of petroleum pollutants, water evaporation, and adsorbent regeneration. However, related research on the use of porous conductive carbon materials to generate Joule heat to activate PS has not been reported. Summary of the invention

[0004] The present invention provides a water treatment oxidation device using a porous conductive carbon material to generate Joule heat to activate PS, including a water inlet regulating box and a reactor;

[0005] The water inlet regulating box comprises a first water inlet pump, a first water inlet, a feed port, a first agitator, a pH meter and a first water outlet, wherein the first water inlet pump is connected to the first water inlet;

[0006] The reactor comprises a second water inlet pump, a second water inlet, an insulating inner shell, a reactor outer shell, a conductive carbon material, an insulating clamp, a DC power supply, a second agitator, a thermometer, a sampling port and a second water outlet, the second water inlet pump is connected to the second water inlet, the insulating clamp is clamped on the busbar edges at both ends of the conductive carbon material to fix the conductive carbon material, the DC power supply is connected to the insulating clamp by an external wire, and the conductive carbon material is suspended in the reactor;

[0007] The first water outlet is connected to the second water inlet pump.

[0008] In one embodiment of the present invention, the reactor is a cylindrical container, and a hemispherical cabin is provided on the top of the reactor. A digital display screen and an electrical control box are provided on the outer surface of the hemispherical cabin, both of which are connected to the second agitator and the thermometer. The digital display screen is used to view the real-time temperature in the reactor, and the electrical control box is used to control the working power of the agitator.

[0009] In one embodiment of the present invention, the conductive carbon material is a curved thin plate structure, and the conductive carbon material is one of graphite felt, carbon fiber, carbon cloth, carbon felt and graphene paper.

[0010] The present invention also provides an application of an advanced oxidation device for water treatment, the steps comprising:

[0011] Step 1: pumping the wastewater into the water inlet regulating tank from the first water inlet by the first water inlet pump, stirring with the first agitator and adding a certain amount of PS solid from the feeding port;

[0012] Step 2: After the wastewater and PS solid are evenly mixed, the wastewater and PS solid are pumped into the reactor from the second water inlet by the second water inlet pump, and a voltage is applied to both ends of the conductive carbon material by the DC power supply, and the thermal-catalytic simultaneous activation of PS is achieved by utilizing the Joule heat generated by the conductive carbon material and the oxygen-containing functional groups on its surface, thereby generating active oxygen to degrade pollutants in the water;

[0013] Step three: as the reaction proceeds, the sampling port is intermittently opened to sample the wastewater in the reactor, and the sampling port is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet, and is discharged from the second water outlet.

[0014] In one embodiment of the present invention, the external voltage applied to both ends of the conductive carbon material by the DC power supply is 1V to 10V.

[0015] In one embodiment of the present invention, the PS is activated by Joule heat and oxygen-containing functional groups on the surface of the carbon material to produce strong oxidizing active oxygen species, including SO4·ˉ, ·OH, ·O2ˉ, 1 O2, degrades pollutants.

[0016] In one embodiment of the present invention, the PS solid added to the feed port comprises monoperoxysulfate or peroxydisulfate.

[0017] In the present invention, SMX is sulfamethoxazole, PS is persulfate, PMS is monoperoxysulfate, PDS is potassium persulfate, COD is chemical oxygen demand, and B / C is the ratio of biochemical oxygen demand to chemical oxygen demand.

[0018] Unless otherwise specified, the “connection” described in the present invention refers to a pipeline connection.

[0019] Beneficial effects of the present invention:

[0020] 1. The present invention utilizes the Joule heat generated by the conductive carbon material to achieve rapid heating of the sewage, so that PS is activated to produce strong oxidizing free radicals (SO4˙ - , ·OH, ·O2 - , 1 O2) and can reduce heating energy consumption.

[0021] 2. The conductive carbon material of the present invention can catalytically activate PS and has a synergistic effect with PS thermal activation, thereby achieving a higher PS activation efficiency, which is beneficial to the rapid removal of pollutants.

[0022] 3. The conductive carbon material of the present invention is a curved thin plate structure, which can increase the heating area and improve the sewage heating rate.

[0023] 4. The DC power supply of the present invention is connected to the insulating fixing clamp by an external wire, and the two ends of the conductive carbon material are clamped and fixed by the insulating fixing clamp, which can better fix the position of the external power supply and the conductive carbon material in the reactor, reduce the damage of the conductive carbon material, and prevent electrons from being lost into the water through the edge of the conductive carbon material. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is an overall side view and a top view of the device in the embodiment of the present invention.

[0025] Figure 2 (a) The change of water temperature of the reaction system under different heating methods; (b) The degradation curve of sulfamethoxazole; (c) The statistical diagram of energy consumption and heat energy generated.

[0026] In the figure, 1 is a water inlet regulating box, 2 is a reactor, 3 is a first water inlet pump, 4 is a first water inlet, 5 is a feeding port, 6 is a first agitator, 7 is a pH meter, 8 is a first water outlet, 9 is a second water inlet pump, 10 is a second water inlet, 11 is an insulating and heat-preserving inner shell, 12 is a reactor outer shell, 13 is a conductive carbon material, 14 is an insulating clamp, 15 is a DC power supply, 16 is a second agitator, 17 is a thermometer, 18 is a sampling port, and 19 is a second water outlet. DETAILED DESCRIPTION

[0027] Example 1

[0028] like Figure 1 As shown, the present invention provides a water treatment oxidation device, including a water inlet regulating box 1 and a reactor 2.

[0029] The water inlet regulating box 1 comprises a first water inlet pump 3 , a first water inlet 4 , a feed port 5 , a first agitator 6 , an online pH meter 7 and a first water outlet 8 , and the first water inlet pump 3 is connected to the first water inlet 4 .

[0030] The reactor 2 is a cylindrical container, and a hemispherical cabin is provided on the top of the reactor 2.

[0031] The reactor 2 includes a second water inlet pump 9, a second water inlet 10, an insulating inner shell 11, a reactor outer shell 12, a conductive carbon material 13, an insulating clamp 14, a DC power supply 15, a second agitator 16, a thermometer 17, a sampling port 18 and a second water outlet 19. The second water inlet pump 9 is connected to the second water inlet 10, and both ends of the conductive carbon material 13 are clamped and fixed by the insulating clamp 14. The DC power supply 15 is connected to the insulating clamp 14 by an external wire, so that the conductive carbon material 13 is suspended in the reactor 2.

[0032] The outer surface of the hemispherical cabin is provided with a digital display screen and an electric control box, both of which are connected to the second agitator 16 and the thermometer 17 . The digital display screen is used to view the real-time temperature in the reactor 2 , and the electric control box controls the working power of the second agitator 16 .

[0033] The first water outlet 8 is connected to the second water inlet pump 9. The conductive carbon material 13 is a curved thin plate structure, and its material is one of graphite felt, carbon fiber, carbon cloth, carbon felt and graphene paper.

[0034] Example 2

[0035] Step 1: The antibiotic wastewater containing sulfamethoxazole (SMX) (COD 1000 mg / L, SMX 100 mg / L, B / C 0.15) is pumped into the water inlet regulating box 1 from the first water inlet 4 by the first water inlet pump 3, and the water inlet regulating box 1 is a rectangular container with a working volume of 80 L (length 40 cm×width 40 cm×height 50 cm); the reactor 2 is a cylindrical container with a working volume of 50 L (diameter 40 cm×height 40 cm); the sampling port 18 is in a closed state; while mechanically stirring with the first agitator 6 (100 r / min), a certain amount of potassium persulfate (PDS) is added from the feeding port 5 so that its concentration in the wastewater is 50 mM, and the pH value is detected using a pH meter;

[0036] Step 2: The conductive carbon material 13 used inside is a bent graphite felt (length 40cm×width 25cm×thickness 6mm in the straight state); after the wastewater potassium persulfate (PDS) is evenly mixed, it is pumped into the reactor 2 from the second water inlet 10 by the second water inlet pump 9, and after the DC power supply 15 applies an external voltage of 5V to both ends of the conductive carbon material 13, the thermometer 17 measures the temperature in the reactor 2 and then feeds back information to the digital display screen, and it is detected that the wastewater is heated to 60°C after 40 minutes. The user then controls the second stirrer 16 through the electric control box to fully stir (100r / min), and utilizes the Joule heat generated by the conductive carbon material 13 and the oxygen-containing functional groups on its surface to realize the thermal-catalytic synchronous activation of PS, and generate highly oxidizing ROS, including SO4· - , ·OH, ·O2 - , 1 O2, degrade pollutants in water, these ROS react with pollutants in wastewater to undergo oxidative degradation reaction, after 60 minutes of reaction, the sampling port 18 is opened for sampling and testing, the COD concentration of antibiotic wastewater is reduced to 402 mg / L, the removal rate is 59.8%, the SMX degradation rate is 100%, and the B / C ratio is increased to 0.37;

[0037] Step three: As the reaction proceeds, the sampling port 18 is intermittently opened to sample the wastewater in the reactor 2, and the sampling port 18 is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet 19, and is discharged from the second water outlet 19.

[0038] Example 3

[0039] Step 1: Pump the printing and dyeing wastewater (COD 2000mg / L, B / C 0.20) into the water inlet regulating box 1 from the first water inlet 4 by the first water inlet pump 3, the water inlet regulating box 1 is a rectangular container with a working volume of 80L (length 40cm×width 40cm×height 50cm); the reactor 2 is a cylindrical container with a working volume of 50L (diameter 40cm×height 40cm); the sampling port 18 is in a closed state; while mechanically stirring with the first agitator 6 (100r / min), a certain amount of potassium persulfate (PDS) is added from the feeding port 5 so that its concentration in the wastewater is 50mM, and the pH value is detected using a pH meter;

[0040] Step 2: The conductive carbon material 13 used inside is a rectangular conductive component (40 cm long × 25 cm wide in the straight state) assembled from carbon fibers after bending; after the wastewater potassium persulfate (PDS) is evenly mixed, it is pumped into the reactor 2 from the second water inlet 10 by the second water inlet pump 9, and after the DC power supply 15 applies an external voltage of 5V to both ends of the conductive carbon material 13, the thermometer 17 measures the temperature in the reactor 2 and then feeds back information to the digital display screen, and it is detected that the wastewater is heated to 59°C after 60 minutes. The user then controls the second stirrer 16 through the electric control box to fully stir (100 r / min), and the Joule heat generated by the conductive carbon material 13 and the oxygen-containing functional groups on its surface are used to realize the thermal-catalytic synchronous activation of PS, and generate highly oxidizing ROS, including SO4· - , ·OH, ·O2 - , 1 O2, degrades pollutants in water, these ROS react with pollutants in wastewater to undergo oxidation degradation reaction, after 1.5h of reaction, the sampling port 18 is opened for sampling and testing, the COD concentration of printing and dyeing wastewater is reduced to 852mg / L, the removal rate is 57.4%, the decolorization rate is 75%, and the B / C ratio is increased to 0.36;

[0041] Step three: As the reaction proceeds, the sampling port 18 is intermittently opened to sample the wastewater in the reactor 2, and the sampling port 18 is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet 19, and is discharged from the second water outlet 19.

[0042] Example 4

[0043] Step 1: Pump the printing and dyeing wastewater (COD 2000mg / L, B / C 0.20) into the water inlet regulating box 1 from the first water inlet 4 by the first water inlet pump 3, the water inlet regulating box 1 is a rectangular container with a working volume of 80L (length 40cm×width 40cm×height 50cm); the reactor 2 is a cylindrical container with a working volume of 50L (diameter 40cm×height 40cm); the sampling port 18 is in a closed state; while mechanically stirring with the first agitator 6 (100r / min), a certain amount of potassium persulfate (PDS) is added from the feeding port 5 so that its concentration in the wastewater is 50mM, and the pH value is detected using a pH meter;

[0044] Step 2: The conductive carbon material 13 used inside is a bent conductive carbon cloth (40 cm long × 25 cm wide); after the wastewater potassium persulfate (PDS) is evenly mixed, it is pumped into the reactor 2 from the second water inlet 10 by the second water inlet pump 9, and after the DC power supply 15 applies an external voltage of 5V to both ends of the conductive carbon material 13, the thermometer 17 measures the temperature in the reactor 2 and then feeds back the information to the digital display screen, and it is detected that the wastewater is heated to 57°C after 60 minutes. The user then controls the second stirrer 16 through the electric control box to fully stir (100r / min), and the Joule heat generated by the conductive carbon material 13 and the oxygen-containing functional groups on its surface are used to realize the thermal-catalytic synchronous activation of PS, and generate highly oxidizing ROS, including SO4· - , ·OH, ·O2 - , 1 O2, degrades pollutants in water, these ROS react with pollutants in wastewater to undergo oxidation degradation reaction, after 2 hours of reaction, the sampling port 18 is opened for sampling and testing, the COD concentration of phenol-containing wastewater is reduced to 429 mg / L, the removal rate is 61.0%, and the B / C ratio is increased to 0.35;

[0045] Step three: As the reaction proceeds, the sampling port 18 is intermittently opened to sample the wastewater in the reactor 2, and the sampling port 18 is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet 19, and is discharged from the second water outlet 19.

[0046] Comparative Example 1

[0047] Under the same reaction conditions, the 80°C water bath heating mode and the graphite felt / 5V mode were investigated respectively: the temperature change of the reaction system, the degradation of the target pollutant sulfamethoxazole and the reaction energy consumption were compared. The graphite felt / 5V mode is an implementation method for heating the conductive carbon material of the present invention.

[0048] The reaction conditions were: [SMX]0=10 mg / L; [PMS]0=0.5 mM; pH=7.0.

[0049] like Figure 2 As shown in (a), after heating for 30 minutes, the temperature of both the 80°C water bath heating and the graphite felt / 5V mode can reach about 80°C, which is enough to activate persulfate to generate free radicals to degrade pollutants.

[0050] The specific steps are as follows:

[0051] Step 1: Pumping antibiotic wastewater containing sulfamethoxazole (SMX) ([SMX]0=10 mg / L) into the water inlet regulating tank 1 through the first water inlet 4 by the first water inlet pump 3;

[0052] Step 2: Use 80°C water bath and graphite felt / 5V to heat the wastewater in the reactor 2 respectively. After the thermometer 17 measures the temperature in the reactor 2, it feeds back the information to the digital display screen and controls the second agitator 16 through the electric control box to fully stir (100r / min).

[0053] like Figure 2 As shown in (b), after 30 minutes of reaction, the pollutant removal rate in the 80°C water bath mode was only 15.3%, while it reached 97.5% in the graphite felt / 5V mode; after 60 minutes of reaction, the pollutant removal rate in the 80°C water bath mode was only 21.6%, while it reached 100% in the graphite felt / 5V mode. It can be seen that the degradation efficiency of pollutants in the graphite felt / 5V mode is significantly higher than that in the traditional water bath heating.

[0054] Step three: As the reaction proceeds, the sampling port 18 is intermittently opened to sample the wastewater in the reactor 2, and the sampling port 18 is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet 19, and is discharged from the second water outlet 19.

[0055] From the perspective of energy consumption, Figure 2 As shown in (c), the energy consumption of 80℃ water bath heating reaches 2160J in 60min, while the energy consumption in graphite felt / 5V mode is only 55.6J. Therefore, the energy consumption required to remove unit mass of pollutants is: 10kJ / mg in 80℃ water bath, which is significantly greater than 57.0J / mg in graphite felt / 5V mode.

[0056] Comparative Example 2

[0057] Under the same reaction conditions, the ceramic heating rod / 5V heating mode and the graphite felt / 5V mode were investigated respectively: the temperature change of the reaction system, the degradation of the target pollutant sulfamethoxazole and the reaction energy consumption, and compared. The graphite felt / 5V mode is an implementation method of heating the conductive carbon material of the present invention.

[0058] The reaction conditions were: [SMX]0=10 mg / L; [PMS]0=0.5 mM; pH=7.0.

[0059] like Figure 2 As shown in (a), after heating for 30 minutes, the temperature of both the ceramic heating rod / 5V and graphite felt / 5V modes can reach about 80°C, which is enough to activate persulfate to generate free radicals to degrade pollutants.

[0060] The specific steps are as follows:

[0061] Step 1: Pumping antibiotic wastewater containing sulfamethoxazole (SMX) ([SMX]0=10 mg / L) into the water inlet regulating tank 1 through the first water inlet 4 by the first water inlet pump 3;

[0062] Step 2: Use ceramic heating rod / 5V and graphite felt / 5V to heat the wastewater in the reactor 2 respectively. After the thermometer 17 measures the temperature in the reactor 2, it feeds back the information to the digital display screen and controls the second agitator 16 through the electric control box to fully stir (100r / min).

[0063] like Figure 2 As shown in (b), after 30 minutes of reaction, the pollutant removal rate in the ceramic heating rod / 5V mode was only 6.7%, while it reached 97.5% in the graphite felt / 5V mode; after 60 minutes of reaction, the pollutant removal rate in the ceramic heating rod / 5V mode was only 29.8%, while it reached 100% in the graphite felt / 5V mode. It can be seen that the pollutant degradation efficiency in the graphite felt / 5V mode is significantly higher than that in the traditional ceramic heating rod / 5V mode.

[0064] Step three: As the reaction proceeds, the sampling port 18 is intermittently opened to sample the wastewater in the reactor 2, and the sampling port 18 is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet 19, and is discharged from the second water outlet 19.

[0065] From the perspective of energy consumption, Figure 2 As shown in (c), the energy consumption of the ceramic heating rod / 5V heating mode reached 136.8J in 60min, while the energy consumption in the graphite felt / 5V mode was only 55.6J. The energy consumption required to remove unit mass of pollutants is converted to: 459.1J / mg in an 80℃ water bath, which is significantly greater than 57.0J / mg in the graphite felt / 5V mode.

[0066] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. An application of a water treatment oxidation device, using a water treatment oxidation device, characterized in that: The water treatment oxidation device comprises a water inlet regulating box and a reactor; the water inlet regulating box comprises a first water inlet pump, a first water inlet, a feeding port, a first agitator, a pH meter and a first water outlet, and the first water inlet pump is connected to the first water inlet; the reactor is a cylindrical container; the reactor comprises a second water inlet pump, a second water inlet, an insulating and heat-insulating inner shell, a reactor outer shell, a conductive carbon material, an insulating clamp, a DC power supply, a second agitator, a thermometer, a sampling port and a second water outlet, the second water inlet pump is connected to the second water inlet, the two ends of the conductive carbon material are fixed by the insulating clamp, and the DC power supply is connected to the insulating clamp by an external wire; a hemispherical cabin is provided on the top of the reactor, and a digital display screen and an electric control box are provided on the outer surface of the hemispherical cabin, both of which are connected to the second agitator and the thermometer; the conductive carbon material is a curved thin plate structure; the first water outlet is connected to the second water inlet pump; the conductive carbon material is one of graphite felt, carbon fiber, carbon cloth, carbon felt and graphene paper; The application comprises the following steps: Step 1: pumping the wastewater into the water inlet regulating tank from the first water inlet by the first water inlet pump, adding a certain amount of monopersulfate solid from the feed port while stirring with the first agitator; Step 2: After the wastewater and the monopersulfate solid are uniformly mixed, the wastewater and the monopersulfate solid are pumped into the reactor from the second water inlet by the second water inlet pump, and a voltage is applied to both ends of the conductive carbon material by the DC power supply, and the Joule heat generated by the conductive carbon material and the oxygen-containing functional groups on its surface are utilized to achieve thermal-catalytic simultaneous activation of the monopersulfate solid, thereby generating active oxygen to degrade pollutants in the water; Step three: as the reaction proceeds, the sampling port is intermittently opened to sample the wastewater in the reactor, and the sampling port is closed after each sampling. After sampling, it is detected that the degradation rate reaches the production requirement of the user, and the wastewater accumulates to the height of the second water outlet, and is discharged from the second water outlet.

2. The use of a water treatment oxidation device according to claim 1, characterized in that: The external voltage applied to the two ends of the conductive carbon material by the DC power supply is 1V to 10V.

3. The use of a water treatment oxidation device according to claim 2, characterized in that: Synchronous activation of monopersulfate solids by Joule heat and oxygen-containing functional groups on the surface of carbon materials to produce strong oxidizing active oxygen Substances, including SO4·, ·OH, ·O2, 1 O2, degrades pollutants.

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