Reaction device with multiple induction electrodes connected in series and used for removing antimonate in water through hydrogen autotrophy

Abstract

The utility model relates to a reaction device with multiple serially-connected induction electrodes for removing antimonate in water through hydrogen autotrophy. The reaction device comprises a reactor shell and a direct-current power supply, a water inlet is formed in the bottom of the reactor shell, and an exhaust port and an overflow port are formed in the top of the reactor shell; a cathode electrolysis net, a plurality of induction electrodes and an anode electrolysis net are sequentially arranged in the reactor shell from bottom to top, the anode electrolysis net is connected with a positive electrode of a direct-current power supply, and the cathode electrolysis net is connected with a negative electrode of the direct-current power supply; a water inlet cavity is formed between the water inlet of the reactor shell and the anode electrolysis net, and an overflow cavity is formed between the top of the reactor shell and the anode electrolysis net; a biological reaction cavity is formed between the anode electrolysis net and the cathode electrolysis net in the reactor shell, and the biological reaction cavity is filled with a biological carrier attached with hydrogen autotrophic microorganisms. According to the device, antimonate in sewage can be efficiently removed, the treatment cost is reduced, and the technological process is simplified.

Description

Technical Field

[0001] The utility model relates to the field of wastewater treatment technology and equipment, in particular to a reaction device with multiple induction electrodes connected in series for hydrogen autotrophic removal of antimonate in water. Background Art

[0002] Antimony is a common amphoteric metal element widely present on the earth's surface. It is potentially toxic and carcinogenic. It has four valence states: -3, 0, +3, and +5. The valence states in the environment are mainly +3 and +5. At the same time, the form of antimony in wastewater such as printing and dyeing wastewater is mainly antimonate. The commonly used methods for treating high-concentration antimonate in water bodies are physical and chemical methods and biological methods.

[0003] The most commonly used antimony removal technology in the physicochemical method is coagulation and sedimentation process, and the commonly used coagulant is iron salt. However, the coagulation and removal effect of iron salt is related to the form of antimony, among which Sb(Ⅲ) is more easily removed by iron salt coagulation. The inorganic antimony in the polluted water is mainly Sb(V), which increases the difficulty of coagulation treatment. It is necessary to add additional acid solution to adjust the pH value of the water body or increase the amount of iron salt, resulting in an increase in treatment costs. The biological method can be divided into heterotrophic reduction and autotrophic reduction according to the required carbon source. Both methods remove Sb(V) by reducing it to Sb(Ⅲ) which is easy to coagulate and precipitate. The heterotrophic reduction method mainly uses organic matter as an electron donor, and the additional organic matter can easily cause secondary pollution of the effluent. The autotrophic reduction method uses sulfur or hydrogen as an electron donor to reduce Sb(V) in the water body, and has the advantages of no secondary pollution of organic matter in the effluent, but its high energy consumption also limits the application of electrochemical treatment technology in the field of water pollution control. Utility Model Content

[0004] Compared with the prior art, the utility model aims to provide a reaction device for removing antimonate in water by hydrogen autotrophic method with multiple induction electrodes connected in series, which can efficiently remove antimonate in sewage while reducing treatment cost and simplifying process flow.

[0005] In order to solve the above technical problems, the specific scheme adopted by the utility model is a reaction device for removing antimonate from water by hydrogen autotrophically with multiple induction electrodes connected in series, comprising a reactor shell and a DC power supply; a water inlet is arranged at the bottom of the reactor shell, and an exhaust port and an overflow port are arranged at the top of the reactor shell; a cathode electrolysis network, a plurality of induction electrodes and an anode electrolysis network are arranged in sequence from bottom to top in the reactor shell, the anode electrolysis network is connected to the positive pole of the DC power supply, and the cathode electrolysis network is connected to the negative pole of the DC power supply; a water inlet cavity is formed between the water inlet of the reactor shell and the anode electrolysis network, and an overflow cavity is formed between the top of the reactor shell and the anode electrolysis network; a biological reaction cavity is formed between the anode electrolysis network and the cathode electrolysis network in the reactor shell, and the biological reaction cavity is filled with a biological carrier attached with hydrogen autotrophic microorganisms.

[0006] As an optimization scheme for the above-mentioned reaction device for autotrophic removal of antimonate in water with multiple sensing electrodes in series: the anode electrolysis mesh is a mesh plate made of one or more materials selected from the group consisting of iron, carbon and aluminum; the cathode electrolysis mesh is a mesh plate made of any one or more materials selected from the group consisting of nickel, stainless steel, iron, aluminum, copper, carbon, platinum, titanium, ruthenium, palladium and iridium; and the sensing electrode is a mesh plate made of one or more materials selected from the group consisting of iron, carbon and aluminum.

[0007] As another optimization scheme of the above-mentioned reaction device for autotrophic removal of antimonate in water with hydrogen using multiple sensing electrodes in series: the water inlet is connected to a wastewater tank through an inlet pipe, and a sewage pump is connected to the inlet pipe.

[0008] As another optimization scheme of the above-mentioned reaction device for autotrophic removal of antimonate in water with hydrogen using multiple sensing electrodes in series: a porous partition is installed in the water inlet cavity of the reactor shell.

[0009] As another optimization scheme for the above-mentioned reaction device for autotrophic removal of antimonate in water with hydrogen using multiple sensing electrodes connected in series: the number of sensing electrodes is two, and five groups of support members are arranged on the inner side wall of the reactor shell along its height direction, and the five groups of support members are respectively used to support the anode electrolysis network, two sensing electrodes, the cathode electrolysis network and the porous partition; each group of support members includes four support bosses, and the four support bosses are evenly spaced along the radial direction of the reactor shell.

[0010] As another optimization scheme for the above-mentioned reaction device for autotrophic removal of antimonate in water with multiple sensing electrodes in series: a circulating water outlet is provided on the side wall of the overflow chamber of the reactor shell, and a circulating water inlet is provided on the side wall of the water inlet chamber of the reactor shell.

[0011] As another optimization scheme for the above-mentioned reaction device for autotrophic removal of antimonate in water by hydrogen with multiple sensing electrodes in series: the reactor shell is a vertical rectangular parallelepiped or a vertical cylinder.

[0012] Another optimization scheme of the above-mentioned reaction device for autotrophic removal of antimonate from water using multiple sensing electrodes connected in series: a plurality of sampling ports are arranged on the reactor shell along its height direction.

[0013] Compared with the prior art, the utility model has the following beneficial effects:

[0014] In the utility model, a cathode electrolysis net, a plurality of induction electrodes and an anode electrolysis net are sequentially arranged in the reactor shell from bottom to top, and a biological carrier of hydrogen autotrophic microorganisms attached with oxygen is filled in the biological reaction chamber formed between the anode electrolysis net and the cathode electrolysis net, and the side of the induction motor close to the cathode electrolysis net is the anode area, and the side close to the anode electrolysis net is the cathode area. When wastewater enters through the water inlet arranged at the bottom of the reactor shell and flows through the biological reaction chamber from bottom to top, hydrogen microbubbles generated by the cathode electrolysis net and the cathode area of ​​the induction electrode electrolyzing water are enriched at the cathode electrolysis net and the cathode area of ​​the induction electrode, retained in the biological reaction chamber, and passed through the biological reaction chamber under the action of the water flow, thereby providing electron donors for the microorganisms on the biological carrier for removing antimonate in water.

[0015] Since the oxygen microbubbles generated by the electrolysis of water by the anode electrolysis network are above the anode electrolysis network, they will not destroy the anoxic environment required by the microorganisms in the biological reaction chamber, and no oxygen will be generated by electrolyzing iron instead of water in the anode area of ​​the sensing electrode, so the electrolysis product will not have an adverse effect on the biochemical reaction process. Therefore, the device does not require a proton exchange membrane to block oxygen and maintain the power-on state between the cathode electrolysis network and the anode electrolysis network, thereby eliminating the investment cost of the proton exchange membrane and simplifying the internal structure of the reactor shell.

[0016] In addition, since the device does not require a proton exchange membrane, the hydroxide ions at the cathode electrolysis network can migrate to the anode electrolysis network without obstacles under the action of buoyancy and water flow driving force, which reduces the power loss on the one hand and can timely compensate for the continuous consumption of hydroxide ions caused by the electrolysis reaction of the anode electrolysis network on the other hand. In addition, in the device, water electrolysis will occur in the cathode area of ​​the multi-sensing electrode to produce more hydrogen, which can improve the removal effect of antimonate while saving electricity. The iron ions and Sb (III) produced in the anode area of ​​the sensing electrode can combine with the hydroxide ions produced on the upper part of the sensing electrode to form a precipitate to remove Sb (III), so that the device can always maintain the pH neutral state in the reactor shell without adding additional acid and alkali solution for leveling, avoiding the situation where the pH value in the device is too high (> 9.5) and causing a significant decrease in the biochemical rate of microorganisms, thereby further reducing the investment cost of sewage treatment and simplifying the treatment process. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of the internal structure of the utility model;

[0018] Figure numerals: 1. Reactor shell, 101. Overflow port, 102. Lead wire opening, 103. Water inlet chamber, 104. Support boss, 105. Water inlet, 106. Support leg, 107. Porous partition, 108. Cathode electrolysis net, 109. Bio-carrier, 110. Sensing electrode, 111. Sampling port, 112. Bio-reaction chamber, 113. Anode electrolysis net, 114. Overflow chamber, 115. Circulating water outlet, 116. Exhaust port, 117. Sewage pump, 118. Circulating water inlet, 2. DC power supply, 3. Wastewater tank. DETAILED DESCRIPTION

[0019] like Figure 1 As shown, a reaction device for removing antimonate from water by hydrogen autotrophic with multiple inductive electrodes connected in series includes a reactor shell 1, which is a vertical cylinder, and support legs 106 are respectively arranged on both sides of the bottom of the reactor shell 1, so that the bottom of the reactor shell 1 is kept away from the ground by the support legs 106.

[0020] The bottom of the reactor shell 1 is conical in shape. A water inlet 105 is provided at the center column at the bottom of the reactor shell 1. The water inlet 105 is connected to a water inlet pipe. One end of the water inlet pipe is connected to the water inlet 105, and the other end is connected to a water outlet provided on the bottom side wall of the wastewater tank 3. A sewage pump 117 is provided on the water inlet pipe. The sewage pump 117 can push wastewater into the reactor shell 1 and flow the wastewater from bottom to top along the height direction of the reactor shell 1. In addition, an overflow port 101 is provided on the side wall of the reactor shell 1 near its top, so that the water in the reactor shell 1 can flow out through the overflow port 101.

[0021] A cathode electrolysis net 108, two sensing electrodes 110 and an anode electrolysis net 113 are evenly spaced from bottom to top in the reactor shell 1, and the cathode electrolysis net 108, the two sensing electrodes 110 and the anode electrolysis net 113 are arranged in the horizontal direction. Five groups of support members are evenly spaced in the reactor shell 1 along its height direction, and each group of support members includes four support bosses 104 fixed on the inner side wall of the reactor shell 1, and the four support bosses 104 are evenly spaced along the radial direction of the reactor shell 1. The anode electrolysis net 113, the two sensing electrodes 110 and the cathode electrolysis net 108 are fixed on the support members at corresponding positions in sequence from top to bottom.

[0022] A water inlet chamber 103 is formed between the water inlet 105 and the cathode electrolysis net 108 in the reactor shell 1, and an overflow chamber 114 is formed between the overflow port 101 and the anode electrolysis net 113 in the reactor shell 1. A biological reaction chamber 112 is formed between the cathode electrolysis net 108 and the anode electrolysis net 113 in the reactor shell 1. The biological reaction chamber 112 is filled with biological carriers 109 attached with hydrogen autotrophic microorganisms, and the attached hydrogen autotrophic microorganisms provide electron donors for removing antimonate in water. A porous partition 107 is arranged on a group of support members located at the water inlet chamber 103 in the reactor shell 1. The porous partition 107 is evenly distributed with mesh holes for water to pass through and isolate the falling microorganisms. The arrangement of the porous partition 107 can prevent the microorganisms from falling off the biological carrier 109 and falling into the water inlet pipe to cause pollution. In addition, the microorganisms on the porous partition 107 need to be cleaned regularly to prevent the microorganisms from clogging the mesh holes on the porous partition 107 and affecting the passage of wastewater into the bioreactor chamber 112 .

[0023] The anode electrolysis net 113 is a mesh plate made of aluminum, the cathode electrolysis net 108 is a mesh plate made of copper, and the induction electrode 110 is a mesh plate made of iron. A DC power supply 2 is fixedly arranged on the outer wall of the reactor shell 1 through a support frame, and two lead openings 102 are provided at intervals on the side wall of the reactor shell 1. The anode electrolysis net 113 is connected to the positive electrode of the DC power supply 2 through a wire, and the cathode electrolysis net 108 is connected to the negative electrode of the DC power supply 2 through a wire. The wire is connected to the anode electrolysis net 113 or the cathode electrolysis net 108 through the lead openings 102 at the corresponding positions in turn. The side of the induction electrode 110 close to the cathode electrolysis net 108 is the anode area, and the side of the induction electrode 110 close to the anode electrolysis net 113 is the cathode area.

[0024] When the wastewater enters the bioreactor chamber 112, the anode electrolysis network 113 and the cathode electrolysis network 108 are energized, and the cathode electrolysis network 108 and the cathode region of the induction electrode 110 electrolyze water to produce: 2H2O+2e - =H2+OH - The hydrogen microbubbles generated by the electrolysis of water are enriched at the cathode electrolysis grid 108 and the cathode area of ​​the sensing electrode 110, and are retained in the bioreactor chamber 112. Under the action of the water flow, they pass through the bioreactor chamber 112, thereby providing electron donors for the microorganisms on the biological carrier 109 for removing antimonate in the water.

[0025] The anode electrolysis net 113 electrolyzes water to produce oxygen microbubbles, which are located above the anode electrolysis net 113. The oxygen microbubbles will not move downward to destroy the anoxic environment of the anaerobic microorganisms in the bioreactor chamber 112. And the anode area of ​​the sensing electrode 110 can replace the electrolysis of water by electrolyzing iron, so it will not produce oxygen, an electrolysis product that has an adverse effect on the biochemical reaction process. Therefore, compared with the existing horizontal antimonate removal device, this device does not need to set a proton exchange membrane to block oxygen and maintain the power-on state between the cathode electrolysis net 108 and the anode electrolysis net 113, thereby eliminating the investment cost of the proton exchange membrane and simplifying the internal structure of the reactor shell 1.

[0026] Cathode electrolysis network 108 occurs: 4OH - -4e - =O2+2H2O, the hydroxide ions at the cathode electrolysis network 108 can migrate to the anode electrolysis network 113 without obstacles under the action of buoyancy and water flow driving force, which on the one hand reduces the power loss, and on the other hand can timely compensate for the continuous consumption of hydroxide ions caused by the electrolysis reaction of the anode electrolysis network 113.

[0027] In addition, in the device, water electrolysis occurs in the cathode region of the multi-sensing electrode 110 to produce more hydrogen, which can improve the antimonate removal effect and save electricity. - =Fe 2+ The generated iron ions and Sb(III) can combine with the hydroxide ions generated on the upper part of the sensing electrode 110 to form a precipitate to remove Sb(III), so that the device can always maintain the pH neutral state in the reactor shell 1 without adding additional acid and alkali solution for leveling, avoiding the situation where the pH value in the device is too high (>9.5) and causing a significant decrease in the biochemical rate of microorganisms, thereby further reducing the investment cost of sewage treatment and simplifying the treatment process. In other embodiments of the utility model, the sensing electrode 110 made of aluminum can also be used to produce similar technical effects.

[0028] The open end at the top of the reactor shell 1 is provided with flanges distributed along its radial direction and toward the outside, and a top cover is installed on the top of the reactor shell 1, and the top cover is fixed to the flange of the reactor shell 1 by bolts. An exhaust port 116 connected to the inner cavity of the reactor shell 1 is provided in the middle of the top cover, and the exhaust port 116 is provided to allow excess hydrogen microbubbles and oxygen microbubbles generated by the reaction in the biological reaction chamber 112 to be discharged from the reactor shell 1.

[0029] In addition, seven sampling ports 111 are provided on the reactor shell 1, five of which are distributed on the right side wall of the bioreactor chamber 112 along its height direction, and the five sampling ports 111 are evenly spaced. Two of the sampling ports 111 are located between the two lead wire holes 102, and the two sampling ports 111 are evenly spaced along the height direction of the reactor shell 1. The provision of the sampling ports 111 facilitates the work monitoring personnel to sample and test various water bodies at any time.

[0030] A circulating water outlet 115 is provided on the side wall of the reactor shell 1 at the overflow chamber 114, and the position of the circulating water outlet 115 is slightly lower than the position of the overflow port 101. A circulating water inlet 118 is provided on the side wall of the reactor shell 1 at the water inlet chamber 103, and the circulating water inlet 118 is connected to the circulating water outlet 115 through a circulating water pipeline (not shown in the figure), so that a part of the treated wastewater flows out through the overflow port 101, while a part of the treated wastewater flows out from the circulating water outlet 115 and flows into the water inlet chamber 103 of the reactor shell 1 through the circulating water pipeline from the circulating water inlet 118, and the circulating wastewater is mixed with new untreated wastewater and further treated with antimonate in the wastewater through the biological reaction chamber 112.

[0031] The specific implementation of the utility model is as follows: First, start the sewage pump 117 and the DC power supply 2, and the wastewater in the sewage pool enters the water inlet chamber 103 of the reactor shell 1 through the water inlet 105. The wastewater rises under the push of the subsequent wastewater and enters the biological reaction chamber 112 through the cathode electrolysis network 108. The attached hydrogen autotrophic microorganisms in the biological reaction chamber 112 remove antimonate in the water. The wastewater rises with the hydrogen and hydroxide ions produced by the electrolysis of water in the cathode area of ​​the sensing electrode 110, and the hydroxide ions combine with iron ions and Sb (III) to form precipitation. The wastewater continues to rise, and the oxygen microbubbles and hydrogen ions produced by the electrolysis of water at the anode electrolysis network 113 are discharged through the exhaust port 116. A part of the treated water rises and is discharged from the reactor shell 1 through the overflow port 101.

[0032] The wastewater test results of this embodiment are as follows:

[0033] After the sewage containing 10 mg / L antimonate is transferred to the reactor shell 1 through the sewage pump, the hydraulic retention time in the reactor shell is 12 hours, and the current intensity of the DC power supply is 10 mA. The work monitoring personnel detected the antimonate in the wastewater flowing out of the overflow port and found that the antimonate removal rate of the device can reach 92.32%. The original pH value of the wastewater is 7.3, and the pH value of the water after antimonate treatment is 7.70.

[0034] After the sewage containing 10 mg / L antimonate is transferred to the reactor shell 1 through the sewage pump, the hydraulic retention time in the reactor shell is 12 h. When the current intensity of the DC power supply is 20 mA, the removal rate of antimonate in the device can reach 96.68%. The original pH value of the wastewater is 7.5, and the pH value of the water after antimonate treatment is 7.95.

Claims

1. A reaction device for removing antimonate from water by hydrogen autotrophic reaction with multiple induction electrodes connected in series, characterized in that: The invention comprises a reactor shell (1) and a direct current power supply (2); a water inlet (105) is arranged at the bottom of the reactor shell (1), and an exhaust port (116) and an overflow port (101) are arranged at the top of the reactor shell (1); a cathode electrolysis network (108), a plurality of induction electrodes (110) and an anode electrolysis network (113) are arranged in sequence from bottom to top in the reactor shell (1); the anode electrolysis network (113) is connected to the positive electrode of the direct current power supply (2), and the cathode electrolysis network (108) is connected to the direct current power supply (2). (2); a water inlet chamber (103) is formed between the water inlet (105) of the reactor shell (1) and the anode electrolysis net (113), and an overflow chamber (114) is formed between the top of the reactor shell (1) and the anode electrolysis net (113); a biological reaction chamber (112) is formed between the anode electrolysis net (113) and the cathode electrolysis net (108) in the reactor shell (1), and the biological reaction chamber (112) is filled with a biological carrier (109) attached with hydrogen autotrophic microorganisms.

2. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 1, characterized in that: The water inlet (105) is connected to the wastewater tank (3) via a water inlet pipe, and a sewage pump (117) is connected to the water inlet pipe.

3. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 1, characterized in that: A porous partition plate (107) is installed in the water inlet chamber (103) of the reactor shell (1).

4. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 3, characterized in that: The number of the sensing electrodes (110) is two, and five groups of support members are arranged on the inner side wall of the reactor shell (1) along its height direction, and the five groups of support members are respectively used to support the anode electrolysis network (113), the two sensing electrodes (110), the cathode electrolysis network (108) and the porous partition (107); each group of support members includes four support bosses (104), and the four support bosses (104) are evenly spaced along the radial direction of the reactor shell (1).

5. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 1, characterized in that: A circulating water outlet (115) is provided on the side wall of the overflow chamber (114) of the reactor shell (1), and a circulating water inlet (118) is provided on the side wall of the water inlet chamber (103) of the reactor shell (1).

6. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 1, characterized in that: The reactor shell (1) is a vertical rectangular parallelepiped or a vertical cylinder.

7. The reaction device for removing antimonate from water by hydrogen autotrophic with multiple induction electrodes connected in series according to claim 1, characterized in that: A plurality of sampling ports (111) are arranged on the reactor shell (1) along its height direction.

Images