CN115465937A - Reaction device and method for simultaneously treating organic wastewater and sulfate wastewater and application thereof - Google Patents

Abstract

The invention discloses a reaction device and method for simultaneously treating organic waste water and sulfate waste water and application thereof. The present invention provides a method for simultaneously treating organic waste water and sulfate waste water containing low-concentration organic matter, the core content of which is: driven by photoelectricity, not only the anode chamber and the cathode chamber of the biological micro-electrolytic cell are used to simultaneously degrade organic matter and sulfate, Also, by rationally designing the hydraulic retention time, the photosynthetic bacteria chamber is used to achieve the effect of carbon fixation, sulfur fixation and resource recovery, and a kind of organic wastewater and sulfate wastewater containing low-concentration organic matter can be removed at the same time, and it can fix carbon and sulfur, and resource recovery. wastewater treatment methods. The present invention also provides a device for simultaneously treating organic waste water and low-organic sulfate waste water, which can not only be used in the above-mentioned waste water treatment method, but also has a reaction device with simple structure, easy operation, easy observation of the reaction process, low cost, and stable Good sex and other advantages.

Description

Reaction device and method for simultaneous treatment of organic wastewater and sulfate wastewater and application thereof

technical field

The invention relates to the technical field of wastewater treatment, in particular to a reaction device and method for simultaneously treating organic wastewater and sulfate wastewater and an application thereof.

Background technique

Pulp and paper industry, food processing, animal husbandry, dye manufacturing, flue gas desulfurization and other processes will produce a large amount of sulfate wastewater. At present, biological desulfurization technology has become one of the mainstream technologies for sulfate wastewater due to its low cost, high degradation efficiency, and environmental friendliness. However, the biological desulfurization technology has the following problems: (1) In the bioelectrochemical treatment, the sulfate wastewater generally does not contain or contains a small amount of organic matter, and it is often necessary to add an additional organic electron donor (organic matter) to improve the treatment of wastewater. (2) Biological desulfurization technology usually uses sulfate reducing bacteria (SRB) to reduce sulfate to sulfide, so as to achieve the purpose of sulfate removal, but a large amount of sulfide will be produced in the actual treatment process, which is not only harmful to Sulfate-reducing bacteria have toxic effects, are not conducive to the removal of sulfate, and are easy to corrode reaction equipment, and even cause secondary pollution to the environment; (3) In order to solve the problem of sulfide pollution in biological desulfurization technology, often in wastewater The method of feeding or preparing oxygen during the treatment process will oxidize the sulfide into elemental sulfur, but because the amount of oxygen feeding is difficult to control, and more oxygen feeding will have a toxic effect on anaerobic bacteria, control the appropriate amount of oxygen infiltration to Maintaining stable sulfate and sulfide removal rates is a technical challenge.

Therefore, there is an urgent need to develop a reaction device and method that can efficiently treat sulfate wastewater poor in electron donors, has strong controllability, low cost, and has no secondary pollution.

Contents of the invention

In order to overcome the problems in the prior art, the object of the present invention is to provide a reaction device and method for simultaneously treating organic waste water and sulfate waste water and its application.

In order to achieve the above object, the technical scheme and the inventive concept adopted in the present invention are:

The inventive idea of the present invention is: the present invention designs the reaction device that microbial electrolysis cell and photosynthetic bacteria reaction chamber are used together, under photoelectric drive, will contain inorganic carbon (inorganic carbon refers to carbonate, carbonic acid) Hydrogen radicals, carbon dioxide) sulfate wastewater, not only realize the process of converting sulfate into sulfide, and then into S ₀ , but also convert the inorganic carbon in sulfate wastewater into bacterial biomass and realize resource recovery. At the same time, the anode area in the microbial electrolysis cell contains Geobacter, which can convert organic matter into carbon dioxide, thereby achieving the technical effect of efficiently removing COD. In addition, the device and method of the present invention can also operate continuously and stably for multiple cycles and batch treat organic wastewater, sulfate wastewater and sulfide wastewater at the same time.

At the same time, the treatment method of the present invention is to place different domesticated bacteria in the microbial electrolysis cell and photosynthetic bacteria reaction chamber, design reasonable technical parameters such as power-on time, hydraulic retention time, and light time, and use the above-mentioned reaction device to realize simultaneous processing of organic matter. , electron-poor sulfates, sulfides, and technical effects of sulfur fixation, carbon fixation and resource recovery.

In a first aspect, the present invention provides a method for simultaneously treating organic waste water and sulfate waste water, comprising the following steps:

1) Add organic waste water and sulfate waste water to the anode chamber containing Geobacter and the cathode chamber containing sulfate-reducing bacteria, respectively, and apply voltage for treatment;

2) Excluding the waste water in the anode chamber to obtain purified organic waste water; while transferring the sulfide waste water generated in the cathode chamber to the photosynthetic bacteria chamber containing photosynthetic bacteria;

3) The photosynthetic bacteria chamber is irradiated with light, and after biochemical reaction, purified sulfate wastewater is obtained.

Preferably, after step 3) re-adding the same organic waste water and sulfate waste water as in step 1) to the anode chamber and the cathode chamber respectively, apply voltage treatment; irradiate the photosynthetic bacteria chamber with light while applying voltage treatment, after biochemical reaction , to obtain purified sulfate wastewater.

Specifically, step 3) after re-adding the untreated organic waste water and sulfate waste water, design the photosynthetic bacteria chamber to irradiate the photosynthetic bacteria chamber with light while applying voltage to realize the synergistic photosynthetic bacteria to carry out sulfur fixation while removing organic matter and sulfate The process of carbon and resource recovery; among them, sulfur fixation refers to photosynthetic bacteria converting sulfide in sulfide wastewater into elemental sulfur (S ₀ ) inside or outside the bacteria, and carbon fixation refers to photosynthetic bacteria converting inorganic carbon in wastewater (CO ₃ ^2- , HCO ₃ ^- , CO ₂ ) is transformed into biomass of photosynthetic bacteria, and the resources are recovered through sulfur and carbon fixation by photosynthetic bacteria.

It should be noted that step 3) has two technical solutions, one is to only use the photosynthetic bacteria chamber to process the sulfide wastewater generated in the cathode chamber; the other is to re-add organic wastewater and sulfate wastewater to the anode chamber and cathode chamber to achieve The three kinds of wastewater are basically treated synchronously and the water retention time of the three chambers is reasonably designed to realize the periodic and uninterrupted treatment of the three kinds of wastewater and the recovery of resources.

Preferably, the amount of organic wastewater added in step 1) is 70%-95% of the internal volume of the anode chamber.

Preferably, the amount of sulfate wastewater added in step 1) is 70% to 95% of the internal volume of the cathode chamber.

Specifically, by controlling the addition amount of the two kinds of wastewater, an anoxic environment can be further created for the bacteria in the anode chamber and the cathode chamber, which is beneficial to the treatment of the two kinds of wastewater.

Preferably, the organic matter in the organic waste water in step 1) is one or more of acetic acid, methanol, formic acid, glucose, and sucrose.

Further preferably, the organic matter in the organic waste water in step 1) is acetic acid.

Preferably, the COD concentration in the organic wastewater in step 1) is 800mg/˜4000mg/L.

Further preferably, the COD concentration in the organic wastewater in step 1) is 1000mg/˜2600mg/L.

Preferably, the pH value of the organic wastewater in step 1) is 6.8-7.2.

Preferably, the sulfate in the sulfate wastewater in step 1) is one or more of sodium sulfate, potassium sulfate, and potassium aluminum sulfate.

Preferably, the sulfate concentration in the sulfate wastewater in step 1) is 100 mg/L-1000 mg/L.

Further preferably, the sulfate concentration in the sulfate wastewater in step 1) is 200 mg/L-550 mg/L.

Preferably, the concentration of organic matter in the sulfate wastewater in step 1) is lower than 10 mg/L.

Preferably, the hydraulic retention time of the cathode chamber and the anode chamber in step 1) is 20h-110h.

Further preferably, the hydraulic retention time of the cathode chamber and the anode chamber in step 1) is 32h-46h.

Preferably, the photosynthetic bacteria in step 2) include: purple sulfur bacteria and green sulfur bacteria.

Preferably, the sulfides in the sulfide wastewater in step 2) include one or more of H ₂ S, HS ⁻ , and S ² −.

Preferably, the sulfide concentration in the sulfide wastewater in step 2) is 50 mg/L-200 mg/L.

Preferably, the sulfide wastewater in step 2) also includes one or more of CO ₃ ²⁻ , HCO ₃ ⁻ , and CO ₂ .

Preferably, the pH value of the sulfate wastewater in step 1) is 5.0-7.2.

Further preferably, the pH value of the sulfate wastewater in step 1) is 6.8-7.2.

Preferably, the organic waste water in step 1), the sulfate waste water in step 1) and the sulfide waste water in step 2) are all subjected to deoxygenation treatment, and the oxygen concentration of the three kinds of waste water is all lower than 0.2 mg/L.

Specifically, the oxygen solubility is the amount of dissolved oxygen.

Preferably, the specific operation of the oxygen removal treatment is to feed nitrogen into the wastewater.

Preferably, the voltage in step 1) is a DC voltage, and the voltage value of the DC voltage is 0.5V-3.0V.

Preferably, the voltage in step 3) is a direct current voltage, and the voltage value of the direct current voltage is 0.5V-3.0V.

Further preferably, the DC voltage in step 1) and step 3) has a voltage value of 0.8V-1.5V.

Specifically, when step 3) is a technical solution of re-adding organic wastewater and sulfate wastewater to the anode chamber and the cathode chamber, the voltage applied in step 3) is as above.

Preferably, the light in step 3) is visible light and/or infrared light.

Preferably, the intensity of the visible light ranges from 1000 lux to 10000 lux.

Further preferably, the intensity of the visible light is 3000lux-5000lux.

Preferably, the infrared light is infrared light with a wavelength of 805nm-1000nm and a luminous intensity of 0.5W/m ² -2.0W/m ² .

Preferably, the hydraulic retention time of the cathode chamber and the anode chamber in step 3) is 20h-110h.

Preferably, the hydraulic retention time in step 3) is 32h-46h.

Preferably, the bacteria in the cathode chamber in step 1), the bacteria in the anode chamber in step 1), the bacteria in the photosynthetic bacteria chamber in step 2) and step 3) are domesticated with bacteria in the soil at 2cm to 10cm underground into.

Preferably, the soil is collected and planted with mangroves.

Specifically, the underground soil planted with mangroves is rich in active nutrients.

Preferably, the bacterium domestication process comprises the following steps:

1) Mix the soil at 2cm to 10cm underground with physiological saline and let it stand to obtain the supernatant; inoculate the supernatant in the anode chamber, cathode chamber and photosynthetic bacteria chamber respectively, and pour the anode chamber, cathode chamber and photosynthetic bacteria chamber The chamber is added with organic waste water, sulfate waste water and sulfide waste water;

2) Apply voltage to the anode in the anode chamber and the cathode in the cathode chamber, and monitor the current signal between the anode and the cathode to obtain the change cycle time of the current signal;

3) Use light to irradiate the photosynthetic bacteria chamber, set the irradiation time to be the same as the change cycle time of the current signal, and regularly replace the organic waste water, sulfate waste water and sulfide in the anode chamber, cathode chamber, and photosynthetic bacteria chamber according to the change cycle time of the current signal waste water, until the end of the continuous cycle, the difference of the COD removal rate of the anode chamber, the difference of the sulfate radical removal rate of the outlet of the cathode chamber, and the difference of the sulfide removal rate of the photosynthetic bacteria chamber are all less than 8%. Chamber and photosynthetic bacteria chamber obtain the bacteria after domestication success;

Wherein, the mass ratio of the soil in step 1) and the physiological saline is 0.1g/mL～0.5g/mL;

Step 1) and step 3) the oxygen concentration of organic waste water, sulfate waste water and sulfide waste water is lower than 0.2mg/L;

The COD concentration in the organic waste water of step 1) and step 3) is 1000mg/L～3000mg/L;

Step 1) and step 3) the sulfate radical concentration in the sulfate wastewater described in step 3) is 200mg/L～550mg/L; Step 1) and step 3) the organic matter concentration in the sulfate wastewater described in step 3) is lower than 10mg/L; Step 1 ) and step 3) the sulfide concentration in the sulfide wastewater is 50mg/L～200mg/L.

Specifically, since one of the technical problems solved by the present invention is: how to effectively treat low-concentration sulfate wastewater that does not contain or contain a small amount of organic matter in the bioelectrolytic cell, the design is similar to the actual situation when the bacteria are refined. The wastewater helps to improve the sulfate removal rate of this type of sulfate wastewater.

Preferably, the applied voltage during the bacterial acclimation process is DC voltage.

Preferably, the voltage value of the direct current voltage is 0.8V-1.2V.

Specifically, the applied voltage treatment in the process of bacterial domestication and the applied voltage in the above-mentioned actual wastewater treatment are both DC voltages, which is to ensure that the current signal is relatively simple to change, so as to facilitate the determination of the change cycle time of the current signal and the study of the wastewater treatment process. Therefore, the hydraulic retention time of the wastewater in the whole wastewater treatment process is set, which facilitates the improvement of the wastewater treatment efficiency.

Specifically, in some embodiments, the irradiation time during the bacterial acclimation process can be set to be the same as the change cycle time of the current signal, in order to synchronously and cooperatively treat organic waste water, sulfate waste water and sulfide waste water with the treatment of the anode chamber and the cathode chamber, so that not only It can remove organic matter and sulfate radicals, and can realize the effect of sulfur sequestration, carbon sequestration and resource recovery at the same time.

Preferably, the method for simultaneously treating organic wastewater and sulfate wastewater further includes: a process of system stabilization and a process of testing current signals during voltage processing.

Specifically, the system stabilization process uses the change period of the current signal to set the difference between the water retention time of the anode chamber, the cathode chamber and photosynthetic bacteria and the change cycle time of the current signal to be less than 1h until the COD removal of the anode chamber for two consecutive cycles The system reaches a steady state when the difference of the removal rate of sulfate, the difference of the removal rate of sulfate radical in the cathode chamber, and the difference of the removal rate of sulfide in the photosynthetic bacteria chamber are all less than 10%.

In a second aspect, the present invention provides a reaction device for simultaneously treating organic waste water and sulfate waste water comprising: an electrolytic cell composed of an anode chamber, a proton exchange membrane, a cathode chamber, a power supply, a resistor, an anode electrode, and a cathode electrode, and the The cathode chamber and the anode chamber are separated by a proton exchange membrane; the reaction device for simultaneously treating organic waste water and sulfate waste water also includes: a data collector, a photosynthetic bacteria chamber, a light-emitting reaction device, an attachment, a pump, and a valve ;

The water outlet provided in the cathode chamber is directly connected to the water inlet of the photosynthetic bacteria chamber through a pipeline, and the pipeline is also provided with a pump and a valve;

The attachment is arranged on the inner wall of the photosynthetic bacteria chamber, and at the same time, the light-emitting reaction device is arranged at a position where the light can irradiate the attachment;

The data collector and the resistor are connected in parallel by wires, and the wires are connected in series with the anode electrode, the cathode electrode, and the power supply to monitor the current signal flowing from the anode electrode in the anode chamber to the cathode electrode in the cathode chamber.

Preferably, the anode chamber and the cathode chamber are spliced by two cuboids.

Preferably, the material of the cuboid is one of borosilicate glass, plexiglass and quartz.

Preferably, the capacity of the cuboid is 30mL-500mL.

Further preferably, the capacity of the cuboid is 40mL-150mL.

Preferably, the material of the photosynthetic bacteria chamber is one of borosilicate glass, plexiglass and quartz.

Preferably, the capacity of the photosynthetic bacteria chamber is 30mL-500mL.

Further preferably, the capacity of the photosynthetic bacteria chamber is 40mL-150mL.

Preferably, the material of the anode electrode and the cathode electrode is one of carbon brush, carbon cloth and porous carbon rod.

Further preferably, the material of the anode electrode and the cathode electrode is selected from carbon brushes.

Preferably, the material of the attachment is one of carbon brush, carbon cloth and porous carbon rod.

Further preferably, the material of the attachment is carbon cloth.

Preferably, the luminescent reaction device is arranged at a position opposite to the attachment, and ensures that the light of the luminescence reaction device can be irradiated on the attachment horizontally.

Specifically, the preferred solution used in the embodiment is to ensure that the light level is irradiated on the attachment, which can further improve the utilization of light by bacteria, thereby improving the efficiency of sulfur fixation.

Preferably, the resistance of the resistor is 1Ω-10Ω

Further preferably, the resistance is 0.1Ω˜1.5Ω.

Still further preferably, the resistance of the resistor is 1Ω.

Preferably, the wire is one of copper wire, silver wire and titanium wire.

Further preferably, the wire is titanium wire.

Preferably, the power supply is a DC power supply.

Preferably, the light emitting device is an LED lamp or an infrared lamp.

Preferably, the luminous intensity of the LED lamp is 1000 lux-10000 lux.

Further preferably, the luminous intensity of the LED lamp is 3000 lux-5000 lux.

Preferably, the infrared lamp is a lamp with a wavelength of 805 nm to 1000 nm and a luminous intensity of 0.5 W/m ² to 2.0 W/m ² .

Preferably, the data collector is one of a voltmeter, a multimeter, and an electrochemical workstation.

In a third aspect, the present invention provides the application of the reaction device described in the second aspect in wastewater treatment.

The beneficial effects of the present invention are: the method of the present invention can not only degrade organic waste water and sulfate waste water poor in electron donors at the same time, but also realize the technical effects of carbon and sulfur fixation, resource recovery, and no secondary pollution. It also has a reaction device It has the advantages of simple structure, easy operation, low cost and good stability. Specifically:

(1) The method of the present invention is under the condition that oxygen concentration is lower, while degrading organic waste water by photoelectrically driven anode electroactive microorganism, the electron that produces is passed to negative electrode by wire, and the sulfate-reducing bacteria in cathode chamber is with H ⁺ H ₂ generated by accepting electrons or directly using electrons as electron donors makes SO ₄ ^2- reduced to S ^2- without adding organic matter at the cathode; then the sulfide wastewater obtained in the cathode chamber is directly supplied to phototrophic photosynthetic bacteria, Photosynthetic bacteria use light energy to carry out anaerobic photosynthesis, oxidize S ^2- to intermediate sulfur element (S ₀ ), and then store S ₀ inside or outside the cell; thus, they can simultaneously treat organic wastewater and electron-poor donors. Sulfate wastewater and sulfur fixation, and solve the problems of cost increase and secondary pollution in traditional biological treatment technology;

(2) The present invention adopts the coupling mode of microbial electrolysis cell and anaerobic photosynthetic bacteria, which avoids the poisonous effect brought by oxygen, reduces the implementation difficulty of wastewater treatment, and can generate photosynthetic bacteria under the condition of low oxygen concentration. substances, so as to realize simultaneous sulfur sequestration and carbon sequestration and resource recovery;

(3) The present invention mainly uses electroactive microorganisms coupled with photosynthetic bacteria to synchronously treat organic wastewater and sulfate wastewater poor in electron donors, which is a low-cost, environmentally friendly and economically beneficial method;

Wherein, electroactive microorganisms are a type of microorganisms capable of "two-way" electron and energy exchange with the external environment. In the present invention, the microorganisms on the anode and cathode all belong to electroactive microorganisms;

(4) bacterium or microorganism among the present invention obtain mixed bacterial liquid from the subterranean soil of nature, and the domestication process of bacterium can successfully obtain the bacterium with good sulfate radical, organic matter and sulfide removal effect;

(5) The reaction device of the present invention has the advantages of simple structure, easy observation, and convenient operation, and is suitable for studying wastewater treatment process conditions and observing the reaction process of wastewater treatment;

(6) The reaction device and method of the present invention have good stability, can treat various waste waters in multiple cycles, and the treatment effect remains basically unchanged.

Description of drawings

Fig. 1 is a schematic diagram of a reaction device for simultaneously treating organic wastewater and sulfate wastewater in an embodiment of the present invention.

Reference signs: 1 anode chamber; 2 proton exchange membrane; 3 cathode chamber; 4 DC power supply; 5 resistance; 6 anode electrode; 7 cathode electrode; 8 data collector; 9 pump; 10 photosynthetic bacteria chamber; 12 attachments.

Fig. 2 is a current curve diagram during operation of the reaction device in Example 1 of the present invention.

Fig. 3 is a graph showing the change of COD concentration at the water inlet and water outlet of the anode chamber during one treatment cycle of the reaction device in Example 1 of the present invention.

Fig. 4 is a graph showing changes in the concentration of sulfate and soluble sulfide in the cathode during a treatment cycle of the reaction device in Example 1 of the present invention.

Fig. 5 is a graph showing the change in concentration of sulfide produced by photosynthetic bacteria treating the cathode during one treatment cycle of the reaction device in Example 1 of the present invention.

Fig. 6 is a diagram of pigment content in photosynthetic bacteria biomass in the wastewater treatment process of Example 1 of the present invention.

detailed description

The content of the present invention will be described in further detail below through specific examples.

Unless otherwise specified, the soil at 2-5cm underground in Examples 1-5 comes from the Mangrove Wetland Park in Hailing Island, Yangjiang City, Guangdong Province (latitude: 21.6482102 °, longitude: 111.968589 °); the anode chamber is mainly Geobacter , the cathode chamber is mainly sulfate-reducing bacteria, the photosynthetic bacteria chamber is mainly purple sulfur bacteria and green sulfur bacteria, the supernatant containing bacteria, the bacteria in the anode chamber, cathode chamber and photosynthetic bacteria chamber after domestication are mixed bacteria; trace element solution Contains: 1.5g/L NTA (nitrilotriacetic acid), 3g/L MgSO ₄ , 0.5g/L MnSO ₄ ·H ₂ O, 0.1g/L FeSO ₄ ·7H ₂ O, 0.1g/L CaCl ₂ ·2H ₂ O , 0.1g/L CoCl ₂ ·6H ₂ O, 0.13g/L ZnCl ₂ , 0.01g/L CuSO ₄ ·5H ₂ O and 0.01g/LH ₃ BO ₃ ; vitamin solution includes: 0.2g/L folic acid, 1g/L L vitamin B6, 0.5g/L vitamin B2, 0.5g/L niacin, 0.5g/L pantothenic acid, 0.5g/L p-aminobenzoic acid, 0.5g/L vitamin B-14; bacteria in Examples 1-5 The inoculation process, the domestication process of bacteria, the stabilization process of the reaction device, and the waste water in the waste water treatment process are all treated with oxygen removal.

It should also be noted that, in the present invention, the terms "electron donor-poor sulfate wastewater" and "electron donor-poor wastewater" both refer to sulfate wastewater containing no organic matter or containing a small amount of organic matter.

Example 1

This embodiment provides a reaction device (i.e. a photoelectric bioelectrochemical system) for simultaneously treating organic waste water and sulfate waste water, including a microbial electrolysis cell and a light-driven redox reaction device (see Figure 1);

The microbial electrolysis cell includes: an anode chamber 1, a proton exchange membrane 2, a cathode chamber 3, a DC power supply 4, a resistor 5, an anode electrode 6, a cathode electrode 7 and a data collector 8;

The anode chamber 1 and the cathode chamber ³ in the microbial electrolytic cell are spliced by two plexiglass cuboids of 6 × 6 × 4 cm, and the middle of the anode chamber 1 and the cathode chamber 3 is separated by a proton exchange membrane 2, which can facilitate The H ⁺ produced in the anode chamber 1 can migrate to the cathode chamber 3, which is beneficial to the redox reaction and the simultaneous removal of acetate (CH ₃ COO ^- ) and sulfate (SO ₄ ^2- ) in the wastewater;

Both the anode chamber 1 and the cathode chamber 3 are provided with a water inlet and a water outlet for adding waste water to be treated and discharging treated water; the anode chamber 1 is provided with an anode electrode 6, and the cathode chamber 3 is provided with a cathode electrode 7, The anode electrode 6 and the cathode electrode 7 are carbon brushes, and the structure of the carbon brushes is convenient for the attachment, cultivation and reproduction of bacteria;

The anode electrode 6 and the cathode electrode 7 are connected by a wire (that is, a titanium wire with a diameter of 0.5 mm), so that the electron transfer generated when the organic matter on the anode electrode 6 is oxidized to CO ₂ (that is, CH ₃ COO ^- is oxidized to CO ₂ ) To the cathode electrode 7, in order to initiate a reduction reaction on the cathode electrode 7 (that is, H ⁺ is converted into H ₂ and SO ₄ ^2- is converted into S ^2- ), and the wire is also provided with a 0.8V DC power supply 4, A 1Ω resistor 5 and a data collector 8, and the data collector 8 is connected in parallel with the resistor 5, and then connected in series with the DC power supply 4, the anode electrode 6 and the cathode electrode 7 to facilitate monitoring of current signals and regulation The process of wastewater treatment; among them, the data collector 8 and the resistance 5 are connected in parallel to monitor the voltage value at the resistance 5, and the voltage signal can be converted into a current signal through data processing, so that the current change of the bioelectrolysis cell can be monitored (i.e. monitoring the transfer of electrons from the anode to the cathode in the microbial electrolytic cell);

The light-driven redox reaction device includes: a pump 9; a photosynthetic bacteria chamber 10, a light-emitting reaction device 11, and an attachment 12 (ie, carbon cloth);

The photosynthetic bacteria chamber 10 in the light-driven redox reaction device is provided with a water outlet and a water inlet, and the water outlet of the photosynthetic bacteria chamber 10 is to facilitate the discharge of treated waste water; the water inlet of the photosynthetic bacteria chamber 10 and the cathode chamber 3 The water outlet is connected by a pipeline, and a valve and a pump 9 are arranged on the connecting pipeline, so that the wastewater containing soluble sulfide (soluble sulfide mainly includes hydrogen sulfide) discharged from the cathode chamber 3 can be introduced into the photosynthetic bacteria chamber;

The inwall of the photosynthetic bacteria chamber 10 is provided with an attachment 12, which facilitates the attachment, cultivation and reproduction of the photosynthetic bacteria; the luminescence reaction device 11 and the photosynthetic bacteria chamber 10 are arranged side by side, and the distance between the two is less than 30cm, so as to ensure that the luminescence reaction device The light of visible light (VIS) or infrared light (IR) emitted by 11 can be horizontally irradiated on the attachment body 12 inside the photosynthetic bacteria chamber 10, which can make the photosynthetic bacteria in the photosynthetic bacteria chamber 10 fully utilize the light source and increase the sulfide (S ^2- ) the efficiency of conversion into elemental sulfur (S ₀ );

Wherein, because the plexiglass material has a certain thickness, the anode chamber 1, the cathode chamber 3 and the photosynthetic bacteria chamber 10 can hold about 50 mL of liquid; the ellipse in Fig. 1 represents bacteria in different reaction chambers.

The present embodiment provides a method for treating organic waste water and sulfate waste water simultaneously, comprising the following steps:

1) Preparation of simulated wastewater:

Prepare simulated organic wastewater with deionized water, each 1L simulated organic wastewater contains 1.5g CH ₃ COOH, 15.3g Na ₂ HPO ₄ 12H ₂ O, 3.82g NaH ₂ PO ₄ , 0.3g NH ₄ Cl, 0.13g KCl, 5g NaCl, 1mL trace element solution and 1mL vitamin solution;

Use deionized water to prepare simulated electron donor-poor sulfate wastewater, containing 2.0g NaHCO ₃ , 3.3g Na ₂ HPO ₄ 12H ₂ O, 7.9g NaH ₂ PO ₄ per 1L of simulated electron-donor-poor sulfate wastewater , 0.6g Na ₂ SO ₄ , 0.3g NH ₄ Cl, 0.1gKCl, 0.1g MgCl ₂ , 5g NaCl, 1mL trace element solution and 1mL vitamin solution;

Prepare simulated sulfide wastewater with deionized water, each 1L of simulated sulfide wastewater contains 5g NaCl, 0.5gNH ₄ Cl, 2.0g NaHCO ₃ , 0.05g CaCl ₂ 2H ₂ O, 1g KH ₂ PO ₄ , 0.15g MgCl ₂ , 0.3g Na ₂ S·9H ₂ O, 1mL trace element solution and 1mL vitamin solution;

It is necessary to pass nitrogen into the simulated organic wastewater, simulated sulfate wastewater with poor electron donors, and simulated sulfide wastewater until the oxygen concentration is lower than 0.2mg/L to obtain hypoxic or anaerobic simulated organic wastewater and simulated poor electron donors. sulfate wastewater and simulated sulfide wastewater, and then the simulated wastewater after deoxygenation is used for the subsequent treatment process.

2) Bacteria inoculation process:

Take 10g of soil at 2-5cm underground, dilute it with 40mL of normal saline, shake it well and let it stand for 10min to obtain the supernatant containing bacteria;

The inoculation process of the anode chamber: take 5mL of the supernatant containing bacteria and inject it into the anode chamber of the built microbial electrolysis cell, and add 35mL of simulated organic wastewater (ie anolyte), to complete the inoculation of the anode chamber;

The inoculation process of the cathode chamber: take 5mL of the supernatant containing bacteria and inject it into the cathode chamber of the microbial electrolysis cell that has been built, and add 35mL of sulfate wastewater (catholyte) that simulates poor electron donors to complete the inoculation of the cathode chamber;

The inoculation process of the photosynthetic bacteria chamber: add 35mL of simulated sulfide wastewater after exposure to _N2 deoxygenation to the photosynthetic bacteria chamber, and then add 5mL of the supernatant containing bacteria to complete the inoculation of the photosynthetic bacteria chamber.

3) The domestication process of bacteria:

The domestication process of bacteria in the anode chamber and cathode chamber of the microbial electrolysis cell: apply an external voltage of 0.8V to the microbial electrolysis cell, use simulated organic wastewater and simulated sulfate wastewater with poor electron donors to domesticate the anode microorganisms and cathode microorganisms, set 46h as One water inlet and outlet cycle, and monitor the COD concentration of the water inlet and outlet, the sulfate concentration of the cathode inlet and outlet water, and the sulfide concentration. And when the concentration of sulfide is basically constant, the bacteria in the anode chamber and the bacteria in the cathode chamber after the domestication are successful;

Among them, the anode bacteria are mainly Geobacter, and the cathode bacteria are mainly sulfate-reducing bacteria;

The domestication process of photosynthetic bacteria: Use visible light with an intensity of 3000lux to irradiate the photosynthetic bacteria room, and use carbon cloth as an attachment to allow photosynthetic bacteria to grow on the carbon cloth, set 46h as a water in and out cycle, and wait for multiple cycles of sulfide The removal rate is stable, that is, the photosynthetic bacteria (photosynthetic bacteria mainly include purple sulfur bacteria and green sulfur bacteria) after domestication is successful.

4) Wastewater treatment process:

S1: Dosing 35mL of simulated organic wastewater with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor wastewater with a pH of 6.8-7.2 in the cathode chamber, and applying an external voltage of 0.8V to the microbial electrolytic cell, setting The processing time is 46h;

S2: Discharging the treated water in the anode chamber after treatment to obtain water after removing organic matter; and draining the sulfide wastewater in the cathode chamber into the photosynthetic bacteria chamber under the drainage of the pump;

S3: Dosing 35mL of simulated organic wastewater with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor waste water with a pH of 6.8-7.2 in the cathode chamber, and then irradiating the photosynthetic bacteria chamber with visible light with an intensity of 3000lux , and the processing time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber is set to be 46h, and the water after the sulfide removal is obtained and discharged;

S4: Set the cycle treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber as 46 hours, and repeat the steps from S1 to S3.

Example 2

This embodiment provides a method for simultaneously treating organic wastewater and sulfate wastewater. The reaction device in this embodiment is the same as in Example 1, and the difference from Example 1 is that it also includes a step for system stabilization, and in the waste water During the process, the 0.8V external power supply (direct current) is replaced by the 1.2V external power supply (direct current), and the specific method is as follows:

1) The preparation of simulated wastewater is the same as in Example 1.

2) The inoculation process of bacteria is the same as in Example 1.

3) The domestication process of bacteria is the same as in Example 1.

4) The process of stabilizing the reaction device: apply an external voltage of 1.2V to the microbial electrolysis cell, use the bacteria on the anode electrode and the bacteria on the cathode electrode to treat the simulated organic wastewater and the simulated sulfate wastewater with poor electron donors, and monitor The COD concentration at the water inlet and water outlet, the sulfate radical concentration and the sulfide concentration in the cathode inlet and outlet water, the current signal for several consecutive cycles, the COD concentration at the water inlet and outlet, the sulfate radical concentration and the sulfide concentration in the cathode inlet and outlet water are basically unchanged , that is, the bioelectrolytic cell reaction device is in a steady state, and the treatment period in the steady state is 32h.

5) Wastewater treatment process:

S1: Dosing 35mL of simulated organic wastewater with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor wastewater with a pH of 6.8-7.2 in the cathode chamber, and applying an external voltage of 1.2V to the microbial electrolytic cell, setting The processing time is 32h;

S2: Discharging the treated water in the anode chamber after treatment to obtain water after removing organic matter; and draining the sulfide wastewater in the cathode chamber into the photosynthetic bacteria chamber under the drainage of the pump;

S3: Dosing 35mL of simulated organic wastewater with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor waste water with a pH of 6.8-7.2 in the cathode chamber, and then irradiating the photosynthetic bacteria chamber with visible light with an intensity of 3000lux , and set the treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber to be 32h, obtain the water after removing the sulfide and discharge it;

S4: Set the cycle treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber as 32 hours, and repeat the steps from S1 to S3.

Example 3

This embodiment provides a method for simultaneously treating organic waste water and sulfate waste water. The reaction device in this embodiment is the same as in Example 1, and its difference from Example 1 is that it also includes a step for system stabilization, and improves the The concentration of organic matter in the simulated organic wastewater and the concentration of sulfate in the simulated sulfate wastewater with poor electron donors in the wastewater treatment process are specifically as follows:

1) The preparation of simulated wastewater is the same as in Example 1.

2) The inoculation process of bacteria is the same as in Example 1.

3) The domestication process of bacteria is the same as in Example 1.

4) The process of stabilizing the reaction device:

Prepare simulated organic wastewater A1: prepare simulated organic wastewater A1 with deionized water, each 1L of simulated organic wastewater A1 contains 3.0g CH ₃ COOH, 15.3g Na ₂ HPO ₄ 12H ₂ O, 3.82g NaH ₂ PO ₄ , 0.3g NH ₄ Cl, 0.13g KCl, 5g NaCl, 1mL trace element solution and 1mL vitamin solution;

Simulated electron donor-poor wastewater B1: prepare simulated electron-donor-poor sulfate wastewater B1 with deionized water, and each 1L of simulated electron-donor-poor sulfate wastewater B1 contains 2.0g NaHCO ₃ , 3.3g Na ₂ HPO ₄ · 12H ₂ O, 7.9g NaH ₂ PO ₄ , 1.0g Na ₂ SO ₄ , 0.3g NH ₄ Cl, 0.1g KCl, 0.1g MgCl ₂ , 5g NaCl, 1mL trace element solution and 1mL vitamin solution;

Apply an external voltage of 0.8V to the microbial electrolysis cell, use the bacteria on the anode electrode and the bacteria on the cathode electrode to treat the simulated organic wastewater A and simulate the sulfate wastewater B with poor electron donors, and monitor the water inlet and outlet COD concentration, cathode influent sulfate concentration and sulfide concentration, when the current signal of continuous multiple cycles, the COD concentration of water inlet and water outlet, the cathode influent and effluent sulfate concentration and sulfide concentration are basically unchanged, that is, the bioelectrolysis cell The reaction device is in a steady state, and the treatment period in the steady state is 80h.

5) Wastewater treatment process:

S1: Dosing 35mL of simulated organic wastewater A1 with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor wastewater B1 with a pH of 6.8-7.2 in the cathode chamber, and applying an external voltage of 0.8V to the microbial electrolysis cell , set the processing time to 80h;

S2: Discharging the treated water in the anode chamber after treatment to obtain water after removing organic matter; and draining the sulfide wastewater in the cathode chamber into the photosynthetic bacteria chamber under the drainage of the pump;

S3: Dosing 35mL of simulated organic wastewater A1 with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor donor wastewater B1 with a pH of 6.8-7.2 in the cathode chamber, and then irradiating the photosynthetic bacteria with visible light with an intensity of 3000lux chamber, and the treatment time of the anode chamber, cathode chamber and photosynthetic bacteria chamber is set to be 80h, and the water after the sulfide removal is obtained and discharged;

S4: Set the cycle treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber as 80 h, and repeat the steps from S1 to S3.

Example 4

This embodiment provides a method for simultaneously treating organic waste water and sulfate waste water. The reaction device in this embodiment is the same as that of Embodiment 1, and its difference from Embodiment 1 is that it also includes steps for system stabilization, and reduces the The pH value of the sulphate wastewater simulating poor electron donors in the wastewater treatment process, the method is specifically:

1) The preparation of simulated wastewater is the same as in Example 1.

2) The inoculation process of bacteria is the same as in Example 1.

3) The domestication process of bacteria is the same as in Example 1.

4) The process of adjusting and stabilizing the reaction device:

Prepare simulated organic wastewater A2: prepare simulated organic wastewater A2 with deionized water, each 1L of simulated organic wastewater A2 contains 1.5g CH ₃ COOH, 15.3g Na ₂ HPO ₄ 12H ₂ O, 3.82g NaH ₂ PO ₄ , 0.3g NH ₄ Cl, 0.13g KCl, 5g NaCl, 1mL trace element solution and 1mL vitamin solution;

Simulated electron-donor-poor wastewater B2: using 1M H ₃ PO ₄ and 1M NaOH phosphoric acid to adjust the pH value of the electron-donor-poor wastewater in Example 1 to 5.0 to obtain simulated electron-donor-poor wastewater B2;

Apply an external voltage of 0.8V to the microbial electrolysis cell, use the bacteria on the anode electrode and the bacteria on the cathode bacteria electrode to treat the simulated organic wastewater A2 and simulate the sulfate wastewater B2 with poor electron donors, and monitor the water inlet and outlet The COD concentration of the cathode, the concentration of sulfate radicals in the cathode water and the concentration of sulfide, when the current signal for multiple consecutive cycles, the COD concentration of the water inlet and outlet, the concentration of sulfate radicals in the cathode inlet and outlet water, and the concentration of sulfide are basically unchanged, that is, bioelectrolysis The pool reaction device is in a steady state, and the treatment period in the steady state is 46h.

5) Wastewater treatment process:

S1: Dosing 35mL of simulated organic wastewater A2 with a pH of 6.8 to 7.2 in the anode chamber, adding 35mL of simulated electron-poor wastewater B2 with a pH of 5.0 in the cathode chamber, and applying an external voltage of 0.8V to the microbial electrolytic cell, setting The processing time is 46h;

S2: Discharging the treated water in the anode chamber after treatment to obtain water after removing organic matter; and draining the sulfide wastewater in the cathode chamber into the photosynthetic bacteria chamber under the drainage of the pump;

S3: Add 35mL of simulated organic wastewater A2 with a pH of 6.8 to 7.2 in the anode chamber, and 35mL of simulated electron-poor donor wastewater B2 with a pH of 5.0 in the cathode chamber, and then irradiate the photosynthetic bacteria chamber with visible light with an intensity of 3000lux. And set the treatment time of anode chamber, cathode chamber and photosynthetic bacteria chamber to be 46h, obtain the water after removing sulfide and discharge;

S4: Set the cycle treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber as 46 hours, and repeat the steps from S1 to S3.

Example 5

This embodiment provides a method for treating organic wastewater and sulfate wastewater at the same time. The reaction device in this embodiment is the same as in Embodiment 1, and the difference from Embodiment 1 is that an infrared light source is used instead in the wastewater treatment process. , the specific method is:

1) The preparation of simulated wastewater is the same as in Example 1.

2) The inoculation process of bacteria is the same as in Example 1.

3) The domestication process of bacteria is the same as in Example 1.

4) Wastewater treatment process:

S1: Dosing 35mL of simulated organic wastewater with a pH of 6.8-7.2 in the anode chamber, adding 35mL of simulated electron-poor wastewater with a pH of 6.8-7.2 in the cathode chamber, and applying an external voltage of 0.8V to the microbial electrolytic cell, setting The processing time is 46h;

S2: Discharging the treated water in the anode chamber after treatment to obtain water after removing organic matter; and draining the sulfide wastewater in the cathode chamber into the photosynthetic bacteria chamber under the drainage of the pump;

S3: Add 35mL of simulated organic wastewater with a pH of 6.8 to 7.2 in the anode chamber, add 35mL of simulated electron-poor wastewater with a pH of 6.8 to 7.2 in the cathode chamber, and then use a wavelength of 850nm and an intensity of 1W/m ² , the infrared light irradiates the photosynthetic bacteria room, and the treatment time of the anode room, the cathode room and the photosynthetic bacteria room is set to be 46 hours, and the water after the sulfide removal is obtained and discharged;

S4: Set the cycle treatment time of the anode chamber, the cathode chamber and the photosynthetic bacteria chamber as 46 hours, and repeat the steps from S1 to S3.

Performance Testing

1) The current curve diagram of the reaction device in embodiment 1 during operation, as shown in FIG. 2 .

It can be seen from Figure 2 that: at the beginning of each cycle of the reaction device, the current appears to be in a state of significant increase. Taking the first operating cycle as an example, the current rises rapidly to the highest current value (2.5mA), and maintains a current value higher than 0.5mA for a period of time, indicating that there are a large number of electrons flowing from the anode to the cathode, so Embodiment 1 can process synchronously High-concentration organic wastewater (COD concentration of 1170mg/L) and sulfate wastewater containing no organic matter or a small amount of organic matter (that is, electron donor-poor sulfate wastewater with a sulfate concentration of 312mg/L) is feasible.

Simultaneously, from different treatment periods, the change law, maximum value, and minimum value of its overall current signal all change little, illustrate that the method and reaction device operation of simultaneously processing organic waste water and sulfate waste water among the embodiment 1 have good stability and reproducibility.

Although the change law of the current value fluctuates slightly in different treatment cycles, the effect of wastewater treatment from the second to the fifth treatment cycle is similar to that of the first treatment cycle, and their COD removal rate can be maintained at 78%. ~83% (above 78%), the removal rate of sulfate can be maintained at 87%~93% (above 87%), and the removal rate of sulfide can be maintained at 93%~98% (above 93%), which shows that the treatment method Has good stability.

2) The COD concentration change curve of the water inlet and water outlet of the anode chamber within one treatment cycle of the reaction device in embodiment 1 is shown in FIG. 3 .

It can be seen from Figure 3 that the COD concentration at the water inlet of the anode chamber is 1170mg/L, and the COD concentration at the water outlet of the anode chamber is 240mg/L, that is, the COD removal rate is 79.5%, indicating that this technical solution has the ability to treat high-concentration organic wastewater .

3) The cathode sulfate and soluble sulfide concentration change curves within one treatment cycle of the reaction device in embodiment 1 are shown in FIG. 4 . The reaction device in Example 1 operates a graph of the concentration change curve of the sulfide produced by the photosynthetic bacteria in the cathode during one treatment cycle, as shown in FIG. 5 . It should be noted that the water inflow of the photosynthetic bacteria in this cycle is the effluent in the previous cycle of the cathode, and the wastewater treatment of the photosynthetic bacteria chamber and the cathode chamber is separated by a cycle.

It can be seen from Fig. 4 and Fig. 5 that the concentration of sulfate radicals in the cathode chamber decreases from 312mg/L to 23mg/L, and the sulfate radical removal rate is 93%; while the soluble sulfide increases from 6mg/L to 95mg/L, it can be seen that the removed sulfuric acid The roots are almost completely converted to soluble sulfides.

From Fig. 5, under the effect of photosynthetic bacteria, soluble sulfide concentration reduces to 3.5mg/L from 95mg/L, and the removal rate of soluble sulfide is 96%, illustrates that adopting the method for embodiment 1 can make photosynthetic bacteria have Excellent sulfide wastewater treatment capacity.

Combined analysis of Fig. 3, Fig. 4 and Fig. 5 can illustrate that the method of embodiment 1 can not only treat organic waste water and the waste water of low concentration sulfate radical simultaneously, and the removal rate of sulfate radical and organic matter removal rate are all higher.

4) The pigment content figure in the photosynthetic bacteria biomass in the wastewater treatment process of Example 1 of the present invention, as shown in FIG. 6 .

It can be seen from Figure 6 that during the monitoring of a treatment cycle during wastewater treatment, the content of bacteriochlorophyll in the photosynthetic bacterial biomass at 0h was 160 μg/g, the content of carotenoids was 48 μg/g, and the content of bacteriochlorophyll in the photosynthetic bacterial biomass at 46h The content of carotenoids is 1285μg/g, and the content of carotenoids is 390μg/g. It can be seen that the content of bacteria and chlorophyll in a treatment cycle in the photosynthetic bacteria chamber has increased, so that the substances in the wastewater can be converted into useful biomass. In turn, it is beneficial to the recovery of resources in wastewater and the improvement of wastewater treatment efficiency. At the same time, by monitoring the inorganic carbon content of the photosynthetic bacteria room, compared with the beginning of treatment without sulfide treatment, the inorganic carbon content of the sulfide wastewater treatment decreased by 30mg/L, indicating that the photosynthetic bacteria room can fix sulfur while also being able to Realize the technical effect of converting inorganic carbon into carbon fixation process and resource recovery of photosynthetic bacteria biomass.

5) The results of different wastewater treatment methods in Examples 1-5 are shown in Table 1.

The results of different wastewater treatment methods in Table 1 Examples 1 to 5

Note:

Sulfate concentration was detected by ion chromatography.

The detection method of sulfide concentration refers to the methylene blue spectrophotometric method in "GB/T 16489-1996 Determination of Sulfide in Water Quality by Methylene Blue Spectrophotometry".

The COD concentration detection method refers to the potassium dichromate method in "GB11914-1989 Determination of Chemical Oxygen Demand in Water Quality by Dichromate Method".

COD removal rate = (initial COD concentration - COD concentration after treatment) / initial COD concentration × 100%

Sulfate radical removal rate=(initial sulfate radical concentration-treated sulfate radical concentration)/initial sulfate radical concentration×100%

Soluble sulfide removal rate = (initial sulfide - treated sulfide) / initial sulfide × 100%

As can be seen from Table 1: Embodiment 1～Example 5 all can realize the waste water of treating organic waste water and low-concentration sulfate radical simultaneously, and COD removal rate keeps on more than 73% basically, and sulfate radical removal rate keeps on more than 82% basically, soluble The sulfide removal rate basically remained above 89%.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention , should be equivalent replacement methods, and should be included within the protection scope of the present invention.

Claims (10)

1. A method for treating organic waste water and sulfate waste water simultaneously, is characterized in that, comprises the following steps: 1) adding organic wastewater and sulfate wastewater to the anode chamber containing Geobacter and the cathode chamber containing sulfate-reducing bacteria, and applying voltage for treatment; 2) Excluding the waste water in the anode chamber to obtain purified organic waste water; while transferring the sulfide waste water generated in the cathode chamber to the photosynthetic bacteria chamber containing photosynthetic bacteria; 3) The photosynthetic bacteria chamber is irradiated with light, and after biochemical reaction, purified sulfate wastewater is obtained. 2. method according to claim 1, it is characterized in that, step 3) to anode chamber and cathode chamber respectively re-add after step 1) same organic waste water and sulfate waste water, apply voltage treatment; At the same time, the photosynthetic bacteria chamber is irradiated with light, and after biochemical reaction, purified sulfate wastewater is obtained. 3. The method according to claim 2, further comprising: repeating the operation process of step 2) and step 3) multiple times. 4. according to the described method of claim 1 and 2, it is characterized in that: the organic matter in the described organic waste water of step 1) is one or more in acetic acid, methyl alcohol, formic acid, glucose, sucrose; Step 1) described The sulfate in the sulfate wastewater is one or more of sodium sulfate, potassium sulfate, aluminum potassium sulfate; the sulfide in the sulfide wastewater in step ₂ ) includes H2S, HS- ^{, S2-} One or more; Step 2) The sulfide wastewater also includes one or more of CO ₃ ²⁻ , HCO ₃ ⁻ , and CO ₂ . 5. according to the described method of claim 1 and 2, it is characterized in that: the COD concentration in the described organic matter waste water of step 1) is 800mg/～4000mg/L; The sulfate concentration in the described sulfate waste water of step 1) is 200mg/L～1000mg/L; the organic matter concentration in the sulfate wastewater in step 1) is lower than 10mg/L; the sulfide concentration in the sulfide wastewater in step 2) is 50mg/L～200mg/L. 6. according to the described method of claim 1 and 2, it is characterized in that: the pH value of step 1) described sulfate waste water is 5.0～7.2; Step 1) described organic waste water, step 1) described sulfate waste water and Step 2) The sulfide wastewater has been subjected to oxygen removal treatment, and the oxygen concentration of the three wastewaters is lower than 0.2 mg/L. 7. The method according to claim 1, characterized in that: step 1) said applied voltage is a DC voltage, and the voltage value of the DC voltage is 0.5V-3.0V; step 3) said light is visible light and/or infrared light. 8. A reaction device for treating organic waste water and sulfate waste water simultaneously, an electrolytic cell made up of an anode chamber, a proton exchange membrane, a cathode chamber, a power supply, a resistor, an anode electrode, and a cathode electrode, and between the cathode chamber and the anode chamber The room is separated by a proton exchange membrane, and it is characterized in that: the reaction device also includes: a data collector, a photosynthetic bacteria chamber, a light-emitting reaction device, an attachment, a pump, and a valve; The water outlet provided in the cathode chamber is directly connected to the water inlet of the photosynthetic bacteria chamber through a pipeline, and the pipeline is also provided with a pump and a valve; The attachment is arranged on the inner wall of the photosynthetic bacteria chamber, and at the same time, the light-emitting reaction device is arranged at a position where the light can irradiate the attachment; The data collector and the resistor are connected in parallel by wires, and the wires are connected in series with the anode electrode, the cathode electrode, and the power supply to monitor the current signal flowing from the anode electrode in the anode chamber to the cathode electrode in the cathode chamber. 9. reaction device according to claim 8, is characterized in that, the material of described anode electrode and the material of cathode electrode are a kind of in carbon brush, carbon cloth, porous carbon rod; The material of described attachment is carbon cloth. 10. An application of the reaction device as claimed in claim 8 or 9 in wastewater treatment.

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