Environment-friendly biological treatment mode for synchronously detoxifying and efficiently denitrifying high-arsenic wastewater

Through multi-stage acclimation in an anaerobic bioreactor, anaerobic bacteria with high concentration As(III) resistance was cultivated, and the problems of low efficiency and high cost of high concentration As(III) wastewater treatment in the prior art were solved. The effect of efficient nitrogen removal and detoxification is achieved.

CN119461632AActive Publication Date: 2025-02-18UNIV OF SCI & TECH OF CHINA
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Patent Information

Application Number
CN202411625047.7
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-14
Publication Date
2025-02-18
Estimated Expiration
2044-11-14

AI Technical Summary

Technical Problem

The prior art has problems of high cost, low treatment efficiency and secondary pollution risk when treating high concentrations of As(III) industrial wastewater, and biological laws face the problems of biotoxicity and poor treatment efficiency.

Method used

Adopting an environmentally friendly biological treatment method, using an upstream anaerobic sludge reactor, combined with magnetic stirring, three-phase separator and sludge reflux device, aversion with high concentration of As(III) resistance is cultivated through multi-stage acclimation. Oxygen flora, achieving efficient nitrogen removal and detoxification.

Benefits of technology

Complete conversion and efficient nitrogen removal of high-concentration As(III) industrial wastewater is achieved, which reduces sludge loss and energy consumption, improves treatment efficiency and stress resistance, and reduces the risk of secondary pollution.

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Abstract

The invention discloses an environment-friendly high-arsenic wastewater detoxification and efficient denitrification synchronous biological treatment mode, and belongs to the technical field of sewage treatment. Firstly, anaerobic granular sludge is inoculated into a used anaerobic bioreactor for short-term stabilization; then simulated industrial wastewater containing As (III) with gradient concentration is introduced into the stabilized anaerobic sludge for multi-stage domestication, a transition period is added in each domestication stage, growth of anaerobic microorganisms is indirectly promoted by utilizing a micro-aerobic (anoxic) environment, high-concentration stable transition of As (III) is performed, the domestication time is greatly shortened, and the domestication efficiency is improved. The flora which can be used for completely converting high-concentration As (III) within 24 hours and simultaneously retaining an efficient denitrification property is rapidly cultured. The invention solves the problems of long domestication transition period of As (III) flora, reduction of denitrification performance due to high toxicity of As (III) to flora under high concentration, serious sludge loss, slow As (III) conversion speed and the like.
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Description

Technical Field

[0001] The invention relates to the technical field of water treatment, and in particular to an environmentally friendly biological treatment method for detoxifying high-arsenic wastewater and simultaneously removing nitrogen with high efficiency. Background Art

[0002] With the acceleration of industrialization, the discharge of arsenic-containing wastewater has brought many problems. Arsenic is a toxic metal element, and its compounds are widely present in nature, especially As(III), which poses a serious threat to the environment and human health due to its high toxicity and high mobility. Although traditional treatment methods such as chemical precipitation, coagulation precipitation, electrochemical method, adsorption method, etc. can remove arsenic from wastewater to a certain extent, they often have problems such as low treatment efficiency, high cost, and secondary pollution. For example, the chemical precipitation method increases the cost of sewage treatment and produces a large amount of sludge by adding chemical agents to chelate As(III) after the secondary process of sewage treatment. It is difficult to purify arsenic-containing wastewater to the discharge standard at one time, and it may cause waste of arsenic resources and secondary pollution. The coagulation precipitation method requires the addition of coagulants, which will also increase the amount of sludge, and the treatment effect of low-concentration arsenic-containing wastewater is not good.

[0003] Biological treatment technology has always been the main wastewater treatment process in practical applications. Compared with traditional denitrification technology, anaerobic biological treatment technology does not require the addition of a carbon source. The nitrogen produced by its own reaction can save the energy loss caused by aeration. In addition, since anaerobic organisms are mostly autotrophic microorganisms, their slow growth can greatly reduce the sludge output of the process, showing significant advantages in green environmental protection. However, high concentrations of As(III) have a broad spectrum of biological toxicity in the environment and will have a significant impact on the normal physiological functions of microorganisms. Not only that, when the As(III) concentration suddenly increases, it will also affect the immediate stability of the anaerobic biological technology and may even directly lead to the collapse of the reactor. There is still a great risk of failure in the acclimation stage of anaerobic sludge. Therefore, anaerobic biological treatment technology is also a challenge for the treatment of high-concentration As(III)-containing industrial wastewater.

[0004] At the same time, due to the slow growth of anaerobic organisms, certain measures need to be taken to maintain the biomass in the system. In addition to removing suspended solids in sewage to ensure clear effluent, the sedimentation effect of the secondary sedimentation tank can also ensure that the activated sludge can be effectively returned to the biological treatment system to maintain the stable operation of the biological treatment system. Therefore, incorporating the principles of this process into the anaerobic bioreactor can greatly reduce the loss of activated sludge. In summary, after the acclimation of the anaerobic bioreactor, it is expected that the anaerobic bioreactor can smoothly transition when the As(III) concentration changes exponentially, so that it can always maintain stable growth and development under the toxic effects of As(III), greatly shortening the acclimation time, and quickly cultivating anaerobic bacteria with high-concentration As(III) resistance and the ability to maintain the original denitrification performance to adapt to a wide range of As(III) influent conditions. Summary of the invention

[0005] In view of the problems of high cost and secondary pollution risk in treating high-arsenic industrial wastewater by existing chemical precipitation or physical precipitation methods, as well as the problems of biological toxicity and low treatment efficiency in biological methods, the present invention provides a biological treatment method for treating industrial wastewater containing high concentration of As(III) and simultaneously performing efficient nitrogen removal, aiming to completely convert As(III) in the wastewater while ensuring the efficient nitrogen removal performance of the reactor itself.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] An environmentally friendly biological treatment method for detoxifying high-arsenic wastewater and simultaneously removing nitrogen with high efficiency is characterized in that the anaerobic bioreactor used in the biological treatment method is an upflow anaerobic sludge reactor, including a reactor body and a sludge return device.

[0008] On the reactor body, from the bottom to the top, a sludge discharge port, a water inlet, a sludge return port and a water outlet are sequentially arranged; the top of the reactor body is sealed by a top plate, and an air outlet is arranged on the top plate;

[0009] A three-phase separator is arranged inside the reactor body, between the sludge return port and the water outlet; the three-phase separator is composed of a first annular plate in an inverted cone shape and a second annular plate in a cone shape, and the second annular plate is located above the first annular plate, and an annular gap is formed between the two annular plates; the top of the first annular plate is fixed on the side wall of the reactor body, and the middle of the bottom is open; the top of the second annular plate is fixed on the top plate of the reactor body through an outlet pipe, and is connected to the outlet on the top plate; the bottom opening diameter of the second annular plate is larger than the bottom opening diameter of the first annular plate; the bottom position of the second annular plate is lower than the top position of the first annular plate.

[0010] In the reactor body, a stirring magnet is added to the bottom, and an aeration head is arranged between the water inlet and the sludge return port; the aeration head is connected to the aeration pipe, and the aeration pipe is led to the outside through the bottom opening of the first annular plate, the bottom opening of the second annular plate and the outlet pipe in sequence, and a gap for gas to flow out is formed between the aeration pipe and the outlet pipe;

[0011] The sludge return device is provided with a water inlet at the top, a water outlet in the middle, and a mud outlet at the bottom; the water outlet of the reactor body is connected to the water inlet at the top of the sludge return device, and the mud outlet at the bottom of the sludge return device is connected to the sludge return outlet of the reactor body;

[0012] Anaerobic granular sludge is inoculated in the reactor body, and the anaerobic granular sludge is subjected to multi-stage domestication using simulated industrial wastewater containing gradient concentrations of As(III), so that an anaerobic bacterial community with high-concentration As(III) resistance and the ability to maintain original denitrification performance is cultivated.

[0013] The method for treating high-arsenic wastewater using the anaerobic bioreactor is as follows:

[0014] The reactor body is placed on a magnetic stirrer; an inert gas aeration device is externally connected to the aeration pipe to ensure an anaerobic environment inside the reactor during the operation stage; the industrial wastewater to be treated is introduced into the reactor body from the water inlet in an upward flow manner, and the anaerobic granular sludge is stirred by a magnetic particle to mix the sludge and the industrial wastewater evenly, and the sludge is evenly distributed below the three-phase separator; after being treated by the anaerobic bacteria, the formed suspension continues to pass upward through the three-phase separator and then flows into the sludge reflux device through the water outlet, and the excess nitrogen is naturally discharged into the air through the gas outlet at the top of the reactor; the anaerobic bioreactor adopts a continuous flow operation mode;

[0015] After the suspended liquid entering the sludge return device settles naturally, the bottom sludge is returned to the reactor body through a peristaltic pump to control the flow rate, and the upper clear water is discharged from the outlet of the sludge return device as treated wastewater.

[0016] Furthermore, the method for multi-stage domestication of the anaerobic granular sludge is:

[0017] The reactor body inoculated with anaerobic granular sludge is placed on a magnetic stirrer; the aeration pipe is externally connected to an inert gas aeration device;

[0018] First, the anaerobic granular sludge in the reactor is stabilized for a period of time using simulated industrial wastewater without As(III) until the denitrification efficiency is not less than 50%, which is recorded as stage I;

[0019] Then, the anaerobic granular sludge in the reactor was acclimated in stages II, III, and IV using simulated industrial wastewater containing As(III), and the As(III) concentration in the wastewater used in stages II to IV increased exponentially;

[0020] A transition period is set between two adjacent stages; nitrogen aeration is maintained during the operation of the reactor except during the transition period to maintain an anaerobic environment; aeration is stopped during the transition period, so that the internal environment of the reactor becomes an anoxic environment.

[0021] Furthermore, the acclimation time for stages II and III was 30 days, and the acclimation time for stage IV was 20 days. The As(III) concentrations of the simulated industrial wastewater used in each stage were as follows:

[0022] Phase II: acclimatization using simulated industrial wastewater containing 20 mg / L As(III);

[0023] Phase III: acclimatization using simulated industrial wastewater containing 40 mg / L As(III);

[0024] Phase IV: Acclimatization using simulated industrial wastewater containing 80 mg / L As(III).

[0025] Furthermore, each transition period lasts for 6 days, including the last three days of the previous stage and the first three days of the next stage.

[0026] The simulated industrial wastewater contains: 500mg / L NaHCO3, 100mg / L NH4Cl, 130mg / L NaNO2, 27.2mg / LK2HPO4, 300mg / LMgSO4·7H2O, 180mg / L CaCl2·2H2O, 5mg / L FeSO4 and 1mL / L trace element solution. As(III) in the simulated industrial wastewater is provided by sodium arsenite NaAsO2. The trace element solution contains 430mg / LZnSO4·7H2O, 240mg / L CoCl2·6H2O, 990mg / LMnCl2·4H2O, 250mg / L CuSO4·5H2O, 220mg / LNaMoO4·2H2O, 190mg / LNiCl2·6H2O, 210mg / LNaSeO4·10H2O, and 14mg / L H3BO3.

[0027] In the technical solution of the present invention:

[0028] Anaerobic granular sludge is inoculated in the bottom area of ​​the reactor, and the internal magnetic particles are driven by a magnetic stirrer to stir the sludge to promote its better contact with industrial wastewater and improve the utilization rate of the sludge; the built-in three-phase separator and sludge reflux device can reduce the sludge loss inside the reactor, improve the stable operation of the reactor and its ability to cope with different concentrations of As(III) and nitrogen load shocks.

[0029] The anaerobic sludge is subjected to multi-stage acclimation with simulated industrial wastewater containing As(III) ranging from low concentration to high concentration, and a transition period of stopping aeration is set between two adjacent stages. The micro-oxic (anoxic) environment is used to indirectly promote the growth of anaerobic microorganisms, and a smooth transition to high concentration of As(III) is performed, so that the anaerobic sludge always maintains stable growth and development under the toxic effect of As(III), greatly shortening the acclimation time, and quickly cultivating an anaerobic bacterial community with high concentration As(III) resistance and the ability to maintain the original denitrification performance, so as to adapt to the inlet conditions of a wide range of As(III) concentrations.

[0030] The three-phase separator consists of two parts, which are used to reduce sludge loss. Both the upper and lower parts are annular plates. The first annular plate located at the bottom with an inverted cone is directly welded to the inner wall of the reactor body, and the bottom opening is used for normal upper drainage; the top of the second annular plate located at the top with a cone is welded to the top plate of the reactor body through an outlet pipe. The outlet pipe can discharge nitrogen to maintain the internal air pressure stable.

[0031] The principle of the present invention is: through the domestication of As(III) in four stages of 0mg / L, 20mg / L, 40mg / L and 80mg / L, the concentration of As(III) in the influent is doubled from low concentration to high concentration, a transition period of stopping aeration is added in each stage change, and a short-term micro-oxygen (anoxic) environment is used to promote the metabolic activity of aerobic microorganisms in the sludge and indirectly promote the growth of anaerobic microorganisms to enhance the stress resistance of the activated sludge, so that the microorganisms in the reactor quickly adapt to As(III) to cultivate anaerobic bacteria with high concentration As(III) resistance. Microscopically, it is manifested in the enrichment of arsenic oxidation genes detected in the extracted microbial DNA, and the extracted microbial protein has the activity of arsenic conversion enzyme; macroscopically, it is manifested in that the reactor can smoothly transition when the As(III) concentration changes multiple times, so that it can always maintain stable and efficient denitrification under the toxic effect of As(III) and realize the complete conversion of As(III) within 24 hours. The agitator at the bottom allows the sludge and wastewater in the reactor to be fully mixed and reacted. The setting of the sludge return device can ensure sufficient biomass in the reactor through sludge return and prevent the loss of the cultivated bacteria.

[0032] The present invention provides an environmentally friendly biological treatment method for detoxification and simultaneous efficient nitrogen removal of high-arsenic wastewater, which has the following beneficial effects:

[0033] 1. In the anaerobic bioreactor provided by the present invention: the magnetic stirrer at the bottom of the reactor allows the sludge to fully contact with the industrial wastewater, thereby avoiding the deterioration of the treatment effect caused by bottom sedimentation; the three-phase separator can separate the sludge area from the water outlet to achieve sludge-water separation; the sludge return device can ensure sufficient biomass in the reactor through sludge return, thereby preventing the loss of the cultivated strains.

[0034] 2. The acclimatization method of the sludge in the reactor of the present invention can stably resist the toxic effect of As(III) during the process of concentration multiple changes from 0 to 80 mg / LAs(III), always maintain normal growth and metabolism, and maintain high denitrification efficiency.

[0035] 3. The UASB reactor of the present invention can achieve efficient treatment of industrial wastewater under the condition of 0-80 mg / LAs(III), and the removal rate of ammonia nitrogen and nitrite nitrogen is stable at more than 95%, while achieving complete conversion of As(III). BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 is a schematic diagram of an anaerobic bioreactor used in an embodiment of the present invention;

[0037] Figure 2 The changes of ammonia nitrogen and nitrite nitrogen in the reactor in the four acclimatization stages (with transition period) in the embodiment;

[0038] Figure 3 The changes of As(III) in the reactor in the four acclimatization stages (with transition period) in the embodiment;

[0039] Figure 4 The changes of ammonia nitrogen and nitrite nitrogen in the reactor in the four acclimatization stages (without transition period) in the embodiment;

[0040] Figure 5 The changes of As(III) in the reactor in the four acclimatization stages (without transition period) in the embodiment;

[0041] Figure 6 It is a heat map of the relative abundance changes of As(III) oxidation genes in the anaerobic granular sludge of the reactor after each acclimation stage in the embodiment;

[0042] Figure 7 This is a graph showing the test results of arsenic oxidase activity extracted from the anaerobic granular sludge in the reactor before and after acclimatization in the embodiment;

[0043] Figure 8 This is the treatment effect of the reactor that completed the anaerobic granular sludge acclimation in the example to treat high-concentration As(III)-containing simulated industrial wastewater. DETAILED DESCRIPTION

[0044] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below.

[0045] Example 1

[0046] like Figure 1 As shown, the anaerobic bioreactor used in this embodiment for treating high-concentration As(III) industrial wastewater is an upflow anaerobic sludge reactor, including a reactor body and a sludge return device.

[0047] On the reactor body, from the bottom to the top, a sludge discharge port, a water inlet, a sludge return port and a water outlet are sequentially arranged; the top of the reactor body is sealed by a top plate, and an air outlet is arranged on the top plate.

[0048] A three-phase separator is arranged inside the reactor body, between the sludge return port and the water outlet; the three-phase separator is composed of a first annular plate in an inverted cone shape and a second annular plate in a cone shape, and the second annular plate is located above the first annular plate, and an annular gap is formed between the two annular plates; the top of the first annular plate is fixed on the side wall of the reactor body, and the middle of the bottom is open; the top of the second annular plate is fixed on the top plate of the reactor body through an outlet pipe, and is connected to the outlet on the top plate; the bottom opening diameter of the second annular plate is larger than the bottom opening diameter of the first annular plate.

[0049] In the reactor body, a stirring magnet is added to the bottom, and an aeration head is arranged between the water inlet and the sludge return port; the aeration head is connected to the aeration pipe, and the aeration pipe is led out to the outside through the bottom opening of the first annular plate, the bottom opening of the second annular plate and the outlet pipe in sequence, and a gap is formed between the aeration pipe and the outlet pipe for gas to flow out.

[0050] The sludge return device is provided with a water inlet at the top, a water outlet in the middle and a mud outlet at the bottom; the water outlet of the reactor body is connected to the water inlet at the top of the sludge return device, and the mud outlet at the bottom of the sludge return device is connected to the sludge return outlet of the reactor body.

[0051] The present invention has no special restrictions on the size of the reactor body. The reactor body used in this embodiment is 52.2 cm high and has a bottom area of ​​78.5 cm. 2 , effective volume 3.94L, actual usage volume 3L.

[0052] Anaerobic granular sludge is inoculated in the reactor body. The present invention has no special limitation on the inoculated anaerobic granular sludge, and commercially available anaerobic granular sludge can be directly used. In this embodiment, the concentration of the anaerobic granular sludge in the reactor is 3 g / L.

[0053] In this embodiment, the inoculated anaerobic granular sludge was subjected to multi-stage domestication using simulated industrial wastewater containing gradient concentrations of As(III), so that an anaerobic bacterial community with high concentration As(III) resistance and the ability to maintain the original denitrification performance was cultivated. The domestication method (the operation method of the reactor is the same as the method for treating high arsenic wastewater) is:

[0054] The reactor body inoculated with anaerobic granular sludge is placed on a magnetic stirrer; the aeration pipe is connected to an inert gas aeration device. Simulated industrial wastewater containing corresponding concentrations of As(III) is introduced into the reactor body from the water inlet in an upward flow manner, and the anaerobic granular sludge is stirred by a magnetic agitator.

[0055] First, the anaerobic granular sludge in the reactor was stabilized for 30 days using simulated industrial wastewater containing 0 mg / L As(III); then, the anaerobic granular sludge in the reactor was acclimated for 30 days using simulated industrial wastewater containing 20 mg / L As(III); then, the anaerobic granular sludge in the reactor was acclimated for 30 days using simulated industrial wastewater containing 40 mg / L As(III); finally, the anaerobic granular sludge in the reactor was acclimated for 20 days using simulated industrial wastewater containing 80 mg / L As(III). A transition period was set between two adjacent stages, and each transition period lasted for 6 days, including the last three days of the previous stage and the first three days of the next stage in the two adjacent stages. During the operation of the reactor, nitrogen aeration was maintained except during the transition period to maintain an anaerobic environment; aeration was stopped during the transition period, so that the internal environment of the reactor became an anoxic environment.

[0056] As described above, in this embodiment, the acclimation is divided into four stages, and the anaerobic granular sludge in the reactor is acclimated for 30 days, 30 days, 30 days, and 20 days respectively using simulated industrial wastewater containing 0 mg / L, 20 mg / L, 40 mg / L, and 80 mg / L As (III). During the acclimation process, the hydraulic retention time of the reactor is 24 h, the pH is 8.0, and the temperature is 35°C.

[0057] The simulated industrial wastewater used in this embodiment contains: 500mg / LNaHCO3, 100mg / LNH4Cl, 130mg / L NaNO2, 27.2mg / L K2HPO4·, 300mg / L MgSO4·7H2O, 180mg / L CaCl2·2H2O, 5mg / L FeSO4 and 1mL / L trace element solution. The trace element solution contains 430mg / L ZnSO4·7H2O, 240mg / L CoCl2·6H2O, 990mg / LMnCl2·4H2O, 250mg / L CuSO4·5H2O, 220mg / LNaMoO4·2H2O, 190mg / LNiCl2·6H2O, 210mg / LNaSeO4·10H2O, and 14mg / L H3BO3. The As(III) in the simulated industrial wastewater is NaAsO2 (sodium arsenite).

[0058] This example investigates the treatment effect of simulated industrial wastewater during the acclimation process, and compares the wastewater treatment effects with and without a transition period (the difference between the acclimation method without a transition period and the acclimation method with a transition period is that nitrogen aeration is maintained during the entire acclimation period).

[0059] The treatment effect of adding transition period acclimation process on simulated industrial wastewater is as follows Figure 2 As shown in Figure 2, with the increase of As(III) in the influent, the nitrogen removal efficiency of the reactor remains above 90%. Figure 3 As shown, the As(III) in the influent water was always able to complete the complete conversion.

[0060] The treatment effect of the acclimatization process without adding a transition period on the simulated industrial wastewater is as follows Figure 4 and Figure 5 As shown, with the increase of influent As(III), the reactor experienced an increase in effluent nitrogen and As(III) concentrations each time the influent As(III) concentration was increased, indicating that its denitrification and arsenic removal effects would deteriorate, and gradually stabilized after a few days.

[0061] This example investigates the enrichment of arsenic oxidation genes in the granular sludge DNA after each stage of acclimation. The arsenic oxidation-related genes are aioA, aioB and arxA, and their changes are presented in the relative abundance heat map of the genes, as shown in Figure 2. Figure 6 As shown in the figure, the values ​​in the figure are the standardized relative abundance values, and the larger the value, the higher the relative abundance. It can be seen from the figure that with the increase of As(III) in the influent, the relative abundance of aioA, aioB and arxA in the sludge all increased.

[0062] This example investigates the changes in arsenic oxidase activity in protein extracted from granular sludge before and after acclimation. Arsenic oxidase activity is defined as the amount of DCIP reduced per milligram of protein per minute, with the unit being μmol DCIP / (min·mg). The more DCIP is reduced, the stronger the activity. Figure 7 As shown, the reduction amount of DCIP by the domesticated anaerobic granular sludge is much greater than that by the undomesticated anaerobic granular sludge, and the undomesticated anaerobic granular sludge has almost no reduction of DCIP.

[0063] The anaerobic bioreactor of this embodiment can be used to treat high-arsenic wastewater after multi-stage acclimation of anaerobic granular sludge in the above manner. This embodiment has no special restrictions on the composition and source of the industrial wastewater containing As(III) to be treated, and its treatment method is: during operation, the reactor body is placed on a magnetic stirrer; the aeration pipe is externally connected to an inert gas aeration device to ensure the anaerobic environment inside the reactor during the operation stage, and the industrial wastewater to be treated is passed into the reactor body from the water inlet in an upward flow manner, and the anaerobic granular sludge is stirred by a magnetic particle to mix the sludge and the industrial wastewater evenly, and the sludge is evenly distributed below the three-phase separator; after being treated by the anaerobic bacteria, most of the granular sludge is intercepted under the three-phase separator to continue to react, and the suspension containing a small amount of sludge is formed. After passing through the three-phase separator, it flows into the sludge reflux device through the outlet, and the excess nitrogen is naturally discharged into the air through the outlet at the top of the reactor. After the suspended liquid entering the sludge return device settles naturally, the active granular sludge at the bottom is returned to the reactor body through the peristaltic pump to control the flow rate, and the upper layer of clear water is discharged from the outlet of the sludge return device as treated wastewater. The anaerobic bioreactor adopts a continuous flow operation mode.

[0064] The anaerobic granular sludge acclimated in this example was used to treat simulated industrial wastewater containing 120 mg / LAs(III) in a continuous flow manner for eight days. The hydraulic retention time of the reactor was 24 h, the pH was 8.0, and the temperature was 35°C. The nitrogen and As(III) concentrations of the treated wastewater were tested every 1 or 2 days. The results were as follows: Figure 8 As shown, 120 mg / LAs (III) can be completely removed while ensuring a nitrogen removal efficiency of more than 90%.

[0065] The above are merely exemplary embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An environmentally friendly biological treatment method for detoxification and simultaneous efficient nitrogen removal of high-arsenic wastewater, characterized by: The anaerobic bioreactor used in the biological treatment method is an upflow anaerobic sludge reactor, including a reactor body and a sludge return device; On the reactor body, from the bottom to the top, a sludge discharge port, a water inlet, a sludge return port and a water outlet are sequentially arranged; the top of the reactor body is sealed by a top plate, and an air outlet is arranged on the top plate; A three-phase separator is provided inside the reactor body, between the sludge return port and the water outlet; the three-phase separator is composed of a first annular plate in an inverted cone shape and a second annular plate in a cone shape, and the second annular plate is located above the first annular plate, and an annular gap is formed between the two annular plates; the top of the first annular plate is fixed to the side wall of the reactor body, and the middle of the bottom is open; the top of the second annular plate is fixed to the top plate of the reactor body through an outlet pipe, and is connected to the outlet on the top plate; the bottom opening diameter of the second annular plate is larger than the bottom opening diameter of the first annular plate; In the reactor body, a stirring magnet is added to the bottom, and an aeration head is arranged between the water inlet and the sludge return port; the aeration head is connected to the aeration pipe, and the aeration pipe is led to the outside through the bottom opening of the first annular plate, the bottom opening of the second annular plate and the outlet pipe in sequence, and a gap for gas to flow out is formed between the aeration pipe and the outlet pipe; The sludge return device is provided with a water inlet at the top, a water outlet in the middle, and a mud outlet at the bottom; the water outlet of the reactor body is connected to the water inlet at the top of the sludge return device, and the mud outlet at the bottom of the sludge return device is connected to the sludge return outlet of the reactor body; Anaerobic granular sludge is inoculated in the reactor body, and the anaerobic granular sludge is subjected to multi-stage domestication using simulated industrial wastewater containing gradient concentrations of As(III), so that an anaerobic bacterial community with high concentration As(III) resistance and the ability to maintain the original denitrification performance is cultivated; The method for treating high-arsenic wastewater using the anaerobic bioreactor is as follows: The reactor body is placed on a magnetic stirrer; an inert gas aeration device is externally connected to the aeration pipe to ensure an anaerobic environment inside the reactor during the operation stage; the industrial wastewater to be treated is introduced into the reactor body from the water inlet in an upward flow manner, and the anaerobic granular sludge is stirred by a magnetic particle to mix the sludge and the industrial wastewater evenly, and the sludge is evenly distributed below the three-phase separator; after being treated by the anaerobic bacteria, the formed suspension continues to pass upward through the three-phase separator and then flows into the sludge reflux device through the water outlet, and the excess nitrogen is naturally discharged into the air through the gas outlet at the top of the reactor; the anaerobic bioreactor adopts a continuous flow operation mode; After the suspended liquid entering the sludge return device settles naturally, the bottom sludge is returned to the reactor body through a peristaltic pump to control the flow rate, and the upper clear water is discharged from the outlet of the sludge return device as treated wastewater.

2. The biological treatment method according to claim 1, characterized in that: The method for multi-stage domestication of the anaerobic granular sludge is as follows: The reactor body inoculated with anaerobic granular sludge is placed on a magnetic stirrer; the aeration pipe is externally connected to an inert gas aeration device; First, the anaerobic granular sludge in the reactor is stabilized for a period of time using simulated industrial wastewater without As(III) until the denitrification efficiency is not less than 50%, which is recorded as stage I; Then, the anaerobic granular sludge in the reactor was acclimated in stages II, III, and IV using simulated industrial wastewater containing As(III), and the As(III) concentration in the wastewater used in stages II to IV increased exponentially; A transition period is set between two adjacent stages; nitrogen aeration is maintained during the operation of the reactor except during the transition period to maintain an anaerobic environment; aeration is stopped during the transition period, so that the internal environment of the reactor becomes an anoxic environment.

3. The biological treatment method according to claim 2, characterized in that: The acclimatization time for phases II and III was 30 days, and the acclimatization time for phase IV was 20 days. The As(III) concentrations of the simulated industrial wastewater used in each phase were as follows: Phase II: acclimatization using simulated industrial wastewater containing 20 mg / L As(III); Phase III: acclimatization using simulated industrial wastewater containing 40 mg / L As(III); Phase IV: Acclimatization using simulated industrial wastewater containing 80 mg / L As(III).

4. The biological treatment method according to claim 2 or 3, characterized in that: Each transition period lasts for 6 days, including the last three days of the previous stage and the first three days of the next stage.

5. The biological treatment method according to claim 2 or 3, characterized in that: The simulated industrial wastewater contains: 500 mg / LNaHCO3, 100 mg / LNH4Cl, 130 mg / LNaNO2, 27.2 mg / LK2HPO4, 300 mg / LMgSO4·7H2O, 180 mg / LCaCl2·2H2O, 5 mg / L FeSO4 and 1 mL / L trace element solution; As(III) in the simulated industrial wastewater is provided by sodium arsenite NaAsO2.

6. The biological treatment method according to claim 5, characterized in that: The trace element solution contains 430 mg / L ZnSO4·7H2O, 240 mg / L CoCl2·6H2O, 990 mg / L MnCl2·4H2O, 250 mg / L CuSO4·5H2O, 220 mg / L NaMoO4·2H2O, 190 mg / L NiCl2·6H2O, 210 mg / L NaSeO4·10H2O, and 14 mg / L H3BO3.

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