A treatment device for adsorption combined with electroactive biofilm and a method for treating phenol-ammonia pollutants in coal pyrolysis wastewater using the device

Abstract

A treatment device of adsorption combined with electroactive biofilm and a method for treating phenol-ammonia pollutants in coal pyrolysis wastewater using the device, relate to the technical field of sewage treatment. The purpose of the present invention is to solve the problems in the prior art that it is difficult to remove phenol-ammonia pollutants simultaneously by biochemical degradation, the conventional anoxic-aerobic unit operation is complex, the stability is low, the energy consumption is high, and the utilization rate of the secondary sedimentation tank is low. Method: The coal pyrolysis wastewater is adsorbed by zeolite in pool A to quickly remove most of the ammonia nitrogen, and the formed biofilm can be further nitrified and denitrified; the adsorption by nano-Fe3O4-loaded activated coke particles in pool B can quickly reduce phenols, polycyclic aromatic hydrocarbons and other difficult-to-degrade organic matter, and the adsorbed organic pollutants are degraded by accumulated and domesticated electroactive biofilms; the water is discharged after the inclined plate sedimentation area in pool C, and the turbidity and SS of the outlet water can be reduced. The present invention can obtain a treatment device of adsorption combined with electroactive biofilm and a method for treating phenol-ammonia pollutants in coal pyrolysis wastewater using the device.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to an adsorption-combined electroactive biofilm treatment device and a method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using the device. Background Art

[0002] Coal pyrolysis wastewater is a typical difficult-to-degrade industrial wastewater, and its main pollutants are high concentrations of phenols and ammonia nitrogen. The conventional process of coal pyrolysis wastewater treatment is physicochemical pretreatment-biodegradation-deep treatment. The pretreatment mainly recovers a large amount of phenol and ammonia substances in the wastewater through extraction and evaporation. Biodegradation is the core link of coal pyrolysis wastewater treatment. It mainly removes phenol and ammonia pollutants in the wastewater through carbon-nitrogen cycle transformation of heterotrophic and autotrophic microorganisms in activated sludge. It usually needs to undergo anaerobic biological pretreatment, and then enter the anoxic-aerobic biological treatment unit. After the mud and water are separated in the secondary sedimentation tank, the effluent enters deep treatment. Deep treatment usually uses aerated biological filters, ozone oxidation, and membrane filtration to deeply remove phenol and ammonia pollutants in the biochemical effluent. The process is complicated and requires high energy consumption. The adsorption-biodegradation method has the high efficiency of the adsorption method and the cost advantages of the biological method. It is suitable for the simultaneous removal of phenol and ammonia pollutants in the anaerobic treatment effluent in the biodegradation process.

[0003] Zeolite is a kind of porous hydrated silicate mineral with a framework structure. my country has abundant zeolite reserves, which can reach 4 billion tons. Clinoptilolite is the main zeolite in industrial applications. The structural water of zeolite is different from general structural water (OH). Since it exists as a water molecule, the structure of zeolite water is not destroyed after heating and dehydration at a specific temperature. Pores still remain at the position of the original water molecules, forming a structure similar to a sponge lattice. It has the characteristics of re-adsorbing water molecules or gases in the gaps. Therefore, zeolite has good material exchange and adsorption regeneration properties, and has selective adsorption properties. It is easy to adsorb ammonium ions and free ammonia, and can slowly release ammonia nitrogen in water. Semi-coke produced in the process of coal pyrolysis is a cheap by-product. The conventional utilization route is power plant fuel. After low-temperature activation, it can be used as an adsorbent. Because it contains a large number of mesopores and oxygen-containing functional groups, it can selectively adsorb difficult-to-degrade hydrophobic phenols such as methylphenol, polycyclic aromatic hydrocarbons, etc., and reduce the chromaticity of the effluent. Activated coke is often used alone as an adsorbent in the process of deep wastewater treatment, but the regeneration cost is high. In recent years, granular activated coke has been used as a biological carrier to simultaneously adsorb pollutants and enrich functional microorganisms. At the same time, activated coke loaded with iron oxide can further enrich electroactive bacteria and promote the formation of electroactive biofilms. It can accelerate the degradation of cyclic organic matter such as phenols in micro-aerobic and anaerobic environments by relying on the reduction of dissimilatory iron.

[0004] At present, the traditional biodegradation process of coal pyrolysis wastewater has the following problems:

[0005] (1) The anoxic-aerobic unit used to remove phenolic and ammonia pollutants in the current coal pyrolysis wastewater biodegradation process is complex to operate, has low performance stability, and high energy consumption;

[0006] (2) Activated coke is not easy to regenerate when used alone as an adsorbent for treating coal pyrolysis wastewater, and the regeneration cost is higher than the production cost of activated coke;

[0007] (3) The end of the traditional biochemical process of coal pyrolysis wastewater is generally an aerobic tank. Due to the toxicity of the wastewater, the sludge yield is low, resulting in low utilization of the secondary sedimentation tank. Summary of the invention

[0008] The purpose of the present invention is to solve the above-mentioned technical problems existing in the traditional coal pyrolysis wastewater biodegradation process, and to provide an adsorption combined with electroactive biofilm treatment device and a method for treating phenol ammonia pollutants in coal pyrolysis wastewater using the device.

[0009] An adsorption combined with electroactive biofilm treatment device is located below the ground and is a semi-underground combined structure. The treatment device includes pool A, adsorption-biodegradation pool (pool B) and pool C. Pool A is composed of a pool A water inlet pipe, zeolite filter material, a support layer and a pool A water outlet pipe. The adsorption-biodegradation pool is composed of a support layer, a stainless steel grid steel inclined plate, a nano-Fe 3 O 4 The activated coke particles are loaded, the overflow weir of the B tank and the sludge pipe, and the C tank is composed of an inclined plate filler, a C tank outlet pipe, a sludge hopper and a sludge discharge pipe;

[0010] A supporting layer is arranged at the bottom of the A pool, an A pool water inlet pipe is arranged at the upper part of the A pool, the A pool is filled with zeolite filter material, an A pool water outlet pipe is arranged at the lower part of the A pool, and the A pool is connected with the adsorption-biodegradation pool through the A pool water outlet pipe; a supporting layer is arranged at the bottom of the adsorption-biodegradation pool, a stainless steel grid steel inclined plate is arranged obliquely in the adsorption-biodegradation pool, one end of the stainless steel grid steel inclined plate is against the top of the adsorption-biodegradation pool adjacent to the A pool, and the other end of the stainless steel grid steel inclined plate is against the top of the supporting layer adjacent to the C pool, and nano-Fe is evenly distributed on the stainless steel grid steel inclined plate 3 O 4Active coke particles are loaded, an overflow weir of pool B is arranged on the upper part of the adsorption-biodegradation pool, and a sludge pipe is arranged on the lower part of the adsorption-biodegradation pool; backwash pipes are arranged on the bottom of the A pool and the adsorption-biodegradation pool, the backwash pipes are connected with the power device through pipelines, and a valve is arranged on the backwash pipe between the A pool and the adsorption-biodegradation pool; a water outlet pipe of pool C is arranged on the upper part of the C pool, an inclined plate filler is arranged in the C pool, and active coke is arranged on the inclined plate filler, a sludge hopper is arranged on the bottom of the C pool, the adsorption-biodegradation pool is connected with the sludge hopper through the sludge pipe, a sludge discharge pipe is arranged on the lower part of the sludge hopper, and the sludge discharge pipe leads to the outside of the C pool.

[0011] The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device is carried out in the following steps:

[0012] The effluent from the anaerobic unit of coal pyrolysis wastewater is added to pool A through the inlet pipe of pool A, and after adsorption by zeolite filter material, primary effluent is obtained; the primary effluent enters the adsorption-biodegradation pool through the outlet pipe of pool A, passes through the nano-Fe 3 O 4 After the adsorption of the loaded activated coke particles, the secondary effluent is obtained; the secondary effluent enters the C pool through the overflow weir of the B pool, and after separation by the inclined plate filler, it is discharged through the outlet pipe of the C pool, completing the treatment of phenol and ammonia pollutants in the coal pyrolysis wastewater; the sludge in the adsorption-biodegradation pool and the nano-Fe ions falling off the stainless steel grid steel inclined plate 3 O 4 The loaded activated coke particles flow into the sludge hopper through the sludge pipe, and the sludge in the C pool and the failed activated coke that falls off the inclined plate filler fall into the sludge hopper. All the contents in the sludge hopper are regularly discharged to the outside of the C pool through the sludge discharge pipe.

[0013] Beneficial effects of the present invention:

[0014] (1) The present invention uses an adsorption combined with electroactive biofilm treatment device to treat phenolic and ammonia pollutants in coal pyrolysis wastewater. The effluent from the anaerobic unit of the coal pyrolysis wastewater is subjected to zeolite adsorption and biofilm degradation to remove ammonia nitrogen. 3 O 4 The activated coke particles are loaded with adsorption and the biofilm is used to degrade phenols, achieving the simultaneous and deep removal of phenols and ammonia from coal pyrolysis wastewater, greatly reducing the pressure of subsequent membrane treatment and advanced oxidation, and even replacing the advanced oxidation process, thereby significantly reducing wastewater treatment costs and improving material and energy utilization efficiency.

[0015] (2) The clinoptilolite in the present invention can efficiently adsorb ammonium ions and free ammonia in wastewater, reducing the competition of ammonia nitrogen with oxygen molecules in the phenol oxidation degradation process. At the same time, zeolite has strong exchangeability and is easy to regenerate after adsorption saturation. In addition, when zeolite intercepts sludge in the effluent of the anaerobic unit and forms a biofilm, the ammonia nitrogen adsorbed by the zeolite can be slowly released into the water, and the autotrophic microorganisms on the biofilm nitrify and the heterotrophic microorganisms denitrify, and finally denitrify. In addition, clinoptilolite is widely available and low in cost.

[0016] (3) Nano-Fe 3 O 4 On the one hand, the loaded activated coke particles can selectively adsorb hydrophobic phenols and polycyclic aromatic hydrocarbons that are difficult to biodegrade in wastewater. On the other hand, they can selectively enrich electroactive microorganisms, promote the microbial heterotrophic iron reduction process, and accelerate the ring opening, chain breaking and final mineralization of difficult-to-degrade substances. This adsorption-biodegradation process has low oxygen consumption and does not require aeration. Compared with traditional aerobic biological units, it can significantly reduce energy consumption and costs. With the consumption of Fe during the reaction process, the failed activated coke particles can be easily recycled and continued to be used as cheap fuel, etc., to improve resource utilization.

[0017] Nano-Fe 3 O 4 The raw material semi-coke of the activated coke particles comes from the coal pyrolysis process. It is formed by the release of phenols, ammonia, tar and other products by coal pyrolysis. It has a large number of active sites suitable for the adsorption of phenols and can selectively adsorb phenols and polycyclic aromatic hydrocarbons that are difficult to biodegrade. 3 O 4 The electrochemical performance of activated coke is improved, which makes it easy to enrich electroactive bacteria and form electroactive microbial membranes. Its excellent conductivity accelerates the electron transfer of microorganisms on the biofilm. Activated coke particles can also adsorb color-developing substances in wastewater and reduce the chromaticity of the effluent.

[0018] (4) The sludge with higher activity carried by the effluent of the anaerobic unit in the present invention can adhere to the surface of zeolite or activated coke to form a biofilm, further improving the sludge utilization efficiency. The inclined plate sedimentation effect can effectively intercept the sludge with lower activity flowing out with the water, reduce the effluent turbidity, replace the secondary sedimentation tank of the traditional biochemical treatment unit, and reduce the infrastructure cost.

[0019] The zeolite filter material and nano-Fe in the present invention 3 O 4 The loaded activated coke particles can intercept the highly active activated sludge carried in the effluent of the anaerobic unit, form a biofilm, promote the biotransformation and degradation of phenol and ammonia pollutants, and improve the sludge utilization efficiency.

[0020] The invention can obtain an adsorption combined with electroactive biofilm treatment device and a method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The overall structure diagram of the treatment device of adsorption combined with electroactive biofilm in Example 1 is shown in Figure 1. 1 is the water inlet pipe of pool A, 2 is the zeolite filter material, 3 is the backwash pipe, 4 is the support layer, 5 is the water outlet pipe of pool A, 6 is the stainless steel grid steel inclined plate, 7 is the nano-Fe 3 O 4 Loaded activated coke particles, 8 is the overflow weir of pool B, 9 is the sludge pipe, 10 is the inclined plate filler, 11 is the outlet pipe of pool C, 12 is the sludge hopper, 13 is the ground, 14 is the sludge discharge pipe, 15 is pool A, 16 is the adsorption-biodegradation pool, and 17 is pool C.

[0022] Figure 2 6 is a schematic diagram of an enlarged stainless steel grid steel inclined plate in Example 1, 6 is a stainless steel grid steel inclined plate, 7 is a nano-Fe 3 O 4 Loaded activated coke particles. DETAILED DESCRIPTION

[0023] Specific implementation method 1: This implementation method is an adsorption combined with electroactive biofilm treatment device, which is located below the ground 13 and is a semi-underground combined structure. The treatment device includes a pool A 15, an adsorption-biodegradation pool 16 and a pool C 17. The pool A 15 is composed of a pool A water inlet pipe 1, a zeolite filter material 2, a supporting layer 4 and a pool A water outlet pipe 5. The adsorption-biodegradation pool 16 is composed of a supporting layer 4, a stainless steel grid steel inclined plate 6, a nano-Fe 3 O 4 The loaded activated coke particles 7, the overflow weir of the B tank 8 and the sludge pipe 9 are composed of the C tank 17 which is composed of the inclined plate filler 10, the C tank outlet pipe 11, the sludge hopper 12 and the sludge discharge pipe 14;

[0024] A supporting layer 4 is provided at the bottom of the A pool 15, an A pool water inlet pipe 1 is provided at the upper part of the A pool 15, the A pool 15 is filled with zeolite filter material 2, and an A pool water outlet pipe 5 is provided at the lower part of the A pool 15, and the A pool 15 is connected with the adsorption-biodegradation pool 16 through the A pool water outlet pipe 5; a supporting layer 4 is provided at the bottom of the adsorption-biodegradation pool 16, a stainless steel grid steel inclined plate 6 is obliquely provided in the adsorption-biodegradation pool 16, one end of the stainless steel grid steel inclined plate 6 is against the top of the adsorption-biodegradation pool 16 adjacent to the side of the A pool 15, and the other end of the stainless steel grid steel inclined plate 6 is against the top of the supporting layer 4 adjacent to the side of the C pool 17, and nano-Fe is evenly distributed on the stainless steel grid steel inclined plate 6 3 O 4Active coke particles are loaded, and an overflow weir 8 of pool B is arranged on the upper part of the adsorption-biodegradation pool 16, and a sludge pipe 9 is arranged on the lower part of the adsorption-biodegradation pool 16; a backwash pipe 3 is arranged on the bottom of the A pool 15 and the adsorption-biodegradation pool 16, and the backwash pipe 3 is connected with the power device through a pipeline, and a valve is arranged on the backwash pipe 3 between the A pool 15 and the adsorption-biodegradation pool 16; a pool C outlet pipe 11 is arranged on the upper part of the C pool 17, an inclined plate filler 10 is arranged in the C pool 17, and activated coke is arranged on the inclined plate filler 10, and a sludge hopper 12 is arranged on the bottom of the C pool 17, and the adsorption-biodegradation pool 16 is connected with the sludge hopper 12 through the sludge pipe 9, and a sludge discharge pipe 14 is arranged on the lower part of the sludge hopper 12, and the sludge discharge pipe 14 leads to the outside of the C pool 17.

[0025] The sludge and biofilm trapped by the zeolite filter material 2 and the stainless steel grid steel inclined plate 6 for a long time will cause the system to be blocked, and regular backwashing is also required. The A pool 15 and the adsorption-biodegradation pool 16 share a backwash pipe 3, which is separated by a valve and can be backwashed separately. The blower, pump and pipeline required for backwashing can be arranged nearby in the space below the supporting layer 4 and above the bottom of the A pool 15.

[0026] Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the zeolite filter material 2 is clinoptilolite with a particle size of 3 to 5 cm. The clinoptilolite is arranged between 1 / 2 of the water depth in pool A 15 and the supporting layer 4, and can adsorb a large amount of ammonia nitrogen in the wastewater.

[0027] The other steps are the same as those in the first specific implementation.

[0028] Specific implementation method 3: This implementation method is different from specific implementation method 1 or 2 in that: the nano-Fe 3 O 4 The loaded activated coke particles 7 were prepared according to the following steps: first, the activated coke was screened to obtain activated coke particles with a particle size of 1 to 3 cm; the activated coke particles, ferric chloride and ferrous sulfate were added to oxygen-free water saturated with nitrogen aeration, and then heated to 50°C under a nitrogen atmosphere, and stirred at a stirring speed of 120 r / min for 12 h, and then 150 mL of 15 mol / L ammonia water was added, and heated to 60°C under a nitrogen atmosphere, and shaken for 24 h, and finally, nano-Fe was obtained by magnetic decantation. 3 O 4 The activated coke particles 7 are loaded, wherein the mass ratio of the activated coke particles to ferric chloride is 1:6, and the mass ratio of the activated coke particles to ferrous sulfate is 1:5.

[0029] The other steps are the same as those in the first or second embodiment.

[0030] Specific implementation method 4: The difference between this implementation method and specific implementation methods 1 to 3 is that the power device is a backwash water pump, a blower or a gas tank.

[0031] The other steps are the same as those in Specific Embodiments 1 to 3.

[0032] Specific implementation method 5: This implementation method uses an adsorption combined with electroactive biofilm treatment device to treat phenol and ammonia pollutants in coal pyrolysis wastewater, and is carried out according to the following steps:

[0033] 1. The effluent from the anaerobic unit of coal pyrolysis wastewater is added to the A pool 15 through the A pool inlet pipe 1. The wastewater carries part of the sludge from the anaerobic unit and is fully mixed in the A pool 15. A large amount of free ammonia and ammonium ions in the water are adsorbed by the zeolite filter material 2 to obtain primary effluent. In this process, part of the anaerobic sludge with higher activity intercepted by the wastewater can accumulate and form a biofilm. The biofilm close to the water surface is easy to contact the oxygen dissolved in the water, and the nitrification reaction is carried out to convert part of the ammonium adsorbed by the zeolite and the influent into nitrate and nitrite. The biofilm close to the bottom of the pool is in anoxic and anaerobic state for a long time, and the nitrate and nitrite can be reduced to nitrogen gas through denitrification to complete biological denitrification.

[0034] Second, the primary effluent enters the adsorption-biodegradation tank 16 through the A tank outlet pipe 5, passes through the stainless steel grid steel inclined plate 6 and passes through the nano-Fe 3 O 4 The activated coke particles 7 can absorb a large amount of refractory phenols, polycyclic aromatic hydrocarbons and other organic substances, and can also intercept the sludge mixed in the wastewater, and then accumulate and domesticate the electroactive bacteria to form an electroactive biofilm, thereby degrading the adsorbed pollutants and releasing the adsorption sites, thus forming an adsorption-degradation cycle to obtain secondary effluent; when nano-Fe 3 O 4 After the activated coke particles 7 are trapped and enriched in the electrochemical bacterial group, the electrochemical biofilm formed can efficiently degrade nano-Fe in a micro-aerobic environment without aeration. 3 O 4 The activated coke particles 7 absorb the hard-to-degrade organic matter and release the easily degradable organic acid, thus accelerating the degradation cycle. During the degradation process, the electroactive bacteria consume the solid Fe on the activated coke particles and convert it into a free state. 3 O 4 When consumed to a certain extent, the activated coke particles will separate from the stainless steel grid steel inclined plate 6 and gradually slide to the bottom of the inclined plate. Therefore, it is necessary to discharge the sludge regularly through the sludge pipe 9 to clean up the invalid activated coke particles at the same time.

[0035] The effluent from the third and second levels enters the C pool 17 through the overflow weir 8 of the B pool. After separation by the inclined plate filler 10, most of the sludge flowing out with the water is intercepted, reducing the turbidity and SS in the effluent, replacing the secondary sedimentation tank of the conventional biochemical unit, and is discharged through the C pool outlet pipe 11 to complete the treatment of phenol-ammonia pollutants in the coal pyrolysis wastewater; since this embodiment is mainly based on the biofilm method, the suspended sludge content in the wastewater is low, the sludge production rate is low, the inclined plate has a high efficiency in separating sludge and water, and the zeolite and activated coke effectively absorb part of the chromaticity, the turbidity, chromaticity and SS of the effluent can be greatly reduced. The sludge in the C pool 17 and the failed activated coke that falls off the inclined plate filler 10 fall into the sludge hopper 12, and all the contents in the sludge hopper 12 are regularly discharged to the outside of the C pool 17 through the sludge discharge pipe 14.

[0036] Specific embodiment 6: The difference between this embodiment and specific embodiment 5 is that the zeolite filter material 2 is clinoptilolite with a particle size of 3 to 5 cm, and the clinoptilolite is arranged between 1 / 2 of the water depth in pool A 15 and the supporting layer 4 .

[0037] The other steps are the same as those in the fifth embodiment.

[0038] Specific implementation method 7: This implementation method is different from specific implementation methods 5 or 6 in that: the nano-Fe 3 O 4 The loaded activated coke particles 7 were prepared according to the following steps: first, the activated coke was screened to obtain activated coke particles with a particle size of 1 to 3 cm; the activated coke particles, ferric chloride and ferrous sulfate were added to oxygen-free water saturated with nitrogen aeration, and then heated to 50°C under a nitrogen atmosphere, and stirred at a stirring speed of 120 r / min for 12 h, and then 150 mL of 15 mol / L ammonia water was added, and heated to 60°C under a nitrogen atmosphere, and shaken for 24 h, and finally, nano-Fe was obtained by magnetic decantation. 3 O 4 The activated coke particles 7 are loaded, wherein the mass ratio of the activated coke particles to ferric chloride is 1:6, and the mass ratio of the activated coke particles to ferrous sulfate is 1:5.

[0039] The other steps are the same as those in the fifth or sixth embodiment.

[0040] Specific embodiment eight: The difference between this embodiment and specific embodiments five to seven is that the zeolite filter material 2 in the A pool 15 and the inclined plate filler 10 in the adsorption-biodegradation pool 16 are backwashed regularly by the backwash pipe 3 .

[0041] The other steps are the same as those in Specific Embodiments 5 to 7.

[0042] Specific embodiment 9: The difference between this embodiment and any one of specific embodiments 5 to 8 is that the power device used during backwashing is a backwashing water pump, a blower or a gas tank.

[0043] The other steps are the same as those in Specific Embodiments 5 to 8.

[0044] Specific embodiment ten: The difference between this embodiment and specific embodiments five to nine is that the inclined plate filler 10 is a honeycomb filler.

[0045] The other steps are the same as those in Specific Embodiments 5 to 9.

[0046] The following examples are used to verify the beneficial effects of the present invention:

[0047] Embodiment 1: An adsorption combined with electroactive biofilm treatment device, located below the ground 13, is a semi-underground combined structure, the treatment device comprises a pool A 15, an adsorption-biodegradation pool 16 and a pool C 17, the pool A 15 is composed of a pool A water inlet pipe 1, a zeolite filter material 2, a support layer 4 and a pool A water outlet pipe 5, the adsorption-biodegradation pool 16 is composed of a support layer 4, a stainless steel grid steel inclined plate 6, a nano-Fe 3 O 4 The loaded activated coke particles 7, the overflow weir of the B tank 8 and the sludge pipe 9 are composed of the C tank 17 which is composed of the inclined plate filler 10, the C tank outlet pipe 11, the sludge hopper 12 and the sludge discharge pipe 14;

[0048] A supporting layer 4 is provided at least 0.5 m above the bottom of the pool A 15 to support the zeolite filter material 2. An A pool water inlet pipe 1 is provided at the upper portion of the pool A 15. The pool A 15 is filled with the zeolite filter material 2. The zeolite filter material 2 is clinoptilolite with a particle size of 3 to 5 cm. The clinoptilolite is provided between 1 / 2 of the water depth in the pool A 15 and the supporting layer 4. A pool A outlet pipe 5 is provided at the lower part of the pool A 15, and the pool A 15 is connected with the adsorption-biodegradation pool 16 through the pool A outlet pipe 5; a supporting layer 4 is provided at the bottom of the adsorption-biodegradation pool 16, and the supporting layer 4 and the pool bottom of the pool A 15 and the adsorption-biodegradation pool 16 are located at the same height, and a stainless steel grid steel inclined plate 6 is obliquely provided in the adsorption-biodegradation pool 16, one end of the stainless steel grid steel inclined plate 6 is against the top of the adsorption-biodegradation pool 16 on the side adjacent to the pool A 15, and the other end of the stainless steel grid steel inclined plate 6 is against the top of the supporting layer 4 on the side adjacent to the pool C 17, and slits are evenly spaced on the stainless steel grid steel inclined plate 6 for water passing, and nano-Fe is provided at each interval of the slits. 3 O 4The activated coke particles are loaded and attached to the slits by magnetism; the upper part of the adsorption-biodegradation tank 16 is provided with a B tank overflow weir 8, and the lower part of the adsorption-biodegradation tank 16 is provided with a sludge pipe 9; the bottoms of the A tank 15 and the adsorption-biodegradation tank 16 are provided with a backwash pipe 3, and the backwash pipe 3 is connected to the power device through a pipeline, and the power device is a backwash water pump, a blower or a gas tank. A valve is provided on the backwash pipe 3 between the A tank 15 and the adsorption-biodegradation tank 16, and the backwash pipe 3 is located in the A tank 15. A certain space is reserved above the supporting layer 4 and between the supporting layer 4 and the bottom of the A pool 15 to install the required backwash water pump, blower or gas tank; a C pool outlet pipe 11 is arranged on the upper part of the C pool 17, an inclined plate filler 10 is arranged in the C pool 17, and activated coke is arranged on the inclined plate filler 10, a sludge hopper 12 is arranged at the bottom of the C pool 17, the adsorption-biodegradation pool 16 is connected to the sludge hopper 12 through the sludge pipe 9, and a sludge discharge pipe 14 is arranged at the lower part of the sludge hopper 12, and the sludge discharge pipe 14 leads to the outside of the C pool 17.

[0049] Example 2: A method for treating phenol-ammonia pollutants in coal pyrolysis wastewater using the adsorption combined with electroactive biofilm treatment device in Example 1 is carried out according to the following steps:

[0050] The effluent from the anaerobic unit of coal pyrolysis wastewater is added to the A pool 15 through the A pool inlet pipe 1, and after being adsorbed by the zeolite filter material 2, the primary effluent is obtained; the primary effluent enters the adsorption-biodegradation pool 16 through the A pool outlet pipe 5, passes through the stainless steel grid steel inclined plate 6 and passes through the nano-Fe 3 O 4 After the adsorption of the activated coke particles 7, the secondary effluent is obtained; the secondary effluent enters the C pool 17 through the overflow weir 8 of the B pool, and after separation by the inclined plate filler 10, it is discharged through the C pool outlet pipe 11, completing the treatment of phenol and ammonia pollutants in the coal pyrolysis wastewater; the sludge in the adsorption-biodegradation pool 16 and the nano-Fe ions shed from the stainless steel grid steel inclined plate 6 3 O 4 The loaded activated coke particles 7 flow into the sludge hopper 12 through the sludge pipe 9, and the sludge in the C tank 17 and the ineffective activated coke falling off the inclined plate filler 10 fall into the sludge hopper 12. The entire contents in the sludge hopper 12 are regularly discharged to the outside of the C tank 17 through the sludge discharge pipe 14. The zeolite filter material 2 in the A tank 15 and the inclined plate filler 10 in the adsorption-biodegradation tank 16 are regularly backwashed using the backwash pipe 3, and the power device used for backwashing is a backwashing water pump, a blower or a gas tank.

[0051] The zeolite filter material 2 is clinoptilolite with a particle size of 3 to 5 cm. The clinoptilolite is arranged between 1 / 2 of the water depth in pool A 15 and the supporting layer 4; the inclined plate filler 10 is a honeycomb filler.

[0052] The nano-Fe3 O 4 The loaded activated coke particles 7 were prepared according to the following steps: first, the activated coke was screened to obtain activated coke particles with a particle size of 1 to 3 cm; the activated coke particles, ferric chloride and ferrous sulfate were added to oxygen-free water saturated with nitrogen aeration, and then heated to 50°C under a nitrogen atmosphere, and stirred at a stirring speed of 120 r / min for 12 h, and then 150 mL of 15 mol / L ammonia water was added, and heated to 60°C under a nitrogen atmosphere, and shaken for 24 h, and finally, nano-Fe was obtained by magnetic decantation. 3 O 4 The activated coke particles 7 are loaded, wherein the mass ratio of the activated coke particles to ferric chloride is 1:6, and the mass ratio of the activated coke particles to ferrous sulfate is 1:5.

Claims

1. An adsorption combined with electroactive biofilm treatment device, located below the ground (13), is a semi-underground combined structure, characterized in that The treatment device comprises an A pool (15), an adsorption-biodegradation pool (16) and a C pool (17), wherein the A pool (15) is composed of an A pool water inlet pipe (1), a zeolite filter material (2), a support layer (4) and an A pool water outlet pipe (5), the adsorption-biodegradation pool (16) is composed of a support layer (4), a stainless steel grid steel inclined plate (6), nano-Fe3O4 loaded activated coke particles (7), a B pool overflow weir (8) and a sludge pipe (9), and the C pool (17) is composed of an inclined plate filler (10), a C pool water outlet pipe (11), a sludge hopper (12) and a sludge discharge pipe (14); A supporting layer (4) is arranged at the bottom of the A pool (15), an A pool water inlet pipe (1) is arranged at the top of the A pool (15), the A pool (15) is filled with zeolite filter material (2), an A pool water outlet pipe (5) is arranged at the bottom of the A pool (15), and the A pool (15) is connected with the adsorption-biodegradation pool (16) through the A pool water outlet pipe (5); a supporting layer (4) is arranged at the bottom of the adsorption-biodegradation pool (16), a stainless steel grid steel inclined plate (6) is arranged obliquely in the adsorption-biodegradation pool (16), one end of the stainless steel grid steel inclined plate (6) is against the top of the adsorption-biodegradation pool (16) on the side adjacent to the A pool (15), and the other end of the stainless steel grid steel inclined plate (6) is against the top of the supporting layer (4) on the side adjacent to the C pool (17), and nano-Fe3O4-loaded activated coke particles are evenly distributed on the stainless steel grid steel inclined plate (6), and the adsorption-biodegradation pool (16) is connected with the adsorption-biodegradation pool (16) through the A pool water outlet pipe (5). The upper part of the solution tank (16) is provided with an overflow weir (8) of the B tank, and the lower part of the adsorption-biodegradation tank (16) is provided with a sludge pipe (9); the bottoms of the A tank (15) and the adsorption-biodegradation tank (16) are provided with a backwash pipe (3), the backwash pipe (3) is connected to the power device through a pipeline, and a valve is provided on the backwash pipe (3) between the A tank (15) and the adsorption-biodegradation tank (16); the C tank (17 ) is provided with a C pool outlet pipe (11) at the top, an inclined plate filler (10) is provided in the C pool (17), activated coke is provided on the inclined plate filler (10), a sludge hopper (12) is provided at the bottom of the C pool (17), the adsorption-biodegradation pool (16) is connected to the sludge hopper (12) through a sludge pipe (9), a sludge discharge pipe (14) is provided at the bottom of the sludge hopper (12), and the sludge discharge pipe (14) leads to the outside of the C pool (17).

2. The adsorption combined with electroactive biofilm treatment device according to claim 1 is characterized in that The zeolite filter material (2) is clinoptilolite with a particle size of 3 to 5 cm. The clinoptilolite is arranged between 1 / 2 of the water depth in pool A (15) and the supporting layer (4).

3. The adsorption combined with electroactive biofilm treatment device according to claim 1, characterized in that The nano-Fe3O4-loaded activated coke particles (7) are prepared according to the following steps: first, the activated coke is screened to obtain activated coke particles with a particle size of 1 to 3 cm; the activated coke particles, ferric chloride and ferrous sulfate are added to oxygen-free water saturated with nitrogen aeration, and then heated to 50°C in a nitrogen atmosphere, and stirred at a stirring speed of 120 r / min for 12 hours, and then 150 mL of 15 mol / L ammonia water is added, and heated to 60°C in a nitrogen atmosphere, and shaken for 24 hours, and finally, nano-Fe3O4-loaded activated coke particles (7) are obtained by magnetic decantation, wherein the mass ratio of the activated coke particles to ferric chloride is 1:6, and the mass ratio of the activated coke particles to ferrous sulfate is 1:

5.

4. The adsorption combined with electroactive biofilm treatment device according to claim 1, characterized in that The power device is a backwash water pump, a blower or a gas tank.

5. A method for treating phenol-ammonia pollutants in coal pyrolysis wastewater using an adsorption combined with electroactive biofilm treatment device as claimed in claim 1, characterized in that The method proceeds as follows: The effluent from the anaerobic unit of coal pyrolysis wastewater is added to the A pool (15) through the A pool inlet pipe (1), and after being adsorbed by the zeolite filter material (2), a primary effluent is obtained; the primary effluent enters the adsorption-biodegradation pool (16) through the A pool outlet pipe (5), passes through the stainless steel grid steel inclined plate (6) and is adsorbed by the nano-Fe3O4 loaded activated coke particles (7), and a secondary effluent is obtained; the secondary effluent enters the C pool (17) through the B pool overflow weir (8), and after being separated by the inclined plate filler (10), it passes through the C pool The wastewater is discharged through the outlet pipe (11), completing the treatment of phenol-ammonia pollutants in the coal pyrolysis wastewater; the sludge in the adsorption-biodegradation tank (16) and the nano-Fe3O4-loaded activated coke particles (7) falling off from the stainless steel grid steel inclined plate (6) flow into the sludge hopper (12) through the sludge pipe (9); the sludge in the C tank (17) and the spent activated coke falling off from the inclined plate filler (10) fall into the sludge hopper (12), and all the contents in the sludge hopper (12) are regularly discharged to the outside of the C tank (17) through the sludge discharge pipe (14).

6. The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device according to claim 5, characterized in that The zeolite filter material (2) is clinoptilolite with a particle size of 3 to 5 cm. The clinoptilolite is arranged between 1 / 2 of the water depth in pool A (15) and the supporting layer (4).

7. The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device according to claim 5, characterized in that The nano-Fe3O4-loaded activated coke particles (7) are prepared according to the following steps: first, the activated coke is screened to obtain activated coke particles with a particle size of 1 to 3 cm; the activated coke particles, ferric chloride and ferrous sulfate are added to oxygen-free water saturated with nitrogen aeration, and then heated to 50°C in a nitrogen atmosphere, and stirred at a stirring speed of 120 r / min for 12 hours, and then 150 mL of 15 mol / L ammonia water is added, and heated to 60°C in a nitrogen atmosphere, and shaken for 24 hours, and finally, nano-Fe3O4-loaded activated coke particles (7) are obtained by magnetic decantation, wherein the mass ratio of the activated coke particles to ferric chloride is 1:6, and the mass ratio of the activated coke particles to ferrous sulfate is 1:

5.

8. The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device according to claim 5, characterized in that The zeolite filter material (2) in the A pool (15) and the inclined plate filler (10) in the adsorption-biodegradation pool (16) are backwashed regularly using the backwash pipe (3).

9. The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device according to claim 8, characterized in that The power device used for backwashing is a backwashing water pump, blower or gas tank.

10. The method for treating phenol-ammonia pollutants in coal pyrolysis wastewater by using an adsorption combined with electroactive biofilm treatment device according to claim 5, characterized in that The inclined plate filler (10) is a honeycomb filler.

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