CN110255827B - Antibiotic wastewater treatment process and system - Google Patents

Antibiotic wastewater treatment process and system Download PDF

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CN110255827B
CN110255827B CN201910612343.6A CN201910612343A CN110255827B CN 110255827 B CN110255827 B CN 110255827B CN 201910612343 A CN201910612343 A CN 201910612343A CN 110255827 B CN110255827 B CN 110255827B
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composite bed
bed reactor
anaerobic composite
reactor
upflow anaerobic
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CN110255827A (en
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王昊
卢欢
薄国柱
钟卉元
杨永
罗莉涛
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North China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2866—Particular arrangements for anaerobic reactors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms

Abstract

The invention belongs to the field of sewage treatment, and particularly relates to a treatment process of antibiotic wastewater and a system used in the wastewater treatment process. The process of the invention comprises the following steps: (1) pumping the antibiotic wastewater from a water inlet tank into an upflow anaerobic composite bed reactor through a peristaltic pump for anaerobic treatment; (2) and (3) conveying the water after anaerobic treatment in the step (1) to an electrochemical reactor for continuous treatment, and then discharging the water through a second water outlet. The invention has the beneficial effects that: the method and the system of the invention are adopted to treat the antibiotic wastewater, thus shortening the treatment period of the antibiotic wastewater; the power consumption is low, and the cost is saved; the system is stable in operation, and the removal rate of CO D cr and ammonia nitrogen is kept in a certain interval range; the removal rate of CO D cr and ammonia nitrogen reaches more than 90 percent, and the treatment effect is good.

Description

Antibiotic wastewater treatment process and system
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a treatment process of antibiotic wastewater and a system used in the wastewater treatment process.
Background
Antibiotics are organic substances produced by organisms, including microorganisms, plants and animals (or obtained by other means) during their life activities that selectively inhibit or affect their biological functions at low microbial concentrations. China is a large country for using antibiotics and a large country for producing antibiotics. The antibiotic wastewater has the characteristics of complex components, poor biodegradability, deep chromaticity, high toxicity, high CODcr, SS and ammonia nitrogen, difficult degradation and the like. The anaerobic biological treatment technology has the advantages of high load, less sludge production and higher economic benefit, and can be used for treating organic wastewater with high concentration and difficult degradation. However, the anaerobic biological treatment technology has the disadvantages of long start-up time and difficult discharge requirement: when a single UBF reactor is used for treating antibiotic wastewater, the COD of inlet water is 9000-10000 mg/L, the removal rate of COD can reach 91.7%, but the treated COD outlet water still can reach 700-800 mg/L, so that further treatment is needed. The electrocatalytic oxidation technology has the characteristics of high treatment efficiency and no generation of new pollutants in the treatment process. The electrochemical oxidation technology introduces a catalyst, and can improve the degradation rate and efficiency to a certain extent. When the electrocatalytic oxidation technology is used for treating antibiotic wastewater, the degradation time is 3h, COD can be degraded from 450mg/L to 40mg/L, the removal rate reaches more than 91%, the lower the COD is, the shorter the degradation time is, the less the power consumption is, and the cost can be effectively saved.
Regarding the treatment process of antibiotic wastewater, the following patent/patent application documents are disclosed:
CN 108558003A is a method and a device for removing multiple pollutants in antibiotic wastewater by using two-stage MBR, which adopts a two-stage anaerobic MBR device to treat antibiotic wastewater. The disadvantage is also that there is a problem that the treatment time is long, and there are also the following problems: the water treated by the anaerobic biological treatment technology cannot meet the requirement of direct discharge and needs to be further treated.
CN 106745532A antibiotic wastewater treatment method is characterized by comprising the following steps:
(1) taking a certain amount of filled particle electrode, which may be Fe3O4One of titanium foam, activated carbon, ceramic, zeolite, kaolin, carbon nanofiber, graphene, carbon aerogel and the like. After the sequential treatment, the mixture is charged into an electro-catalytic oxidation device. Adjusting pH, controlling air flow, reacting for a certain time, and sampling for analysis.
(2) The bottom of the tank body of the electrocatalytic oxidation device is provided with evenly distributed thin pipes, and holes are formed in the bottom of the tank body so as to ensure even water distribution and air inlet. The anode is Ti/SnO2The cathode is a stainless steel plate electrode, and electrode plates are fixed on the groove bodies on two sides.
The above patents employ electrocatalytic oxidation tanks to treat antibiotic wastewater. The disadvantages are that the electric catalytic oxidation device is only used for treating the wastewater, the power consumption is large, and the treatment cost is high.
Therefore, it is necessary to improve the above-mentioned drawbacks and invent a wastewater treatment method which can effectively treat antibiotic wastewater and has low power consumption and low cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a wastewater treatment process which can effectively treat antibiotic wastewater and has low power consumption and low cost;
the invention also provides a system used in the process;
the antibiotic wastewater treatment process mainly comprises the following steps:
(1) inoculating granular sludge under an aerobic condition until filamentous bacteria are propagated, transferring the inoculated granular sludge into an upflow anaerobic composite bed reactor to form a granular sludge layer, laying a suspended sludge layer on the granular sludge layer, and then laying a filler layer polyurethane foam; introducing oxygen into the upflow anaerobic composite bed reactor through a first circulation port and a second circulation port on the upflow anaerobic composite bed reactor, and controlling the dissolved oxygen in the upflow anaerobic composite bed reactor to be 1-3 mg/L; the film amount reaches 3-5 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment;
(2) conveying the nutrient solution into an up-flow anaerobic composite bed reactor, and controlling the COD (chemical oxygen demand) of the nutrient solution to be 800-1200 mg/L and the pH value to be 6.5-7.5; the nutrient solution sequentially passes through a granular sludge layer, a suspended sludge layer and a polyurethane foam packing layer in the upflow anaerobic composite bed reactor, and the retention time of the nutrient solution in the upflow anaerobic composite bed reactor is 22-26 h;
then, pumping the antibiotic wastewater from a water inlet tank to an up-flow anaerobic composite bed reactor through a peristaltic pump for anaerobic treatment, wherein the feed water quality CODcr of the antibiotic wastewater is 6400-6600 mg/L, the ammonia nitrogen is 120-130 mg/L and the pH is 6.5-7.5, the feed water flow is controlled to be 0.3-0.5L/h, and the organic load is 1-3 kgCOD/m3D, continuously feeding water for 3-5 hours;
regularly detecting the sludge concentration and the biofilm formation amount of the packing layer from the sampling port, and after the sludge concentration and the biofilm formation amount are stable, conveying the sludge to the upflow anaerobic composite bed reactor for dilution to different degreesThe multiple of antibiotic wastewater is improved to 1-2 kgCOD/m by controlling the influent COD concentration3D until CODcr and ammonia nitrogen removal rates stabilize;
(3) and (3) conveying the wastewater subjected to anaerobic treatment in the step (1) to an electrochemical reactor through a first water outlet, treating the wastewater by using hydrogen peroxide as a catalyst, and discharging the wastewater through a second water outlet.
Preferably, in the step (1), the height ratio of the granular sludge layer to the suspended sludge layer to the polyurethane foam packing layer is as follows: 3: 3: 4.
the height ratio of the granular sludge layer to the upflow anaerobic composite bed reactor is 1: 6.
(1) in the middle, the amount of the film to be hung reaches 4 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment.
(2) Conveying the nutrient solution into an upflow anaerobic composite bed reactor, and controlling the COD (chemical oxygen demand) of the nutrient solution to be 1000mg/L and the pH value to be 7; the nutrient solution sequentially passes through the granular sludge layer, the suspended sludge layer and the polyurethane foam packing layer in the reaction, and the retention time in the up-flow anaerobic composite bed reactor is 24 hours;
then pumping the antibiotic wastewater from a water inlet tank into an up-flow anaerobic composite bed reactor by a peristaltic pump for anaerobic treatment, wherein the feed water quality CODcr of the antibiotic wastewater is 6500mg/L, the ammonia nitrogen is 125mg/L and the pH is 7, the feed water flow is controlled to be 0.4L/h, and the organic load is 1.5kgCOD/m3D, continuously feeding water for 4 hours; introducing oxygen into the upflow anaerobic composite bed reactor through a first circulation port and a second circulation port on the upflow anaerobic composite bed reactor, and controlling the dissolved oxygen of the water in the upflow anaerobic composite bed reactor to be 2 mg/L;
detecting the sludge concentration and the biofilm formation amount of the packing layer from a sampling port regularly, and after the sludge concentration and the biofilm formation amount are stable, conveying the antibiotic wastewater diluted to different times into an upflow anaerobic composite bed reactor; the increase gradient of the organic load is 1.5kgCOD/m by controlling the COD concentration of the inlet water3D; until the CODcr and ammonia nitrogen removal rate are stable.
(3) In the method, the mass concentration of the hydrogen peroxide is 26-30%, and the dosage of the hydrogen peroxide is 0.1-0.3% of the volume of the wastewater body;
preferably, in the step (3), the mass concentration of the hydrogen peroxide is 28%, and the dosage of the hydrogen peroxide is 0.2% of the volume of the wastewater body.
The system for the antibiotic wastewater treatment process comprises the following structures:
the system comprises a water inlet tank, wherein the water inlet tank is connected with a water inlet of an up-flow anaerobic composite bed reactor through a pipeline, and a granular sludge layer, a suspended sludge layer and a packing layer are sequentially arranged in the up-flow anaerobic composite bed reactor from bottom to top; a sampling port is arranged on the left side of the upflow anaerobic composite bed reactor, an exhaust port is arranged at the upper top of the upflow anaerobic composite bed reactor, and a sealing cover corresponding to the exhaust port is arranged at the exhaust port;
a first circulation port is arranged at the lower bottom of the upflow anaerobic composite bed reactor close to the right end, and a second circulation port is arranged at the right end of the middle lower part of the upflow anaerobic composite bed reactor;
the first water outlet at the upper part of the upflow anaerobic composite bed reactor is connected with an electrochemical reactor through a pipeline, an electrode is arranged in the electrochemical reactor and is connected with a power supply device, and the right side of the electrochemical reactor is provided with a second water outlet.
The upflow anaerobic composite bed reactor is a cylindrical organic glass container, and the ratio of the diameter to the height of the upflow anaerobic composite bed reactor is 1: 6, the ratio of the wall thickness to the diameter is 1: 20; the sampling port is arranged at the 2/3 height from top to bottom at the left end of the upflow anaerobic composite bed reactor; the first water outlet is arranged at the 1/12 height from top to bottom on the right side of the upflow anaerobic composite bed reactor; the central position department of upflow anaerobic composite bed reactor upper cover has circular gas vent, and the diameter ratio of the diameter of gas vent and upflow anaerobic composite bed reactor cross section is: 1: 5.
the electrochemical reactor is a square container, and the length, width and height ratio of the electrochemical reactor is as follows: 16: 15: 16, a second water outlet is arranged at the height 1/8 of the electrochemical reactor from bottom to top, the pipe diameter of a water outlet pipe connected with the second water outlet is 1/50 of the width of the electrochemical reactor, and the length of the water outlet pipe is 2/15 of the width of the electrochemical reactor.
The electrode material comprises an anode and a cathodeThe anode is SnO2-Sb/Ti, the cathode is made of stainless steel material.
The invention has the beneficial effects that:
(1) the invention adopts the UBF reactor and the electrocatalytic oxidation device to jointly act on the antibiotic wastewater, thereby shortening the treatment period of the antibiotic wastewater;
(2) the antibiotic wastewater treated by the device and the process of the invention meets the discharge requirement;
(3) in consideration of energy consumption and cost saving, the UBF reactor is adopted for pretreatment, and then the UBF reactor is combined with the electrocatalytic oxidation device for treatment, so that compared with the method of singly adopting electrocatalytic oxidation to treat the antibiotic wastewater, the method greatly saves the power consumption, greatly reduces the power consumption of the effluent of the electrocatalytic oxidation treatment reactor, and saves the cost;
(4) the system of the invention has stable operation, and the removal rate of CODcr and ammonia nitrogen is kept in a certain interval range;
(5) the removal rate of CODcr and ammonia nitrogen of the effluent of the UBF reactor in stable operation of the antibiotic wastewater treated by the device and the process reaches 54 percent and 65 percent, the removal rate of CODcr and ammonia nitrogen of the effluent after electrocatalytic oxidation reaches more than 90 percent, and the treatment effect is good.
Drawings
FIG. 1 is a schematic structural diagram of a system according to embodiment 1A of the present invention;
in the figure, 1-a water inlet tank, 2-a peristaltic pump, 3-a water inlet, 31-a sampling port, 32-a packing layer, 33-suspended sludge, 34-granular sludge, 4-a UBF reactor, 5-an exhaust port, 6-a first water outlet, 7-a second circulation port, 8-a first circulation port, 9-a circulation pump, 10-a power supply device, 11-an electrode, 12-an electrochemical reactor and 13-a second water outlet.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
Example 1A
The structure schematic diagram of the device of the invention is shown in the attached figure 1, and the specific structure is as follows:
the system comprises a water inlet tank 1, wherein the water inlet tank 1 is connected with a water inlet 3 of an up-flow anaerobic composite bed reactor 4 (hereinafter referred to as UBF reactor) through a pipeline, and a granular sludge layer 34, a suspended sludge layer 33 and a packing layer 32 are sequentially arranged in the up-flow anaerobic composite bed reactor 4 from bottom to top;
a first circulation port 8 is arranged at the lower bottom of the upflow anaerobic composite bed reactor 4 close to the right end, and a second circulation port 7 is arranged at the middle lower part of the right side of the upflow anaerobic composite bed reactor 4;
the upflow anaerobic composite bed reactor 4 is a cylindrical organic glass container, and the ratio of the diameter to the height of the reactor is 1: 6, the ratio of the wall thickness to the diameter is 1: 20; the sampling port 31 is arranged at the 2/3 height from top to bottom at the left end of the upflow anaerobic composite bed reactor 4; a first water outlet 6 is arranged at the 1/12 height from top to bottom at the right end of the upflow anaerobic composite bed reactor 4; the central point department of the upper cover of the upper portion of upflow anaerobic composite bed reactor 4 has circular shape gas vent 5, and gas vent 5 is located the central point department of the upper cover of upflow anaerobic composite bed reactor 4, and the diameter ratio of the diameter of gas vent 5 and the cross section of upflow anaerobic composite bed reactor 4 is: 1: 5;
the first water outlet 6 at the upper part of the upflow anaerobic composite bed reactor 4 is connected with an electrochemical reactor 12 through a pipeline, an electrode 11 is arranged in the electrochemical reactor 12, the electrode 11 is connected with a power supply device 10, and a second water outlet 13 is arranged at one side of the electrochemical reactor 12.
The electrochemical reactor 12 is a square container with a length to width ratio of: 16: 15: 16, a second water outlet 13 is arranged at the height 1/8 from bottom to top on the electrochemical reactor 12, the pipe diameter of a water outlet pipe connected with the second water outlet 13 is 1/50 of the width of the electrochemical reactor 12, and the length is 2/15 of the width of the electrochemical reactor 12. The anode of the electrode material is SnO2-Sb/Ti, the cathode is made of stainless steel material.
Example 1B
Compared with example 1, example 1B is a pilot plant test case in a specific industrial production, and specifically as follows:
the UBF reactor 4 is a cylindrical barrel-shaped organic glass reactor, the diameter of which is 100mm, the height of which is 600mm and the wall thickness of which is 5 mm; a water inlet 3 at the bottom of a UBF reactor 4 is communicated with a water inlet tank 1 through a pipeline, a sampling port 31 is arranged at the position 200mm away from the bottom of the UBF reactor 4 at the left end of the UBF reactor 4, a circulating port 2 is arranged at the position 200mm away from the bottom of the UBF reactor 4 at the right end of the UBF reactor, a first water outlet 6 is arranged at the position 50mm away from the top end of the UBF reactor 4, an upper cover is arranged at the top of the UBF reactor 4, a circular exhaust port 5 is arranged at the central position of the upper cover, and the diameter of the upper cover is 100 mm;
the bottom of the UBF reactor 4 is a mature granular sludge layer 34 (granular sludge layer treated in the step (1) in the example 1) in the UASB reactor, the height of the mature granular sludge layer is 120mm, the upper layer of the granular sludge layer 34 is laid on a return sludge layer 33 (namely a suspended sludge layer) in a secondary sedimentation tank of a sewage plant, the height of the return sludge layer is 120mm, and the upper part of the granular sludge layer is laid on a polyurethane foam packing layer 32, and the height of the granular sludge layer is 160 mm;
the electrochemical reactor 12 is a square container, and the length, width and height thereof are respectively as follows: 160mm, 150mm and 160mm, a second water outlet 13 is arranged at the position of the electrochemical reactor 12 with the height of 20mm from bottom to top, and a water outlet pipe connected with the second water outlet 13 has the pipe diameter of 3mm and the length of 20 mm.
Example 1C
In the specific operation of the system in embodiment 1, the principle is as follows:
the fast start of the UBF reactor 4 mainly depends on the speed of the film forming speed and the amount of the film forming amount, in order to improve the start efficiency of the reactor, the invention adopts an aerobic sludge inoculation mode to lead filamentous bacteria to be fast propagated, the inoculated sludge is moved into the UBF reactor 4, and after the film forming is stable, nitrogen is introduced to lead the previous aerobic environment to be converted into an anaerobic environment. The aerobic inoculated strain is a conventional strain. The carrier of the strain is common activated sludge, namely the strain in the activated sludge is adopted, and the inoculation volume of the sludge is 25 percent.
The antibiotic wastewater enters the UBF reactor 4 to be subjected to anaerobic treatment, and the wastewater subjected to the anaerobic treatment cannot meet the requirement of direct discharge and needs to be further treated continuously; the invention adopts electrocatalytic oxidation to further treat the effluent in the UBF reactor 4, uses hydrogen peroxide as a catalyst, and utilizes a polar plate to carry out electrocatalytic oxidation treatment on the wastewater, so that the wastewater not only can be effectively treated to reach the standard of direct discharge, but also can reduce high energy consumption and high cost caused by single use of electrocatalytic oxidation treatment.
Example 2
The system in example 1 is used for treating antibiotic wastewater (the following examples and comparative examples, without specific description, refer to the treatment by the system in example 1), and the treatment process of antibiotic wastewater mainly comprises the following steps:
(1) inoculating granular sludge under aerobic conditions until filamentous bacteria are propagated, transferring the inoculated granular sludge into an up-flow anaerobic composite bed reactor 4 to form a granular sludge layer 34, paving a suspended sludge layer 33 on the granular sludge layer 34, wherein the suspended sludge layer 33 is return sludge in a secondary sedimentation tank of a sewage plant; then laying a filler layer polyurethane foam 32; the film amount reaches 4 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment;
(2) the nutrient solution is conveyed to an upflow anaerobic composite bed reactor 4, the COD of the nutrient solution is controlled to be 1000mg/L, and the pH of the nutrient solution is controlled to be 7; the nutrient solution sequentially passes through the granular sludge layer 34, the suspended sludge layer 33 and the polyurethane foam packing layer 32 in the reaction, and the retention time in the upflow anaerobic composite bed reactor 4 is 24 hours;
then pumping the antibiotic wastewater from a water inlet tank 1 to an up-flow anaerobic composite bed reactor 4 by a peristaltic pump for anaerobic treatment, controlling the influent water quality CODcr of the antibiotic wastewater to be 6500mg/L, the ammonia nitrogen to be 125mg/L and the pH to be 7, controlling the influent water flow to be 0.4L/h and the organic load to be 2kgCOD/m3D, continuously feeding water for 4 hours; oxygen is introduced into the upflow anaerobic composite bed reactor 4 through a first circulation port 8 and a second circulation port 7 on the upflow anaerobic composite bed reactor 4, and the water dissolved oxygen of the upflow anaerobic composite bed reactor 4 is controlled to be 2 mg/L;
regularly detecting the sludge concentration and the biofilm formation amount of the packing layer from the sampling port 31, and after the sludge concentration and the biofilm formation amount are stable, replacing the inlet water with the antibiotic wastewater diluted to different times; the increase gradient of the organic load is 2kgCOD/m by controlling the COD concentration of the inlet water3D; until the removal rate of CODcr and ammonia nitrogen is stable;
(3) conveying the water after anaerobic treatment in the step (1) to an electrochemical reactor, treating the water by taking hydrogen peroxide as a catalyst, and discharging the water through a second water outlet 13; the mass concentration of the hydrogen peroxide is 28 percent, and the dosage of the hydrogen peroxide is 0.2 percent of the volume of the wastewater body.
Example 3
The antibiotic wastewater treatment process mainly comprises the following steps:
(1) inoculating granular sludge under aerobic conditions until filamentous bacteria are propagated, transferring the inoculated granular sludge into an up-flow anaerobic composite bed reactor 4 to form a granular sludge layer 34, paving a suspended sludge layer 33 on the granular sludge layer 34, wherein the suspended sludge layer 33 is return sludge in a secondary sedimentation tank of a sewage plant; then laying a filler layer polyurethane foam 32; the film amount reaches 3.5 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment;
(2) the nutrient solution is conveyed to an upflow anaerobic composite bed reactor 4, the COD of the nutrient solution is controlled to be 900mg/L, and the pH value is controlled to be 6.8; the nutrient solution sequentially passes through the granular sludge layer 34, the suspended sludge layer 33 and the polyurethane foam packing layer 32 in the reaction, and the retention time in the upflow anaerobic composite bed reactor 4 is 24 hours;
then pumping the antibiotic wastewater from a water inlet tank 1 to an up-flow anaerobic composite bed reactor 4 for anaerobic treatment by a peristaltic pump, controlling the influent water quality CODcr of the antibiotic wastewater to be 6400mg/L, the ammonia nitrogen to be 120mg/L and the pH to be 7.2, controlling the influent water flow to be 0.35L/h and the organic load to be 2kgCOD/m3D, continuously feeding water for 4 hours; oxygen is introduced into the upflow anaerobic composite bed reactor 4 through a first circulation port 8 and a second circulation port 7 on the upflow anaerobic composite bed reactor 4, and the water dissolved oxygen of the upflow anaerobic composite bed reactor 4 is controlled to be 1.8 mg/L;
regularly detecting the sludge concentration and the biofilm formation amount of the packing layer from the sampling port 31, and after the sludge concentration and the biofilm formation amount are stable, replacing the inlet water with the antibiotic wastewater diluted to different times; the increase gradient of the organic load is 1.8kgCOD/m by controlling the COD concentration of the inlet water3D; until the removal rate of CODcr and ammonia nitrogen is stable;
(3) conveying the water after anaerobic treatment in the step (1) to an electrochemical reactor, treating the water by taking hydrogen peroxide as a catalyst, and discharging the water through a second water outlet 13; the mass concentration of the hydrogen peroxide is about 27 percent, and the dosage of the hydrogen peroxide is about 0.25 percent of the volume of the wastewater body.
Example 4
The antibiotic wastewater treatment process mainly comprises the following steps:
(1) inoculating granular sludge under aerobic conditions until filamentous bacteria are propagated, transferring the inoculated granular sludge into an up-flow anaerobic composite bed reactor 4 to form a granular sludge layer 34, paving a suspended sludge layer 33 on the granular sludge layer 34, wherein the suspended sludge layer 33 is return sludge in a secondary sedimentation tank of a sewage plant; then the polyurethane foam 32 of the filler layer is paved until the film hanging amount reaches 4g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment;
(2) the nutrient solution is conveyed to an upflow anaerobic composite bed reactor 4, the COD of the nutrient solution is controlled to be 1100mg/L, and the pH of the nutrient solution is controlled to be 7.2; the nutrient solution sequentially passes through the granular sludge layer 34, the suspended sludge layer 33 and the polyurethane foam packing layer 32 in the reaction, and the retention time in the upflow anaerobic composite bed reactor 4 is 24 hours;
then the antibiotic wastewater is pumped from a water inlet tank 1 to an up-flow anaerobic composite bed reactor 4 by a peristaltic pump for anaerobic treatment, the influent water quality CODcr of the antibiotic wastewater is 6600mg/L, the ammonia nitrogen is 125mg/L and the pH is 7.2, the influent water flow is controlled to be 0.4L/h, and the organic load is 2.4kgCOD/m3D, continuously feeding water for 4 hours; oxygen is introduced into the upflow anaerobic composite bed reactor 4 through a first circulation port 8 and a second circulation port 7 on the upflow anaerobic composite bed reactor 4, and the water dissolved oxygen of the upflow anaerobic composite bed reactor 4 is controlled to be 2 mg/L;
regularly detecting the sludge concentration and the biofilm formation amount of the packing layer from the sampling port 31, and after the sludge concentration and the biofilm formation amount are stable, replacing the inlet water with the antibiotic wastewater diluted to different times; the increase gradient of the organic load is 2.1kgCOD/m by controlling the COD concentration of the inlet water3D; until the removal rate of CODcr and ammonia nitrogen is stable;
(3) conveying the water after anaerobic treatment in the step (1) to an electrochemical reactor, treating the water by taking hydrogen peroxide as a catalyst, and discharging the water through a second water outlet 13; the volume concentration of the hydrogen peroxide is about 28 percent, and the dosage of the hydrogen peroxide is about 0.2 percent of the volume of the wastewater body.
Comparative example 1
The difference from example 2 is that in (1) of comparative example 1, only the seeded granular sludge was transferred to the upflow anaerobic composite bed reactor 4 in the upflow anaerobic composite bed reactor 4 to form a granular sludge blanket 34; then, a filler layer polyurethane foam 32 is laid; the rest is the same as the embodiment 2, and the concrete is as follows:
(1) inoculating granular sludge under aerobic conditions until filamentous bacteria are propagated, and then transferring the inoculated granular sludge to an up-flow anaerobic composite bed reactor 4 to form a granular sludge layer 34; the film amount reaches 4 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment.
Comparative example 2
The difference from example 2 is that the antibiotic wastewater is not treated in the UBF reactor in the first step, but is directly treated in the electrochemical reactor 12, treated with hydrogen peroxide as a catalyst, and then discharged through the second water outlet.
Comparative example 3
The difference from the example 2 is that the influent water quality CODcr of the antibiotic wastewater is higher than that of the example 2; the rest is the same as the embodiment 2, and the concrete is as follows:
the influent water quality CODcr of the antibiotic wastewater is 14000mg/L, the ammonia nitrogen is 125mg/L and the pH is 7, the influent flow is controlled to be 0.4L/h, and the organic load is 2kgCOD/m3D, continuously feeding water for 4 hours; oxygen is introduced into the upflow anaerobic composite bed reactor through a first circulation port and a second circulation port on the upflow anaerobic composite bed reactor, and the dissolved oxygen in the upflow anaerobic composite bed reactor is controlled to be 2 mg/L.
TABLE 1 comparative treatment effect of examples and comparative examples
Figure GDA0002143421210000141
Figure GDA0002143421210000151
From the data in the tables, it can be seen that the CODcr removal rate of the water discharged from the first water outlet of the water treated by the process in the embodiments 2-4 of the invention reaches about 54%, and the ammonia nitrogen removal rate reaches about 65%; the CODcr removal rate of the water discharged from the second water outlet reaches about 98%, and the ammonia nitrogen removal rate reaches about 96%.
In comparative example 1, only one particle layer was used in the UBF reactor, with the result that the water discharged from the first water outlet had a CODcr removal rate of about 42% and an ammonia nitrogen removal rate of about 43.4%; the removal rate of CODcr of the water body discharged from the second water outlet is about 87.9%, and the removal rate of ammonia nitrogen is about 88.1%, which is not the same as that of the method in the embodiment 2;
in comparative example 2, the treatment effect is far inferior to that of example 1 only after the treatment of the primary electrochemical reactor 12, and the CODcr removal rate and the ammonia nitrogen removal rate of the water discharged from the second water outlet are both about 60% after detection; the requirement of direct discharge of water bodies cannot be met, and the energy consumption is high.
In comparative example 3, the water discharged from the first water outlet is detected, the CODcr removal rate% and the ammonia nitrogen removal rate are respectively 50.5% and 58.7%, and the treatment effect is inferior to that of example 2; and the CODcr removal rate and the ammonia nitrogen removal rate in the second water outlet are respectively 91.6% and 92.5%, which is also poorer than that of the embodiment 2.
Table 2 shows the comparison of the treatment effect and economic benefit using a single UBF reactor and a single electrocatalytic oxidation and combined process, and it can be seen from the contents and data listed in the table that the treatment effect of the process of the present invention is sufficient to meet the emission standards and the economic benefit is acceptable.
TABLE 2 comparison of the treatment effects of the Single Process and the Combined Process
Figure GDA0002143421210000161
According to the wastewater characteristics of the antibiotic wastewater and the treatment effect of the conventional antibiotic wastewater treatment process, the win-win effect and economic benefit are difficult to achieve only by adopting a single method, so that the method for treating the antibiotic wastewater by combining the UBF reactor treatment and the electrocatalytic oxidation provides a new idea for treating the antibiotic wastewater. Combines the advantages and disadvantages of anaerobic biological treatment and electrocatalytic oxidation and the characteristics of antibiotic wastewater, so a two-stage combined treatment process is provided. That is, the present invention is directed to a process for treating antibiotic wastewater with high efficiency, and a single UBF anaerobic biological treatment and a single electrocatalytic oxidation are results that cannot achieve the high efficiency treatment effect and economic efficiency of a two-stage combined treatment process. At present, the combined process is not proposed, so that the secondary combined treatment process has innovation.

Claims (10)

1. The antibiotic wastewater treatment process is characterized by mainly comprising the following steps of:
(1) inoculating granular sludge under an aerobic condition until filamentous bacteria are propagated, transferring the inoculated granular sludge into an up-flow anaerobic composite bed reactor (4) to form a granular sludge layer (34), paving a suspended sludge layer (32) on the granular sludge layer (34), and paving a filler layer of polyurethane foam; introducing oxygen into the upflow anaerobic composite bed reactor (4) through a first circulation port (8) and a second circulation port (7) on the upflow anaerobic composite bed reactor (4), and controlling the dissolved oxygen in the upflow anaerobic composite bed reactor (4) to be 1-3 mg/L; the film amount reaches 3-5 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment;
(2) conveying the nutrient solution to an up-flow anaerobic composite bed reactor (4), and controlling COD = 800-1200 mg/L and pH = 6.5-7.5; the nutrient solution sequentially passes through a granular sludge layer (34), a suspended sludge layer (33) and a polyurethane foam packing layer (32) in the upflow anaerobic composite bed reactor (4), and the retention time of the nutrient solution in the upflow anaerobic composite bed reactor (4) is 22-26 h;
then, pumping the antibiotic wastewater from the water inlet tank (1) to an up-flow anaerobic composite bed reactor (4) through a peristaltic pump for anaerobic treatment, wherein the influent water quality CODcr = 6400-6600 mg/L, the ammonia nitrogen is 120-130 mg/L and the pH = 6.5-7.5 of the antibiotic wastewater, the influent water flow is controlled to be 0.3-0.5L/h, the organic load is 1-3 kgCOD/m and the year.d, and the continuous influent water is fed for 3-5 h;
regularly detecting the sludge concentration and the biofilm formation amount of the packing layer from a sampling port (31), after the sludge concentration and the biofilm formation amount are stable, conveying the antibiotic wastewater diluted to different times into an upflow anaerobic composite bed reactor (4), and controlling the COD concentration of the influent water to enable the improvement gradient of the organic load to be 1-2 kgCOD/m for carrying out year d until the CODcr and the ammonia nitrogen removal rate are stable;
(3) and (3) conveying the wastewater subjected to anaerobic treatment in the upflow anaerobic composite bed reactor in the step (2) to an electrochemical reactor through a first water outlet (6), treating the wastewater by using hydrogen peroxide as a catalyst, and discharging the wastewater through a second water outlet (13).
2. The process for treating antibiotic wastewater as claimed in claim 1, wherein:
in the step (1), the height ratio of the granular sludge layer (34), the suspended sludge layer (33) and the polyurethane foam packing layer (32) is as follows: 3: 3: 4.
3. the process for treating antibiotic wastewater as claimed in claim 1, wherein: the height ratio of the granular sludge layer (34) to the upflow anaerobic composite bed reactor (4) in the step (1) is 1: 6.
4. the process for treating antibiotic wastewater as claimed in claim 1, wherein:
in the step (1), oxygen is introduced into the upflow anaerobic composite bed reactor (4) through a first circulation port (8) and a second circulation port (7) on the upflow anaerobic composite bed reactor (4), and the dissolved oxygen of water in the upflow anaerobic composite bed reactor (4) is controlled to be 2 mg/L; the film amount reaches 4 g.g-1And after stabilization, nitrogen is introduced to convert the previous aerobic environment into anaerobic environment.
5. The process for treating antibiotic wastewater as claimed in claim 1, wherein:
in the step (2), the nutrient solution is conveyed to an upflow anaerobic composite bed reactor (4), and the COD =1000mg/L and the pH =7 are controlled; the nutrient solution sequentially passes through a granular sludge layer (34), a suspended sludge layer (33) and a polyurethane foam packing layer (32) in the reaction, and the retention time in the up-flow anaerobic composite bed reactor (4) is 24 hours;
then, pumping the antibiotic wastewater from the water inlet tank (1) to an up-flow anaerobic composite bed reactor (4) for anaerobic treatment by a peristaltic pump, wherein the influent water quality CODcr =6500mg/L, the ammonia nitrogen is 125mg/L and the pH =7 of the antibiotic wastewater, the influent water flow is controlled to be 0.4L/h, the organic load is 1.5kgCOD/m and the year d, and the continuous influent water is carried out for 4 h;
the sludge concentration and the biofilm formation amount of the packing layer are regularly detected from the sampling port (31), and after the sludge concentration and the biofilm formation amount are stable, the antibiotic wastewater diluted to different times is conveyed into the upflow anaerobic composite bed reactor (4); by controlling the COD concentration of the inlet water, the gradient of the increase of the organic load is 1.5kgCOD/m and D; until the CODcr and ammonia nitrogen removal rate are stable.
6. The process for treating antibiotic wastewater as claimed in claim 1, wherein:
in the step (3), the mass concentration of the hydrogen peroxide is 26-30%, and the dosage of the hydrogen peroxide is 0.1-0.3% of the volume of the wastewater body.
7. The system for use in a process for the treatment of antibiotic wastewater as set forth in claim 1, wherein:
the system comprises a water inlet tank (1), wherein the water inlet tank (1) is connected with a water inlet (3) of an up-flow anaerobic composite bed reactor (4) through a pipeline, and a granular sludge layer (34), a suspended sludge layer (33) and a polyurethane foam packing layer (32) are sequentially arranged in the up-flow anaerobic composite bed reactor (4) from bottom to top; a sampling port (31) is arranged on the left side of the upflow anaerobic composite bed reactor (4), an exhaust port (5) is arranged at the upper top of the upflow anaerobic composite bed reactor (4), and a sealing cover corresponding to the exhaust port (5) is arranged at the exhaust port;
a first circulation port (8) is arranged at the lower bottom of the upflow anaerobic composite bed reactor (4) close to the right end, and a second circulation port (7) is arranged at the right end of the middle lower part of the upflow anaerobic composite bed reactor (4);
a first water outlet (6) at the upper part of the upflow anaerobic composite bed reactor (4) is connected with an electrochemical reactor (12) through a pipeline, an electrode (11) is arranged in the electrochemical reactor (12), the electrode (11) is connected with a power supply device (10), and a second water outlet (13) is arranged at the right side of the electrochemical reactor (12).
8. The system for use in a process for the treatment of antibiotic wastewater as set forth in claim 7, wherein:
the upflow anaerobic composite bed reactor (4) is a cylindrical organic glass container, and the ratio of the diameter to the height of the reactor is 1: 6, the ratio of the wall thickness to the diameter is 1: 20; the sampling port (31) is arranged at the 2/3 height from top to bottom at the left end of the upflow anaerobic composite bed reactor (4); the first water outlet (6) is arranged at the 1/12 height from top to bottom on the right side of the upflow anaerobic composite bed reactor (4); the central point department of upflow anaerobic composite bed reactor (4) upper cover has circular shape gas vent (5), and the diameter of gas vent (5) and the diameter ratio of upflow anaerobic composite bed reactor (4) cross section is: 1: 5.
9. the system for use in a process for the treatment of antibiotic wastewater as set forth in claim 7, wherein:
the electrochemical reactor (12) is a square container, and the length, width and height ratio of the electrochemical reactor is as follows: 16: 15: 16, a second water outlet (13) is arranged at the height of the electrochemical reactor (12) from bottom to top 1/8, the pipe diameter of a water outlet pipe connected with the second water outlet (13) is 1/50 of the width of the electrochemical reactor (12), and the length of the water outlet pipe is 2/15 of the width of the electrochemical reactor (12).
10. The system for use in a process for the treatment of antibiotic wastewater as set forth in claim 7, wherein:
the electrode material comprises an anode and a cathode, wherein the anode is SnO2-Sb/Ti, the cathode is made of stainless steel material.
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