CN113248016A - Method for strengthening one-stage completely autotrophic nitrogen removal process by embedded cathode dynamic membrane - Google Patents
Method for strengthening one-stage completely autotrophic nitrogen removal process by embedded cathode dynamic membrane Download PDFInfo
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Abstract
The invention relates to a method for strengthening a one-section type completely autotrophic nitrogen removal process by using an embedded cathode dynamic membrane, which comprises the following steps: preparing a CANON reactor, short-range nitrification floc sludge successfully domesticated, anaerobic ammonia oxidation floc sludge successfully domesticated, a dynamic membrane component, an iron plate, a nylon net, a direct current power supply and an aeration device; installing a dynamic membrane assembly in the reactor, adopting a stainless steel lining as a cathode, adopting an iron plate as an anode, respectively connecting the cathode and the anode with a direct current power supply, and simultaneously installing an aeration device; d, introducing direct current to the anaerobic ammonia oxidation floc sludge for pretreatment; adding short-cut nitrification floc sludge and anaerobic ammonia oxidation floc sludge into a reactor; the reactor maintains an anoxic state, the reactor operates in a continuous flow mode, the hydraulic retention time is gradually reduced, the high ammonia nitrogen wastewater enters the reactor for treatment and is discharged through a water outlet pipe of the dynamic membrane component, and the operation effect of the reactor is enhanced by controlling electrochemical parameters. The method is favorable for slowing down the membrane pollution rate and enables the reactor to operate stably for a long time.
Description
Technical Field
The invention belongs to the technical field of biological wastewater treatment, and particularly relates to a method for strengthening a one-stage completely autotrophic nitrogen removal process by using an embedded cathode dynamic membrane.
Background
In recent years, the problem of environmental pollution caused by the discharge of nitrogen-containing wastewater into water bodies is receiving more and more attention at home and abroad. Many industries can generate nitrogen-containing wastewater, ammonia nitrogen is a main oxygen-consuming pollutant in a water body, and when the ammonia nitrogen is oxidized and decomposed, dissolved oxygen in the water can be continuously consumed, so that the problem of black and odorous water body is caused. Meanwhile, ammonia nitrogen is easily oxidized into nitrite nitrogen by microorganisms in water and is further oxidized into nitrate nitrogen. Nitrite nitrogen has carcinogenic and teratogenic activities, and both nitrite nitrogen and nitrate nitrogen are listed in the list of carcinogens published by the world health organization international agency for research on cancer. Meanwhile, the nitrogen can provide a nutrient source for the growth of algae, and water eutrophication is easily caused. At present, the traditional biological denitrification process faces the condition of insufficient carbon source, the effluent nitrogen of sewage treatment cannot reach the standard due to insufficient carbon source, the treatment cost is obviously increased by adding the carbon source to remove the nitrogen, and the concentration of the organic matter in the effluent is possibly increased.
In recent years, various novel biological denitrification technologies for treating nitrogen-containing wastewater are developed at home and abroad, and a completely autotrophic denitrification process (CANON) is provided. However, the functional floras in the process are autotrophic bacteria, and the growth rate is low, so that the reactor is long in starting time and difficult to stably operate.
In order to solve the technical bottleneck of the CANON process, the dynamic membrane component is combined with the CANON reactor to intercept sludge as much as possible, so that the sludge loss is avoided, the sludge amount of the CANON process is increased, the problem of sludge loss is partially solved, and the stability of the reactor is improved. However, the technical idea is only beneficial to keeping the sludge amount in the reactor, the problem of low growth rate of functional flora is not fundamentally solved, and dynamic membrane pollution is easily caused, so that the membrane flux is reduced, the transmembrane pressure difference is increased, the stable operation of CANON is not facilitated, and the further application of the process is severely restricted.
Disclosure of Invention
The invention aims to provide a method for strengthening a one-stage completely autotrophic nitrogen removal process by using a dynamic membrane with an embedded cathode, which is favorable for slowing down the membrane pollution rate and ensuring that a reactor can run stably for a long time.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for strengthening a one-stage completely autotrophic nitrogen removal process by using a dynamic membrane with an embedded cathode comprises the following steps:
preparing a one-stage completely autotrophic nitrogen removal reactor, namely a CANON reactor, successfully domesticated short-range nitrified floc sludge, successfully domesticated anaerobic ammonia oxidation floc sludge, a dynamic membrane component, an iron plate, a nylon net, a direct-current power supply and an aeration device;
installing a dynamic membrane component in the CANON reactor, adopting a stainless steel lining as a cathode and an iron plate as an anode, respectively connecting the cathode and the anode with a direct current power supply, and installing an aeration device at the bottom of the CANON reactor;
d, introducing direct current to the successfully domesticated anaerobic ammonia oxidation floc sludge for pretreatment;
adding prepared short-range nitrification floc sludge and anaerobic ammonia oxidation floc sludge into a CANON reactor according to a set mass ratio, so that the concentration of suspended floc sludge in the CANON reactor reaches a set value;
the CANON reactor maintains CANON anoxic state, adopts continuous flow mode operation, and hydraulic retention time reduces gradually, and high ammonia nitrogen waste water gets into the CANON reactor and discharges through the outlet pipe of dynamic membrane subassembly after handling, strengthens CANON reactor operation effect through controlling electrochemical parameter, realizes the rapid multiplication and the miniaturation of shortcut nitrobacteria and anaerobic ammonium oxidation fungus to improve CANON system's denitrogenation ability, and reduce membrane pollution rate.
Further, a layer of nylon net is coated outside the stainless steel lining.
Further, the specification of the nylon net is 260 meshes.
And further, the anaerobic ammonia oxidation floc sludge is pretreated by supplying direct current for 1 hour so as to improve the activity of flora contained in the anaerobic ammonia oxidation floc sludge.
Further, the mass ratio of the short-cut nitrification floc sludge to the anaerobic ammonia oxidation floc sludge is 1: 1.3, the concentration of suspended floc sludge in the CANON reactor is 7000 mg/L.
Furthermore, the direct current power supply controls the current to be 0.02-0.04A, and the low current state is favorable for exciting the activity of the flora with the functions of shortcut nitrification and anaerobic ammonium oxidation.
Further, after the electrification, iron ions are separated out from the anode, and under the action of electrochemistry, Fe (OH) is formed by the iron ions3The crystal nucleus is beneficial to forming particles by floc sludge; and the combined action of the electric field and the iron ions is beneficial to the proliferation of the short-cut nitrification and anaerobic ammonium oxidation functional flora and the granulation of floc sludge.
Furthermore, the CANON reactor controls the anoxic state, the dissolved oxygen is controlled below 0.2mg/L, the CANON reactor operates in a continuous flow mode, the hydraulic load is gradually reduced from 8 hours to 4 hours, and the high ammonia nitrogen wastewater enters the CANON reactor for treatment and is discharged through a water outlet pipe of the dynamic membrane module.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, an electrochemical system taking a dynamic membrane component and an iron plate as the anode and cathode is constructed in the CANON reactor, so that the activity of functional flora in the reactor is effectively improved, the biomass of the functional flora and the specific gravity of granular sludge are increased, the sludge loss is reduced, the problems of low membrane flux, high membrane pollution rate and short membrane operation period of the membrane component in anaerobic and anoxic environments are solved, and the problems of sludge loss and unsuitability for long-term stable operation are effectively solved.
(2) The invention constructs an electrochemical system which takes a dynamic membrane component and an iron plate as a cathode and an anode in a CANON reactor, wherein the iron plateThe anode separates out iron ions, sludge flocs with negative electricity in the electric flocculation process and Fe (OH) generated by the electric flocculation3The soluble extracellular polymeric substance is absorbed and reduced by the electric neutralization, and the soluble extracellular polymeric substance is an important factor for aggravating membrane pollution on the cell surface adhered to sludge and biomembranes in the wastewater treatment process. Therefore, the membrane pollution can be effectively slowed down by the invention.
(3) The multivalent metal ions may compress the electric double layer, facilitating cell-to-cell contact. The invention constructs an electrochemical system which takes a dynamic membrane component and an iron plate as a cathode and an anode in a CANON reactor, iron ions are continuously electrolyzed from an anode electrode, cell aggregation is enhanced, the flora in the reactor is more compact, and Fe (OH) formed by the iron ions is formed3The 'crystal nucleus' is beneficial to forming particles of floc sludge, and the iron ions have a promoting effect on the proliferation of anaerobic ammonium oxidation bacteria.
Drawings
FIG. 1 is a schematic diagram of a CANON reactor constructed in an example of the present invention.
FIG. 2 is a statistical chart of denitrification rate effect of CANON reactor in the example of the present invention.
FIG. 3 is a statistical graph of the particle size distribution of the sludge in the CANON reactor in the example of the present invention.
FIG. 4 is a graph showing dynamic membrane fouling of a CANON reactor in an example of the present invention.
FIG. 5 shows the composition and relative abundance of the bacterial flora in the CANON reactor sludge at the phylum level in an example of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The embodiment provides a method for strengthening a one-section type completely autotrophic nitrogen removal process by using an embedded cathode dynamic membrane, which comprises the following steps:
preparing a one-stage completely autotrophic nitrogen removal reactor, namely a CANON reactor, successfully domesticated short-cut nitrification floc sludge, successfully domesticated anaerobic ammonia oxidation floc sludge, a dynamic membrane component, an iron plate, a nylon net, a direct current power supply and an aeration device.
A dynamic membrane assembly is arranged in the CANON reactor, a stainless steel lining is used as a cathode, an iron plate is used as an anode, the cathode and the anode are respectively connected with a direct current power supply, and an aeration device is arranged at the bottom of the CANON reactor. The CANON reactor constructed in this example is shown in figure 1.
And (3) introducing direct current to the successfully domesticated anaerobic ammonia oxidation floc sludge for pretreatment.
Adding the prepared short-range nitrification floc sludge and anaerobic ammonia oxidation floc sludge into the CANON reactor according to a set mass ratio, so that the concentration of the suspended floc sludge in the CANON reactor reaches a set value.
The CANON reactor maintains CANON anoxic state, adopts continuous flow mode operation, and hydraulic retention time reduces gradually, and high ammonia nitrogen waste water gets into the CANON reactor and discharges through the outlet pipe of dynamic membrane subassembly after handling, strengthens CANON reactor operation effect through controlling electrochemical parameter, realizes the rapid multiplication and the miniaturation of shortcut nitrobacteria and anaerobic ammonium oxidation fungus to effectively improve CANON system's denitrogenation ability, and reduce membrane pollution rate.
By adopting an artificial water distribution mode, after the CANON reactor is stably operated for 42 days, the CANON speed reaches 0.27KgN (KgVSS. d)-1The content of granular floc sludge (not less than 200 μm) is 43.43%, the average particle diameter is increased to 157 μm, and the content of Planctomycetes belonging to ANAMMOX phylum is 5.18%.
Wherein, the outside of stainless steel inside lining cladding one deck nylon wire net. In this embodiment, the nylon mesh size is 260 mesh.
In this example, the anammox floc sludge was pretreated by applying dc for 1 hour to increase the activity of the bacterial flora contained in the anammox floc sludge.
In this embodiment, the mass ratio of the shortcut nitrification floc sludge to the anaerobic ammonia oxidation floc sludge is 1: 1.3, the concentration of suspended floc sludge in the CANON reactor is 7000 mg/L.
In this embodiment, the dc power supply controls the current to be 0.02-0.04A, preferably 0.03A, and the low current state is favorable for activating the activity of the bacteria with the functions of shortcut nitrification and anammox.
After the power is switched on, iron ions are separated out from the anode, and Fe (OH) is formed by the iron ions under the action of electrochemistry3The crystal nucleus is beneficial to forming particles by floc sludge; and the combined action of the electric field and the iron ions is beneficial to the proliferation of the short-cut nitrification and anaerobic ammonium oxidation functional flora and the granulation of floc sludge.
The CANON reactor controls the anoxic state, the dissolved oxygen is controlled below 0.2mg/L, the CANON reactor operates in a continuous flow mode, the hydraulic load (HRT) is gradually reduced from 8 hours to 4 hours, and the high ammonia nitrogen wastewater enters the CANON reactor to be treated and then is discharged through a water outlet pipe of the dynamic membrane module.
The following examples are given for comparison.
A dynamic membrane assembly is installed on the CANON reactor, stainless steel as a cathode is adopted, a nylon net with the specification of 260 meshes is coated outside the dynamic membrane assembly, an iron plate is used as an anode, the cathode and the anode are respectively connected with a direct current power supply, and meanwhile, an aeration device is arranged at the bottom of the CANON reactor. And (3) introducing direct current to the successfully domesticated anaerobic ammonia oxidation floc sludge for pretreatment, and then treating the sludge in a CANON reactor according to the proportion of 1: 1.3 (mass ratio), adding the prepared short-range nitrification floc sludge and anaerobic ammonia oxidation floc sludge, and controlling the initial concentration of the suspended sludge to be 7000 mg/L. The CANON reactor maintains 0.2mg/L CANON dissolved oxygen, the continuous flow mode is adopted for operation, the Hydraulic Retention Time (HRT) is gradually reduced from 8h to 4h, and the high ammonia nitrogen wastewater enters the CANON reactor for treatment and is discharged through a water outlet pipe of the dynamic membrane module. The R2 reactor is not electrified as a contrast, the R1 strengthens the operation effect of the CANON reactor by controlling the current to be 0.03A, so as to realize the rapid proliferation and granulation of the shortcut nitrifying bacteria and the anaerobic ammonium oxidation bacteria, and after the R1 reactor is stably operated for 42 days, the CANON rate reaches 0.27KgN (KgVSS. d)-1The content of the granular sludge (more than or equal to 200 mu m) accounts for 43.43 percent, the average particle size is increased to 157 mu m, the content of the planctomycete (Planctomycetes) belonging to the ANAMMOX phylum reaches 5.18 percent, and all indexes are obviously superior to those of an R2 reactor.
The reactor of the invention is a CANON reactor, but is also suitable for other types of short-cut nitrification-anaerobic ammonia oxidation reactors. According to the invention, high ammonia nitrogen sewage is treated in the CANON reactor, and an electrochemical system taking a dynamic membrane component and an iron plate as a cathode and an anode is constructed, so that the activity of functional flora in the reactor is effectively improved, the biomass of the functional flora and the specific gravity of granular sludge are increased, the sludge loss is reduced, the problems of low membrane flux, high membrane pollution rate and short membrane operation period of the membrane component in anaerobic and anoxic environments are solved, and the problems of sludge loss and unsuitability for long-term stable operation are effectively solved.
FIG. 2 shows the effect of denitrification reaction rate in CANON reactor. The CANON rate and the specific anaerobic ammonia oxidation rate of the R1 and R2 reactors are both gradually increased, which shows that the synergistic activity of the shortcut nitrifying bacteria and the anaerobic ammonia oxidation bacteria is gradually increased; meanwhile, due to the coupling of electrochemical action, the generated iron ions promote the proliferation of the shortcut nitrifying bacteria and the anaerobic ammonium oxidation bacteria, and promote the CANON reaction rate and the specific anaerobic ammonium oxidation rate of R1 to be slightly higher than R2. While the nitrification rates for both reactors R1 and R2 were maintained at very low levels.
Figure 3 shows the sludge particle size distribution in the CANON reactor. The proportion of floc sludge (10-200 mu m) in the sludge initially inoculated by R1 is 70.70%, and the average grain diameter of the sludge is 95.7 mu m; in R2, the ratio of floc sludge is 67.71%, and the average grain diameter of the sludge is 101 mu m. Through culture, the proportion of the R1 formed granular sludge (more than or equal to 200 mu m) is increased from 29.30 percent to 43.43 percent, and the average particle size is increased to 157 mu m; the proportion of R2 granular sludge is reduced from 32.29% to 26.37%, and the average particle size is increased to 125 μm and then reduced to 107 μm. It can be seen that Fe (OH)3 "nuclei" formed by the continuous electrolysis of iron ions are favorable for the formation of particles from floc sludge under the action of electrochemistry. The reduction of the sludge particle size in the reactor R2 may result in the reduction of the activity of microorganisms and the disintegration of part of the sludge due to the temperature shock.
Fig. 4 shows a plot of CANON reactor dynamic membrane fouling. The pollution rate of R1 is 2.901 KPa/d, the pollution rate of R2 is 5.156 KPa/d, the membrane pollution rate of the R2 reactor is 1.78 times of that of the R1 reactor, the running effect of R1 is obviously better than that of R2, and the effect of electricity on delaying the membrane pollution is obvious.
Fig. 5 shows the composition and relative abundance changes of the flora in CANON reactor sludge at the phylum level. G0 is sludge at initial inoculation, H1 and H2 are sludge in R1 and R2, respectively. Anammox bacteria belong to the phylum planctomycete (planctomyces) and are present in the G0, H1 and H2 samples at 2.88%, 5.18% and 3.6%, respectively, indicating a significant increase in anammox bacteria content during CANON reactor operation. Under the conditions of electrochemistry and high ammonia nitrogen, the ANAMMOX bacteria content of H1 is higher than that of H2. The main reason is that the rapid proliferation of the ANAMMOX bacteria is facilitated by high ammonia nitrogen and continuous generation of iron ions under the electrified condition.
During the culture period, the CANON speed, specific anaerobic ammonia oxidation activity, nitrification speed, sludge average grain size, dynamic membrane transmembrane pressure difference, flora composition and other indexes of the CANON reactor can be monitored to master the starting process of the process.
According to the invention, the dynamic membrane module is added in the CANON reactor, so that the sludge loss is reduced, the sludge amount in the reactor is ensured, meanwhile, the dynamic membrane module and the iron plate are respectively used as the anode and cathode of an electrochemical system, an electrochemical reaction is constructed in the CANON, the activity of functional flora in the reactor is further improved, the biomass of the functional flora and the specific gravity of granular sludge are increased, the problem that the membrane module is easy to be polluted is solved, the problems of sludge loss and unsuitability for long-term stable operation are effectively solved, and the rapid start and stable operation of the process are facilitated.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (8)
1. A method for strengthening a one-stage completely autotrophic nitrogen removal process by using a dynamic membrane with an embedded cathode is characterized by comprising the following steps:
preparing a one-stage completely autotrophic nitrogen removal reactor, namely a CANON reactor, successfully domesticated short-range nitrified floc sludge, successfully domesticated anaerobic ammonia oxidation floc sludge, a dynamic membrane component, an iron plate, a nylon net, a direct-current power supply and an aeration device;
installing a dynamic membrane component in the CANON reactor, adopting a stainless steel lining as a cathode and an iron plate as an anode, respectively connecting the cathode and the anode with a direct current power supply, and installing an aeration device at the bottom of the CANON reactor;
d, introducing direct current to the successfully domesticated anaerobic ammonia oxidation floc sludge for pretreatment;
adding prepared short-range nitrification floc sludge and anaerobic ammonia oxidation floc sludge into a CANON reactor according to a set mass ratio, so that the concentration of suspended floc sludge in the CANON reactor reaches a set value;
the CANON reactor maintains CANON anoxic state, adopts continuous flow mode operation, and hydraulic retention time reduces gradually, and high ammonia nitrogen waste water gets into the CANON reactor and discharges through the outlet pipe of dynamic membrane subassembly after handling, strengthens CANON reactor operation effect through controlling electrochemical parameter, realizes the rapid multiplication and the miniaturation of shortcut nitrobacteria and anaerobic ammonium oxidation fungus to improve CANON system's denitrogenation ability, and reduce membrane pollution rate.
2. The method of claim 1, wherein the stainless steel liner is covered with a nylon mesh.
3. The method of claim 2, wherein the nylon mesh size is 260 mesh.
4. The method of claim 1, wherein the anammox floc sludge is pretreated by applying direct current for 1 hour to increase the activity of the bacteria contained in the anammox floc sludge.
5. The method for strengthening the one-stage completely autotrophic nitrogen removal process by using the dynamic membrane with embedded cathode as claimed in claim 1, wherein the mass ratio of the shortcut nitrification floc sludge to the anaerobic ammonia oxidation floc sludge is 1: 1.3, the concentration of suspended floc sludge in the CANON reactor is 7000 mg/L.
6. The method of claim 1, wherein the DC power supply controls the current to be 0.02-0.04A, and the low current state is favorable for activating the activity of bacteria with shortcut nitrification and anammox functions.
7. The method of claim 1, wherein the anode is charged to separate iron ions, and the iron ions form Fe (OH) under electrochemical action3The crystal nucleus is beneficial to forming particles by floc sludge; and the combined action of the electric field and the iron ions is beneficial to the proliferation of the short-cut nitrification and anaerobic ammonium oxidation functional flora and the granulation of floc sludge.
8. The method for strengthening the one-stage completely autotrophic nitrogen removal process by using the dynamic membrane with embedded cathode according to claim 1, wherein the CANON reactor is controlled to be in an anoxic state, the dissolved oxygen is controlled to be below 0.2mg/L, the continuous flow operation is adopted, the hydraulic load is gradually reduced from 8 hours to 4 hours, and the high ammonia nitrogen wastewater enters the CANON reactor for treatment and is discharged through a water outlet pipe of the dynamic membrane module.
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| CN114314808A (en) * | 2021-12-16 | 2022-04-12 | 济南大学 | Microbial fuel cell coupled completely autotrophic dynamic membrane reactor denitrification device and method |
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