CN112225404A - Micro-nano bubble-zero-valent iron advanced wastewater treatment system - Google Patents
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Abstract
The invention relates to the technical field of chemical wastewater treatment, in particular to a micro-nano bubble-zero-valent iron advanced wastewater treatment system, wherein the advanced wastewater treatment system comprises a pretreatment unit and a micro-nano bubble-zero-valent iron unit, and the micro-nano bubble-zero-valent iron unit comprises: the gas-liquid mixing unit is used for mixing the wastewater treated by the pretreatment unit with introduced air and/or oxygen and enabling the oxygen in the wastewater to reach super-saturated solubility; a zero-valent iron reactor for degrading the wastewater treated by the pretreatment unit; and the separation unit is used for removing iron ions in the wastewater after the zero-valent iron reactor is degraded. The advanced wastewater treatment system provided by the invention breaks air and/or oxygen into micro-nano bubbles, and excites the micro-nano bubbles to generate a large amount of hydroxyl free radicals under the catalytic action of iron, so that organic matters, cyanides, thiocyanides and the like which are difficult to biochemically treat are effectively degraded, the biodegradability of wastewater is improved, and the problems of high concentration of toxic and harmful substances, poor biodegradability and the like of coal chemical wastewater are solved.
Description
Technical Field
The invention relates to the technical field of chemical wastewater treatment, in particular to a micro-nano bubble-zero-valent iron advanced wastewater treatment system.
Background
The development of environmental science is promoted by industrial pollution, and the environmental protection is from the conventional atmospheric pollutants (such as dust and SO)2Etc.), water body routine contaminants (such as: COD, BOD, ammonia nitrogen, phosphorus, etc.) and heavy metal pollution control, and develops towards organic pollutants difficult to biodegrade.
The basic characteristics of energy in China are rich coal, poor oil and less gas, the development of novel coal chemical industry is the strategic demand of energy in China, and the method plays an important role in relieving the supply-demand contradiction of high-quality resources such as petroleum and natural gas in China and promoting the development of chemical industry, steel, light industry and agriculture.
Coal coking, coal gasification, coal liquefaction, coal-to-methanol, olefin and other coal chemical processes need mass production of water, but China's coal chemical project development is mainly in northwest and north China areas with rich coal resources, the water resources in these areas are deficient, the occupation amount is less than 20% of the total amount of the whole country, the geospatial distribution of rich coal and little water becomes the bottleneck of China's coal chemical development, a coal chemical wastewater treatment process with low investment, good water quality of produced water, stable process and low operation cost is sought, water conservation and recycling are realized to the greatest extent, and the process becomes an urgent demand for the development of the coal gas industry.
The coal chemical industry generates a large amount of wastewater which contains high-concentration pollutants, the water quality components are complex and fluctuate frequently, and under the normal condition, CODcr is about 2500-; the phenols are about 500-14000mg/L (the phenols are about 300-6800 mg/L); the ammonia nitrogen is about 1800-14000 mg/L; the trace nitrate nitrogen is about 0.2-2 mg/L; the organic nitrogen is about 4-140 mg/L; the trace phosphorus is about 0.5-29 mg/L; cyanide is about 0.1 to 110 mg/L; thiocyanide is from about 8 mg/L to about 1500 mg/L; sulfide (S)2-) About 60-29000 mg/L; oil content of 50-110000mg/L, TDS content of 32000mg/L and pH value of 7.5-9.5, and suspension, colloid, calcium, magnesium, strontium and barium in certain concentrationScale-causing ions, heavy metal ions, fluoride, and a chromaticity of hundreds of degrees. The high concentration ammonia nitrogen causes the C/N ratio to be greatly unbalanced; a large amount of long-chain alkanes, aromatic naphthalene, anthracene and the like, heterocyclic compounds such as pyridine and the like, oil and other biodegradable organic matters, and high concentration phenols/cyanides/thiocyanides seriously harm the metabolism of microorganisms, BOD/COD is about 0.18-0.25 or lower, the concentration of toxic and harmful substances is high, the wastewater has strong microbial inhibition, the biodegradability of water quality is poor, and the wastewater is typical high-concentration industrial wastewater which is difficult to biodegrade.
The treatment process of the coal chemical industry wastewater in China generally comprises four parts, namely: pretreatment, biochemical treatment, advanced treatment and zero emission;
the pretreatment process mainly completes oil removal, dephenolization and deamination, and the main oil removal process comprises an oil separation tank and an air floatation method; the main dephenolizing process is solvent extraction; the main deamination process is steam stripping-ammonia steaming.
The biochemical treatment is to decompose and mineralize organic matters in the pretreated produced water by using microbial metabolism, and the commonly used biochemical treatment process mainly comprises A/O and A2The method comprises the following steps of an O process, a fluidized bed biofilm reactor, a PACT method, an anaerobic biological treatment method, an aeration biological filter and the like.
The application number 201510170671.7 'a coal coking wastewater treatment system' discloses a coal coking wastewater treatment system, and the publication date is 2015, 7 and 22, which firstly carries out biological treatment after different types of wastewater are classified, but does not fully remove macromolecules, macromolecule refractory organics, fine suspended matters and colloids before biochemical treatment, and easily influences the treatment effect of the subsequent biological treatment process.
Because the water quality components of the coal chemical industry wastewater are complex and variable, the fluctuation is frequent, the theoretical basis and the engineering design specification aiming at characteristic pollutants and treatment thereof are lacked, the conventional treatment process has serious limitations, the process cannot obtain satisfactory effluent water quality, the process is complex, the engineering cost and the operation and maintenance cost are high, the high-efficiency and low-cost advanced treatment technology of the coal chemical industry wastewater is developed, the great reduction of the pollutants in the coal chemical industry wastewater and the reutilization of water resources are realized, and the self-demand and the external environmental protection requirement of the sustainable development of coal chemical industry enterprises are met.
Disclosure of Invention
In order to solve the problem mentioned in the background art that part of organic pollutants which are difficult to degrade need to be degraded before biological treatment, the invention provides a micro-nano bubble-zero-valent iron advanced wastewater treatment system, which comprises a pretreatment unit and a micro-nano bubble-zero-valent iron unit, wherein the micro-nano bubble-zero-valent iron unit comprises:
the gas-liquid mixing unit is used for mixing the wastewater treated by the pretreatment unit with introduced air and/or oxygen and enabling the oxygen in the wastewater to reach super-saturated solubility;
a zero-valent iron reactor for degrading the wastewater treated by the pretreatment unit;
and the separation unit is used for removing iron ions in the wastewater after the zero-valent iron reactor is degraded.
On the basis of the structure, further, the pretreatment unit is used for treating the wastewater, and the treatment comprises one or more of flocculation, softening, oil removal, dephenolization and deamination.
On the basis of the structure, the gas-liquid mixing unit further comprises a micro-nano bubble generator.
On the basis of the structure, the diameter of the micro-nano bubbles generated in the micro-nano bubble generator is 500nm-1 μm.
On the basis of the structure, further, the separation unit comprises a clarification tank for receiving wastewater degraded by the zero-valent iron reactor, and precipitates of iron are generated by adjusting the pH of the wastewater in the clarification tank.
On the basis of the structure, further, the micro-nano bubble-zero-valent iron unit further comprises a filtering unit arranged between the zero-valent iron reactor and the separation unit.
On the basis of the structure, the device further comprises a biomembrane processing unit, wherein the biomembrane processing unit is used for removing one or more pollutants in COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide and thiocyanide contained in the wastewater treated by the micro-nano bubble-zero-valent iron unit.
On the basis of the structure, the biomembrane treatment unit further comprises an anaerobic biofilter, a facultative biofilter and an aerated biofilter which are arranged in sequence.
On the basis of the structure, carriers for filling immobilized microorganisms are further arranged in the anaerobic biological filter, the facultative biological filter and the aeration biological filter.
On the basis of the structure, a backflow device is further arranged at the rear end of the biological aerated filter, and the backflow device is used for enabling effluent water treated by the biological aerated filter to flow back to the anaerobic biological filter and/or the facultative biological filter.
The invention provides a micro-nano bubble-zero-valent iron advanced wastewater treatment system, which has the following advantages compared with the prior art:
air and/or oxygen are broken into micro-nano bubbles, and a large amount of hydroxyl radicals are generated under the catalytic action of iron; the hydroxyl free radical has ultrahigh oxidation-reduction potential (EOP is 2.8V), the reaction speed is very high, and the generated ultrahigh oxidation effect can convert macromolecular and macromolecular organic matters which are difficult to biodegrade into micromolecular organic matters which can be biodegraded or completely mineralize, so that cyanide and thiocyanide are completely mineralized.
In order to further improve the treatment effect of the system, the system is also provided with a tubular ultrafiltration membrane group which can effectively intercept various macromolecules and macromolecular organic matters and fine suspended matters and colloids in the wastewater, so that the wastewater enters concentrated water for circulating treatment, and the produced water is ensured not to contain macromolecules and macromolecular refractory organic matters and fine suspended matters and colloids;
moreover, in order to effectively treat pollutants in the wastewater, a biological membrane treatment unit is additionally arranged, and the immobilization technology is effectively combined with a biological filter and a biological strengthening process, so that the pollutants such as organic matters, nitrogen and the like in the coal chemical wastewater can be simultaneously removed, and simultaneously, the pollutants can be decolored and deodorized; the denitrification efficiency is high, and an additional organic carbon source is not needed; the high-efficiency bacteria are fixedly grown on the carrier, so that the inhibition effect of high ammonia nitrogen on organisms is reduced; because the immobilization technology is adopted, microorganisms in the reactor are rapidly propagated, dominant strains are remarkable, the biomass is large, the biological species are rich, a large number of zoogles exist, nitrifying bacteria, denitrifying bacteria and the like with long generation time can be effectively immobilized on the carrier, and the loss of the bacteria in the traditional method is avoided; bearing the load change of the water inlet pollutants and having strong capability of resisting the impact of the system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a structural block diagram of a micro-nano bubble-zero-valent iron advanced wastewater treatment system provided by the invention;
FIG. 2 is another structural block diagram of a micro-nano bubble-zero-valent iron advanced wastewater treatment system provided by the invention;
FIG. 3 is a structural block diagram of a micro-nano bubble-zero-valent iron unit provided by the invention;
FIG. 4 is a structural block diagram of a micro-nano bubble-zero-valent iron advanced wastewater treatment system with a filtering unit, provided by the invention;
FIG. 5 is a structural block diagram of a micro-nano bubble-zero-valent iron advanced wastewater treatment system with a biofilm treatment unit, provided by the invention;
FIG. 6 is a block diagram of a biofilm treatment unit according to the present invention.
Reference numerals:
10 micro-nano bubble-zero-valent iron 21 gas-liquid mixing unit of pretreatment unit 20
22 zero-valent iron reactor 23 separation unit 24 filtration unit
30 biological membrane treatment unit 31 anaerobic biological filter 32 facultative biological filter
33 aeration biological filter 34 reflux device
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The invention provides a micro-nano bubble-zero-valent iron advanced wastewater treatment system, which comprises a pretreatment unit 10 and a micro-nano bubble-zero-valent iron unit 20, wherein the micro-nano bubble-zero-valent iron unit 20 comprises:
a gas-liquid mixing unit 21 for mixing the wastewater treated by the pretreatment unit 10 with introduced air and/or oxygen and making the oxygen in the wastewater reach a super-saturated solubility; a zero-valent iron reactor 22 for degrading the wastewater treated by the pretreatment unit 10; and a separation unit 23 for removing iron ions in the wastewater after the zero-valent iron reactor 22 is degraded.
In specific implementation, as shown in fig. 1-3, after the coal chemical wastewater is subjected to pretreatment processes such as flocculation, softening, oil removal, dephenolization, deamination and the like in the pretreatment unit 10, the pretreated wastewater is sent to the micro-nano bubble-zero-valent iron unit 20;
the micro-nano bubble-zero-valent iron unit 20 comprises a gas-liquid mixing unit 21, a zero-valent iron reactor 22 and a separation unit 23, wherein the gas-liquid mixing unit 21 is used for mixing the entering wastewater with the introduced air and/or oxygen to ensure that the oxygen in the wastewater reaches the super-saturated solubility, the pretreated coal chemical wastewater firstly enters the gas-liquid mixing unit 21, the gas-liquid mixing unit 21 preferably but not limited to a micro-nano bubble generator, the oxygen in the wastewater reaches the super-saturated solubility by efficiently mixing the wastewater with 500nm to 1 mu m of air and/or oxygen generated by the micro-nano bubble generator, the 500nm to 1 mu m micro-nano bubbles have a self-pressurization dissolving effect, the dissolving of the micro-nano bubbles in the wastewater is a process that the bubbles gradually decrease, the pressure rise can increase the dissolving speed of the gas, and the specific surface area is increased, the speed of reducing the bubbles becomes faster and faster, and the bubbles are finally dissolved in water, theoretically, the pressure applied to the bubbles is infinite when the bubbles disappear, the huge pressure causes the micro bubbles to burst instantly, and because the gas-liquid interface disappears violently, high-concentration ions accumulated on the interface release the accumulated chemical energy at once, and can excite to generate a large amount of hydroxyl radicals;
then, wastewater rich in micro-nano bubbles of 500nm to 1 mu m is sent into a zero-valent iron reactor 22, and zero-valent iron (ZVI) degrades toxic and harmful organic matters, so that the wastewater has the advantages of mild reaction conditions, safety, no secondary pollution and the like, not only can directly reduce and degrade halogen-substituted pollutant organic pollutants (formula 1), but also can oxidize and degrade the organic matters (formula 2 to 5) by activating molecular oxygen in the air to form a Fenton-like system;
Fe0+RX+H+→Fe2++RH+X- (1)
Fe0+O2+2H+→Fe2++H2O2 (2)
Fe2++O2→Fe3++·O2- (3)
Fe2++·O2-+2H+→Fe3++H2O2 (4)
Fe2++H2O2+H+→Fe3++H2O+·OH (5)；
however, conventional ZVI is not highly active ((Fe) in practical water treatment processes2+Fe) — 0.44V), and the effect of degrading the refractory organic substances is not good. In order to improve the activity of zero-valent iron, the patent mainly utilizes O of micro-nano scale bubbles2The property of being more easily activated by ZVI forms a Fenton-like system to carry out the oxidative degradation of organic matters. The micro-nano bubbles with the particle size of 500nm-1 mu m have extremely high solubility in the wastewater, and at the moment of bubble rupture, due to the violent change of disappearance of a gas-liquid interface, chemical energy accumulated on the interface is released instantly, and a large amount of strong oxidizing substances such as hydroxyl free radicals and the like are generated under the catalytic action of iron, so that the oxidative degradation of organic matters difficult to degrade in the wastewater is realized;
the hydroxyl free radical has ultrahigh oxidation-reduction potential (EOP is 2.8V), belongs to free radical reaction, has very high reaction speed, and can convert macromolecular and macromolecular organic matters which are difficult to biodegrade into micromolecular organic matters or be completely mineralized by the generated ultrahigh oxidation effect, so that cyanide and thiocyanide are completely mineralized;
finally, the wastewater is sent into a separation unit 23 after being oxidized and degraded by a zero-valent iron reactor 22, the pH of the wastewater can be adjusted to be neutral by the separation unit 23 through adding alkali liquor, and Fe3+Becomes Fe (OH) under neutral environment3The flocs are precipitated, and the precipitate sludge is disposed of, so that the biochemically treated wastewater can be separated.
Through the design of above-mentioned constructional device, get rid of partial pollutant through pretreatment unit 10 earlier, and then make waste water and air and/or two-phase intensive mixing of oxygen through the gas-liquid mixing unit 21 of micro-nano bubble-zerovalent iron unit 20 again to make oxygen in the waste water reach super saturated solubility, the waste water that is rich in micro-nano bubble gets into zerovalent iron reactor 22 and can effectively degrade difficult biochemical treatment organic matter, cyanide, thiocyanide etc. and improve waste water biodegradability.
Preferably, the pretreatment unit 10 is used for treating wastewater, and the treatment comprises one or more of flocculation, softening, oil removal, dephenolation and deamination.
In specific implementation, the pretreatment unit 10 is mainly used for sending pretreatment water to the micro-nano bubble-zero-valent iron unit 20 after the pretreatment processes such as flocculation, softening, oil removal, dephenolization and deamination are performed on the input coal chemical wastewater.
Preferably, the gas-liquid mixing unit 21 includes a micro-nano bubble generator.
In specific implementation, the gas-liquid mixing unit 21 includes a micro-nano bubble generator, and the micro-nano bubble generator may be a DJ-TM/NBG micro-nano bubble generator manufactured by tianjindingjiu technologies ltd.
Preferably, the diameter of the micro-nano bubbles generated in the micro-nano bubble generator is 500nm-1 μm.
During specific implementation, the micro-nano bubble generator can generate bubbles with the diameter of 500nm-1 mu m, the micro-nano bubbles with the diameter of 500nm-1 mu m have extremely high solubility in wastewater, and at the moment of bubble breakage, chemical energy accumulated on an interface is released instantly due to violent change of disappearance of a gas-liquid interface, a large amount of strong oxidizing substances such as hydroxyl radicals and the like are generated under the catalytic action of iron, and the oxidative degradation of organic matters difficult to degrade in the wastewater is realized.
Preferably, the separation unit 23 comprises a clarifier for receiving the wastewater from the zero valent iron reactor 22 after degradation, and adjusting the pH of the wastewater in the clarifier to produce iron precipitate.
In specific implementation, the separation unit 23 comprises a clarification tank, the clarification tank is used for receiving the wastewater degraded by the zero-valent iron reactor 22, and aiming at the collected wastewater, the pH of the wastewater can be adjusted to be neutral by adding alkali liquor into the clarification tank, and Fe is contained3+Becomes Fe (OH) under neutral environment3Precipitating flocs so as to classify and dispose the sludge of the precipitate;
it is understood that the separation unit 23 may be provided with a feeding device and a pH meter adapted to perform corresponding operations such as adding alkali solution, measuring pH value, and the like, or may be provided with an automatic device, or according to actual conditions, the pH value of the wastewater may be manually added and monitored to ensure that the pH value of the wastewater is stable.
Preferably, the micro-nano bubble-zero-valent iron unit 20 further includes a filtering unit 24 disposed between the zero-valent iron reactor 22 and the separating unit 23.
In specific implementation, as shown in fig. 4, after being subjected to oxidative degradation by a zero-valent iron reactor 22, the wastewater is sent to a filtering unit 24, wherein the filtering unit 24 is preferably a tubular ultrafiltration membrane group with a filtering precision of 20 nm;
wherein, the zero-valent iron reactor 22 can adopt HXL-ZVIR type zero-valent iron reactor manufactured by Hua Xiongsheng (Beijing) science and technology Limited company; the tubular ultrafiltration membrane group can adopt TMF tubular ultrafiltration membrane group produced by Porex company, Duraflow company or Kehong polymer technology, Inc. of Suzhou.
Preferably, the device further comprises a biofilm treatment unit 30, wherein the biofilm treatment unit 30 is used for removing one or more pollutants selected from COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide and thiocyanide contained in the wastewater treated by the micro-nano bubble-zero-valent iron unit 20.
In specific implementation, as shown in fig. 5-6, the biological treatment is a process in the coal chemical industry, and is mainly used for removing organic matters, nitrogen and phosphorus, and decomposing and mineralizing toxic and harmful organic matters, while the biofilm treatment unit 30 adopted in the invention is mainly used for removing COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide, thiocyanide and the like contained in the wastewater treated by the micro-nano bubble-zero-valent iron unit 20.
Preferably, the biofilm treatment unit 30 comprises an anaerobic biofilter 31, a facultative biofilter 32 and an aerated biofilter 33 arranged in sequence.
In specific implementation, the biofilm treatment unit 30 of the invention mainly comprises anaerobic-facultative-aerobic biological treatment modules, namely an anaerobic biological filter 31, a facultative biological filter 32 and an aeration biological filter 33.
Anaerobic biological filter 31, facultative biological filter 32 and bological aerated filter 33 that set up all are equipped with the biological filter reactor in, and its inside packing has the microorganism carrier, in biological filter biomembrane domestication culture process, throws high-efficient compound microorganism, strengthens biological treatment through immobilized microorganism technology, belongs to "biological filter + immobilized biological enhancement" mixed biological filter reactor, wherein: the aeration biological filter 33 can be set at 1-3 levels according to the water quality. The number and volume ratio of the anaerobic biological filter 31, the facultative biological filter 32 and the aeration biological filter 33 are designed and manufactured according to the quality and quantity of the treated wastewater and corresponding technical specifications.
Preferably, carriers for filling immobilized microorganisms are arranged in the anaerobic biological filter 31, the facultative biological filter 32 and the aeration biological filter 33.
In specific implementation, the wet density of the added biological carrier in the anaerobic biological filter 31 is close to that of water, the filling rate is about 30% -70% according to water quality, the biological carrier is suspended in a reactor and is in a fluidized state, conjunctiva blockage is not easy to occur between the carriers, the reactor does not need back flushing, meanwhile, in the biofilm domestication culture process of the anaerobic biological filter 31, high-efficiency composite anaerobic bacteria are added, the added high-efficiency composite anaerobic bacteria are commercially available products, the added high-efficiency composite anaerobic bacteria are self-fixed on the biological carrier, immobilized microorganisms are not easy to lose, the microbial load is high, the biomass in the reactor is large, the biological species is rich, a large number of bacterial micelles exist, denitrifying bacteria species are effectively fixed on the carrier for a long generation time, the loss of the strains is avoided, and the biological carrier has strong capacity of bearing the load change of water inflow pollutants and the capacity of resisting system impact;
the wet density of the added biological carrier in the facultative biological filter 32 is close to that of water, the biological carrier is suspended in a reactor and is in a fluidized state according to the water quality filling rate of about 30% -70%, conjunctiva blockage is not easy to occur between carriers, back washing is not needed in the reactor, high-efficiency composite facultative bacteria are added in the biofilm domestication culture process of the facultative biological filter 32, the added high-efficiency composite facultative bacteria are commercially available products, the added high-efficiency composite facultative bacteria are self-fixed on the biological carrier, immobilized microorganisms are not easy to lose, the microorganism load is high, the biomass in the reactor is large, the biological species are rich, a large number of zoogloea is formed, nitrification and denitrification strains are effectively fixed on the carrier for a long generation time, loss of the strains is avoided, and the capacity of bearing the load change of water inflow pollutants and resisting system impact is strong.
Most degradable organic matters and toxic substances in the wastewater are degraded in the anaerobic and facultative biological filter, organic nitrogen is degraded into ammonia nitrogen, and meanwhile, nitrogen oxides in the return water are removed through denitrification.
The wet density of the biological carriers added into the biological aerated filter 33 is close to that of water, the biological carriers are suspended in the reactor and are in a fluidized state according to the water quality filling rate of about 30-70%, conjunctiva blockage is not easy to occur between the carriers, and the reactor does not need back flushing. In the biological membrane domestication and culture process of the aeration biological filter 33, high-efficiency composite aerobic bacteria are added, the added high-efficiency composite aerobic bacteria are commercially available products, the added high-efficiency composite aerobic bacteria are self-fixed on a biological carrier, immobilized microorganisms are not easy to lose, the microbial load is high, the biomass in a reactor is large, the biological types are rich, a large number of zoogloea exists, the nitrifying bacteria with generation time length are effectively fixed on the carrier, the loss of the bacteria is avoided, and the biological membrane domestication and culture device has strong capacity of bearing the load change of water inflow pollutants and strong capacity of resisting system impact. In the reactor, because the biological carriers and the high-efficiency composite aerobic bacteria in the biological aerated filter 33 are immobilized, an anaerobic-anoxic-aerobic microenvironment is formed in the biological carriers at the same time, synchronous nitrification and denitrification are carried out, and a part of total nitrogen is removed while complete nitrification is carried out.
Preferably, a backflow device 34 is arranged at the rear end of the biological aerated filter 33, and the backflow device 34 is used for returning the effluent treated by the biological aerated filter 33 to the anaerobic biological filter 31 and/or the facultative biological filter 32.
In specific implementation, as shown in fig. 6, a reflux device 34 is arranged at the rear end of the biological aerated filter 33, ammonia nitrogen is removed after the biological aerated filter 33 is subjected to thorough nitration reaction, a part of total nitrogen and residual degradable organic matters are removed at the same time, the effluent can flow back to the anaerobic filter or the anoxic filter, the reflux route and the reflux proportion are determined according to water quality, when the concentration of the ammonia nitrogen in the influent is greater than 1500mg/L, the effluent flows back to the anaerobic biological filter 31 and is mixed with the influent to enter a reactor, so that the concentration of the ammonia nitrogen in the influent is reduced, and the inhibition effect on microorganisms is reduced; when the concentration of the ammonia nitrogen in the inlet water is less than 1500mg/L, the outlet water flows back to the facultative biological filter 32 to remove the residual nitrogen oxides generated by the biological aerated filter 33.
It can be seen that the wastewater enters the biofilm treatment unit 30, most of biodegradable organic matter and nitrite nitrogen, nitrate nitrogen are removed first in the anaerobic and facultative reactors through denitrification, hydrolytic acidification and anaerobic methanogenic reactions, and the organic nitrogen is converted into ammonia nitrogen. High-concentration ammonia nitrogen and residual organic matters in effluent of the facultative reactor are further degraded in the biological aerated filter 33, complete nitration reaction is carried out to remove high ammonia nitrogen, part of total nitrogen and the rest biodegradable organic matters are removed at the same time, effluent flows back to the anaerobic filter reactor or the facultative reactor (the reflux route and the reflux proportion are determined according to water quality), and the rest biodegradable organic matters, nitrite nitrogen and nitrate nitrogen generated in the biological aerated filter 33 section are removed. The anaerobic/facultative/aerobic biomembrane reactor is characterized in that efficient composite anaerobic/facultative/aerobic bacteria are respectively added through a biological carrier with the humidification density close to water, the efficient bacteria are fixedly grown on the carrier through an immobilized microorganism technology, particularly nitrifying bacteria, denitrifying bacteria and the like with long generation time are effectively fixed on the biological carrier, the loss of the efficient bacteria is avoided, the inhibition effect of high ammonia nitrogen and toxic substances on organisms is reduced, the dominant bacteria in the reactor are fast in propagation, large in biomass and rich in biological species, and have a large number of bacterial micelles, so that the capacity of bearing the load change of inflow pollutants and resisting the impact of a system is strong, biodegradable organic matters, nitrogen and trace phosphorus in coal chemical wastewater can be efficiently removed, and simultaneously, the decoloration and deodorization can be realized.
The biological treatment of the coal chemical industry wastewater is enhanced, COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide and thiocyanide in the coal chemical industry wastewater are effectively removed, the water quality of produced water is superior to the requirement of GB8978-1996 integrated wastewater discharge standard, and the produced water is further treated for reuse or directly discharged.
To this end, the following specific examples are also provided:
pretreated water firstly enters the micro-nano bubble generator, wastewater is efficiently mixed with 500nm-1 mu m bubbles generated by the micro-nano bubble generator, the 500nm-1 mu m micro-nano bubbles are finally dissolved in water, and a large amount of hydroxyl radicals can be generated under the catalytic action of iron at the moment of burst of micro bubbles. The hydroxyl free radical has very fast reaction speed, and the generated super strong oxidation can convert the organic matters which are difficult to be biodegraded into small molecules or completely mineralize, so that cyanide and thiocyanide are completely mineralized.
Sending the wastewater rich in micro-nano bubbles of 500nm-1 mu m into a zero-valent iron reactor 22, and adding acid liquor, such as: acetic acid, sulfuric acid and/or hydrochloric acid, and adjusting the pH value to 2-4; depending on water quality, 0.5-100 g/L of zero-valent iron is added, such as: micron-sized iron powder and/or iron shavings; continuously reacting for 20min to 12h at the stirring speed of 30 to 100 rpm;
the water from the zero-valent iron reactor 22 is pumped to a tubular ultrafiltration membrane group with the filtering precision of 20nm, so that various macromolecular and macromolecular organic matters, unreacted zero-valent iron, micro-nano bubbles, fine suspended matters, colloids and the like in the wastewater can be effectively intercepted, and the wastewater returns to the zero-valent iron reactor 22 of the process system for circular treatment. So that the produced water does not contain macromolecules, macromolecular organic matters, fine suspended matters and colloids.
Feeding the produced water of the tubular ultrafiltration membrane group into a clarification tank, adding sodium hydroxide and/or potassium hydroxide alkali liquor, and adjusting the pH value of the wastewater to 6.8-7.5, wherein the produced water of the tubular ultrafiltration membrane group contains Fe3+Becomes Fe (OH) under neutral environment3Precipitating flocs, and treating precipitate sludge; supernatant in the clarification tank overflows to a water production tank so as to be beneficial to further treatment of the biofilm reactor.
And then, when the system puts the produced water of the water producing tank into operation, 30-70% of biological carriers are added to the anaerobic/facultative/aerobic biomembrane reactor according to the water quality.
During the biological domestication, the micro-nano bubble-zero-valent iron unit 20 is adopted to produce water, water is manually distributed, and the proportion of actual wastewater is gradually increased until the water completely enters the micro-nano bubble-zero-valent iron unit 20 to produce raw water. Respectively adding high-efficiency composite anaerobic/facultative/aerobic bacteria in the acclimation culture process of the anaerobic/facultative/aerobic biomembrane reactor, and fixing the bacteria on the surface and inside the carrier.
After the anaerobic/facultative/aerobic biomembrane reactor is formally started, the micro-nano bubble-zero-valent iron unit 20 produces water and sends the water into the anaerobic reactor and the facultative reactor. Most of biodegradable organic matters, nitrite nitrogen and nitrate nitrogen are removed in the anaerobic reactor and the facultative reactor, and the organic nitrogen is converted into ammonia nitrogen. The temperature of the anaerobic/facultative biomembrane reactor is kept between 30 and 35 ℃, the hydraulic retention time is 12 to 48 hours, and the COD volume load can reach 20 kg/(m)3D), the removal rate is 70% -90%, and the concentration of nitrite nitrogen and nitrate nitrogen in the effluent of the facultative biomembrane reactor is obviously reduced.
The effluent of the facultative biomembrane reactor enters an aeration biological filter 33, is thoroughly nitrified to remove ammonia nitrogen, and simultaneously removes a part of total nitrogen and the rest biochemical organic matters. In the biological aerated filter 33, an anaerobic-anoxic-aerobic microenvironment can be formed inside the carrier due to the immobilization of the efficient composite microorganisms, the nitrifying bacteria are fixed on the surface layer of the carrier, and the denitrifying bacteria are fixed inside the carrier, so that an environment is created for the occurrence of synchronous nitrification and denitrification reactions, and the removal of total nitrogen is facilitated. The temperature of the biological aerated filter 33 is kept between 20 ℃ and 30 ℃, the retention time is 12 to 36 hours, and the concentration of dissolved oxygen is 2 to 6 mg/L; the volume load of COD can reach 10 kg/(m)3D), the removal rate is 65% -98%; the ammonia nitrogen volume load can reach 0.5-2.0 kg/(m)3D), the removal rate is as high as 99%; the total nitrogen removal rate of the aeration biological filter 33 part can reach 50-70%, and the effluent part flows back to the anaerobic biomembrane reactor or the facultative biomembrane reactor for further removing the residual nitrogen oxides.
The biological treatment of the coal chemical industry wastewater is enhanced, COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide and thiocyanide in the coal chemical industry wastewater are effectively removed, the water quality of produced water is superior to the requirement of GB8978-1996 integrated wastewater discharge standard, and the produced water is further treated for reuse or directly discharged.
For example, after certain coal chemical industry wastewater is pretreated, the oil content of the pretreated water is 8.5 mg/L; phenols 586 mg/L; the ammonia nitrogen is 1265 mg/L; CODcr is 12000 mg/L; BOD5 at 2200 mg/L; cyanide is about 0.2 mg/L; thiocyanide is about 26 mg/L; the pH was 8.6.
Pretreated water firstly enters a micro-nano bubble generator, wastewater is efficiently mixed with 500nm-1 mu m bubbles generated by the micro-nano bubble generator, the wastewater rich in the 500nm-1 mu m micro-nano bubbles is sent to a zero-valent iron reactor 22, and acetic acid is added to adjust the pH value to 3; adding 60g/L of micron-sized iron powder zero-valent iron; continuously reacting for 2 hours at the stirring speed of 60 rpm; pumping the water discharged from the zero-valent iron reactor 22 to a tubular ultrafiltration membrane group with the filtering precision of 20nm, returning the concentrated water of the tubular ultrafiltration membrane group to the zero-valent iron reactor 22 of the process system for circular treatment, sending the water produced by the tubular ultrafiltration membrane group to a clarification tank, adding sodium hydroxide to adjust the PH of the wastewater to 7, and treating the sediment sludge in the clarification tank; supernatant in the clarification tank overflows to a water production tank so as to be beneficial to further treatment of the biofilm reactor.
The biofilm treatment unit 30 is composed of an anaerobic/facultative/aerobic biofilter.
The biological carrier filling rate of the anaerobic/facultative/aerobic biological filter pool is 50 percent, high-efficiency composite anaerobic/facultative/aerobic bacteria are respectively added in the acclimation culture process of the anaerobic/facultative/aerobic biological membrane reactor, the temperature of the anaerobic/facultative biological membrane reactor is kept at about 33 ℃, the hydraulic retention time is 36h, the COD volume load is 20kg/(m & lt/& gt)3D); the temperature of the biological aerated filter 33 is kept at about 25 ℃, the retention time is 24 hours, and the concentration of dissolved oxygen is 6 mg/L; COD volumetric load 10 kg/(m)3D), ammonia nitrogen volume load 1.25 kg/(m)3·d)。
The main water quality indexes of the produced water reach: CODcr is less than or equal to 24 mg/L; BOD5 is less than or equal to 3.1 mg/L; phenols are less than or equal to 0.35 mg/L; ammonia nitrogen is less than or equal to 2.6 mg/L; cyanide, thiocyanate, and oil were not detected and the pH was about 6.84.
Although terms such as pretreatment unit, micro-nano bubble-zero valent iron unit, gas-liquid mixing unit, zero valent iron reactor, separation unit, filtration unit, biofilm treatment unit, anaerobic biofilter, facultative biofilter, aerated biofilter, reflux unit, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The utility model provides a micro-nano bubble-zeroth order iron advanced treatment wastewater system, includes pretreatment unit (10) and micro-nano bubble-zeroth order iron unit (20), its characterized in that, micro-nano bubble-zeroth order iron unit (20) include:
a gas-liquid mixing unit (21) which mixes the wastewater treated by the pretreatment unit (10) with the introduced air and/or oxygen and enables the oxygen in the wastewater to reach the super-saturated solubility;
a zero-valent iron reactor (22) for degrading the wastewater treated by the pretreatment unit (10);
and a separation unit (23) for removing iron ions in the wastewater after the zero-valent iron reactor (22) is degraded.
2. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 1, characterized in that: the pretreatment unit (10) is used for treating wastewater, and the treatment comprises one or more modes of flocculation, softening, oil removal, dephenolization and deamination.
3. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 1, characterized in that: the gas-liquid mixing unit (21) comprises a micro-nano bubble generator.
4. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 3, characterized in that: the diameter of the micro-nano bubbles generated in the micro-nano bubble generator is 500nm-1 μm.
5. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 1, characterized in that: the separation unit (23) comprises a clarification tank for receiving wastewater degraded by the zero-valent iron reactor (22), and precipitates of iron are produced by adjusting the pH of the wastewater in the clarification tank.
6. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 1, characterized in that: the micro-nano bubble-zero-valent iron unit (20) further comprises a filtering unit (24) arranged between the zero-valent iron reactor (22) and the separating unit (23).
7. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 1, characterized in that: the biological membrane treatment unit (30) is used for removing one or more pollutants of COD, phenols, ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, organic nitrogen, trace phosphorus, cyanide and thiocyanide in the wastewater treated by the micro-nano bubble-zero-valent iron unit (20).
8. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 7, characterized in that: the biological membrane treatment unit (30) comprises an anaerobic biological filter (31), a facultative biological filter (32) and an aeration biological filter (33) which are arranged in sequence.
9. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 8, characterized in that: and carriers for filling immobilized microorganisms are arranged in the anaerobic biological filter (31), the facultative biological filter (32) and the aeration biological filter (33).
10. The micro-nano bubble-zero-valent iron advanced wastewater treatment system according to claim 8, characterized in that: and a backflow device (34) is arranged at the rear end of the biological aerated filter (33), and the backflow device (34) is used for returning the effluent water treated by the biological aerated filter (33) to the anaerobic biological filter (31) and/or the facultative biological filter (32).
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