CN117326692A - Integrated ozone catalytic backwashing SiC ceramic membrane bioreactor and process method for treating hydrocarbon-containing wastewater - Google Patents
Integrated ozone catalytic backwashing SiC ceramic membrane bioreactor and process method for treating hydrocarbon-containing wastewater Download PDFInfo
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Abstract
The invention relates to an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor and a process method for treating hydrocarbon-containing wastewater, which belong to the field of wastewater treatment and comprise a vertically arranged reactor main body, wherein the reactor main body is sequentially divided into an aerobic reaction zone, an anoxic reaction zone and an anaerobic reaction zone from top to bottom; the top of the anaerobic reaction zone is connected with a submerged gas collecting device which is used for collecting methane generated in the anaerobic reaction zone, a plate-type ceramic membrane is arranged in the aerobic reaction zone, the outer wall of the aerobic reaction zone is connected with the bottom of the anaerobic reaction zone through a pipeline to form external circulation, the bottom of the anaerobic reaction zone is connected with a matrix barrel, wastewater, a carbon source, nutrient salt and trace elements are arranged in the matrix barrel, and the wastewater flows out from a water outlet of the plate-type ceramic membrane after being treated in the anaerobic reaction zone, the anoxic reaction zone and the aerobic reaction zone. The invention combines chemical repair and microbial repair, which complement each other, and can solve the problem of high chemical treatment cost and make up the defect of low biological treatment efficiency.
Description
Technical Field
The invention relates to an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor and a process method for treating hydrocarbon-containing wastewater, in particular to an integrated vertical circulating flow membrane bioreactor which utilizes an ozone catalytic oxidation process to couple a silicon carbide ceramic membrane, which efficiently degrades polycyclic aromatic hydrocarbon, has important significance for advanced treatment of difficult-degradation wastewater, recovery of biological methane gas and reduction of carbon emission, and belongs to the technical field of wastewater treatment.
Background
Multi-modal, widely distributed polycyclic aromatic hydrocarbons are detrimental to all forms of life, are a tough, hydrophobic contaminant, are carcinogenic and cumulative, and are a serious threat to human health and ecosystem safety worldwide. Therefore, the environmental remediation of the polycyclic aromatic hydrocarbon polluted site has important significance for ecological remediation.
Current treatments of hydrocarbon-containing wastewater mostly utilize singly physical, chemical methods or bioremediation techniques. Wherein, the physical and chemical methods such as supercritical extraction, steam extraction, chemical oxidation, electrochemistry and the like have high cost and are easy to cause secondary pollution to the environment. In contrast, the bioremediation technology has less energy expenditure and can realize in-situ remediation, becomes a promising green technology for remedying the polycyclic aromatic hydrocarbon polluted site, improves the possibility of environmental safety, but has the problem of longer restoration period.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the integrated ozone catalytic backwashing SiC ceramic membrane bioreactor and the process method for treating the hydrocarbon-containing wastewater, which combine chemical restoration and microbial restoration, and supplement each other, so that the problems of high chemical treatment cost can be solved, and the defect of low biological treatment efficiency can be overcome.
The invention adopts the following technical scheme:
an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor comprises a vertically arranged reactor main body, wherein the reactor main body is sequentially divided into an aerobic reaction zone, an anoxic reaction zone and an anaerobic reaction zone from top to bottom;
the top of the anaerobic reaction zone is connected with a submerged gas collecting device which is used for collecting methane generated in the anaerobic reaction zone, a plate-type ceramic membrane is arranged in the aerobic reaction zone, an aeration port and a water outlet are arranged on the upper part of the plate-type ceramic membrane, the aeration port is connected with an ozone micro-aeration device, and the water outlet is connected with a water outlet pump;
the outer wall of the aerobic reaction zone is connected with the bottom of the anaerobic reaction zone through a pipeline to form an external circulation, the bottom of the anaerobic reaction zone is connected with a substrate barrel, wastewater, a carbon source (such as cyclodextrin), nutritive salt and microelements are contained in the substrate barrel, the wastewater contains medium-to-low-ring PAHs, and the wastewater in the substrate barrel flows out from a water outlet of the plate-type ceramic membrane after being treated by the anaerobic reaction zone, the anoxic reaction zone and the aerobic reaction zone. Because the substances in the substrate barrel enter from the bottom of the anaerobic reaction zone, the concentration of the bottom of the whole reactor main body is larger, the concentration of the upper part is small, and the substances can flow circularly by external circulation, so that the inside of the reactor main body is ensured to be more homogeneous, and the reaction is more thorough.
The invention has a three-section special structure for enriching aerobic, facultative and anaerobic different functional floras, realizes the vertical circulation flow of organic substances in fluid mechanics, and can quickly domesticate compact facultative/anaerobic granular sludge;
ozone prepared by an ozone micro-aeration device in the aerobic reaction zone is in contact reaction with PAH in the aerobic zone, ozone in the catalytic oxidation zone in the cavity of the plate-type ceramic membrane is uniformly introduced into the inner cavity of the micron-sized plate-type ceramic membrane (the pore diameter of the membrane is 0.45-0.1 micron), and released to the upper layer zone of the reactor through the membrane pores, and the ozone is used for flushing dirt oxidation degradation synchronous gas in the cavity when passing through the membrane pores, so that the self-cleaning of the ceramic membrane is realized. Ozone microbubbles generated during the aeration of the microporous ceramic membrane are beneficial to the gas-liquid mass transfer process, and the residual ozone diffused from the catalytic oxidation area in the cavity is used as an electron acceptor in the reactor to oxidize and degrade polycyclic aromatic hydrocarbon and is used as a carbon source to provide a matrix for microorganisms.
In the anaerobic reaction zone, hydrolytic bacteria and zymophyte can convert macromolecular organic matters into monosaccharides, amino acids, fatty acids, glycerol and the like; the interaction bacteria can decompose small molecular substances generated by the hydrolytic fermentation bacteria to generate acetic acid and hydrogen; methanogens can utilize hydrogen and carbon dioxide to produce methane or to methyl decarboxylate to produce methane; the nitrate reducing bacteria can reduce nitrate into nitrite through nitrate reductase; the sulfate reducing bacteria can oxidize PAHs by microorganisms and reduce sulfate ions to generate S 2- The method comprises the steps of carrying out a first treatment on the surface of the PAH degrading bacteria (Pseudomonas, thick-walled bacteria, clostridium and the like) can degrade PAHs into small molecular compounds by using nitrate, sulfate and the like as electron acceptors, wherein the basic way of the process is to add aromatic succinic acid generated by fumaric acid through glycyl free radicals, and further carry out methylation reaction, hydroxylation reaction and hydroxylation reaction, so as to finally carry out beta-oxidative degradation on the PAHs;
in the anoxic reaction zone, facultative heterotrophic anaerobic microorganisms (denitrifying bacteria) utilize NO in the absence of molecular oxygen 3 - And NO 2 - As electron acceptors, organic matters including pollutants are used as electron donors to complete the reaction process;
PAH degrading bacteria in the aerobic reaction zone convert PAHs into dihydro diol compounds under the action of dioxygenase, then intermediate products such as diol and the like are generated under the action of dehydrogenase, and then the intermediate products are generated through degradation of internal/external oxygenase, and finally the intermediate products are converted into small molecules participating in tricarboxylic acid circulation.
Preferably, the ozone micro-aeration device is connected with an ozone variable frequency delivery pump, a pressure sensor and a check valve are sequentially arranged on a pipeline of the water outlet pump, the check valve can prevent water from flowing back due to pressure difference when the pump is closed, stable and effective data of the pressure sensor meter is realized, the pressure sensor can reflect the film passing pressure to a certain extent, the film passing pressure is used for monitoring the film passing pressure in real time, judging the blocking condition of the film, the pressure sensor is in signal connection with a multifunctional display control device, the display control device is in signal connection with the ozone micro-aeration device, and the ozone micro-aeration device is intelligently started when the pressure is overlarge.
Preferably, the aerobic reaction zone is connected with a liquid level sensor, the liquid level sensor is connected with a microcontroller, the microcontroller is connected with a water outlet pump through a switch, when the liquid level in the aerobic reaction zone exceeds a certain upper limit value, the microcontroller controls the switch to be started, and when the liquid level is lower than a certain lower limit value, the microcontroller controls the switch to be closed, and the water outlet pump stops working.
Preferably, the reactor main body is cylindrical, a separator is arranged between the anoxic reaction zone and the anaerobic reaction zone, the separator is an arc-shaped cap, the outer diameter of the separator is the same as the inner diameter of the reactor main body, the separator is made of plastic materials, the top of the separator is provided with an air outlet, and the air outlet is connected with a submerged gas collecting device;
preferably, a plurality of sampling ports are further arranged on the anaerobic reaction zone, so that experimental study is facilitated.
Preferably, the submerged gas collecting device is connected with the collecting container through a gas flowmeter, and the gas flowmeter is used for measuring and recording the methane production amount, so that the methane is effectively separated from the upper-layer ozone and oxygen;
preferably, the upper part of the aerobic reaction zone of the reactor main body is also provided with an overflow port;
preferably, the reactor main body is arranged in a water bath, and inlets and outlets are arranged on the water bath and the reactor and used for circulating water to flow, so that the temperature of the reactor main body is ensured to be 37 ℃.
Preferably, there is no obvious structural boundary between the aerobic reaction zone and the anoxic reaction zone, and the microorganisms in the aerobic reaction zone and the anoxic reaction zone are enriched on the arc-shaped cap between the anoxic reaction zone and the anaerobic reaction zone, and a small number of aerobic microorganisms are attached to the plate-type ceramic membrane.
The aerobic reaction zone is positioned at the uppermost layer of the reactor, the top of the reactor main body is semi-sealed, oxygen dissolved in water and oxygen catalytically converted by ozone ensure the concentration of dissolved oxygen, an aeration device is not needed to be added, the middle layer of the reactor is an anoxic reaction zone, and the lower layer of the reactor is isolated from oxygen to form an anaerobic reaction zone. Through reasonable design of longitudinal space, functional flora with different oxygen demands is enriched, and metabolic diversity of the functional flora is realized.
Preferably, the outer circulation pipeline is provided with an electromagnetic valve A and a water inlet pump, and the substrate barrel is connected with the water inlet pump through an electromagnetic valve B;
preferably, the plate-type ceramic membrane is a rectangular silicon carbide plate-type ceramic membrane, the top end of the plate-type ceramic membrane is stuck with a groove with two openings, namely an aeration opening for ozone inlet and a water outlet for water pumping, the rest part of the plate-type ceramic membrane is composed of the silicon carbide ceramic membrane, the volume of the plate-type ceramic membrane accounts for 1/4 of the total volume of the aerobic reaction zone, the plate-type ceramic membrane is immersed in liquid in the aerobic reaction zone, and the membrane aperture of the plate-type ceramic membrane is 0.45-0.1 micron;
the silicon carbide ceramic membrane has the characteristic of high-efficiency interception, further improves the solid-liquid separation efficiency, intercepts organic matters and microorganisms, realizes enrichment and concentration of PAH degrading bacteria in a long generation period, and is beneficial to maintaining the stable operation of the reactor. Therefore, the invention can realize the resource recovery of biological methane gas and the efficient degradation of polycyclic aromatic hydrocarbon, realize the functional division in the integrated reactor to enrich different functional bacterial groups, the degradation rate can reach more than 80 percent, provide viable references for the multifunctional integrated large-scale membrane bioreactor, and provide a solution for the treatment of difficult-to-degrade PAH pollutants and the application bottleneck of membrane pollution.
Further preferably, the rotation speed of the water outlet pump is 60rpm, and the water outlet flux of the water outlet pump control plate type ceramic membrane is 7.8x10 -3 m 3 /m 2 Min, when the pressure sensor is 60Kpa, the membrane passing flux is zero, and the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite.
The device scientifically and reasonably adopts the coupling technology of ozone catalytic oxidation and inorganic ceramic membrane in-pore catalytic conversion and separation, ozone is released from a ceramic membrane cavity in the form of micro bubbles, so that the high-efficiency advanced treatment of ozone is realized, the quality of effluent is guaranteed, meanwhile, the dual targets of shearing and flushing in an ozone gas cavity to lighten membrane pollution are realized, gas is sprayed from membrane micropores, the generated shearing force enables pollutants to fall off from the membrane pores, meanwhile, liquid turbulence around the membrane is caused, the hydraulic shearing force flushes the surface of the membrane, the formation of a filter cake layer is effectively controlled, and the flux is increased. In addition, micro-bubble ozone in an aerobic/anoxic zone at the upper part of the reaction device enters a system, ozone free radicals are simultaneously used as high-efficiency electron acceptors to promote the degradation process of the polycyclic aromatic hydrocarbon, microorganisms in the anaerobic zone at the lower part obtain most or all carbon sources and energy sources from a matrix, then the polycyclic aromatic hydrocarbon substances in the same medium are degraded, and PAH is efficiently converted to produce methane. The device is also provided with a submerged gas collecting device, and the top of the device is connected with a silica gel hose and a gas flowmeter, so that the separation and recovery of methane gas and ozone aeration are realized.
The technological process of treating hydrocarbon-containing waste water with integral ozone catalytic back washing SiC ceramic film bioreactor includes the first opening solenoid valve A and water inlet pump for 70 sec, the subsequent opening solenoid valve B, and the subsequent opening solenoid valve B to make waste water, carbon source, nutritive salt and trace elements enter anaerobic reaction area, anoxic reaction area and aerobic reaction area successively, so as to degrade pollutant with different bacteria, collecting methane produced in the anaerobic reaction area via the submerged gas collector, measuring methane yield with the gas flowmeter, and the ozone micro aeration device to work, ozone entering the plate ceramic film, catalyzing and oxidizing colloid matter in the plate ceramic film to slow down film pollution, gas flushing and hydraulic shearing to slow down the formation of filter cake layer, and the subsequent catalytic oxidation of residual ozone released to the aerobic reaction area to further degrade pollutant to realize the biochemical combined efficient degradation of pollutant, i.e. the pollutant is fully contacted with the substrate and the pollutant, and the pollutant is degraded through microbial degradation and ozone catalytic oxidation;
and (3) discharging water from the reactor, filtering the wastewater by the plate-type ceramic membrane, and outputting the wastewater from a water outlet of the plate-type ceramic membrane by means of a water discharge pump.
Preferably, the process of degrading the contaminant is:
the anaerobic microorganism in the anaerobic reaction zone can utilize electron acceptors such as nitrate, sulfate and the like to oxidize and degrade PAHs organic matters and generate carbon dioxide and methane;
facultative heterotrophic anaerobic microorganisms in anoxic reaction zones utilize NO in the absence of molecular oxygen 3 - And NO 2 - As electron acceptors, organic matters including pollutants are used as electron donors to complete the reaction process;
bacteria in the aerobic reaction zone convert PAHs into dihydrodiol compounds under the action of dioxygenase, then intermediate products such as diol and the like are generated under the action of dehydrogenase, and then the intermediate products are generated through degradation of internal/external oxygenase, and finally the intermediate products are converted into small molecules participating in tricarboxylic acid circulation.
Preferably, after the substances in the substrate barrel sequentially enter the anaerobic reaction zone, the anoxic reaction zone and the aerobic reaction zone, the substances are fully mixed in the reactor main body through hydraulic stirring, gas stripping stirring and pneumatic stirring;
the hydraulic stirring means that substances in a substrate barrel enter from the bottom of the anaerobic reaction zone through a water inlet pump, and then enter the bottom of the anaerobic reaction zone again through pumping water from the aerobic reaction zone through external circulation, so that the hydraulic stirring is realized;
the gas stripping stirring is realized by causing liquid to vertically move in the process that methane gas generated by microorganisms in an anaerobic reaction zone ascends into a submerged gas collecting device;
the pneumatic stirring means that ozone gas enters the plate-type ceramic membrane and is sprayed out through membrane holes to cause the turbulence of liquid around the membrane to perform hydraulic shearing stirring so as to realize pneumatic stirring.
Preferably, when the liquid level sensor senses that the liquid level exceeds the upper limit value, the microcontroller controls the switch to be turned on, so that the water outlet pump works to start water outlet of the reactor, when the liquid level sensor senses that the liquid level is lower than the lower limit value, the water outlet pump is turned off, water outlet is stopped, the water outlet pump is controlled by the liquid level sensor, when the liquid level at the upper end is reached, the water outlet pump is turned on, and when the liquid level at the lower end is discharged, the water outlet pump is turned off, and the silicon carbide ceramic membrane is ensured to be immersed in water phase during the reaction;
the pressure sensor records the pipeline pressure in real time and displays the pipeline pressure on the display control device in real time, and when the display pressure on the display control device is 60Kpa, the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite;
preferably, the ozone micro-aeration device is periodically started, and the frequency calculation formula for controlling the ozone to be introduced is as follows:
f(P)＝P max
wherein:
p is the pressure of the passing film, kilopascals;
p max is the maximum film pressure within a period of 10 minutes, kilopascals;
t is the working time of the ozone micro-aeration device in a period of 10 minutes, and is seconds;
further preferably, the rotation speed of the water inlet pump is 60rpm, the electromagnetic valve A and the electromagnetic valve B are intermittently operated, the external circulation controlled by the electromagnetic valve A is 70 seconds/10 minutes, the water inlet period controlled by the electromagnetic valve B is 40 seconds/10 minutes, and the reaction device also comprises a time controller which can control the intermittent opening and closing of the electromagnetic valve A and the electromagnetic valve B;
ozone addition amount in the aerobic reaction zone is 2-10mg/L, and dissolved oxygen (mg/L): the aerobic reaction zone is about 2.2mg/L, the anoxic reaction zone is about 0.6mg/L, and the anaerobic reaction zone is less than 0.2mg/L;
the pH value in the matrix barrel is 7.5, the hydraulic retention time is 2-24 hours, the main body of the reactor is made of organic glass, the total volume is preferably 7L, and the volume ratio of the aerobic reaction zone to the anoxic reaction zone to the anaerobic reaction zone is 3:1:1, the Total Solid (TS) in the aerobic reaction zone is 9.41%, the anoxic reaction zone is 9.49% and the anaerobic reaction zone is 10.00%.
According to the characteristic of difficult degradation of the hydrocarbon-containing wastewater, the ozone oxidation technology, the microorganism restoration technology and the membrane separation technology are combined, so that the degradation problem of the difficult degradation pollutants is solved, the ceramic membrane is delayed from being blocked, the utilization rate of the ceramic membrane is improved, and theoretical basis and technical support are provided for efficiently treating the hydrocarbon-containing wastewater and collecting biogas resources.
Reference is made to the prior art for details not specifically mentioned in this application.
The beneficial effects of the invention are as follows:
1) The invention solves the problems that the hydrocarbon-containing wastewater is difficult to degrade and the microporous ceramic membrane in the bioreactor is easy to block. Aiming at the water quality characteristics of the hydrocarbon-containing wastewater, the device integrates the high-efficiency membrane separation process and advanced oxidation and microorganism restoration. The longitudinal vertical functional division is used for enriching various functional bacterial groups, so that the occupied area is saved, and pollutants in the wastewater are fully contacted with microorganisms with different functions through hydraulic shearing stirring, air stripping stirring and pneumatic stirring, so that the wastewater is efficiently degraded. At the same time, ozone micro-bubbles are released to the upper layer of the reactor to oxidize and degrade polycyclic aromatic hydrocarbon, the ozone micro-bubbles are beneficial to the gas-liquid mass transfer process, and the purpose of high-efficiency degradation is achieved by biochemical organic combination.
2) The anaerobic microorganism (the microorganism which has activity in wastewater and high removal efficiency and produces gas) is adopted to carry out high-density anaerobic digestion to produce methane at the bottom of the reactor, and methane is collected in a submerged gas collection mode, so that the methane is effectively separated from ozone and oxygen, and the high-efficiency degradation of pollutants and the recovery of clean energy are simultaneously realized in the reactor.
3) The plate-type ceramic membrane is immersed in the aerobic reaction zone and is positioned at the front end of the water outlet pump of the reactor, so that the sludge loss is reduced, the solid-liquid separation is effectively carried out, and the treatment performance of the bioreactor is maintained stable. The free radicals such as hydroxyl generated by ozone in the membrane can effectively degrade colloid substances causing membrane pollution, so that the permeation flux is improved, the ozone gas flushing also plays a role in assisting membrane cleaning, the membrane blockage is effectively delayed, and the service cycle of the microporous ceramic membrane is prolonged.
Drawings
FIG. 1 is a schematic diagram of an integrated ozone catalytic backwash SiC ceramic membrane bioreactor structure;
the device comprises a 1-aerobic reaction zone, a 2-anoxic reaction zone, a 3-anaerobic reaction zone, a 4-water inlet pump, a 5-electromagnetic valve B, a 6-electromagnetic valve A, a 7-substrate barrel, an 8-aeration port, a 9-water outlet, a 10-submerged gas collecting device, an 11-gas flowmeter, a 12-liquid level sensor, a 13-switch, a 14-microcontroller, a 15-plate type ceramic membrane, a 16-ozone micro-aeration device, a 17-ozone variable frequency delivery pump, a 18-pressure sensor, a 19-display control device, a 20-check valve, a 21-water outlet pump, a 22-separator and a 23-sampling port.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments, but not limited thereto, and the present invention is not fully described and is according to the conventional technology in the art.
Example 1
An integrated ozone catalytic backwashing SiC ceramic membrane bioreactor is shown in figure 1, and comprises a vertically arranged reactor main body, wherein the reactor main body is sequentially divided into an aerobic reaction zone 1, an anoxic reaction zone 2 and an anaerobic reaction zone 3 from top to bottom;
the top of the anaerobic reaction zone 3 is connected with a submerged gas collecting device 10, the submerged gas collecting device 10 is used for collecting methane generated in the anaerobic reaction zone, a plate-type ceramic membrane 15 is arranged in the aerobic reaction zone 1, an aeration port 8 and a water outlet 9 are arranged at the upper part of the plate-type ceramic membrane 15, the aeration port 8 is connected with an ozone micro-aeration device 16, and the water outlet 9 is connected with a water outlet pump 21;
the outer wall of the aerobic reaction zone 1 is connected with the bottom of the anaerobic reaction zone 3 through a pipeline to form an outer circulation, the bottom of the anaerobic reaction zone 3 is connected with a matrix barrel 7, wastewater, a carbon source (such as cyclodextrin), nutritive salt and microelements are contained in the matrix barrel 7, the wastewater contains medium-to-low-ring PAHs, and the wastewater in the matrix barrel 7 flows out from a water outlet of the plate-type ceramic membrane 15 after being treated by the anaerobic reaction zone 3, the anoxic reaction zone 2 and the aerobic reaction zone 1. Because the substances in the substrate barrel 7 enter from the bottom of the anaerobic reaction zone, the concentration of the bottom of the whole reactor main body is larger, the concentration of the upper part is small, and the substances can flow circularly by external circulation, so that the inside of the reactor main body is ensured to be more homogeneous, and the reaction is more thorough.
The invention has a three-section special structure for enriching aerobic, facultative and anaerobic different functional floras, realizes the vertical circulation flow of organic substances in fluid mechanics, and can quickly domesticate compact facultative/anaerobic granular sludge;
ozone prepared by an ozone micro-aeration device in the aerobic reaction zone 1 is in contact reaction with PAH in the aerobic zone, ozone in a catalytic oxidation zone in a cavity of the plate-type ceramic membrane 15 is uniformly introduced into an inner cavity of a micron-sized plate-type ceramic membrane (the pore diameter of the membrane is 0.45-0.1 micron), the ozone is released to an upper layer zone of the reactor through a membrane pore, and dirt is oxidized and degraded in the cavity and synchronously gas is flushed when the ozone passes through the membrane pore, so that the self-cleaning of the ceramic membrane is realized. Ozone microbubbles generated during the aeration of the microporous ceramic membrane are beneficial to the gas-liquid mass transfer process, and the residual ozone diffused from the catalytic oxidation area in the cavity is used as an electron acceptor in the reactor to oxidize and degrade polycyclic aromatic hydrocarbon and is used as a carbon source to provide a matrix for microorganisms.
In the anaerobic reaction zone 3, hydrolytic bacteria and zymophyte can convert macromolecular organic matters into monosaccharides, amino acids, fatty acids, glycerol and the like; the interaction bacteria can decompose small molecular substances generated by the hydrolytic fermentation bacteria to generate acetic acid and hydrogen; methanogens can utilize hydrogen and carbon dioxide to produce methane or to methyl decarboxylate to produce methane; the nitrate reducing bacteria can reduce nitrate into nitrite through nitrate reductase; the sulfate reducing bacteria can oxidize PAHs by microorganisms and reduce sulfate ions to generate S 2- The method comprises the steps of carrying out a first treatment on the surface of the PAH degrading bacteria (Pseudomonas, thick-walled bacteria, clostridium and the like) can degrade PAHs into small molecular compounds by using nitrate, sulfate and the like as electron acceptors, wherein the basic way of the process is to add aromatic succinic acid generated by fumaric acid through glycyl free radicals, and further carry out methylation reaction, hydroxylation reaction and hydroxylation reaction, so as to finally carry out beta-oxidative degradation on the PAHs;
in the anoxic reaction zone 2, facultative heterotrophic anaerobic microorganisms (denitrifying bacteria) utilize NO in the absence of molecular oxygen 3 - And NO 2 - As electron acceptors, organic matters including pollutants are used as electron donors to complete the reaction process;
PAH degrading bacteria in the aerobic reaction zone 1 convert PAHs into dihydro diol compounds under the action of dioxygenase, then intermediate products such as diol and the like are generated under the action of dehydrogenase, and then the intermediate products are generated through degradation of internal/external oxygenase, and finally the intermediate products are converted into small molecules participating in tricarboxylic acid circulation.
Example 2
An integrated ozone catalytic backwashing SiC ceramic membrane bioreactor has a structure as shown in an embodiment 1, and is characterized in that an ozone micro-aeration device 16 is connected with an ozone variable frequency conveying pump 17, a water outlet 9 is connected with a pipeline of a water outlet pump 21, a pressure sensor 18 and a check valve 20 are sequentially arranged on the pipeline, the check valve 20 can prevent water from flowing back due to pressure difference at the closing moment of the pump, stable and effective data of the pressure sensor meter is realized, the pressure sensor 18 can reflect the membrane passing pressure to a certain extent, the pressure sensor is used for monitoring the membrane passing pressure in real time and judging the membrane blocking condition, the pressure sensor 18 is in signal connection with a multifunctional display control device 19, the display control device 19 is in signal connection with the ozone micro-aeration device 16, and the ozone micro-aeration device is intelligently started when the pressure is overlarge.
Example 3
The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor has the structure shown in an embodiment 2, and is characterized in that a liquid level sensor 12 is connected to an aerobic reaction zone 1, the liquid level sensor 12 is connected with a microcontroller 14, the microcontroller 14 is connected with a water outlet pump 21 through a switch 13, when the liquid level in the aerobic reaction zone exceeds a certain upper limit value, the microcontroller 14 controls the switch to be turned on, the water outlet pump 21 works, and when the liquid level is lower than a certain lower limit value, the microcontroller 14 controls the switch to be turned off, and the water outlet pump 21 stops working.
Example 4
An integrated ozone catalytic backwashing SiC ceramic membrane bioreactor has a structure as shown in an embodiment 3, and is characterized in that a reactor main body is cylindrical, a separator 22 is arranged between an anoxic reaction zone and an anaerobic reaction zone, the separator 22 is an arc-shaped cap, the outer diameter of the arc-shaped cap is the same as the inner diameter of the reactor main body, the separator 22 is made of plastic material, and the top of the separator is provided with an air outlet hole which is connected with a submerged gas collecting device;
preferably, a plurality of sampling ports 23 are further arranged on the anaerobic reaction zone, so that experimental study is facilitated.
Example 5
An integrated ozone catalytic backwashing SiC ceramic membrane bioreactor has a structure as shown in an embodiment 4, and is characterized in that a submerged gas collecting device is connected with a collecting container through a gas flowmeter 11, and the gas flowmeter 11 is used for measuring and recording methane production and realizing effective separation of methane from upper-layer ozone and oxygen;
preferably, the upper part of the aerobic reaction zone of the reactor main body is also provided with an overflow port;
preferably, the reactor body is placed in a water bath, and inlets and outlets are arranged on the water bath and the reactor for circulating water to flow, so that the temperature of the reactor body is ensured to be 37 ℃.
Preferably, there is no obvious structural boundary between the aerobic reaction zone and the anoxic reaction zone, and the microorganisms in the aerobic reaction zone and the anoxic reaction zone are enriched on the arc-shaped cap between the anoxic reaction zone and the anaerobic reaction zone, and a small number of aerobic microorganisms are attached to the plate-type ceramic membrane.
The aerobic reaction zone is positioned at the uppermost layer of the reactor, the top of the reactor main body is semi-sealed, oxygen dissolved in water and oxygen catalytically converted by ozone ensure the concentration of dissolved oxygen, an aeration device is not needed to be added, the middle layer of the reactor is an anoxic reaction zone, and the lower layer of the reactor is isolated from oxygen to form an anaerobic reaction zone. Through reasonable design of longitudinal space, functional flora with different oxygen demands is enriched, and metabolic diversity of the functional flora is realized.
Example 6
An integrated ozone catalytic backwashing SiC ceramic membrane bioreactor has the structure shown in an embodiment 5, and is different in that an electromagnetic valve A6 and a water inlet pump 4 are arranged on an outer circulation pipeline, and a substrate barrel 7 is connected with the water inlet pump 4 through an electromagnetic valve B5;
preferably, the plate type ceramic membrane 15 is a rectangular silicon carbide plate type ceramic membrane, the top end of the plate type ceramic membrane is stuck with a groove with two openings, namely an aeration opening for ozone inlet and a water outlet for water pumping, the rest part of the plate type ceramic membrane is composed of silicon carbide ceramic membranes, the volume of the plate type ceramic membrane accounts for 1/4 of the total volume of the aerobic reaction zone, the plate type ceramic membrane is immersed in liquid in the aerobic reaction zone, and the membrane aperture of the plate type ceramic membrane is 0.45-0.1 micron;
the silicon carbide ceramic membrane has the characteristic of high-efficiency interception, further improves the solid-liquid separation efficiency, intercepts organic matters and microorganisms, realizes enrichment and concentration of PAH degrading bacteria in a long generation period, and is beneficial to maintaining the stable operation of the reactor. Therefore, the invention can realize the resource recovery of biological methane gas and the efficient degradation of polycyclic aromatic hydrocarbon, realize the functional division in the integrated reactor to enrich different functional bacterial groups, the degradation rate can reach more than 80 percent, provide viable references for the multifunctional integrated large-scale membrane bioreactor, and provide a solution for the treatment of difficult-to-degrade PAH pollutants and the application bottleneck of membrane pollution.
Further preferably, the rotation speed of the water outlet pump 21 is 60rpm, and the water is dischargedThe water flux of the pump control plate type ceramic membrane is 7.8-10 -3 m 3 /m 2 Min, when the pressure sensor is 60Kpa, the membrane passing flux is zero, and the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite.
The device scientifically and reasonably adopts the coupling technology of ozone catalytic oxidation and inorganic ceramic membrane in-pore catalytic conversion and separation, ozone is released from a ceramic membrane cavity in the form of micro bubbles, so that the high-efficiency advanced treatment of ozone is realized, the quality of effluent is guaranteed, meanwhile, the dual targets of shearing and flushing in an ozone gas cavity to lighten membrane pollution are realized, gas is sprayed from membrane micropores, the generated shearing force enables pollutants to fall off from the membrane pores, meanwhile, liquid turbulence around the membrane is caused, the hydraulic shearing force flushes the surface of the membrane, the formation of a filter cake layer is effectively controlled, and the flux is increased. In addition, micro-bubble ozone in an aerobic/anoxic zone at the upper part of the reaction device enters a system, ozone free radicals are simultaneously used as high-efficiency electron acceptors to promote the degradation process of the polycyclic aromatic hydrocarbon, microorganisms in the anaerobic zone at the lower part obtain most or all carbon sources and energy sources from a matrix, then the polycyclic aromatic hydrocarbon substances in the same medium are degraded, and PAH is efficiently converted to produce methane. The device is also provided with a submerged gas collecting device, and the top of the device is connected with a silica gel hose and a gas flowmeter, so that the separation and recovery of methane gas and ozone aeration are realized.
Example 7
A process for treating hydrocarbon-containing wastewater by an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor comprises the steps of firstly, starting an electromagnetic valve A6 and a water inlet pump 4, externally circulating for 70 seconds, then starting an electromagnetic valve B5, sequentially entering wastewater, a carbon source, nutrient salts and microelements in a matrix barrel 7 into an anaerobic reaction zone 3, an anoxic reaction zone 2 and an aerobic reaction zone 1, degrading pollutants by utilizing different bacterial groups, collecting methane generated in the anaerobic reaction zone by a submerged gas collecting device 10, and metering the methane yield by a gas flowmeter 11. When the ozone micro-aeration device is started, ozone enters the plate-type ceramic membrane 15, catalytic oxidation of colloid substances in the plate-type ceramic membrane and membrane pollution alleviation are carried out, gas flushing and hydraulic shearing alleviation filter cake layer formation are carried out, and residual ozone released to an aerobic reaction zone continues to catalyze and oxidize refractory pollutants, so that biochemical combined high-efficiency degradation of the pollutants is realized, namely, the sludge is fully contacted with a substrate and the pollutants, and the pollutants are efficiently degraded through microbial degradation and ozone catalytic oxidation;
the reactor is discharged, and the wastewater is filtered by the plate-type ceramic membrane and then is output from the water outlet of the plate-type ceramic membrane by means of the water outlet pump 21.
Preferably, the process of degrading the contaminant is:
the anaerobic microorganism in the anaerobic reaction zone can utilize electron acceptors such as nitrate, sulfate and the like to oxidize and degrade PAHs organic matters and generate carbon dioxide and methane;
facultative heterotrophic anaerobic microorganisms in anoxic reaction zones utilize NO in the absence of molecular oxygen 3 - And NO 2 - As electron acceptors, organic matters including pollutants are used as electron donors to complete the reaction process;
bacteria in the aerobic reaction zone convert PAHs into dihydrodiol compounds under the action of dioxygenase, then intermediate products such as diol and the like are generated under the action of dehydrogenase, and then the intermediate products are generated through degradation of internal/external oxygenase, and finally the intermediate products are converted into small molecules participating in tricarboxylic acid circulation.
Example 8
A process for treating hydrocarbon-containing wastewater by an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor is characterized in that substances in a substrate barrel 7 sequentially enter an anaerobic reaction zone 3, an anoxic reaction zone 2 and an aerobic reaction zone 1 and are fully mixed in a reactor main body through hydraulic stirring, gas stripping stirring and pneumatic stirring as described in an embodiment 7;
the hydraulic stirring means that substances in a substrate barrel enter from the bottom of the anaerobic reaction zone through a water inlet pump, and then enter the bottom of the anaerobic reaction zone again through pumping water from the aerobic reaction zone through external circulation, so that the hydraulic stirring is realized;
the gas stripping stirring is realized by causing liquid to vertically move in the process that methane gas generated by microorganisms in an anaerobic reaction zone ascends into a submerged gas collecting device;
the pneumatic stirring means that ozone gas enters the plate-type ceramic membrane and is sprayed out through membrane holes to cause the turbulence of liquid around the membrane to perform hydraulic shearing stirring so as to realize pneumatic stirring.
Example 9
In the process method for treating the hydrocarbon-containing wastewater by the integrated ozone catalytic backwashing SiC ceramic membrane bioreactor, as in the embodiment 7, when the liquid level sensor 12 senses that the liquid level exceeds the upper limit value, the microcontroller 14 controls the switch to be turned on, so that the water outlet pump works the reactor to start water outlet, when the liquid level sensor senses that the liquid level is lower than the lower limit value, the water outlet pump is turned off, water outlet is stopped, the water outlet pump 21 is controlled by the liquid level sensor 12, when the liquid level reaches the upper end, the water outlet pump is turned on, and when the liquid level reaches the lower end, the water outlet pump is turned off, and the silicon carbide ceramic membrane is ensured to be immersed in water phase during the reaction;
the pressure sensor records the pipeline pressure in real time and displays the pipeline pressure on the display control device in real time, and when the display pressure on the display control device is 60Kpa, the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite;
preferably, the ozone micro-aeration device is periodically started, and the frequency calculation formula for controlling the ozone to be introduced is as follows:
f(P)＝P max
wherein:
p is the pressure of the passing film, kilopascals;
p max is the maximum film pressure within a period of 10 minutes, kilopascals;
t is the working time of the ozone micro-aeration device in a period of 10 minutes, and is seconds;
further preferably, the rotation speed of the water inlet pump is 60rpm, the electromagnetic valve A and the electromagnetic valve B are intermittently operated, the external circulation controlled by the electromagnetic valve A is 70 seconds/10 minutes, the water inlet period controlled by the electromagnetic valve B is 40 seconds/10 minutes, and the reaction device also comprises a time controller which can control the intermittent opening and closing of the electromagnetic valve A and the electromagnetic valve B;
ozone addition amount in the aerobic reaction zone is 2-10mg/L, and dissolved oxygen: the aerobic reaction zone is about 2.2mg/L, the anoxic reaction zone is about 0.6mg/L, and the anaerobic reaction zone is less than 0.2mg/L;
the pH value in the matrix barrel is 7.5, the hydraulic retention time is 2-24 hours, the main body of the reactor is made of organic glass, the total volume is preferably 7L, and the volume ratio of the aerobic reaction zone to the anoxic reaction zone to the anaerobic reaction zone is 3:1:1, the Total Solid (TS) in the aerobic reaction zone is 9.41%, the anoxic reaction zone is 9.49% and the anaerobic reaction zone is 10.00%.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor is characterized by comprising a vertically arranged reactor main body, wherein the reactor main body is sequentially divided into an aerobic reaction zone, an anoxic reaction zone and an anaerobic reaction zone from top to bottom;
the top of the anaerobic reaction zone is connected with a submerged gas collecting device which is used for collecting methane generated in the anaerobic reaction zone, a plate-type ceramic membrane is arranged in the aerobic reaction zone, an aeration port and a water outlet are arranged on the upper part of the plate-type ceramic membrane, the aeration port is connected with an ozone micro-aeration device, and the water outlet is connected with a water outlet pump;
the outer wall of the aerobic reaction zone is connected with the bottom of the anaerobic reaction zone through a pipeline to form an external circulation, the bottom of the anaerobic reaction zone is connected with a matrix barrel, waste water, a carbon source, nutrient salts and microelements are arranged in the matrix barrel, and the waste water in the matrix barrel flows out from a water outlet of the plate-type ceramic membrane after being treated by the anaerobic reaction zone, the anoxic reaction zone and the aerobic reaction zone.
2. The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor of claim 1, wherein the ozone micro-aeration device is connected with an ozone variable frequency delivery pump, a pressure sensor and a check valve are sequentially arranged on a pipeline of the water outlet connected with the water outlet pump, the pressure sensor is in signal connection with a display control device, the display control device is in signal connection with the ozone micro-aeration device, and the ozone micro-aeration device is intelligently started when the pressure is overlarge.
3. The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor of claim 2, wherein the aerobic reaction zone is connected with a liquid level sensor, the liquid level sensor is connected with a microcontroller, the microcontroller is connected with a water outlet pump through a switch, when the liquid level in the aerobic reaction zone exceeds a certain upper limit value, the microcontroller controls the switch to be started, the water outlet pump works, when the liquid level is lower than a certain lower limit value, the microcontroller controls the switch to be closed, and the water outlet pump stops working.
4. The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor of claim 1, wherein the reactor body is cylindrical, a separator is placed between the anoxic reaction zone and the anaerobic reaction zone, the separator is an arc cap, the outer diameter of the separator is the same as the inner diameter of the reactor body, the separator is made of plastic material, the top of the separator is provided with an air outlet hole, and the air outlet hole is connected with a submerged gas collecting device;
preferably, a plurality of sampling ports are further arranged on the anaerobic reaction zone, so that experimental study is facilitated.
5. The integrated ozone catalyzed backwashed SiC ceramic membrane bioreactor of claim 4, wherein the submerged gas collection device is connected to the collection vessel through a gas flow meter for measuring methane production;
preferably, the upper part of the aerobic reaction zone of the reactor main body is also provided with an overflow port.
6. The integrated ozone catalytic backwashing SiC ceramic membrane bioreactor of claim 5, wherein an electromagnetic valve A and a water inlet pump are arranged on an outer circulation pipeline, and the substrate barrel is connected with the water inlet pump through an electromagnetic valve B;
preferably, the plate-type ceramic membrane is a rectangular silicon carbide plate-type ceramic membrane, the volume of the plate-type ceramic membrane accounts for 1/4 of the total volume of the aerobic reaction zone, the plate-type ceramic membrane is completely immersed in the liquid in the aerobic reaction zone, and the membrane pore diameter of the plate-type ceramic membrane is 0.45-0.1 micrometer;
further preferably, the rotation speed of the water outlet pump is 60rpm, when the pressure sensor is 60Kpa, the flux of the membrane is zero, and the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite.
7. A process for treating hydrocarbon-containing wastewater by an integrated ozone catalytic backwashing SiC ceramic membrane bioreactor disclosed in claim 6 is characterized in that firstly, an electromagnetic valve A and a water inlet pump are started for external circulation for 70 seconds, then an electromagnetic valve B is started, wastewater, a carbon source, nutrient salt and trace elements in a matrix barrel sequentially enter an anaerobic reaction zone, an anoxic reaction zone and an aerobic reaction zone, pollutants are degraded by utilizing different floras, methane generated in the anaerobic reaction zone is collected by a submerged gas collecting device, the methane yield is measured by a gas flowmeter, meanwhile, an ozone micro-aeration device works, ozone enters a plate-type ceramic membrane, colloid substances are catalytically oxidized in the plate-type ceramic membrane and membrane pollution is slowed down, and residual ozone released to the aerobic reaction zone is continuously catalyzed and oxidized to be difficult to degrade the pollutants, so that biochemical combination high-efficiency degradation of the pollutants is realized;
after the wastewater is treated by the plate-type ceramic membrane, the wastewater flows out from the water outlet of the plate-type ceramic membrane by means of the water outlet pump.
8. The process for treating hydrocarbon-containing wastewater by using the integrated ozone catalytic backwash SiC ceramic membrane bioreactor according to claim 7, wherein the pollutant degradation process is as follows:
anaerobic microorganisms in the anaerobic reaction zone utilize electron acceptors to oxidatively degrade PAHs organic matters and produce carbon dioxide and methane;
facultative heterotrophic anaerobic microorganisms in anoxic reaction zones utilize NO in the absence of molecular oxygen 3 - And NO 2 - As electron acceptors, organic matters including pollutants are used as electron donors to complete the reaction process;
bacteria in the aerobic reaction zone convert PAHs into dihydrodiol compounds under the action of dioxygenase, then intermediate products such as diol and the like are generated under the action of dehydrogenase, and then the intermediate products are generated through degradation of internal/external oxygenase, and finally the intermediate products are converted into small molecules participating in tricarboxylic acid circulation.
9. The process for treating hydrocarbon-containing wastewater by an integrated ozone catalytic backwash SiC ceramic membrane bioreactor according to claim 7, wherein after substances in a substrate barrel enter an anaerobic reaction zone, an anoxic reaction zone and an aerobic reaction zone in sequence, the substances are fully mixed in a reactor main body through hydraulic stirring, air stripping stirring and pneumatic stirring;
the hydraulic stirring means that substances in a substrate barrel enter from the bottom of the anaerobic reaction zone through a water inlet pump, and then enter the bottom of the anaerobic reaction zone again through pumping water from the aerobic reaction zone through external circulation, so that the hydraulic stirring is realized;
the gas stripping stirring is realized by causing liquid to vertically move in the process that methane gas generated by microorganisms in an anaerobic reaction zone ascends into a submerged gas collecting device;
the pneumatic stirring means that ozone gas enters the plate-type ceramic membrane and is sprayed out through membrane holes to cause the turbulence of liquid around the membrane to perform hydraulic shearing stirring so as to realize pneumatic stirring.
10. The process for treating hydrocarbon-containing wastewater by the integrated ozone catalytic backwashing SiC ceramic membrane bioreactor according to claim 7, wherein when the liquid level sensor senses that the liquid level exceeds an upper limit value, the microcontroller controls the switch to be turned on, so that the water outlet pump works the reactor to start water outlet, and when the liquid level sensor senses that the liquid level is lower than a lower limit value, the water outlet pump is turned off, and water outlet is stopped;
the pressure sensor records the pipeline pressure in real time and displays the pipeline pressure on the display control device in real time, and when the display pressure on the display control device is 60Kpa, the ceramic membrane is taken down and soaked and cleaned by sodium hypochlorite;
preferably, the ozone micro-aeration device is periodically started, and the frequency calculation formula for controlling the ozone to be introduced is as follows:
f(P)＝P max
wherein:
p is the pressure of the passing film, kilopascals;
p max is the maximum film pressure within a period of 10 minutes, kilopascals;
t is the working time of the ozone micro-aeration device in a period of 10 minutes, and is seconds;
further preferably, the rotation speed of the water inlet pump is 60rpm, the electromagnetic valve A and the electromagnetic valve B are intermittently operated, the external circulation controlled by the electromagnetic valve A is 70 seconds/10 minutes, and the water inlet period controlled by the electromagnetic valve B is 40 seconds/10 minutes;
ozone addition amount in the aerobic reaction zone is 2-10mg/L, and dissolved oxygen: the aerobic reaction zone is about 2.2mg/L, the anoxic reaction zone is about 0.6mg/L, and the anaerobic reaction zone is less than 0.2mg/L;
the pH value in the matrix barrel is 7.5, the hydraulic retention time is 2-24 hours, the main body of the reactor is made of organic glass, and the volume ratio of the aerobic reaction zone to the anoxic reaction zone to the anaerobic reaction zone is 3:1:1.
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