WO2020124635A1 - 一种负荷增强的废水处理流态化反应装置、系统及方法 - Google Patents

一种负荷增强的废水处理流态化反应装置、系统及方法 Download PDF

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WO2020124635A1
WO2020124635A1 PCT/CN2018/123848 CN2018123848W WO2020124635A1 WO 2020124635 A1 WO2020124635 A1 WO 2020124635A1 CN 2018123848 W CN2018123848 W CN 2018123848W WO 2020124635 A1 WO2020124635 A1 WO 2020124635A1
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sludge
fluid
fluidized bed
zone
reactor
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English (en)
French (fr)
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韦朝海
吴海珍
陈奔
杨兴舟
冯春华
吴超飞
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/08—Aerobic processes using moving contact bodies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • the invention relates to the field of a water treatment bioreactor device and a method for treating high-concentration industrial organic wastewater by using the water treatment bioreactor device, in particular to a fluidized reaction device, system and method for wastewater treatment with enhanced load.
  • FBBR fluidized bed bioreactor
  • the gas-water mixing area at the bottom of the fluidized bed is the area with the most significant energy dissipation, followed by the top of the rising area.
  • the activated sludge with better sedimentation performance settles to the bottom of the fluidized bed under the action of gravity and water drag, and then is discharged from the reactor as excess sludge.
  • the sludge with better sedimentation performance contains higher concentration of microbial micelles that efficiently degrade pollutants, and its loss will reduce the treatment efficiency of the reactor.
  • the scale of the engineering reaction device is limited, limited by the constraints of high-diameter ratio and fluidization, affecting the sludge slip at the bottom of the reactor and the uniform mixing of the three phases.
  • one of the objects of the present invention is to provide a fluidized reaction device for wastewater treatment with increased load, which can identify and separate sludge with different degrees of apoptosis in situ
  • the sludge with high and low apoptosis ratio is retained in the reactor, and the sludge with low activity and high apoptosis ratio is discharged out of the reactor.
  • the realization of this functional selectivity overall improves the pollution inside the fluidized bed reactor. Sludge activity, to achieve high-load operation conditions, under the same operating conditions to improve the reactor's degradation efficiency of pollutants in wastewater.
  • the second object of the present invention is to provide a fluidized reaction system with enhanced load for wastewater treatment, which can operate industrial wastewater, especially coking wastewater, against high-toxic loads , Including advanced treatment of denitrification and reduction of COD, to achieve zero concentration and improve effluent quality.
  • the third objective of the present invention is: to combine objective one and objective two to construct high-concentration (COD and total nitrogen), high-toxicity (cyanide, sulfide, thiocyanide, phenol) wastewater
  • the new treatment process forms a short-range low-consumption and energy-saving high-efficiency process for coking wastewater treatment.
  • a fluidized reaction device for wastewater treatment with enhanced load includes a fluidized bed reactor body, the fluidized bed reactor body is provided with at least one fluid descending zone and fluid rising zone, and the fluidized bed reactor body is provided with a water inlet, The water inlet is provided in the fluid descending area, and the fluidized bed reactor body is provided with a three-phase separator relatively independent of the fluidized bed reactor body in the upper part of the fluid descending area.
  • the three-phase separator includes a three-phase separator barrel with an open upper end The lower end of the three-phase separator is provided with a sludge hopper that communicates with the body of the fluidized bed reactor.
  • the upper part of the three-phase separator is provided with an overflow outflow tank that communicates with the outside of the body of the fluidized bed reactor.
  • an overflow outflow tank that communicates with the outside of the body of the fluidized bed reactor.
  • a water inlet pipe that communicates with the body of the fluidized bed reactor.
  • the three-phase separator is connected with a cyclone separator to separate the remaining sludge from the water phase.
  • the port of the separator water intake pipe is located between the sludge hopper and the overflow outflow tank, and collects a certain proportion of sludge.
  • the water inlet pipe of the three-phase separator includes a vertical pipe arranged longitudinally inside the three-phase separator, a horizontal pipe horizontally arranged outside the three-phase separator, and a connecting pipe connecting the vertical pipe and the horizontal pipe, and one end of the connecting pipe is connected In the middle of the flat tube, the other end of the connecting tube is connected to the lower part of the riser. Both ends of the flat tube can enter the water, and the collision of the two fluids can cause the bubbles to gather and then reverse the water flow in the riser. Row.
  • the fluid drop area of the fluidized bed reactor body is set in the middle area
  • the fluidized bed has a rectangular structure
  • the fluid rise area is located around the fluid drop area
  • the three-phase separator is set at the upper middle position of the fluidized bed reactor body .
  • the fluid drop zone of the fluidized bed reactor body is set at the periphery
  • the fluid rise zone is set to one, located in the center area
  • the fluid drop zone is located around the fluid rise zone
  • the three-phase separator is set at the outer periphery of the fluid drop zone .
  • the aeration device includes an air compressor, an air separation device, an oxygen-enriched gas inlet pipe, and a nitrogen-enriched gas inlet pipe.
  • the air separation device is connected to the air compressor, the oxygen-enriched gas inlet pipe, and One end of the nitrogen-enriched gas inlet pipe is connected to the air separation device, the other end of the oxygen-enriched gas inlet pipe is located in the middle of the fluid drop zone, the end is connected with a microporous aerator, and the other end of the nitrogen-enriched gas inlet pipe It is located at the bottom of the fluid rising zone, and its end is connected with a nitrogen-rich gas distributor.
  • a water flow guiding device is provided at the bottom of the fluid descending zone, and the water flow guiding apparatus is a slope facing the fluid rising zone.
  • a zooming tube is provided in the fluid rising area, and the zooming tube is arranged along the direction of water flow, and the zooming tube is a plurality of continuous tubular pieces arranged at intervals between a large diameter and a small diameter.
  • a fluidized reaction system for wastewater treatment with enhanced load includes a grease trap, an air floatation tank, a regulation tank, a first-level aerobic reactor (O1, carbon removal reaction unit), and a hydrolytic denitrification reactor (H, Hydrolysis and denitrification unit), two-stage aerobic reactor (O2, complete nitrification unit), coagulation sedimentation tank and filter tank, of which one-stage aerobic reactor adopts a fluidized reaction device with enhanced load for wastewater treatment, The two-stage aerobic reactor adopts another kind of fluidized reaction device for wastewater treatment with enhanced load.
  • a fluidized reaction method for wastewater treatment with enhanced load which separates the sludge inside the body of the fluidized bed reactor, introduces the mixed liquid in the body of the fluidized bed reactor into the three-phase separator, and the precipitation performance in the three-phase separator Poor low-activity sludge is discharged from the reactor through an external cyclone separator, and sludge of different apoptotic degrees is identified and separated in situ inside the fluidized bed, and the sludge with high activity and low apoptotic ratio is retained in the reaction In the reactor, the sludge with low activity and high apoptosis ratio is discharged from the reactor to increase the load capacity of wastewater treatment.
  • the high-concentration oxygen is separated by an external air oxygen-nitrogen separation device to form two components of oxygen-enriched gas and nitrogen-enriched gas, and the two components are respectively input into the body of the fluidized bed reactor through two pipes to enrich Nitrogen gas flows into the bottom of the fluid rising zone of the fluidized bed reactor body, which mainly acts as a motive force, and oxygen-rich gas flows into the middle of the fluid falling zone of the fluidized bed reactor body, mainly acts as an oxygen supply.
  • the present invention has the following advantages:
  • a fluidized reaction device for wastewater treatment with enhanced load A three-phase separator in the middle of the settlement area is provided with a water intake pipe for the cyclone separator to separate the sludge with poor settlement performance in the middle of the settlement area.
  • the sludge with better performance Under the effect of gravity and the drag force of the fluid in the fluid descending zone, it re-enters the body of the fluidized bed reactor to participate in the degradation reaction of pollutants, ensuring the stable and high-load operation of the fluidized bed reactor.
  • a load-enhanced waste water treatment fluidization reaction system adopts different types of load-enhanced waste water treatment fluidization reaction devices as a primary aerobic reactor and a secondary aerobic reactor to enhance the treatment capacity of the entire reaction system.
  • load-enhanced waste water treatment fluidization reaction devices for the treatment of high-concentration wastewater, by separating the air, the oxygen-enriched gas and the nitrogen-enriched gas are passed into different locations respectively, and the synergistic effect with the sludge management mode can obtain an efficient wastewater treatment effect.
  • a fluidized reaction method for wastewater treatment with increased load which separates the sludge inside the bioreactor according to the principle of differential gravity flow, and discharges the low-activity sludge with poor sedimentation performance in the three-phase separator through the external cyclone separator and out of the reactor
  • the sludge with low activity and high apoptosis ratio is discharged out of the reactor, thereby improving the efficiency of the reactor.
  • the separation of high-concentration oxygen by an external air separation device can reduce the aeration amount on the one hand to save energy consumption, and on the other hand improve the oxygen utilization efficiency.
  • FIG. 1 is a schematic structural diagram of an embodiment of a fluidized reaction device for wastewater treatment with enhanced load according to the present invention.
  • FIG. 2 is a schematic structural view of another embodiment of a fluidized reaction device for wastewater treatment with enhanced load according to the present invention.
  • FIG. 3 is a schematic structural view of a water inlet pipe of a three-phase separator of a fluidized reaction device for wastewater treatment with enhanced load according to the present invention.
  • FIG. 4 is a schematic diagram of a guide tube partition of a fluidized reaction device for wastewater treatment with enhanced load according to the present invention.
  • FIG. 5 is a schematic structural view of a cross-shaped member of a fluidized reaction device for wastewater treatment with enhanced load according to the present invention.
  • Figure 6 is a flow chart of coking wastewater treatment.
  • FIG. 7 is a diagram of the turbulent kinetic energy distribution (0.4 m cross section) in the radial direction of the reactor.
  • Fig. 8 is a comparative analysis diagram of the simulated value and experimental value of K La when there is no inner member.
  • Figure 9 is a comparative analysis of K La simulation values when there are no internal components and three different internal components.
  • FIG. 10 is a comparison diagram of the liquid circulation speed before and after the cross-shaped inner member is placed in the bottom gap area.
  • Fig. 11 is a comparison diagram of the total gas content of the reactor before and after the cross-shaped inner member is placed in the bottom gap area.
  • Fig. 12 is a comparison chart of the average turbulent kinetic energy in the rising area of the reactor before and after the cross-shaped inner member is placed in the bottom gap area.
  • Figure 13 is a graph comparing the specific oxygen consumption rate and dehydrogenase activity of the separated sludge.
  • Fig. 15 is an EPS composition diagram of separated sludge.
  • Fig. 16 is a potential energy diagram of the internal interaction of flocs for separating sludge.
  • Fig. 17 is a comparison chart of the distribution of apoptotic cells in the separated sludge.
  • Fig. 18 is a graph showing the relationship between the distribution of apoptotic cells in the separated sludge and the activity of the sludge.
  • Fig. 19 is a ⁇ -diversity heat map of separated sludge and a PCoA analysis chart based on the distance from the species (a, heat map; b, PCoA analysis based on unifrac weighting).
  • Fig. 20 is a comparison chart of the distribution of microbial communities based on genus-level separated sludge.
  • Figure 21 is a heat map of microbial community structure based on genus-level separated sludge.
  • Fig. 22 is a function prediction diagram of separating sludge based on community 16S rDNA.
  • Fig. 23 is a composition characteristic diagram of various nitrogen-containing compounds in total nitrogen during the biological treatment process.
  • Fig. 24 is a treatment effect diagram of first-level aerobic fluidized bed thiocyanide and cyanide.
  • Fig. 25 is a graph showing the concentration changes of NH 4 + -N and NO x -- N in a two-stage aerobic fluidized bed.
  • Figures 1 and 2 include:
  • Example 1 the separation zone is placed in the center of the reactor
  • a fluidized reaction device for wastewater treatment with enhanced load includes a fluidized bed reactor body.
  • the fluidized bed reactor body is provided with a fluid descending zone 2 and a fluid rising zone 1.
  • the fluidized bed reactor The body is provided with a water inlet, the water inlet is provided in the fluid down zone 2, and the fluidized bed reactor body is provided with a three-phase separator relatively independent of the fluid bed reactor body at the upper part of the fluid down zone 2,
  • the three-phase separator includes A three-phase separator barrel with an open upper end, a sludge hopper connected to the fluidized bed reactor body at the lower end of the three-phase separator, a sludge hopper leak pipe 9 connected to the lower end of the sludge hopper, and an upper part of the three-phase separator
  • an inlet pipe communicating with the fluidized bed reactor body is provided in the middle of the settlement area between the overflow effluent tank 7 of the three-phase separator and the sludge hopper.
  • a cyclone separator 18 is connected to the phase separator, and the port of the cyclone separator water intake pipe 6 is located between the sludge hopper and the overflow water tank 7.
  • the three-phase separator water inlet pipe 8 includes a vertical pipe arranged longitudinally inside the three-phase separator, a horizontal pipe arranged laterally outside the three-phase separator, and a connecting pipe connecting the vertical pipe and the horizontal pipe, and one end of the connecting pipe is connected to Lay the middle of the tube horizontally, and connect the other end of the connecting tube to the lower part of the standpipe.
  • the fluid drop zone 2 of the fluidized bed reactor body is set as one, the fluid rise zone 1 is set as the periphery, the fluid rise zone 1 is located around the fluid drop zone 2, and the three-phase separators are set as a group, the number of which is determined by the reactor The length and the ratio of length to width determine that the three-phase separator is placed in the upper middle position of the body of the fluidized bed reactor.
  • an aeration device which includes an air compressor 20, an air separation device 19, an oxygen-enriched gas inlet pipe, and a nitrogen-enriched gas inlet pipe.
  • the air separation device 19 is connected to the air compressor 20, and the oxygen-enriched gas inlet
  • One end of the pipeline and the nitrogen-enriched gas inlet pipe are connected to the air separation device 19, the other end of the oxygen-enriched gas inlet pipe is located in the middle of the fluid descending zone 2, and the other end of the nitrogen-enriched gas inlet pipe is located at the bottom of the fluid rising zone 1
  • the other end of the oxygen-enriched gas inlet pipe is connected to the microporous aerator 13, and the other end of the nitrogen-enriched gas inlet pipe is connected to the nitrogen-enriched gas distributor 24.
  • the bottom of the fluid descending zone 2 is provided with a water flow guiding device 16, which is an inclined surface toward the fluid rising zone 1. Between the fluid rising zone 1 and the fluid descending zone 2, a guide tube partition 14 is provided. The fluid drop zone 2 separates the fluid in different directions by the guide tube partition 14.
  • the fluid rising zone 1 is provided with a zoom tube 15 which is arranged along the water flow direction, and the zoom tube 15 is a plurality of continuous tubular pieces arranged at intervals between a large diameter and a small diameter.
  • FIG. 1 it includes a fluidized bed inlet pipe 4, a cyclone separator outlet pipe 5, a cyclone separator water inlet pipe 6, an overflow and outflow tank 7, a three-phase separator inlet pipe 8, a sludge hopper leak Pipe 9, oxygen-enriched gas inlet pipe 10, air inlet pipe 11, nitrogen-rich gas inlet pipe 12, microporous aerator 13, baffle separator 14, zoom tube 15, water flow guide 16, valve 17, Cyclone separator 18, air separation device 19, air compressor 20, metering pump 21, nitrogen-rich gas distributor 24, sludge discharge pipe 25, inlet water flow meter 26, inlet air flow meter 27, DO online detection 28 and MLSS Online Tester 29.
  • the body of the fluidized bed reactor is divided into a fluid ascending zone 1 and a fluid descending zone 2 by a guide tube separator 14, and a plurality of small holes are distributed on the guide tube separator 14, and the distribution method of the small holes can be set to be evenly distributed as shown in the figure
  • the distribution shown in a in Fig. 4 or the equidistant distribution is shown in b in Fig. 4, so that there are multiple fluid circulation distributions in the ascending zone and the descending zone, which increases the mixing effect and the gas-liquid mass transfer effect.
  • the air enters the air separation device 19 through the air compressor 20, and is separated into oxygen-enriched gas and nitrogen-enriched gas.
  • the oxygen-enriched gas enters the upper part of the fluid descending zone 2 through the oxygen-enriched gas inlet pipe 10, diffuses into the fluid descending zone 2 through the microporous aerator 13, and comes into contact with the fluid in the fluid descending zone 2 countercurrently, greatly increasing the hydraulic power of the bubbles Residence time and gas-liquid mass transfer coefficient.
  • the waste water enters the fluid drop zone 2 from the fluidized bed inlet pipe 4 and controls the flow rate through the inlet water flow meter 26 on the pipe. It makes a rapid downward movement under the drag of the fluid in the drop zone and its own gravity, and when it falls to the reaction At the bottom of the device, it enters the rising zone 1 under the guidance of the water flow guide device 16.
  • the nitrogen-rich gas enters the bottom of the fluid rising zone 1 through the nitrogen-rich gas inlet pipe 12, and the nitrogen-rich gas distributor 24 at the end thereof provides the upward driving force for the fluid in the fluid rising zone 1, so that the wastewater works in the fluidized bed. Circulation movement, and forced to diffuse from the micro-pore aerator 13 into the tiny bubbles of oxygen in the fluid to achieve downward flow.
  • the fluid at the top of the fluid descending zone 2 enters the three-phase separator 3 through the three-phase separator inlet pipe 8.
  • the three-phase separator inlet pipe 8 is a three-way pipe.
  • the gas in the waste water flows upward in the three-phase separator inlet pipe 8. After escaping, water and sludge flow down.
  • the sludge makes a rapid settling movement by gravity and the drag force of the fluid in the fluid descent zone 2.
  • the sludge with poor settling performance enters the cyclone separator 18 for sludge-water separation, and the separated supernatant is returned to the body of the fluidized bed reactor through the metering pump 21.
  • a load-bearing wastewater treatment fluidization reaction process system including a grease trap, an air floatation tank, a regulating tank, a first-level aerobic reactor (O1), a hydrolytic denitrification reactor (H), and a second-level reactor Oxygen reactor (O2), coagulation sedimentation tank and filter tank, in which the first-level aerobic reactor (O1) adopts a fluidized reaction device with enhanced load for wastewater treatment, and the second-level aerobic reactor (O2) adopts another A fluidized reaction device for wastewater treatment with enhanced load.
  • the first-level aerobic reactor (O1) adopts a fluidized reaction device with enhanced load for wastewater treatment
  • the second-level aerobic reactor (O2) adopts another A fluidized reaction device for wastewater treatment with enhanced load.
  • a fluidized reaction method for wastewater treatment with enhanced load which separates the sludge inside the body of the fluidized bed reactor, introduces the mixed liquid in the body of the fluidized bed reactor into the three-phase separator, and the precipitation performance in the three-phase separator
  • the poor low-activity sludge is forced to settle through the external cyclone separator 18 and discharged out of the reactor through the sludge discharge pipe 23, which achieves the purpose of identifying and separating sludge with different degrees of apoptosis in situ inside the fluidized bed.
  • This selective function can keep the sludge with high activity and low apoptosis ratio in the reactor, and discharge the sludge with low activity and high apoptosis ratio out of the reactor.
  • the high-concentration oxygen is separated into an oxygen-enriched gas through an external air oxygen-nitrogen separation device, and the remaining components are nitrogen-enriched gas.
  • the two components are respectively input into the body of the fluidized bed reactor through two pipes.
  • the nitrogen-enriched gas The bottom of the fluid rising zone 1 leading into the fluidized bed reactor body forms the motive force for fluidizing the fluid, and the oxygen-enriched gas passes into the middle of the fluid descending zone 2 of the fluidized bed reactor body to achieve the purpose of oxygen supply.
  • the present invention has the following advantages:
  • a fluidized reaction device for wastewater treatment with enhanced load A three-phase separator in the middle of the settlement area is provided with a cyclone separator water intake pipe 6 to separate sludge with poor settlement performance in the middle of the settlement area.
  • the sewage with better performance The mud re-enters the body of the fluidized bed reactor to participate in the degradation reaction of pollutants under the action of gravity and the drag of the fluid in the fluid drop zone 2 to ensure the stable and high-load operation of the fluidized bed reactor.
  • a load-bearing waste water treatment fluidization reaction system adopts a load-bearing waste water treatment fluidization reaction device as a first-level aerobic reactor and a second-level aerobic reactor to enhance the treatment capacity of the entire reaction system and can handle high Concentrated wastewater, good treatment effect.
  • a fluidized reaction method for wastewater treatment with enhanced load which separates the sludge inside the bioreactor according to the principle of differential gravity flow, and passes the low-activity sludge with poor sedimentation performance in the three-phase separator through the external cyclone separator 18 to force After concentration, the reactor is discharged through the sludge discharge pipe 25 to increase the sludge activity in the fluidized bed reactor to achieve high-load operating conditions and accelerate the degradation of pollutants in sewage.
  • the fluidized bed reactor of this embodiment adopts a fluid circulation mode in which the fluid descending zone 2 is in the middle and the fluid rising zone 1 is all around, and the three-phase separation zone 3 is located above the fluid descending zone 2.
  • the first-level aerobic reactor (O1) hydrolysis denitrification reactor (H) adopts this type of reactor.
  • the gas-water mixing zone at the bottom is the region with the most significant energy dissipation.
  • the present invention adopts a water flow guide device 16 provided with an inverted V-shaped base at the bottom to reduce a large amount of energy dissipation in the collision zone of the bottom fluid and improve the circulation efficiency of the fluid in the fluidized bed.
  • two distribution methods of uniform openings and spacing openings are added to the guide tube partition plate 14. The opening of the small hole allows the fluid in the fluid rising zone 1 to enter the fluid descending zone 2 through the channel, forming a small path circulation, which further enhances the multiphase mixing effect in the reactor and enhances the gas-liquid mass transfer.
  • the top fluid of the reactor enters the three-phase separator through the three-phase separator inlet pipe 8.
  • the schematic diagram of the structure principle of the water inlet pipe 8 of the three-phase separator is shown in FIG. 3.
  • the fluid enters the horizontal flat tube through the two ends of the water inlet.
  • the collision of the fluid in the flat tube causes the fluid flow rate to be greatly reduced, which provides good conditions for the next three-phase separation.
  • the fluid with a reduced flow rate enters the vertical riser.
  • the arrangement of the vertical riser further reduces the flow rate of the fluid, thereby reducing the precipitation effect due to excessive kinetic energy of the fluid entering the three-phase separator.
  • the gas in the fluid escapes upward in the vertical pipe due to the lifting force, and the sludge settles downward due to gravity, which increases the gas-liquid-solid separation effect of the three-phase separator and improves the effluent quality.
  • the sludge with better performance is re-entered into the fluidized bed under the action of gravity and the drag force of the fluid in the descending zone to achieve the separation and retention of residence time.
  • the retention of ZnO exhibits high efficiency for the degradation reaction of pollutants, ensuring the stable and high-load operation of the fluidized bed reactor.
  • the shape of the microporous aerator 13 is an inverted triangular pyramid row, the flow rate of the fluid in the fluid drop zone 2 will increase faster and faster as the drop height increases.
  • the increase in the flow rate increases the gas-liquid mass transfer rate.
  • the increase in the flow rate increases the drag force of the fluid, which causes the bubbles of the microporous aerator 13 to move downward, increasing the residence time of the bubbles and strengthening the gas.
  • Liquid mass transfer effect to achieve efficient use of oxygen.
  • the nitrogen-rich gas flowing out of the air separation device 19 is passed to the bottom of the fluid rising zone 1 to provide liquid circulation power in the fluidized bed, and at the same time, the residual oxygen inside the nitrogen-rich gas is also used.
  • the bottom aeration volume is smaller than that of the traditional fluidized bed, and the total volume of the gas supply is reduced by about 50%, thereby reducing the aeration energy consumption and realizing the energy saving of the reactor.
  • the main structure of this embodiment is the same as that of Embodiment 1, and the similarities are not repeated here.
  • the difference is that, as shown in FIG. 2, the fluid drop zone 2 of the fluidized bed reactor body is set as the periphery, and the fluid rise zone 1 It is set as one, the fluid descending zone 2 is located around the fluid rising zone 1, and the three-phase separator is arranged on the periphery corresponding to the fluid descending zone 2.
  • FIG. 2 it includes a fluidized bed inlet pipe 4, a cyclone separator outlet pipe 5, a cyclone separator water inlet pipe 6, an overflow and outlet water tank 7, a three-phase separator inlet pipe 8, a sludge hopper leak Pipe 9, oxygen-enriched gas inlet pipe 10, air inlet pipe 11, nitrogen-rich gas inlet pipe 12, microporous aerator 13, baffle separator 14, zoom tube 15, water flow guide 16, valve 17, Cyclone separator 18, air separation device 19, air compressor 20, metering pump 21, funnel-shaped baffle 22, cross-shaped member 23, nitrogen-rich gas distributor 24, sludge discharge pipe 25, inlet water flow meter 26, Intake air flow meter 27, DO online detection 28 and MLSS online detector 29.
  • the body of the fluidized bed reactor divides the reactor into a fluid ascending zone 1 and a fluid descending zone 2 by a guide tube separator 14, and a plurality of small holes are distributed on the guide tube separator 14, and the distribution method of the small holes can be set to be uniform Distribution, as shown in a in Figure 4, or equidistant distribution, as shown in b in Figure 4, so that there are multiple fluid circulation distributions in fluid ascending zone 1 and fluid descending zone 2, increasing the mixing effect and gas-liquid mass transfer effect .
  • the air enters the air separation device 19 through the air compressor 20 and separates it into oxygen-enriched gas and nitrogen-enriched gas.
  • the oxygen-enriched gas enters the upper part of the fluid descending zone 2 through the oxygen-enriched gas pipeline 10, diffuses into the fluid descending zone 2 through the microporous aerator 13, and comes into contact with the fluid in the fluid descending zone 2 countercurrently, greatly improving the hydraulic retention of the bubbles Time and gas-liquid mass transfer coefficient.
  • Waste water enters the fluid descending zone 2 from the fluidized bed inlet pipe 4 and makes a downward movement under the drag of the fluid in the fluid descending zone 2 and its own gravity. When it descends to the bottom of the reactor, the bottom cross-shaped member 23 guides Flow enters the rising zone 1 of the fluid.
  • the nitrogen-rich gas enters the bottom of the fluid rising zone 1 through the nitrogen-rich gas pipeline 12, and releases the gas uniformly through the nitrogen-rich gas distributor 24, which provides the rising driving force for the fluid in the fluid rising zone 1, so that the wastewater works in the fluidized bed reactor. Cyclic exercise.
  • the scaling tube 15 makes the cross section of the ascending zone non-uniform, increasing the degree of turbulence of the fluid, thereby adding the mass transfer coefficient of atmospheric liquid, and improving the efficiency of oxygen utilization.
  • the guiding force of the fluid at the top of the fluid rising zone 1 on the funnel-shaped baffle 22 reduces the energy loss due to collision between the fluids.
  • the fluid at the top of the fluid descending zone 2 enters the three-phase separator through the three-phase separator inlet pipe 8.
  • the three-phase separator inlet pipe 8 is a three-way pipe, and the gas in the wastewater escapes upward in the three-phase separator inlet pipe 8.
  • the water phase and sludge flow down.
  • the sludge is settling by gravity and the drag force of the fluid in the fluid descent zone 2.
  • the sludge with poor settling performance enters the cyclone separator 18 for sludge-water separation, and the separated supernatant is returned to the body of the fluidized bed reactor through the metering pump 21.
  • the fluidized bed reactor of this embodiment adopts a fluid circulation mode in which the fluid rising zone 1 is in the middle and the fluid descending zone 2 is around.
  • the surface load of the three-phase separation zone 3 of the fluidized bed reactor of this example is reduced and controllable.
  • it can be separated with smaller/lighter specific gravity Of sludge particles, the sludge separation effect is more excellent, and the amount of sludge discharged is also increased. Therefore, it can be used as the reactor type for the secondary aerobic reactor (O2) with stricter requirements on the effluent water quality.
  • This type of reactor can significantly reduce the amount of reagents required for the subsequent coagulation reaction.
  • a cross-shaped member 23 is provided at the bottom of the fluid rising zone 1, and the rectifying effect of the cross-shaped member 23 can significantly reduce the water head/vector caused by the inelastic collision of the fluid at the bottom of the fluidized bed Loss, the liquid circulation speed of the fluid rising zone 1 and the fluid falling zone 2 in the quadrilateral fluidized bed is increased under the condition of minimum power input of the nitrogen-rich gas.
  • the cross-shaped member 23 can make the liquid circulation velocity in the fluidized bed more evenly distributed in the cross section of the fluid rising zone 1 and reduce the energy dissipation of its turbulent motion.
  • the cross-shaped member 23 realizes the optimization of the hydraulic conditions of the quadrilateral fluidized bed and the energy consumption of the system. Under the action of the cross-shaped member 23, the liquid circulation velocity in the fluidized bed is more evenly distributed in the cross section of the fluid rising zone 1, and the flow dead zone is significantly reduced. From a microscopic perspective, it reduces the generation of vortices of different scales. After the cross-shaped member 23 is placed, the liquid circulates from the fluid descending zone 2 through the bottom of the fluidized bed to the fluid rising zone 1, which reduces the head loss and energy dissipation caused by the inelastic collision between the fluids.
  • the present invention provides a funnel-shaped baffle 22 and a baffle baffle, the funnel-shaped baffle 22 is suitable for circular and square structure fluidized beds, and the baffle baffle is suitable for a rectangular Horizontal fluidized bed.
  • the inner member has the characteristics of simple structure. By inserting the inner member, the gas-liquid two-phase or gas-liquid-solid three-phase movement direction is changed to enhance the multiphase mixing and mass transfer of the reactor, and a custom flow field is obtained.
  • the reactor efficiency is further improved, especially suitable for the biological treatment process of the activated sludge wastewater.
  • the internal circulating fluidized bed strengthened by this internal component of the funnel is applied to aerobic biological treatment of wastewater, the gas can be increased.
  • the liquid-mass transfer interface area and gas-liquid contact time make the utilization efficiency of oxygen provided by aeration significantly increase, and reduce the unit aeration energy consumption.
  • the invention also has the characteristics of easy engineering enlargement and stable flow state.
  • the square fluidized bed can be expanded into a horizontal fluidized bed, and the ratio of length and width can be arbitrarily adjusted.
  • the top three-phase separation zone 3, the bottom cross-shaped member 23, the guide tube baffle 14, and the top funnel baffle 22 can be installed by increasing the length ratio, thereby changing the reactor volume to adapt to the amount of influent and achieving different scales Engineering reactor.
  • the main structure of this embodiment is the same as that of Embodiment 1, and the similarities are not repeated here.
  • the difference is that: a new type of biological reaction device with enhanced load of fluidized wastewater treatment, which treats coking wastewater and main pollutants
  • the indicators are shown in Table 1.
  • Wastewater treatment process The actual treatment process of coking wastewater is shown in Figure 5.
  • the raw water of coking wastewater is first removed through the grease trap and air floatation tank to remove the floating oil components in the wastewater, and then enters the adjustment tank for pH adjustment.
  • the adjusted wastewater enters the first-level aerobic reactor (O1) under the action of the metering pump 21.
  • the first-level aerobic reactor does not have high requirements on the effluent water quality, and the aeration amount is large, so it is made with a new fluidized bed 1 structure.
  • the effluent water quality of the secondary aerobic reactor (O2) has high requirements and high requirements for the separation of sludge. Therefore, it is made with a new type of fluidized bed 2 structure and is used to treat wastewater that has passed through the hydrolysis denitrification reactor (H) In order to further treat it, further reduce COD and ammonia nitrogen, and improve the effluent quality.
  • Hydrolytic denitrification reactor (H) also adopts the same reactor structure type as the first-level aerobic reactor (O1), but controlled conditions such as hydraulic retention time (HRT), sludge residence time (SRT), pH value, etc. different.
  • the local turbulent kinetic energy can determine the mass transfer properties of the reactor, and TKE is also related to the flow shear force, which is the most important biological process for shear-sensitive cells and microbial parameters. Important. At present, some documents have discussed the impact of TKE and shear on biological processes. Some studies have pointed out that the shear stress of the fluid is proportional to TKE. Excess turbulent kinetic energy will cause strong flow shearing, damage the suspended cells, cause loss of growth ability, and even disintegrate the structure. In this section, the influence of internal components before and after the addition of internal components and internal structures of different structures and sizes on the local turbulent kinetic energy of the reactor is compared. Fig. 7 is the radial distribution of turbulent kinetic energy at a cross section of 0.4 m high and an apparent gas velocity of 0.01 m/s.
  • Fig. 7 the placement of different internal member funnel-shaped baffles (22 in Fig. 2) reduces the turbulent kinetic energy of the liquid phase to a certain extent, and the radial distribution of turbulent kinetic energy approximately meets the parabolic distribution, that is, the reactor
  • the central turbulent kinetic energy is much larger than the near-wall surface area, and the turbulent kinetic energy is relatively stable at a constant value within 2 cm from the central axis, which may be related to the distribution of the bubble plume near the center of the bubble, of which the inner member C is the most obvious;
  • the turbulent kinetic energy in the descending zone is relatively low, and its value is almost the same when different internal components are adopted; when the internal member C is adopted, its turbulent kinetic energy is reduced by at most 7.8% compared with the control.
  • the reduction of the local turbulent kinetic energy of the reactor is very beneficial to shear-sensitive microorganisms.
  • many filamentous fungi have strict requirements for shearing in the process of biological fermentation. Excessive shearing will cause bacterial loss; Granular sludge technology requires relatively low flow shear, otherwise granular sludge may not form or the particles may break.
  • funnel-shaped diversion internal components significantly increased the K La value of the reactor. With the increase of the apparent gas velocity, the K La value increased significantly.
  • the effects of the three diversion internal components A, B, and C increased in sequence, and not Compared with the internal component, the internal component C increased the K La value by about 19.0%.
  • the inner member A has a significant obstruction effect on the fluid.
  • the outer diameter of the inner member C is relatively The larger the flow guiding area of the liquid is increased, and it can also play the role of breaking the coalesced large bubbles into small bubbles, which are beneficial to increase the volume oxygen transfer coefficient.
  • Cross-shaped member enhances gas-liquid mass transfer in fluidized bed reactor
  • Fig. 10 shows the variation of the liquid circulation velocity with the apparent gas velocity in the fluid ascending zone 1 and fluid descending zone 2 with or without the cross-shaped member 23 in the bottom gap area
  • Fig. 11 shows when the cross-shaped member 23 is in the bottom gap area The change of the overall gas content of the reactor with the apparent gas velocity.
  • the fluid in the reactor fluid descending zone 2 gradually transforms into an inward curved flow through the bottom conical part, and these curved flows converge toward the center point within 360° , Collide and penetrate each other to cancel out most of the energy; and after the inner member is placed, because these curved streamlines meet the rigid baffle that constitutes the cross member, rigid collisions such as emission and refraction occur, and the collision energy loss is large When it is lowered, the velocity head is reduced less. After collision, it can maintain a higher velocity and the head changes into upward movement along the ascending zone. Therefore, it is manifested as a relatively large increase in the liquid circulation speed during experiments and simulations. The change trend of the liquid circulation velocity with the apparent gas velocity is completely similar to that when it is not inserted into the inner member, and the reason is also similar.
  • the first is the increase in liquid circulation speed, the residence time of the gas in the reactor becomes shorter, and it overflows faster through the free liquid surface, resulting in The overall gas content decreases; the second is that the liquid circulation rate in the descending area is accelerated, and more bubbles can be taken into the descending area, which will cause the overall gas content to increase to a certain extent; the two effects have opposite effects due to the liquid circulation
  • the effect of the faster speed leading to the decrease of gas content is more significant and plays a leading role.
  • the gas-liquid two-phase turbulent process of the internal circulating fluidized bed reactor mainly occurs in the fluid rising zone 1.
  • this study was conducted in six different Under the conditions of apparent gas velocity (0.25, 0.5, 0.75, 1.0, 2.0, 3.0 cm/s), a comparative study was conducted on the average turbulent kinetic energy of the fluid ascending zone 1 of the reactor before and after the inner member was placed, and the results are shown in Figure 12. Show. It can be seen from Fig.
  • the source of the turbulent kinetic energy of the bottom gap is mainly the input of the gas inlet kinetic energy at the inlet of the nitrogen-rich gas distributor 24.
  • the turbulent turbulence occurs due to the transfer of gas kinetic energy, and
  • the addition of the cross-shaped member 23 can play a role in dividing the bottom space.
  • the hydraulic radius of a single space is significantly reduced (taking the cross-shaped four-spoke inner member as an example, the hydraulic radius can be calculated to be only the original 0.44 Times), the Re value of the Reynolds coefficient is significantly reduced, and the value of Fr (Froud number) is significantly increased, so the flow process is more stable and the turbulent kinetic energy is significantly reduced. Therefore, the placement of cross members in the bottom gap can play a rectifying role.
  • the operation of the fluidized bed is controlled at an organic load rate (OLR) of 2.14kg COD/m 3 ⁇ d.
  • OLR organic load rate
  • COD chemical oxygen demand
  • Sludges of different densities and sizes can be separated by sedimentation or drag, by proving that sludge cell decay is accompanied by changes in floc aggregation, EPS (extracellular polymer) content and microbial ALD in sludge of different aggregation levels Apoptosis-like degree) is different, and relatively apoptotic sludge can be separated by drag force in the fluidized bed.
  • EPS extracellular polymer
  • SOUR Specific oxygen consumption rate
  • DHA dehydrogenase activity
  • Extracellular polymer is an important indicator of sludge settling, compaction, density and other characteristics.
  • Sludge EPS usually consists of two layers of loose binding energy EPS (LB-EPS) and tight binding energy EPS (TB-EPS) Composition, this study used protein (PN) and polysaccharide (PS) content to analyze the EPS of different sludges.
  • LB-EPS loose binding energy EPS
  • TB-EPS tight binding energy EPS
  • PS polysaccharide
  • TB-EPS content is relatively low (2.13-2.26mg/g MLVSS) (4.61-5.82mg/g ⁇ MLVSS).
  • the PN/PS ratio of loose sludge is low.
  • sludge with low PN/PS should have a more loose structure.
  • the low PN/PS of loose flocs may be due to the high PS, because PS has rich -OH groups tending to form hydrogen bonds with water molecules, and PN is a long-chain hydrophobic amino acid that tends to aggregate under the driving force of hydrophobic forces. molecular.
  • the lower the PN/PS the higher the water content in the sludge, and as the PS content increases or the PN content decreases, the cells are likely to separate from each other.
  • the physiological state of different sludge on microbial cells is shown in Fig. 17.
  • F1, F2, F3, F4 The cell dots in F3 represent normal cells, and no staining indicates that these cells are neither dead nor apoptotic.
  • the cell dots in F2 represent late apoptotic cells and can be stained by Annexin-V and PI at the same time.
  • the dual-channel fluorescence dot plots show normal cells, apoptotic cells and dead cells, respectively.
  • the results show that there are significant differences in the physiological state of microbial cells in different sludge. In the sludge, it has more apoptotic-like apoptotic cells and dead cells, while in the sludge, it has fewer apoptotic cells.
  • the ALD value of sludge F is 6.64% and 13.5% lower than that of sludge M and S, respectively. This strongly explains the active differentiation of gravity separation sludge.
  • Figure 18 investigates the relationship between ALDCD and sludge activity.
  • the apoptosis of phosphatidylserine externalization was explained in eukaryotic cells, but not in bacteria. In eukaryotic cells, the cell membrane maintains the balance of phosphatidylserine in the inner leaflet by phospholipase and hybrid enzymes.
  • Ca 2+ -inhibited phospholipid transferase transfers phosphatidylserine from the outer leaflet to the inner leaflet
  • Ca 2+ -activated hybrid enzyme transfers phosphatidylserine from the inner leaflet to the outer leaflet.
  • intracellular Ca 2+ increases, and hybrid enzymes can transfer phosphatidylserine to the outer leaflet, and phospholipase transferase cannot transfer phosphatidylserine to the inner leaflet.
  • PCD programmed cell death
  • ALDCD of gravity-distributed sludge is significantly different. This feature will allow us to further understand the attenuation of bacteria in sludge.
  • ALDCD is the highest among sludges with lower PN/PS, while sludge F is the opposite. Based on the above results, it can be speculated that the LB-PS secretion may be improved due to sludge-like apoptosis, while PN/PS is further reduced, resulting in loose sludge accumulation and increased SVI.
  • the community structure of these sludge communities is characterized at the genus level ( Figure 20).
  • the English and Latin names of bacterial species are common.
  • the Latin name of the current bacterial classification is the international common writing, and some bacterial species There is no corresponding Chinese translation.
  • Select genera with relatively high abundance to perform cluster analysis on the abundance heat map of the species ( Figure 21).
  • the English and Latin names for bacterial species are common.
  • the Latin name in the current classification of bacteria is the international general writing There is no corresponding Chinese translation for some strains.
  • CWTS Coking Wastewater Treatment System
  • Thiobacillus Thiobacillus (6.05-10.75%)
  • Comamonas (4.47-5.85%)
  • these two Bacteria of the genus are often considered as functional bacteria in CWTS.
  • Thauera 2.16-5.61%
  • sludge M has the highest abundance of Thauera.
  • some major types of facultative heterotrophic bacteria were found to have high abundance.
  • the abundance of Ignavibacteriaceae in sludge F is higher than that of S and M (7.94-11.36%).
  • the abundance of Cryomorphaceae (6.38-6.76%) is also the highest in sludge F, and this genus always requires complex organic compounds and sea salt to grow.
  • the abundance of a large number of microorganisms with less clear functions in CWTS decreases with the increase of sedimentation speed.
  • Chitinophagaceae (7.65-14.20%), a genus found only in rhizosphere soil, roots, worms and other malnourished environments; Chloracidobacteria Ellin6075gen (3.38-7.61%) is a kind of use of fermentation end products as a carbon source, Genus found in fresh water; Weeksellaceae (2.25-5.90%) is a genus of aerobic organic pathogenic bacteria isolated mainly from humans, rarely reported in CWTS.
  • the PICRUSt method was used to compare the obtained community data with the Green bank database to complete the prediction of the sludge function. 286 prediction functions are obtained from the separation of sludge. Figure 22 lists the top 30 environmental functions. It was found that the digestion and absorption of carbohydrates in sludge F, the three functions of cytochrome P450 and basal transcription factor were 31.6% and 70.8%, 23.5% and 37.3%, 43.5% and 61.3% respectively higher than those of sludge M and S . The abundance of citric acid cycle, energy metabolism, pyruvate metabolism and oxidative phosphorylation in sludge F is 2.2%, 3.2%, 1.0% and 3.3%, 0.6% and 2.0% higher than sludge M and S, respectively.
  • the sludge flocs first rise to the top of the fluidized bed of the diversion cylinder, descend in the fluid drop zone 2, part of the sludge is sucked into the three-phase separator, the light sludge flocs are distributed above the three-phase separation zone 3, and the heavy The sludge flocs are moved downwards by the drag force, and then the light flocs are sucked into the cyclone separator 18 for concentration treatment.
  • the proportions of sludge F, M and S are 81.6%, 16.4% and 2.0%.
  • Using fluidized bed selective sludge separation instead of sludge discharge at the bottom of the bioreactor, most of the sludge M and all sludge S can be discharged. In order to evaluate the improvement effect of selective sludge separation on total sludge activity, further calculations are as follows.
  • the dry sludge discharge of the system is 0.5-0.6kgSS/m 3 , and the sludge discharge accounts for 15.2-19.4% of the total sludge.
  • SV30 is always maintained at 15%-30%, so the total amount of SVI, SOUR, DHA of the sludge is calculated by equations (1)-(2).
  • the ratio of sludge is calculated by formulas (3)-(5).
  • the total sludge SVI can be reduced within the constant SV30 control range, and the MLSS increment (Mincrement) can be obtained (7).
  • the average activity of sludge can be increased with the discharge of sludge M and sludge S, thus the percentage increase of sludge activity can be obtained (8).
  • the comprehensive efficiency increment can be calculated as (9):
  • CE increment [(1+M increment ) ⁇ (1+A increment )-1] ⁇ 100% (9)
  • P The proportion of sludge that is classified by different types of sludge (F, M, S);
  • CEincrement The increase in the overall efficiency of the bioreactor.
  • CWTS light sludge
  • the discharge range of CWTS sludge is 0.5-0.6kgSS/m 3 ⁇ d
  • the MLSS range of CWTS sludge is 3100-3300mg/L
  • the sludge discharge accounts for 15.2-19.4% of the total sludge.
  • the estimated total sludge activity and full MLSS concentration are increased by 1.85-2.79% and 2.0%, respectively.
  • the overall efficiency of sludge treatment defined by the product of MLSS and activity will increase by 3.9-4.8%.
  • organic nitrogen-containing compounds there are many types of organic nitrogen-containing compounds in coking wastewater, and the measurement is complicated.
  • organic nitrogen-containing compounds ON
  • Total nitrogen deducts the contribution ratio of ammonia nitrogen, nitrogen in cyanide, nitrogen in thiocyanide, nitrate nitrogen and nitrite nitrogen to obtain the contribution ratio of organic nitrogen.
  • the conversion efficiency of thiocyanate, complex cyanide and easily released cyanide during the analysis of total nitrogen is not high, only 88%, 75% and 95%.
  • the conversion efficiency of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the analysis of total nitrogen is 100%. Therefore, the proportion of various nitrogen-containing compounds in the coking wastewater in total nitrogen is calculated as follows:
  • FIG. 23 shows the composition characteristics of various nitrogen-containing compounds in total nitrogen during the biological treatment process. It can be seen from Table 4 that the total nitrogen in the biological feedwater decreased slightly, which was due to the addition of ferrous sulfate during the pretreatment stage, and Fe 2+ and cyanide formed ferrous blue (Fe[Fe(CN) 6 ]), Iron blue (Fe 4 [Fe(CN) 6 ] 3 ) precipitates, which corresponds to a decrease in the concentration of cyanide in biological feedwater.
  • the total nitrogen removal in the two-stage aerobic reactor was 115.8 mg/L and 59.9 mg/L, respectively.
  • the reasons for the total nitrogen removal in the aerobic reactor can be summarized as follows: 1The aerobic microorganisms are about BOD:N:P The ratio of 100:5:1 uses the nitrogen-containing compounds in the wastewater as a nitrogen source to synthesize its own cell material, and the total nitrogen in the water phase is transferred to the sludge phase; 2In actual engineering, there is local hypoxia in the reactor Zone, the simultaneous nitrification and denitrification in the aerobic tank can be realized; 3 there are aerobic denitrification bacteria in the system, denitrification is carried out under aerobic conditions, and NH 4 + -N is directly converted into N 2 O; 4 a small amount of ammonia molecules Dissipated during aeration.
  • FIG. 23 The proportion of various nitrogen-containing compounds to total nitrogen in the biological treatment process is shown in Figure 23.
  • inorganic nitrogen compounds are the main contributors to total nitrogen, and their proportions are all higher than 75.0%.
  • inorganic nitrogen compounds accounted for 82.5% of the total nitrogen, of which sulfur cyanide and ammonia nitrogen were the main ones.
  • micro-organisms preferentially degrade volatile phenol, cyanide and thiocyanide, etc., compared with the refractory organic nitrogen compounds. Almost no nitrification occurs in the reactor.
  • the proportion of cyanide and thiocyanide The decline was 1.1% and 23.4%, and the proportion of organic nitrogen and ammonia nitrogen increased accordingly to 24.1% and 49.4%.
  • organic nitrogen compounds are hydrolyzed to release ammonia nitrogen, causing the ammonia nitrogen ratio to rise to 71.4%, while the organic nitrogen compound ratio drops to 2.2%.
  • cyanide and thiocyanide are oxidized by aerobic organisms, and nitrification occurs.
  • Nitrate nitrogen is the main contributor to total nitrogen in biological effluent, accounting for more than 75.0%.
  • the factors affecting the conversion of nitrogen-containing compounds and the removal of total nitrogen in biological processes include pH, HRT, dissolved oxygen, sludge age and sludge concentration, carbon-to-nitrogen ratio, nitrate reflux ratio, and redox potential.
  • pH, HRT, dissolved oxygen, sludge age and sludge concentration, carbon-to-nitrogen ratio, nitrate reflux ratio, and redox potential For coking wastewater with a total nitrogen content of more than 300mg/L in raw water, to achieve the 20mg/L total nitrogen emission limit specified in the new national standard, it is necessary to strengthen the first-level aerobic reactor to achieve local nitrification, and the second-level The aerobic reactor achieves complete nitrification, and the operating condition that the reflux ratio must be greater than 1:1 ensures that the short-range denitrification reaction in the hydrolysis reactor efficiently proceeds and escapes in the form of N 2 .
  • the combination of the two needs to be optimized in the values of the hydraulic retention time of the reactor and the reflux ratio.
  • it is necessary to pursue precise control of the conditions of the first-level aerobic reactor, so that some low-priced nitrogen-containing compounds are converted into NO 2 -- N.
  • the cell lysis releases the total nitrogen into the water again. It is necessary to strictly control the residence time of the sludge in each reaction tank and discharge the sludge regularly.
  • the design structure of the fluidized bed in the actual project mainly includes a three-stage diversion tube and a three-phase separation zone 3.
  • the three-stage diversion tube in the fluidized bed realizes triple circulation of the fluid, which enhances the mixed mass transfer performance of the fluidized bed.
  • the three-phase separation zone 3 provided on both sides of the fluidized bed allows the activated sludge after solid-liquid separation to be self-absorbed from the inclined wall at the bottom of the separation zone into the downflow zone of the main reactor, avoiding the effluent to take away the micelles and ensuring the reactor To reduce the amount of microorganisms in the sludge.
  • the first-level aerobic fluidized bed uses air as the total power to decompose into oxygen-enriched gas and nitrogen-enriched gas to achieve good mixing and mass transfer between wastewater and microorganisms in the reactor. Its function is to minimize organic pollutants concentration. During operation, sufficient aeration must be ensured to achieve fluidization operation and provide dissolved oxygen. At the same time, phosphorus salts need to be added as nutrients for microbial growth.
  • Fig. 24 is the operation data of cyanide and thiocyanide in the first-level aerobic fluidized bed. It can be seen that the first-level aerobic fluidized bed is under the condition that the HRT is 40h and the dissolved oxygen is controlled at 1-3 mg/L.
  • the influent concentration of cyanide and sulfur cyanide is 19.0 ⁇ 36.1mg/L and 482.4 ⁇ 672.1mg/L
  • the effluent concentration is 3.3 ⁇ 4.2mg/L and 87.8 ⁇ 309.1mg/L
  • the removal rate reaches 85.6% and 67.5% .
  • a first-level aerobic fluidized bed is designed to remove phenols and other organic pollutants.
  • the first-level aerobic fluidized bed can realize the simultaneous degradation of cyanide, thiocyanide and phenols, and the degradation of phenols has priority.
  • the organic nitrile compounds in coking wastewater are all aromatic nitriles with benzene ring. Compared with aliphatic nitrile, aromatic nitrile is more difficult to degrade.
  • organic nitriles, cyanides and thiocyanides are collectively called cyanide-containing compounds. Therefore, the degradation behavior of organic nitriles shows certain similarity to cyanide and thiocyanide, mainly in aerobic reactors .
  • the first way is under the catalytic action of nitrilase, the organic nitrile compound is hydrolyzed to the corresponding acid and ammonia nitrogen; the second way is organic The nitrile compound is first hydrolyzed to the corresponding amino compound, and then further hydrolyzed to the corresponding acid and ammonia nitrogen. These two steps are catalyzed by nitrile hydratase and amidase, respectively.
  • Aniline is the main amine compound in coking wastewater.
  • the aniline concentration of the first-level aerobic effluent is 28.0 ⁇ 33.1mg/L, and the conversion rate is as high as 99.8%.
  • the ortho-metabolism pathway is opened between two hydroxyl groups to produce succinic acid and acetyl-CoA, and the meta-metabolism pathway cleaves catechol next to one of the hydroxyl groups. Pyruvate and acetaldehyde are produced.
  • the hydrolytic denitrification fluidized bed relies on the stirring effect of the exhaust gas discharged from the aerobic process or a small amount of nitrogen and the hydraulic conditions of the pump to achieve uniform fluidization. Its main role is to change the local molecular structure of the organic matter through hydrolysis and acidification, and convert the macromolecular organic matter into Easily degradable small-molecule compounds, and at the same time realize anaerobic denitrification and denitrification of reflux nitrification liquid During operation, alkali needs to be added to neutralize the organic acid produced by hydrolysis and maintain the pH between 6.5 and 7.5 to provide conditions for anaerobic denitrification of microorganisms.
  • the high-throughput sequencing results of the research group on the microbial community in the biological system showed that there are microorganisms of Thiobacillus sp in the hydrolytic fluidized bed, which may be related to the degradation of total cyanide and thiocyanide in the hydrolytic fluidized bed.
  • macromolecular organic compounds are converted into small molecular compounds by hydrolytic acidification.
  • the nitrogen element is released into the water in the form of ammonia nitrogen.
  • the average concentration of ammonia nitrogen in the hydrolytic denitrification effluent is 85.9 mg/L.
  • the quinoline and isoquinoline concentrations in the effluent were 3.02-3.67 mg/L and 1.46-2.05 mg/L, respectively, and the concentrations decreased significantly.
  • Most nitrogen-containing heterocyclic compounds are refractory organic compounds, and polycyclic rings are more difficult to degrade than single rings. This may be caused by the increase of steric hindrance effect, the decrease of the density of electron cloud of ring-forming atoms and the increase of hydrophobicity.
  • ring-opening cracking is a major step in their biodegradation process.
  • the design structure of the second-level aerobic fluidized bed is similar to the first-level aerobic fluidized bed, but the flow pattern is reversed, and its function is mainly to perform nitrification and denitrification denitrification with the hydrolytic fluidized bed. Since nitrifying bacteria are sensitive to environmental changes, in order to ensure the normal progress of the nitrification reaction, the requirements of dissolved oxygen must be met during operation, and sufficient alkalinity must be maintained. Cyanide and sulfur cyanide have a good degradation effect in the secondary aerobic fluidized bed. The average concentration of cyanide and sulfur cyanide in the biological effluent are 0.63mg/L and 0.4mg/L, respectively, and the removal rate is 82.3%. And 95.7%.
  • cyanide in biological effluent sometimes still fails to meet the requirements of direct discharge standards. This is because the raw water of coking wastewater contains a variety of metal ions, plus the addition of ferrous sulfate as a coagulant in the pretreatment stage, so that part of the cyanide in the wastewater has formed a stable metal cyanide complex.
  • metal cyanide complexes, especially ferricyanide complexes have thermodynamic stability, and the rate of microbial degradation using ferricyanide is slower than that of free cyanogen molecules/ions.
  • Figure 25 shows the concentration changes of NH 4 + -N and NO x -- N in the two-stage aerobic reactor.
  • the main nitrification product of the reactor is NO 3 -- N, but from the 25th day, the nitration product is mainly NO 2 -- N, combined with other pollutant indicators for analysis, it is found that at this time the secondary aerobic influent sulfur The cyanide concentration rises sharply and maintains above 200 mg/L. Sulfur cyanide has an inhibitory effect on the complete nitrification process, leading to the accumulation of nitrous nitrogen.

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Abstract

一种负荷增强的废水处理流态化反应装置，包括流化床反应器本体，流化床反应器本体设有至少一个流体下降区(2)和流体上升区(1)，流化床反应器本体设有进水口，进水口设置于流体下降区(2)，流化床反应器本体在流体下降区(2)的上部设有相对独立于流化床反应器本体的三相分离器，三相分离器包括上端开口的三相分离器桶体，三相分离器的下端设有与流化床反应器本体连通的污泥斗，三相分离器将沉降区中部沉降性能较差的污泥分离出来，性能较好的污泥在重力以及流体曳力的作用下重新进入到流化床反应器本体内部，确保了流化床反应器的稳定高负荷运行。

Description

一种负荷增强的废水处理流态化反应装置、系统及方法 技术领域
本发明涉及水处理生物反应器装置、采用水处理生物反应器装置处理高浓度工业有机废水的方法领域，特别是涉及一种负荷增强的废水处理流态化反应装置、系统及方法。
背景技术
作为一种新型的废水生物处理技术，流化床生物反应器(FBBR)自20世纪30年代问世以来，因其能维持反应器内部极高的生物质含量而受到行业学者的广泛关注，并于20世纪70年代末80年代初被运用于废水的实际处理。概括来说，FBBR是一种具有活性污泥法和生物膜法的共同特点，同时结合了化工过程流态化技术的反应器。因其高生物量(生物量总固体浓度为15～40g/L)及载体生物膜的巨大比表面积(3000～5000m 2/m 3)而具有良好的传质效果(氧传质和基质传质)和较强的抗负荷冲击能力，是目前被认为效果显著的工业废水处理反应器，已在煤化工、印染、发酵、养殖和食品废水等实际工程中广泛应用，表现出工程启动/调式容易、抵抗负荷能力强、氧利用效率高等方面的特征。这是相对于传统的沸腾床反应器而言。
现有技术中存在的问题：(1)流化床底部的气水混合区是能量耗散最为显著的区域，其次是上升区顶部。有研究指出，在液体射流碰撞能量耗散实验中，当两股流体流量相若，接近对碰的情况下，因碰撞造成的能量损失可达总能量的80％以上。(2)污泥分离过程中会由于气体的上升运动带来三相分离区内废水的扰动，降低分离器内的固液分离效率，会有少量的絮状污泥不能被分离，导致这部分污泥流失，影响出水水质和后续处理工艺。(3)在三相分离器底部，沉降性能更好的活性污泥在重力以及水流曳力的作用下沉降到流化床底部，随后作为剩余污泥排出反应器。但是，沉降性能更好的污泥中含有更高浓度的高效降解污染物的菌胶团，它的流失会降低反应器的处理效率。(4)工程反应装置放大规模有限，受限于高径比与流态化的约束，影响反应器底部的污泥滑落以及三相的均匀混合。
发明内容
针对现有技术中存在的技术问题，本发明的目的之一是：提供一种负荷增强的废水处理流态化反应装置，该装置能够原位识别并分离不同凋亡程度的污泥，将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器外，这种功能选择性的实现整体提高了流化床反应器内部的污泥活性，以达到高负荷运行的条件，在相同操作条件下提升了反应器对废水中污染物质的降解效率。
针对现有技术中存在的技术问题，本发明的目的之二是：提供一种负荷增强的废水处理流态化反应系统，该系统能够对工业废水，特别是焦化废水进行抵抗高毒性负荷的运行，包括脱氮深度处理以及降低COD，实现浓度趋零，提高出水水质。
针对现有技术中存在的问题，本发明的目的之三是：结合目的一和目的二，构建高浓度(COD和总氮)、高毒性(氰化物、硫化物、硫氰化物、苯酚)废水的处理新工艺，形成焦化废水处理的短程低耗与节能高效工艺。
为了达到上述目的，本发明采用如下技术方案：
一种负荷增强的废水处理流态化反应装置，包括流化床反应器本体，流化床反应器本体设有至少一个流体下降区和流体 上升区，流化床反应器本体设有进水口，进水口设置于流体下降区，流化床反应器本体在流体下降区的上部设有相对独立于流化床反应器本体的三相分离器，三相分离器包括上端开口的三相分离器桶体，三相分离器的下端设有与流化床反应器本体连通的污泥斗，三相分离器上部设有与流化床反应器本体外部连通的溢流出水槽，三相分离器的溢流出水槽与污泥斗之间的沉降区中段设有与流化床反应器本体连通的进水管，三相分离器连接有旋流分离器，实现剩余污泥从水相中的分离，旋流分离器取水管的端口位于污泥斗与溢流出水槽之间，收集一定比重的污泥。进一步，三相分离器进水管包括纵向设置于三相分离器内部的立管，横向设置于三相分离器外部的平放管以及连接立管与平放管的连接管，连接管的一端连接于平放管的中部，连接管的另外一端连接于立管的下部，该平放管的两端均可以进水，实现两股流体的碰撞使气泡聚并后在立管中与水流逆向而行。
进一步，流化床反应器本体的流体下降区设置于中间区域，流化床为长方形结构，流体上升区位于流体下降区的四周，三相分离器设置于流化床反应器本体的上部中间位置。
进一步，流化床反应器本体的流体下降区设置在周边，流体上升区设置为一个，位于中心区域，流体下降区位于流体上升区的四周，三相分离器设置在流体下降区的周边外缘。
进一步，还包括曝气装置，曝气装置包括空气压缩机、空气分离装置、富氧气体进气管道和富氮气体进气管道，空气分离装置连接于空气压缩机，富氧气体进气管道和富氮气体进气管道的一端均连接于空气分离装置，富氧气体进气管道的另一端位于流体下降区的中部，端头连接有微孔曝气器，富氮气体进气管道的另一端则位于流体上升区的底部，其端头连接有富氮气体的分布器。
进一步，流体下降区底部设有水流导向装置，水流导向装置为朝向流体上升区的斜面，流体上升区和流体下降区之间设有导流筒隔板，流体上升区与流体下降区之间通过导流筒隔板分隔，降低实现流态化目标的动力消耗。
进一步，流体上升区内设有缩放管，缩放管沿水流方向设置，缩放管为若干个大管径和小管径间隔设置的连续管状件。
一种负荷增强的废水处理流态化反应系统，包括依次相连的隔油池、气浮池、调节池、一级好氧反应器(O1，除碳反应单元)、水解脱氮反应器(H，水解与脱氮单元)、二级好氧反应器(O2，完全硝化单元)、混凝沉淀池以及过滤池，其中一级好氧反应器采用一种负荷增强的废水处理流态化反应装置，二级好氧反应器采用另外一种负荷增强的废水处理流态化反应装置。
一种负荷增强的废水处理流态化反应方法，分离流化床反应器本体内部的污泥，将流化床反应器本体内的混合液导入三相分离器内，三相分离器内沉淀性能差的低活性的污泥通过外接旋流分离器排出反应器外，在流化床内部原位识别并分离不同凋亡程度的污泥，将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器，实现废水处理负荷能力的增强。
进一步，通过外接空气氧氮分离装置将高浓度的氧气分离出来，形成富氧气体与富氮气体两种组分，通过两根管道分别将两种组分输入流化床反应器本体内部，富氮气体通入流化床反应器本体的流体上升区的底部，主要作为动力作用，富氧气体通入流化床反应器本体的流体下降区的中部，主要作为供氧作用。
总的说来，本发明具有如下优点：
一种负荷增强的废水处理流态化反应装置，三相分离器沉降区中段外加旋流分离器取水管，将沉降区中部沉降性能较差的污泥分离出来，此外，性能较好的污泥在重力以及流体下降区的流体曳力的作用下重新进入到流化床反应器本体内部参加污染物的降解反应，确保了流化床反应器的稳定高负荷运行。
一种负荷增强的废水处理流态化反应系统，采用不同型式负荷增强的废水处理流态化反应装置作为一级好氧反应器和二级好氧反应器，使整个反应系统处理能力增强，可处理高浓度废水，通过分离空气，将富氧气体和富氮气体分别通入不同的位置，与污泥的管理模式的协同作用获得高效的废水处理效果。
一种负荷增强的废水处理流态化反应方法，根据异重流原理分离生物反应器内部污泥，将三相分离器内沉淀性能差的低活性污泥通过外接旋流分离器排出反应器外，增大流化床反应器内部的高活性污泥的比例，以达到高负荷运行的条件，加快对污水中污染物质的降解。基于流化床分离区的污泥沉降及凋亡分布的性质关系，原位识别并分离不同凋亡程度的污泥，将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器外，从而提高了反应器的效率。通过外接空气分离装置将高浓度的氧气分离出来，一方面可以减少曝气量从而节省能耗，另一方面提高了氧的利用效率。
附图说明
图1为本发明一种负荷增强的废水处理流态化反应装置一种实施例的结构示意图。
图2为本发明一种负荷增强的废水处理流态化反应装置另外一种实施例的结构示意图。
图3为本发明一种负荷增强的废水处理流态化反应装置三相分离器进水管的结构示意图。
图4为本发明一种负荷增强的废水处理流态化反应装置的导流筒隔板结构示意图。
图5为本发明一种负荷增强的废水处理流态化反应装置的十字形构件结构示意图。
图6为焦化废水处理流程图。
图7为反应器径向的湍动能分布(0.4m横截面)图。
图8为无内构件时K La模拟值与实验值对比分析图。
图9为无内构件及3种不同内构件时K La模拟值对比分析图。
图10为底隙区置入十字形内构件前后液体循环速度对比图。
图11为底隙区置入十字形内构件前后反应器总体气含率对比图。
图12为底隙区置入十字形内构件前后反应器上升区平均湍动能对比图。
图13为分离污泥的比耗氧速率和脱氢酶活比较图。
图14为分离污泥的活性与污泥粒径的相关性图。
图15为分离污泥的EPS组成图。
图16为分离污泥的絮体内部相互作用势能图。
图17为分离污泥的类凋亡细胞分布对比图。
图18为分离污泥的类凋亡细胞分布与污泥活性的关系图。
图19为分离污泥的物种β-多样性热图和与基于物种距离的PCoA分析图(a，热图；b，基于unifrac加权的PCoA分析)。
图20为基于属水平的分离污泥的微生物群落分布对比图。
图21为基于属水平的分离污泥的微生物群落结构热图。
图22为基于群落16S rDNA的分离污泥的功能预测图。
图23为生物处理过程中各类含氮化合物在总氮中的组成特征图。
图24为一级好氧流化床硫氰化物、氰化物的处理效果图。
图25为二级好氧流化床NH 4 +-N、NO x --N的浓度变化图。
其中图1、图2中包括有：
1、流体上升区；2、流体下降区；3、三相分离区；4、流化床进水管；5、旋流分离器出水管；6、旋流分离器取水管；7、溢流出水槽；8、三相分离器进水管；9、污泥斗漏管；10、富氧气体管道；11、空气进气管；12、富氮气体管道；13、微孔曝气器；14、导流筒隔板；15、缩放管；16、水流导向装置；17、阀门；18、旋流分离器；19、空气分离装置；20、空气压缩机；21、计量泵；22、漏斗形挡板；23、十字形构件；24、富氮气体分布器；25、污泥排放管；26、进水流量计；27、进气流量计；28、DO在线检测仪；29、MLSS在线检测仪。
具体实施方式
下面来对本发明做进一步详细的说明。
实施例1、分离区置于反应器中央
如图1所示，一种负荷增强的废水处理流态化反应装置，包括流化床反应器本体，流化床反应器本体设有流体下降区2和流体上升区1，流化床反应器本体设有进水口，进水口设置于流体下降区2，流化床反应器本体在流体下降区2的上部设有相对独立于流化床反应器本体的三相分离器，三相分离器包括上端开口的三相分离器桶体，三相分离器的下端设有与流化床反应器本体连通的污泥斗，污泥斗下端连接有污泥斗漏管9，三相分离器上部设有与流化床反应器本体外部连通的溢流出水槽7，三相分离器的溢流出水槽7与污泥斗之间的沉降区中段设有与流化床反应器本体连通的进水管，三相分离器连接有旋流分离器18，旋流分离器取水管6的端口位于污泥斗与溢流出水槽7之间。
三相分离器进水管8包括纵向设置于三相分离器内部的立管，横向设置于三相分离器外部的平放管以及连接立管与平放管的连接管，连接管的一端连接于平放管的中部，连接管的另外一端连接于立管的下部。
流化床反应器本体的流体下降区2设置为一个，流体上升区1设置为周边，流体上升区1位于流体下降区2的四周，三相分离器设置为一组，其个数由反应器的长度及其长宽比例决定，三相分离器设置于流化床反应器本体的上部中间位置。
还包括曝气装置，曝气装置包括空气压缩机20、空气分离装置19、富氧气体进气管道和富氮气体进气管道，空气分离装置19连接于空气压缩机20，富氧气体进气管道和富氮气体进气管道的一端均连接于空气分离装置19，富氧气体进气管道另一端位于流体下降区2的中部，富氮气体进气管道的另一端位于流体上升区1的底部，富氧气体进气管道的另外一端连接有微孔曝气器13，富氮气体进气管道的另外一端连接有富氮气体分布器24。
流体下降区2底部设有水流导向装置16，水流导向装置16为朝向流体上升区1的斜面，流体上升区1和流体下降区2之间设有导流筒隔板14，流体上升区1与流体下降区2之间通过导流筒隔板14分隔不同方向的流体。
流体上升区1内设有缩放管15，缩放管15沿水流方向设置，缩放管15为若干个大管径和小管径间隔设置的连续管状件。
具体的，如图1所述，包括流化床进水管4、旋流分离器出水管5、旋流分离器取水管6、溢流出水槽7、三相分离器进水管8、污泥斗漏管9、富氧气体进气管道10、空气进气管11、富氮气体进气管道12、微孔曝气器13、导流筒隔板14、缩放管15、水流导向装置16、阀门17、旋流分离器18、空气分离装置19、空气压缩机20、计量泵21、富氮气体分布器24、污泥排放管25、进水流量计26、进气流量计27、DO在线检测28以及MLSS在线检测仪29。流化床反应器本体通过导流筒隔板14分隔为流体上升区1和流体下降区2，导流筒隔板14上分布有多个小孔，小孔分布方式可以设置为均匀分布如图4中a所示或等距离分布如图4中b所示，使得上升区与下降区中存在多个流体循环分布，增加混合效果及气液传质效果。空气通过空气压缩机20进入到空气分离装置19，使其分离为富氧气体和富氮气体。富氧气体通过富氧气体进气管道10进入到流体下降区2上部，通过微孔曝气器13扩散进入流体下降区2，与流体下降区2的流体逆流接触，大幅度提高了气泡的水力停留时间和气液传质系数。废水从流化床进水管4进入到流体下降区2，通过管道上的进水流量计26控制流量，在下降区的流体曳力以及自身重力作用下作快速的下降运动，当其下降到反应器底部时，在水流导向装置16的导流作用下进入上升区1。富氮气体通过富氮气体进气管道12进入到流体上升区1底部，通过其末端的富氮气体分布器24给流体上升区1内流体提供上升的推动力，使得废水在流化床内部作循环运动，并强制从微孔曝气器13扩散进入流体中微小气泡氧气实现向下的逆流。流体上升区1内有缩放管15，缩放管15使得上升区截面不均匀，增大流体的湍流程度，根据双膜理论，从而加大气液传质系数，提高氧的利用效率。流体下降区2顶部的流体通过三相分离器进水管8进入到三相分离器3中，三相分离器进水管8为三通管道，废水中的气体在三相分离器进水管8中向上逸出，水和污泥向下流出。在三相分离区3内，污泥通过重力以及流体下降区2内流体的曳力作用做快速的沉降运动。沉降性能较差的污泥进入到旋流分离器18中进行泥水分离，分离出的上清液通过计量泵21回流到流化床反应器本体中。
一种负荷增强的废水处理流态化反应工艺系统，包括依次相连的隔油池、气浮池、调节池、一级好氧反应器(O1)、水解脱氮反应器(H)、二级好氧反应器(O2)、混凝沉淀池以及过滤池，其中一级好氧反应器(O1)采用一种负荷增强的废水处理流态化反应装置，二级好氧反应器(O2)采用另外一种负荷增强的废水处理流态化反应装置。
一种负荷增强的废水处理流态化反应方法，分离流化床反应器本体内部的污泥，将流化床反应器本体内的混合液导入三相分离器内，三相分离器内沉淀性能差的低活性的污泥通过外接旋流分离器18强制沉淀并通过污泥排放管23排出反应器外，达到了在流化床内部原位识别并分离不同凋亡程度污泥的目的，这种选择性的功能能将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器外。
通过外接空气氧氮分离装置将高浓度的氧气分离出来构成富氧气体，其余组分为富氮气体，两种组分分别通过两根管道输入流化床反应器本体内部，其中，富氮气体通入流化床反应器本体的流体上升区1的底部，形成流体流态化的动力，富氧气体则通入流化床反应器本体的流体下降区2的中部，达到供氧的目的。
总的说来，本发明具有如下优点：
一种负荷增强的废水处理流态化反应装置，三相分离器沉降区中段外加旋流分离器取水管6，将沉降区中部沉降性能 较差的污泥分离出来，此外，性能较好的污泥在重力以及流体下降区2的流体曳力的作用下重新进入到流化床反应器本体内部参加污染物的降解反应，确保了流化床反应器的稳定高负荷运行。
一种负荷增强的废水处理流态化反应系统，采用负荷增强的废水处理流态化反应装置作为一级好氧反应器和二级好氧反应器，使整个反应系统处理能力增强，可处理高浓度废水，处理效果好。
一种负荷增强的废水处理流态化反应方法，根据异重流原理分离生物反应器内部污泥，将三相分离器内沉淀性能差的低活性的污泥通过外接旋流分离器18的强制浓缩作用后通过污泥排放管25排出反应器，增大流化床反应器内部的污泥活性，以达到高负荷运行条件，加快对污水中污染物质的降解。基于流化床分离区的污泥沉降及凋亡的性质关系，原位识别并分离不同凋亡程度的污泥，将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器，从而提高了反应器效率。通过外接空气分离装置19将高浓度的氧气分离出来，一方面可以减少曝气量从而节省能耗，另一方面提高了氧的传质效率。
本实施例的流化床反应器采用中间为流体下降区2，四周为流体上升区1的流体循环模式，其中的三相分离区3位于流体下降区2的上方。一级好氧反应器(O1)水解脱氮反应器(H)均采用这种型式的反应器。在流化床反应器中，底部的气水混合区是能量耗散最为显著的区域，有研究指出，在液体射流碰撞能量耗散实验中，当两股流体流量相若，接近对碰的情况下，因碰撞造成的能量损失可达总能量的80％以上。在流化床内置入优化结构的内构件能改善流体流化质量，而对比起化工领域，废水处理生物流化床内构件的开发远远落后。再者，鉴于流化床内部流态与流场的复杂性，影响因素多，物理实验相对误差大，成本高昂，为了降低成本，需要更准确地预测反应器的流体力学性能。研究者开发了一些新型内构件，如挡板，筛网，填料等，以期通过这些内构件实现反应器效率的进一步提高，或者进一步控制反应器内部的流体流动。在本实施例的流化床反应器中，本发明采用底部设置倒V型底座的水流导向装置16的方式减少底部流体碰撞区的大量能量耗散，提高流化床内流体的循环效率。此外，在导流筒隔板14上增设均匀开孔和间距开孔两种布孔方式。小孔的开设使得流体上升区1内流体可通过孔道进入到流体下降区2，形成小路径循环，进一步增强了反应器内的多相混合效果，强化气液传质。
反应器的顶部流体通过三相分离器进水管8进入到三相分离器中。三相分离器进水管8结构原理示意如图3所示。流体通过进水管口两端进入到横向的平放管内，首先在平放管内发生流体的碰撞使得流体流速大幅度降低，为下一步的三相分离提供良好的条件。随后，流速降低的流体进入到竖向的立管内，竖向的立管的设置一方面进一步降低流体的流速，从而减少由于进入三相分离器的流体动能过大破坏其沉淀效果。另外一方面，流体中的气体在竖向管中由于升力作用而向上逸出，污泥则由于重力作用向下沉降，增加了三相分离器的气液固分离效果，提高了出水水质。
在现有技术中，沉降性能更好的活性污泥在重力以及水流曳力的作用下沉降到流化床底部，随后作为剩余污泥排出反应器。但是，沉降性能更好的污泥中含有更高浓度的高效降解污染物的菌胶团，它的流失会降低反应器的处理效率。因此，在本发明中，我们在三相分离器沉降区中段的混流区(即部分流体向下，部分流体向上)安装旋流分离器取水管6，与旋流分离器18连接，将沉降区中部沉降性能较差的污泥分离出来，此外，性能较好的污泥在重力以及下降区的流体曳力的作用下重新进入到流化床内部实现了停留时间的分离保留，高活性污泥的保留对污染物的降解反应表现出高效率，确保了流化床反应器的稳定高负荷运行。
在曝气系统方面，空气通过空气压缩机20进入到空气分离装置19，将富氧气体通过风机和管道的输送进入到流体下降区2，气体与反应器内废水的流动方向实现逆流接触。由于微孔曝气器13形状为倒三角锥行，流体下降区2的流体会随着下降高度的增加流速会越来越快。流速的增大一方面增大气液传质速率，另外一方面，流速增大带来流体曳力的增加使得微孔曝气器13的气泡向下运动，增大了气泡的停留时间，强化气液传质效果，实现氧的高效利用。从空气分离装置19中流出的富氮气体则通入到流体上升区1底部，提供流化床内的液体循环动力，同时也利用富氮气体内部的剩余氧气。此外，由于增设逆流传质效果，底部曝气量相比传统流化床更小，供气总体积下降50％左右，从而降低曝气能耗，实现反应器的节能。
实施例2、
本实施例的主要结构与实施例1相同，相同之处在此不在赘述，不同之处在于：如图2所示，流化床反应器本体的流体下降区2设置为周边，流体上升区1设置为一个，流体下降区2位于流体上升区1的四周，三相分离器对应流体下降区2设置在周边。
具体的，如图2所示，包括流化床进水管4、旋流分离器出水管5、旋流分离器取水管6、溢流出水槽7、三相分离器进水管8、污泥斗漏管9、富氧气体进气管道10、空气进气管11、富氮气体进气管道12、微孔曝气器13、导流筒隔板14、缩放管15、水流导向装置16、阀门17、旋流分离器18、空气分离装置19、空气压缩机20、计量泵21、漏斗形挡板22、十字形构件23、富氮气体分布器24、污泥排放管25、进水流量计26、进气流量计27、DO在线检测28以及MLSS在线检测仪29。流化床反应器本体通过导流筒隔板14将反应器分隔为流体上升区1和流体下降区2，导流筒隔板14上分布有多个小孔，小孔分布方式可以设置为均匀分布，如图4中a所示，或等距离分布，如图4中b所示，使得流体上升区1与流体下降区2中存在多个流体循环分布，增加混合效果及气液传质效果。空气通过空气压缩机20进入到空气分离装置19中，使其分离为富氧气体和富氮气体。富氧气体通过富氧气体管道10进入到流体下降区2上部，通过微孔曝气器13扩散进入到流体下降区2，与流体下降区2的流体逆流接触，大幅度提高了气泡的水力停留时间和气液传质系数。废水从流化床进水管4进入到流体下降区2，在流体下降区2的流体曳力以及自身重力作用下作下降运动，当其下降到反应器底部时，在底部十字形构件23的导流作用下进入流体上升区1。富氮气体通过富氮气体管道12进入到流体上升区1底部，通过富氮气体分布器24均匀释放气体，给流体上升区1内流体提供上升推动力，使得废水在流化床反应器内部作循环运动。流体上升区1内有缩放管15，缩放管15使得上升区截面不均匀，增大流体的湍流程度，从而加大气液传质系数，提高氧的利用效率。流体上升区1顶部的流体在漏斗形挡板22的导流作用力，减少流体间因碰撞而产生的能量损耗。流体下降区2顶部的流体通过三相分离器进水管8进入到三相分离器中，三相分离器进水管8为三通管道，废水中的气体在三相分离器进水管8中向上逸出，水相和污泥向下流出。在三相分离区3内，污泥通过重力以及流体下降区2内流体的曳力作用做沉降运动。沉降性能较差的污泥进入到旋流分离器18中进行泥水分离，分离出的上清液通过计量泵21回流到流化床反应器本体中。
本实施例的流化床反应器采用中间为流体上升区1，四周为流体下降区2的流体循环模式。相对于实施例1的流化床反应器，本实施例的流化床反应器的三相分离区3的表面负荷降低和可控，根据浅池理论得知，可以分离更小/比重更轻的污泥颗粒，其污泥分离效果更加优良，同时排泥量也增加。因此，可以作为对出水水质要求更严格的二级好氧反应器(O2)的选用反应器型式，这种型式反应器可以明显减少后续混凝反应所需的药剂用量。
在本实施例的流化床反应器中，在流体上升区1底部设置十字形构件23，十字形构件23的整流作用可明显降低流体在流化床底部因非弹性碰撞而造成的水头/矢量损失，实现富氮气体最小动力输入条件下使四边形流化床内流体上升区1和流体下降区2液体循环速度得到提升。十字形构件23能使流化床内液体循环速度在流体上升区1截面较均匀分布并将降低其湍流运动的能量耗散。基于废水处理对反应器流体力学性能的要求，十字形构件23实现了对四边形流化床水力条件和系统能耗的优化。在十字形构件23的作用下，流化床内液体循环速度在流体上升区1断面分布较均匀，流动死角区域明显减少。从微观角度分析，减少了不同尺度漩涡的产生。置入十字形构件23后，液体从流体下降区2经流化床底部循环至流体上升区1的过程中，减少了因流体之间的非弹性碰撞而造成的水头损失和能量耗散。取而代之的是，流体与十字形构件23刚性碰撞后，水平方向动能损失不大，继而折射、弯曲，并在入口气体的推动下，继续在反应器内进行内循环。此外，在流化床导流筒的顶端，本发明设置了漏斗形挡板22和折流挡板，漏斗形挡板22适用于圆形和正方形结构流化床，折流挡板适用于长方形卧式流化床。该内构件具有结构简单的特点，通过该内构件的置入，改变气液两相或气液固三相的运动方向来强化反应器多相混合与传质,获得一个自定义的流场，同时产生较小的流动阻力以降低操作能耗，使反应器效率进一步提高，尤其适用于活性污泥法废水生物处理过程。内构件外直径越大，将导致液体向上的流通通道越窄和更大的能量耗散，进而使液体循环速度会有所降低，相对增加了气泡在反应器内部的停留时间，即增大了反应器的局部和总体的气含率。因此，可以通过增加漏斗内构件的方法来提高反应器气含率，增加气泡停留时间，当把这种漏斗内构件强化的内循环流化床应用于废水好氧生物处理时，则可以增加气液传质界面面积和气液接触时间，使曝气提供的氧气的利用效率明显提高，减少单位曝气能耗。
此外，本发明还具有易实现工程放大且流态稳定的特征，当进水量增加时，可将此正方形流化床扩建为卧式流化床，任意调控长度和宽度的比例。相应的，顶部三相分离区3、底部十字形构件23、导流筒隔板14、顶部漏斗形挡板22可通过增加长度比例进行安装，从而改变反应器容积以适应进水量，实现不同规模的工程型反应器。
实施例3、
本实施例的主要结构与实施例1相同，相同之处在此不在赘述，不同之处在于：一种负荷增强的流态化废水处理新型生物反应装置，其处理对象为焦化废水，主要污染物指标如表1所示。
表1试验废水总和水质指标
Figure PCTCN2018123848-appb-000001
废水处理流程：焦化废水实际处理流程如图5所示，焦化废水原水首先通过隔油池以及气浮池去除废水中的浮油成分，随后进入调节池进行pH调节。调节后的废水在计量泵21的作用下进入一级好氧反应器(O1)，一级好氧反应器对出水水质要求不高，并且曝气量大，因此采用新型流化床1结构制作，通过本专利中的逆流接触传质、污泥原位分离对废水的高效生物降解以及节能降耗。二级好氧反应器(O2)的出水水质要求高，对污泥的分离有着较高的要求，因此采用新型流化床2结构制作，用于处理经过水解脱氮反应器(H)的废水，对其进行深度处理，进一步降低COD和氨氮，提高出水水质。水解脱氮反应器(H)也采用与一级好氧反应器(O1)一样的反应器结构型式，但控制的水力停留时间(HRT)、污泥停留 时间(SRT)、pH值等条件的不同。
内构件增加带来的气液传质效果
漏斗形内构件对流化床反应器的气液传质强化作用
局部的湍动能(Turbulent Kinetic Energy，TKE)能够决定反应器的传质性质，而且TKE还与流动剪切力相关，这种剪切作用力对于剪切敏感的细胞和微生物参数的生物过程是至关重要的。目前已有部分文献讨论了TKE和剪切对生物过程的影响问题。有研究指出，流体的剪切应力与TKE成正比关系，过剩的湍动能将导致强烈的流动剪切作用，伤害悬浮细胞，导致失去生长能力，甚至结构瓦解。本节对比研究了内构件加入前后以及不同结构和尺寸的内构件对反应器局部湍动能的影响。图7是位于0.4m高横截面，在表观气速0.01m/s条件下湍动能的径向分布。
从图7中可以看出：不同内构件漏斗形挡板(图2中的22)的置入使液相湍动能都有一定程度的降低，湍动能径向分布近似满足抛物线分布，即反应器中心湍动能比近壁面区域要大很多，而且在距中心轴线2cm范围内湍动能相对稳定在某一常量值，可能与气泡的气泡羽流的近中心区域分布有关，其中内构件C最明显；下降区湍动能相对较低，而且不同的内构件被采用时其值几乎没有差别；当内构件C被采用时，与对照相比其湍动能最多降低了7.8％。反应器局部湍动能的降低对于剪切敏感的微生物是非常有利的，例如生物发酵过程中很多丝状真菌对剪切作用都有严格的要求，剪切过大会造成菌体损失；废水处理中的颗粒污泥技术就要求相对较低的流动剪切，否则可能导致颗粒污泥无法形成或颗粒破碎。
为了探讨内构件置入循环流化床后对反应器氧传质性能的影响，利用公式求得反应器的体积平均氧传质系数K La，将不加内构件和置入不同内构件条件下的K La进行对比，具体的结果如图8及图9所示。
增加漏斗形导流内构件使反应器K La值显著提高，随着表观气速增大，K La值增长比较明显，A、B、C三种导流内构件的效果依次递增，与不设内构件相比，内构件C使K La值最大提高了约19.0％。在实验过程中也发现，就提高氧传质效果来说，内构件A对于流体阻碍作用明显，使用内构件B时可观察到大量气泡从反应器上升区逃逸进入大气；内构件C外径相对较大，其液体导流面积得到提高，同时还能起到将聚并的大气泡破碎为小气泡的作用，这些都对提高体积氧传质系数是有利的。
十字形构件对流化床反应器的气液传质强化作用
为了分析底隙区置入十字形构件23后对反应器内部水力流动性质的影响，本发明研究分别在6种不同的表观气速条件下(0.25，0.5，0.75，1.0，2.0，3.0cm/s)，针对置入与不置入内构件的反应器的流体上升区1和流体下降区2液体循环速度以及总体气含率的模拟值分别进行了对比研究。图10显示了底隙区有或无十字形构件23时流体上升区1和流体下降区2液体循环速度随表观气速的变化规律，图11是底隙区有或无十字形构件23时反应器总体气含率随表观气速的变化情况。
从图10中可以看出：当底隙区置入十字形构件23以后，流体上升区1和流体下降区2的液体循环速度都得到了明显提高，它们各自最大分别提高了11.8％和15.9％；流体上升区1和流体下降区2的液体循环速度随表观气速的变化趋势在内构件置入前后完全类似，均随表观气速增大而增大，且增加速度先快后放缓。实际上，当十字形构件23置入内循环流化床反应器前，反应器流体下降区2流体通过底部锥形部分逐渐转变为向内弯曲流动，这些弯曲流动在360°范围内向中心点汇聚，互相碰撞和渗透而抵消了大部分能量；而当置入内构件以后，由于这些弯曲流线碰到构成十字构件的刚性挡板，发生发射、 折射等刚性碰撞，这时碰撞能量损失大为降低，速度水头降低较少，碰撞后能保持较高的速度水头转变为沿上升区向上方向的运动。因此，表现为实验和模拟过程中液体循环速度的较大幅度的提高。液体循环速度随表观气速的变化趋势与不置入内构件时完全类似，其原因也是类似的。
从图11中可以看出：随表观气速增加，置入与不置入十字构件反应器的总体气含率均逐渐增加，而且开始阶段增加较快，后来逐渐放缓；值得注意的是，内构件的置入反而导致了反应器总体气含率的小幅度下降，在气速3cm/s时气含率最高下降幅度为4.8％。说明：内构件的置入导致液体循环速度的增加，产生了两方面的效果，第一为液体循环速度提高，气体在反应器内部的停留时间变短，更快地通过自由液面溢出，导致总体气含率下降；第二是下降区的液体循环速度加快，就能卷带更多的气泡进入下降区，会导致总体气含率在一定程度上增加；两种效应作用相反，由于液体循环速度变快导致气含率下降的效应更为显著，起到了主导作用。
内循环流化床反应器的气液两相的湍动过程主要发生在流体上升区1，为了分析底隙置入十字形构件23以后对反应器湍动能的影响，本研究分别在6种不同的表观气速条件下(0.25，0.5，0.75，1.0，2.0，3.0cm/s)，针对置入内构件前后反应器的流体上升区1平均湍动能进行了对比研究，结果如图12所示。从图12中可以看出：随表观气速的增加，底隙置入与不置入十字形构件23，反应器的流体上升区1平均湍动能都逐渐增加，而且开始阶段增加相对较快，然后湍动能增长速度变慢；与不置入内构件的对照相比，内构件的置入引起了流体上升区1平均湍动能的下降，在气速3cm/s时湍动能最高下降幅度为12.8％。其原因分析如下：底隙的湍动能来源主要是富氮气体分布器24入口处的气体入口动能输入，流体下降区2回流液体经过底隙区时，接受气体动能的转移而发生湍动，而十字形构件23的加入能起到分割底部空间的作用，与整个底部空间相比，单个空间的水力半径显著降低(以十字形四辐内构件为例，可计算出水力半径仅为原来的0.44倍)，则雷诺系数Re值显著降低，而Fr(弗罗劳德数)值显著增大，因此流动过程更加稳定，湍动能显著下降，因此，底隙置入十字构件能起到整流作用。
分离区对不同沉降性质污泥的原位分离
本流化床运行控制在2.14kg COD/m 3·d有机负荷率(OLR)下，针对高毒性的焦化废水，流化床化学需氧量(COD)去除效率达到85-93％以上。在流化床分离区，致密絮凝体沉在颗粒底部，少量松散絮凝体漂向反应器顶部的上清。不同密度、不同大小的污泥可以通过沉降或曳力进行分离，通过证明污泥细胞衰变伴随着絮凝物聚集的变化，不同聚集程度的污泥中EPS(胞外聚合物)含量和微生物ALD(类凋亡程度)存在不同，在流化床中通过曳力可以分离出相对凋亡污泥。我们对流化床内部分离区的絮状污泥(50mL/g<SVI<80mL/g)进行了分离，得到了3种沉降速率不同的污泥，包括污泥S(v<5m/h)，污泥M(5m/h<v<10m/h)以及污泥F(v>10m/h)，并对它们的沉降性能，平均粒径，活性，絮体内部聚集能力计算，微生物衰退，群落结构以及基于群落结构信息的功能预测进行了分析表征。发现沉降速率不同的污泥具有显著的性质差异。
表2从分离区中分离得到的3种不同沉降速率的污泥
Figure PCTCN2018123848-appb-000002
Figure PCTCN2018123848-appb-000003
比耗氧速率(SOUR)和脱氢酶活(DHA)是污泥活性最广泛使用的指标。3种沉降速度的污泥S,M和F的SOUR分别为45.4±5.22mg/(g·h),47.1±4.62mg/(g·h)和53.2±4.20mg/(g·h)。污泥S,M和F的DHA分别为21.21±2.50mg TF/(g·h),24.13±3.57mg TF/(g·h),28.86±1.59mg TF/(g·h)，通过方差分析验证，标准差异显著(p<0.05)。结果表明，污泥F的活性比污泥M和S高13.0-36.1％，同时，我们考察了不同结构紧密度的污泥活性，得到了SOUR/SVI和DHA/SVI。结果发现污泥F比污泥M和S有更高的SOUR/SVI和DHA/SVI，这种体积相对较小的活性污泥对反应器有较好的处理效果。不同大小的絮状物的活性污泥F,M和S被发现在10-20μm范围有很强的正相关关系，见图14。因此，我们推测老化污泥随EPS含量的变化而增长和衰减，进而导致污泥形态的变化，如絮凝体大小的变化。
分离污泥的聚集性
胞外聚合物(EPS)是污泥沉降性、压实性和密度等特性的重要指标，污泥EPS通常由松散结合能EPS(LB-EPS)和紧密结合能EPS(TB-EPS)两层组成，本研究采用蛋白质(PN)和多糖(PS)含量分析不同污泥的EPS。在LB-EPS中，PN较PS更占优势，这两种组分分别为2.68-3.02mg/g MLVSS和1.93-2.80mg/g MLVSS，TB-EPS含量相对较低(2.13-2.26mg/g MLVSS)(4.61-5.82mg/g·MLVSS)。推测由于EPS含量较低，使得这些污泥不能形成颗粒污泥并保留针絮状形态。而由于高氧转化率，EPS不得不保持在低水平。同时，EPS的PN和PS成分在污泥沉降性研究中往往起着更为重要的作用。有趣的是，我们发现污泥S的LB-PS 2.80±0.39mg/g·MLVSS的含量最高。此外，LB-EPS和Total-EPS在污泥S和F中的PN/PS均相反(图15b)，两种EPS中污泥的PN/PS均低于污泥F。很明显，松散污泥的PN/PS比值较低。在我们的研究中，PN/PS低的污泥应该有更松散的结构。松絮凝体的PN/PS低可能是由于PS高，因为PS有丰富的-OH基团倾向于与水分子形成氢键，PN是长链疏水氨基酸倾向于在疏水力的驱动下聚集的大生物分子。PN/PS越低，污泥中含水量越高，且随着PS含量的增加或PN含量的降低，细胞之间很可能会相互分离。
为了估算污泥絮体内部的微生物相互作用，我们测定了污泥表面性质包括疏水角和Zeta电位，并用XDLVO方法计算了不同污泥的相互作用势能。污泥与液体的接触表明污泥的疏水性不同于其他污泥，见表3。Wtot,H粒子的作用距离，表明总污泥势能，每一个势能曲线有一个能量势垒(EB)和二次最小值(SMV)，更高的EB表示更稳定的污泥悬浮性而更高的SMV表示更多的聚合性。3种污泥有明显不同的能垒，如图16所示，EBS>EBM>EBF，说明污泥F比其他两种污泥更稳定。与此同时，0>SMVS>SMVM>SMVF同时对EB有类似的趋势，Wtot的EB和SMV结果表明污泥S的凝聚力小于其他两种污泥，会形成松散絮凝体，而污泥F的凝聚力更大，会形成致密絮凝体。
表3分离污泥对3种液体的疏水角和表面性质参数
Figure PCTCN2018123848-appb-000004
Figure PCTCN2018123848-appb-000005
分离污泥的微生物细胞活性
不同污泥的对微生物细胞的生理状态如图17所示。在FL1-FL2图中，将其划分为整个坐标系的四个部分：F1、F2、F3、F4。F3中的细胞点代表正常细胞，未染色表明这些细胞既未死亡也未凋亡。F4中的细胞点代表凋亡细胞由Annexin-V和发射荧光染色(λ＝525nm)。F2中的细胞点代表晚期凋亡细胞，可以同时被Annexin-V和PI染色。F1中的细胞点代表死细胞染色并发射出红色荧光(λ＝620nm)。双通道荧光点图(图17d,e,f)分别显示正常细胞、凋亡细胞和死亡细胞。结果表明，不同污泥微生物细胞生理状态存在显著差异。在污泥中，它有更多的凋亡样凋亡细胞和死亡细胞，而在污泥中，它有更少的凋亡细胞。污泥F的ALD值分别比污泥M和S低6.64％和13.5％。这有力地解释了重力分离污泥的活性分化。图18研究了ALDCD与污泥活性的关系。3种重力分离污泥中ALDCD与DHA或SOUR呈显著负相关(RDHA2＝0.9656,RSOUR2＝0.8711)，表明ALDCD可以作为污泥活性衰减的指标。磷脂酰丝氨酸外化的细胞凋亡在真核细胞中得到了解释，但在细菌中却没有。在真核细胞中，细胞膜通过磷脂转移酶和混杂酶维持内小叶中磷脂酰丝氨酸的平衡。Ca 2+抑制的磷脂转移酶将磷脂酰丝氨酸从外小叶转移到内小叶，Ca 2+激活的混杂酶将磷脂酰丝氨酸从内小叶转移到外小叶。当细胞凋亡开始时，细胞内Ca 2+增加，混杂酶可以将磷脂酰丝氨酸转移到外小叶，磷脂转移酶不能将磷脂酰丝氨酸转移到内小叶。在以往的研究中，研究者发现污泥中的微生物内源性过程是由于程序化细胞死亡(PCD)，而凋亡样凋亡被认为是一种PCD。在这项工作中，重力分布污泥的ALDCD呈现出明显的不同。这一特性将使我们进一步了解污泥中的细菌衰减。在3种污泥中，PN/PS较低的污泥中ALDCD最高，而污泥F则相反。基于以上结果，可以推测，可能由于污泥的类凋亡导致了LB-PS分泌的改善，而PN/PS进一步降低，导致污泥松散聚集，SVI增加。
分离污泥的微生物群落变化
采用分子生物学方法对3种污泥微生物群落进行了分析。每个样品至少获得17148个平均长度为372bp的有效序列。每个样本的相似度为97％，生成372-451 OTUs。共有556个OTUs，其中263个OTUs被3种不同的污泥所共享。这些结果表明，这些污泥间的群落一致性高但差异仍然存在。3种不同的污泥的α-diversity香农指数(H)、chao1和辛普森指数的群落分析表明这些污泥的多样性和丰富性与其他焦化废水污泥相似，但明显低于城市污泥。3种不同的距离热图和PCoA污泥暗示3种污泥距离较远，污泥M的群落多样的介于污泥F和污泥S之间(图19)，这表明污泥沉降速度分布和微生物群落分布的关系相对应。
采用基于距离矩阵的统计方法对样本组间差异进行检验。3种重力分离污泥(Anosim,p＝0.004,R＝1；Adonis,R2＝0.884,p＝0.006)。这些结果也表明，污泥F、污泥M、污泥S与其他污泥有显著性差异，与之前的污泥特性分析相对应。
这些污泥群落的群落结构在属水平上进行了表征(图20)，图中英文均为细菌种属通用的拉丁文学名，目前细菌的分类中的拉丁文学名是国际通用写法，部分菌种尚无对应的中文翻译。选择相对丰度较高的属对物种丰度热图进行聚类分析(图21)，图中英文均为细菌种属通用的拉丁文学名，目前细菌的分类中的拉丁文学名是国际通用写法，部分菌种尚无对应的中文翻译。微生物丰度随着沉降速度增加的物种包括以硫代谢和脱氮能力突出的焦化废水处理系统(CWTS)特征硫杆菌Thiobacillus(6.05-10.75％),和Comamonas(4.47-5.85％)，这两个属的细菌常常被认为是CWTS中的功能菌。同时，我们发现 一种功能性细菌脱氮Thauera(2.16-5.61％)，也大量存在于污泥M和F中。然而，污泥M的Thauera丰度最高。此外，一些主要类型的兼性化能异养细菌被发现有很高的丰度。例如Ignavibacteriaceae在污泥F的丰度比S和M更高(7.94-11.36％)。Cryomorphaceae的丰度(6.38-6.76％)也在污泥F中最高，且该菌属总是需要复杂的有机化合物和海水盐才能增长。另一方面，大量的一些功能不太清晰的微生物在CWTS的丰度随着沉降速度增加而降低。这些微生物包括Chitinophagaceae(7.65-14.20％)，该属仅在根际土壤、根、蠕虫和其他营养不良环境中发现过；Chloracidobacteria Ellin6075gen(3.38-7.61％)是一种利用发酵末端产物作为碳源，在淡水中发现的属；Weeksellaceae(2.25-5.90％)是一种主要从人类中分离得到的需氧有机化能致病菌属，在CWTS中鲜有报道。以上的结果表明，小粒径或沉降速度较慢的污泥中的微生物已经不再含有高丰度的适应CWTS环境的功能菌，而是含有丰富的适应低营养环境的其他菌属，这说明沉降速率较慢的污泥已经是发生衰退了的污泥。
分离污泥的环境功能预测
通过PICRUSt方法将得到的群落数据与Green gene bank数据库进行比较，完成了污泥功能的预测。从分离污泥中得到286个预测功能。图22列出了环境功能的前30种。发现在污泥F中碳水化合物的消化和吸收，细胞色素P450和基底转录因子这三项功能分别比污泥M和S高出31.6％和70.8％，23.5％和37.3％，43.5％和61.3％。而柠檬酸循环、能量代谢、丙酮酸代谢和氧化磷酸化在污泥F中的丰度比污泥M和S分别高出2.2％和3.2％，1.0％和3.3％，0.6％和2.0％，2.4％和3.0％。这些功能与有机物底物的降解和生物氧化高度相关。而离子通道、ABC转运体和转运体在污泥F中的相对丰度分别比污泥M和S低。这些功能进一步证实了污泥F在基因水平上具有较高的活性，说明较高的沉降速度污泥具有较强的活性微生物活性。
选择性排泥带来的反应器效率提升计算
污泥絮体首先上升到导流筒的流化床顶部，在流体下降区2下降，部分污泥被吸入三相分离器，轻污泥絮体分布在三相分离区3的上方，而重污泥絮体受曳力往下运动，随后轻絮凝体被吸进旋流分离器18进行浓缩处理。污泥的比例F,M和S是81.6％、16.4％和2.0％。用流化床选择性污泥分离代替生物反应器底部污泥的排放，可以排出大部分污泥M和全部污泥S。为评价选择性污泥分离对总污泥活性的改善效果，进一步计算如下。
系统干污泥排放量为0.5-0.6kgSS/m 3，污泥排放量约占污泥总量的15.2-19.4％。在实际的污水处理工程系统运行中，SV30始终保持在15％-30％，因此污泥的SVI、SOUR、DHA总量由式(1)-(2)计算得到。将污泥从流化床中选择性分离后，根据一定污泥分离效率(6)，由式(3)-(5)计算污泥的比例。总污泥SVI可在恒定SV30控制范围内降低，可得到MLSS增量百分比(Mincrement)(7)。污泥的平均活性可以随着污泥M和污泥S的排放而增加，从而可以得到污泥活性增加百分比(8)。则综合效率增量可计算为式(9)：
SVI＝∑P sludge×SVI sludge                   (1)
Activity＝∑P sludge×Activity sludge              (2)
Figure PCTCN2018123848-appb-000006
Figure PCTCN2018123848-appb-000007
Figure PCTCN2018123848-appb-000008
Figure PCTCN2018123848-appb-000009
Figure PCTCN2018123848-appb-000010
Figure PCTCN2018123848-appb-000011
CE increment＝[(1+M increment)×(1+A increment)-1]×100％   (9)
P：分质污泥所占污泥的比例(F,M,S)；
AS：实施污泥选择性分离后；
BS：实施污泥选择性分离前；
Eseparation：污泥分离效率，在本研究中估算为85％；
CEincrement：生物反应器综合效率增量。
所以，我们发现在自行设计的CWTS中，轻质污泥可以从流化床中分离出来。CWTS污泥的排放范围为0.5-0.6kgSS/m 3·d,CWTS污泥的MLSS范围为3100-3300mg/L，污泥排放量占污泥总量的15.2-19.4％。选择性污泥分离后，在恒定SV30控制下，全污泥活性和全MLSS浓度的估计分别提高1.85-2.79％和2.0％。与传统的污泥重力沉降排放相比，以MLSS和活性的乘积来定义的污泥处理综合效率将提高3.9-4.8％。
焦化废水处理工艺中含氮化合物的转化
焦化废水中有机含氮化合物种类繁多，测定复杂，在进行焦化废水总氮的组成评价时，将有机含氮化合物(ON)归为一类。总氮扣除氨氮、氰化物中氮、硫氰化物中氮、硝酸盐氮和亚硝酸盐氮的贡献比例，得出有机氮的贡献比例。另外，在总氮的测定中，硫氰酸盐、络合氰化物和易释放氰化物在总氮分析过程中转化效率不高，只有88％、75％和95％。而氨氮、硝酸盐氮、亚硝酸盐氮在总氮分析过程中转化效率都为100％。因此，焦化废水中各种含氮化合物在总氮中的比例计算如下:
Figure PCTCN2018123848-appb-000012
Figure PCTCN2018123848-appb-000013
Figure PCTCN2018123848-appb-000014
Figure PCTCN2018123848-appb-000015
Figure PCTCN2018123848-appb-000016
式中：
Figure PCTCN2018123848-appb-000017
分别表示NH +-N硝态和亚硝态氮、硫氰化物、氰化物和有机氮化合物占总氮的比例，
Figure PCTCN2018123848-appb-000018
和C TN分别表示NH +-N硝态和亚硝态氮、硫氰化物、氰化物和总氮的浓度。
O 1/H/O 2工艺中含氮化合物的转化
从采样时间内水质平均值数据及其变化(表4)可以分析O/H/O生物工艺各工艺段的处理效果。数据显示，采用生物三相流化床O/H/O组合工艺处理焦化废水，可以在设计负荷条件下稳定运行，生物处理出水平均COD、挥发酚、NH 4 +-N、氰化物、硫化物浓度分别为265.1、0.25、12.7、0.63、0.46mg/L。挥发酚、硫化物、NH 4 +-N等污染物指标能达到直接排放标准的要求，COD、氰化物经后续的混凝与臭氧氧化处理后达到《污水综合排放标准》(GB8978—1996)第二类污染物最高允许排放浓度一级标准的要求。图23为生物处理过程中各类含氮化合物在总氮中的组成特征。从表4可以看出，生物进水总氮略有下降，这是由于在预处理阶段加入了硫酸亚铁，Fe 2+与氰化物形成亚铁蓝(Fe[Fe(CN) 6])、铁蓝(Fe 4[Fe(CN) 6] 3)沉淀引起的，这与生物进水中氰化物浓度的下降相对应。两级好氧反应器中总氮的去除量分别为115.8mg/L和59.9mg/L，好氧反应器内总氮去除的原因可以归结如下：①好氧微生物按照BOD∶N∶P约为100∶5∶1的比例利用废水中的含氮化合物作为氮源，合成自身细胞物质，水相中的总氮转移到污泥相中；②在实际工程中，反应器内部存在局部的缺氧区，好氧池内的同步硝化反硝化得以实现；③系统中存在好氧反硝化菌，在好氧条件下进行反硝化，将NH 4 +-N直接转化为N 2O；④少量的氨分子在曝气过程中被逸散。生物处理过程中各类含氮化合物占总氮的比例如图23所示。在焦化废水处理的全过程中，无机氮化合物是总氮的主要贡献者，所占比例均高于75.0％。原水中，无机氮化合物占总氮的比例为82.5％，其中以硫氰化物和氨氮为主。一级好氧流化床中，相对于难降解的有机氮化合物，微生物优先降解挥发酚、氰化物和硫氰化物等，反应器内几乎没有硝化作用发生，氰化物和硫氰化物所占比例下降为1.1％和23.4％，有机氮和氨氮的比例相应上升到24.1％和49.4％。水解脱氮流化床中，有机氮化合物水解释放出氨氮，致使氨氮比例上升到71.4％，而有机氮化合物比例降至2.2％。二级好氧流化床中，氰化物和硫氰化物被好氧生物氧化，发生硝化作用，硝态氮是生物出水中总氮的主要贡献者，所占比例超过75.0％。
表4各工艺段主要水质指标平均值数据
Figure PCTCN2018123848-appb-000019
生物过程中影响含氮化合物转化及总氮去除的因素包括pH、HRT、溶解氧、污泥龄与污泥浓度、碳氮比、硝化液回流比、氧化还原电位等。针对原水总氮含量高于300mg/L的焦化废水，若要达到新国标中规定的20mg/L总氮排放限值要求，需要强化一级好氧反应器使之实现局部硝化反应，并且二级好氧反应器实现完全硝化，以回流比必须大于1∶1的运行条件，保证水解反应器内短程反硝化反应的高效进行，并以N 2的形式逸出。两者的结合，需要在反应器水力停留时间与回流比的取值中求得优化。为实现水解反应器中的短程反硝化，需要追求一级好氧反应器条件的精密控制，使部分低价含氮化合物转化为NO 2 －-N。为充分发挥微生物同化作用对总氮的去除作用，避免微生物进入内源呼吸期，细胞溶胞再次向水中释放出总氮，需要严格控制各反应池污泥停留时间，定期排泥。为保证硝化反硝化过程的顺利进行，需要在二级好氧反应器中提供足够的溶解氧、水解反应器中提供充足的可利用碳源。上述发生的总氮减排过程可以被分解为3个不同功能的反应器内实现。
一级好氧流化床
实际工程中流化床的设计结构主要包括三段导流筒及三相分离区3。流化床内三段导流筒使流体实现三重循环，强化了流化床的混合传质性能。流化床两侧设置的三相分离区3使固液分离后的活性污泥由分离区底部斜壁自吸进入主反应器的降流区内，避免出水带走菌胶团，保证反应器内的微生物量并实现污泥减量化。一级好氧流化床以空气作为总动力，分解为富氧气体与富氮气体，实现反应器内废水与微生物之间良好的混合和传质，其作用主要是最大限度地降低有机污染物浓度。运行过程中需要保证充足的曝气量，以实现流态化操作，提供溶解氧，同时需要投加磷盐作为微生物生长的营养元素。
图24为氰化物和硫氰化物在一级好氧流化床的运行数据，可以看出，在HRT为40h、溶解氧控制在1～3mg/L的情况下，一级好氧流化床氰化物和硫氰化物进水浓度为19.0～36.1mg/L和482.4～672.1mg/L，出水浓度分别为3.3～4.2mg/L和87.8～309.1mg/L，去除率达85.6％和67.5％。在O/H/O生物处理系统中，设计一级好氧流化床以去除酚类等有机污染物为主，在酚类进水浓度在902～1100mg/L的情况下，出水挥发酚平均浓度为11.6mg/L，平均去除负荷为0.54kg·m -3·d -1。因此，一级好氧流化床可实现氰化物、硫氰化物与酚类的同步降解，并且酚类的降解优先。
焦化废水中的有机腈类化合物都是带苯环的芳香族腈。与脂肪族腈相比，芳香族腈更难降解。一般将有机腈类化合物与氰化物、硫氰化物统称为含氰化合物，因此，有机腈类化合物的降解行为与氰化物、硫氰化物表现出一定的相似性，主要在好氧反应器内进行。一级好氧反应器中有机腈类化合物的生物降解主要有两种途径：第一种途径是在腈水解酶催化作用下，有机腈化合物水解成相应的酸和氨氮；第二种途径是有机腈化合物首先水解成对应的氨基化合物，然后再进一步水解成对应的酸和氨氮，这两步分别由腈的水合酶和酰胺酶催化进行。
苯胺是焦化废水中主要的胺类化合物，一级好氧出水的苯胺浓度为28.0～33.1mg/L，转化率高达99.8％。苯胺好氧降解 主要有两种代谢途径，即邻位(ortho)和间位(meta)代谢途径，分别由邻苯二酚-1，2-双加氧酶和邻苯二酚2，3-双加氧酶催化。这两种途径都是先将苯胺氧化成邻苯二酚，释放出NH 3。当苯胺氧化为邻苯二酚之后，邻位代谢途径是在两个羟基之间开环，产生琥珀酸和乙酰辅酶A，间位代谢途径则在其中一个羟基的旁侧切割邻苯二酚，产生丙酮酸和乙醛。
水解脱氮流化床
水解脱氮流化床依靠好氧过程排出的尾气或少量氮气的搅拌作用及泵的水力条件实现均匀流态化，其主要作用是通过水解酸化改变有机物的局部分子结构，将大分子有机物转变为易降解的小分子化合物，同时对回流硝化液实现厌氧反硝化脱氮。运行过程中需要投加碱，中和水解产生的有机酸，并维持pH值在6.5～7.5之间，为微生物的厌氧反硝化提供条件。总氰和硫氰化物浓度在水解脱氮阶段略有下降。本课题组对生物系统中微生物群落的高通量测序结果显示，水解流化床中存在Thiobacillus sp的微生物，这可能与水解流化床中总氰和硫氰化物的降解有关。水解脱氮流化床中通过水解酸化将大分子有机物转变为小分子化合物，氮元素以氨氮的形式释放到水中，水解脱氮出水氨氮平均浓度为85.9mg/L。
经水解脱氮单元处理后，出水中喹啉和异喹啉的浓度分别为3.02～3.67mg/L和1.46～2.05mg/L，浓度显著下降。大部分的含氮杂环化合物属于难降解有机物，多环比单环更难降解，这可能是空间位阻效应增加、成环原子电子云密度减小和疏水性增大所造成的。对于含氮杂环化合物而言，环的开环裂解是它们在生物降解过程中的一个主要的步骤。在好氧条件下，由于好氧微生物开环酶系统的脆弱及不发达，阻止了杂环化合物及多环芳烃的降解。而厌氧微生物对于环的裂解具有不同于好氧菌的代谢过程，而且所涉及的开环酶系也完全不同于好氧微生物。说明水解脱氮单元对焦化废水中含氮化合物的降解具有不可替代的优越性。
二级好氧流化床
二级好氧流化床的设计结构与一级好氧流化床类似，但流型相反，其作用主要是与水解流化床联合进行硝化反硝化脱氮。由于硝化菌对环境的变化敏感，为保证硝化反应的正常进行，运行过程中需要满足溶解氧的要求，同时需要保持足够的碱度。氰化物和硫氰化物在二级好氧流化床有很好的降解效果，生物出水中氰化物和硫氰化物的平均浓度分别为0.63mg/L和0.4mg/L，去除率达82.3％和95.7％。值得注意的是，与挥发酚、硫化物等指标相比，生物出水中氰化物有时候仍未达到直接排放标准的要求。这是因为焦化废水原水中含有多种金属离子，加上预处理阶段加入了硫酸亚铁作为混凝剂，使废水中的部分氰化物形成了稳定的金属氰络合物。这些金属氰络合物，特别是铁氰络合物具有热力学稳定性，微生物降解利用铁氰化物的速率比自由氰分子/离子要慢。一级好氧流化床对有机碳源的充分降解保证了二级好氧流化床内竞争性碳源大量减少，为硝化细菌的培养和选择性增殖提供了良好的环境。图25为二级好氧反应器NH 4 +-N、NO x －-N的浓度变化。二级好氧流化床氨氮进水平均浓度为85.9mg/L，出水NO x －-N平均浓度为47.7mg/L，表现出良好的硝化效果。该反应器主要的硝化产物为NO 3 －-N，但从第25d开始，硝化产物以NO 2 －-N为主，结合其他污染物指标进行分析，发现此时二级好氧进水中硫氰化物浓度急剧升高，并维持在200mg/L以上，硫氰化物对完全硝化过程有抑制作用，导致亚硝氮的积累。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种负荷增强的废水处理流态化反应装置，其特征在于：包括流化床反应器本体，流化床反应器本体设有至少一个流体下降区和流体上升区，流化床反应器本体设有进水口，进水口设置于流体下降区，流化床反应器本体在流体下降区的上部设有相对独立于流化床反应器本体的三相分离器，三相分离器包括上端开口的三相分离器桶体，三相分离器的下端设有与流化床反应器本体连通的污泥斗，三相分离器上部设有与流化床反应器本体外部连通的溢流出水槽，三相分离器的溢流出水槽与污泥斗之间的沉降区中段设有与流化床反应器本体连通的进水管，三相分离器连接有旋流分离器，旋流分离器取水管的端口位于污泥斗与溢流出水槽之间。
  2. 按照权利要求1所述的一种负荷增强的废水处理流态化反应装置，其特征在于：三相分离器进水管包括纵向设置于三相分离器内部的立管，横向设置于三相分离器外部的平放管，以及连接立管与平放管的连接管，连接管的一端连接于平放管的中部，连接管的另外一端连接于立管的下部。
  3. 按照权利要求2所述的一种负荷增强的废水处理流态化反应装置，其特征在于：流化床反应器本体的流体下降区设置于中间区域，流化床为长方形结构，流体上升区位于流体下降区的四周，三相分离器设置于流化床反应器本体的上部中间位置。
  4. 按照权利要求2所述的一种负荷增强的废水处理流态化反应装置，其特征在于：流化床反应器本体的流体下降区设置在周边，流体上升区设置为一个，位于中心区域，流体下降区位于流体上升区的四周，三相分离器设置在流体下降区的周边外缘。
  5. 按照权利要求1所述的一种负荷增强的废水处理流态化反应装置，其特征在于：还包括曝气装置，曝气装置包括空气压缩机、空气分离装置、富氧气体进气管道和富氮气体进气管道，空气分离装置连接于空气压缩机，富氧气体进气管道和富氮气体进气管道的一端均连接于空气分离装置，富氧气体进气管道另一端位于流体下降区的中部，富氮气体进气管道的另一端位于流体上升区的底部，富氧气体进气管道另一端连接有微孔曝气器，富氮气体进气管道另一端与富氮气体分布器相连接。
  6. 按照权利要求1所述的一种负荷增强的废水处理流态化反应装置，其特征在于：流体下降区底部设有水流导向装置，水流导向装置为朝向流体上升区的斜面，流体上升区和流体下降区之间设有导流筒隔板，流体上升区与流体下降区之间通过导流筒隔板分隔。
  7. 按照权利要求1所述的一种负荷增强的废水处理流态化反应装置，其特征在于：流体上升区内设有缩放管，缩放管沿水流方向设置，缩放管为若干个大管径和小管径间隔设置的连续管状件。
  8. 一种负荷增强的废水处理流态化反应系统，其特征在于：包括依次相连的隔油池、气浮池、调节池、一级好氧反应器、水解脱氮反应器、二级好氧反应器、混凝沉淀池以及过滤池，其中一级好氧反应器采用权利要求4所述的一种负荷增强的废水处理流态化反应装置，二级好氧反应器采用权利要求3所述的一种负荷增强的废水处理流态化反应装置。
  9. 一种负荷增强的废水处理流态化反应方法，其特征在于：分离流化床反应器本体内部的污泥，将流化床反应器本体内的混合液导入三相分离器内，三相分离器内沉淀性能差的低活性污泥通过外接旋流分离器排出反应器，在流化床内部原位识别并分离不同凋亡程度的污泥，将活性高而低凋亡比例的污泥保留在反应器中，而将活性低且高凋亡比例的污泥排出反应器外。
  10. 按照权利要求9所述的一种负荷增强的废水处理流态化反应方法及其技术，其特征在于：通过外接空气氧氮分离装置将高浓度的氧气分离出来，富氮气体和富氧气体通过两根管道分别输入流化床反应器本体内部，富氮气体通入流化床反应器本体的流体上升区的底部，主要起动力推动作用，富氧气体通入流化床反应器本体的流体下降区的中部，主要起供氧作用。
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