CN104743677A - Method for treating wastewater by utilizing immobilized photosynthetic bacterium coupled film reaction system - Google Patents
Method for treating wastewater by utilizing immobilized photosynthetic bacterium coupled film reaction system Download PDFInfo
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- CN104743677A CN104743677A CN201510099925.0A CN201510099925A CN104743677A CN 104743677 A CN104743677 A CN 104743677A CN 201510099925 A CN201510099925 A CN 201510099925A CN 104743677 A CN104743677 A CN 104743677A
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
- C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for treating wastewater by utilizing an immobilized photosynthetic bacterium coupled film reaction system. According to the method disclosed by the invention, novel sulfonated SiO2/TiO2 mesoporous composite microspheres which are high in biocompatibility and photo-catalytic performance are taken as a substrate and an embedding method is adopted to prepare immobilized photosynthetic bacterium which is high in light utilization rate, high in degradation efficiency and resistant to wastewater load changes, so the transmission of photoelectrons inside the photosynthetic bacterium and between the photosynthetic bacterium and a carrier, and the degradation performance of the photosynthetic bacterium is remarkably improved; a novel film bio-reaction system is built by utilizing the efficient immobilized photosynthetic bacterium, the treatment effect on hardly-degradable printing and dyeing wastewater is effectively enhanced, the hydraulic retention time in an MBR system is shortened, the size of a biochemical pool is reduced, the operating cost is lowered, and the pollution of an MBR film is effectively alleviated.
Description
(1) technical field
The present invention relates to a kind of method utilizing Membrane Bioreactor for Wastewater Treatment waste water, particularly a kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system process waste water, described Immobilized photosynthetic bacteria is with SO
3h-SiO
2/ TiO
2composite mesoporous microballoon is carrier.
(2) background technology
Membrane bioreactor (Membrane Bioreactor is called for short MBR) is a kind of efficient wastewater processing technology strengthened in conjunction with biological treatment and membrane separating process.Mud granules all in muddy water mixed solution body and bacterium can be trapped in reactor by membrane bioreactor substantially, and active sludge in biological reaction tank is not flowed out with water outlet, and active sludge has the longer residence time and higher concentration.The feature such as high based on membrane bioreactor volumetric loading, effluent quality good, floor space is little, sludge yield is low, has become the focus of industrial applications research so far.But during MBR technical finesse refractory organic industrial sewage, still there is the problems such as the low and fouling membrane of microbial decomposition efficiency is serious, hinder its widespread use in Industrial Wastewater Treatment.
In conventional membrane bioreactor, aerobic activated sludge, as the main body of major microorganisms metabolic degradation, by constantly passing into air in reactor, realizes the Fast-propagation growth of bacterial classification.When adopting Wastewater Treated by Activated Sludge Process municipal administration sanitary wastewater; in mud, microorganism has higher degrading activity; and fast organic contamination is decomposed into carbonic acid gas and water; but when being applied to the process of the organic chemical waste water of difficult for biological degradation; aerobic bacterial classification in active sludge is only relied on to be difficult to obtain higher degradation effect; and in treating processes; often there will be the phenomenons such as bacterial classification is poisoning, inactivation; therefore, cultivate high-efficiency strain according to the water quality characteristics screening of organic chemical waste water and become the important research direction of improving Industrial Wastewater Treatment.
Secondly, in the main and reactor of fouling membrane, the structure of the microorganism of mixed solution, characteristic and metabolism are closely related, on the one hand that in mixed solution, the microorganism adsorption such as bacterial fungus on film surface and breeding forms microbial film, promotes the formation of concentration extreme difference phenomenon and cake layer to cause the reduction of flux; Being on the other hand the organic substance such as polysaccharide, nucleic acid, soil ulmin, protein that microbial metabolism produces, can, in fenestra road inwall and film surface adsorption and deposition, be the main source of fouling membrane in MBR system.In order to reduce fouling membrane, extending the work-ing life of film, improving film aquifer yield, suitable technology or measure must be taked to carry out controlling diaphragm and pollute.Common control membrane fouling technology mainly comprises the aspects such as the modification of mould material, the optimization of processing parameter and Membrane cleaning, but from reactor mixed solution the structure and characteristics angle of microorganism carry out modification to realize control membrane fouling research report less.
In recent years, photosynthetic bacterium (PSB) is as a kind of prokaryotic organism with original luminous energy synthetic system, can decompose under the conditions such as aerobic illumination, anaerobism illumination, aerobic dark, utilize organism, different pathways metabolisms can be shown under various circumstances, ready-made a kind of dominant bacteria for wastewater treatment employing.Compared with traditional active sludge, the efficient objectionable impurities such as organics removal and nitrogen phosphorus that it has (1), (2) environmental friendliness, excess sludge is used as fertilizer and fish meal, and disposal costs is low, can avoid the advantages such as secondary pollution.Photosynthetic bacterium Membrane Bioreactor for Wastewater Treatment waste water is adopted in patent of invention CN101712523A, compared with traditional MBR, obtain higher position reason effect, but, often vulnerable to pollution is there is in suspended state photosynthetic bacterium in wastewater treatment process, low, poor to inorganic salt tolerance to high-concentration hardly-degradable contaminant degradation efficiency, anti-pH load variations impacts the difficult problems such as weak and flocculence is poor.
(3) summary of the invention
The present invention seeks to, for the subject matter existed in current membrane bioreactor application, a kind of method of Immobilized photosynthetic bacteria membrane reaction coupling system process waste water to be provided, photosynthetic bacterium flora to be fixed on the sulfonated SiO of high-biocompatibility
2/ TiO
2on composite mesoporous microballoon, make its fast, amount reproduction, Immobilized photosynthetic bacteria not only significantly improves the treatment effect of reactor to waste water, and effectively controlling diaphragm pollutes, and maintains higher membrane sepn efficiency and flux.
The technical solution used in the present invention is:
The invention provides a kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system process waste water, described Immobilized photosynthetic bacteria membrane reaction coupling system comprises raw water box, collecting tank, controllable electric power unit (exports for working signal, heating signal exports), photosynthetic bacterium bio-reactor, light source and computer controlling center, described raw water box is communicated with photosynthetic bacterium bio-reactor by the pipeline being connected with peristaltic pump, described light source is connected with controllable electric power unit and hangs on above photosynthetic bacterium bio-reactor, described controllable electric power unit is connected with computer controlling center by controlling converting unit, described photosynthetic bacterium bio-reactor comprises reaction tank, Immobilized photosynthetic bacteria filler, heating rod, synthetic glass baffle plate, membrane module, pH probe, dissolved oxygen meter probe, temperature-sensing probe and micro-hole aerator, described reaction tank inner suspension Immobilized photosynthetic bacteria filler, be provided with micro-hole aerator bottom reaction tank, described micro-hole aerator is connected with controllable electric power unit by the pipeline being connected with pneumatic pump, reaction tank is separated into heating chamber and membrane module room by described synthetic glass baffle plate, space that can be through is left bottom described synthetic glass baffle plate and reaction tank, described heating chamber is provided with heating rod, described heating rod is connected with controllable electric power unit, described membrane module room is provided with membrane module, the water outlet of described membrane module by being connected with vacuum pressure gauge in turn, peristaltic pump is communicated with collecting tank with the pipeline of control valve, described membrane module room also arranges pH probe, dissolved oxygen meter probe, temperature-sensing probe, and is connected with computer controlling center respectively by control converting unit, described Immobilized photosynthetic bacteria filler is with sulfonated SiO
2/ TiO
2composite mesoporous microballoon is carrier, adopts freezing entrapping method to be fixed in the carrier by photosynthetic bacterium,
Described method of wastewater treatment is: waste water enters the reaction tank that Immobilized photosynthetic bacteria filler is housed by peristaltic pump from raw water box, open light source simultaneously, carry out the reaction of microbial metabolism decomposing organic matter, reaction tank internal fixtion photosynthetic bacterium concentration is 2-20g/L, dissolved oxygen concentration is set as 0.1-2.0mg/L, temperature controls at 15-37 DEG C, intensity of illumination is set as 1000-5000lux, hydraulic detention time controls at 12-36h, the scope of pH is 4.0-8.0, membrane module in raw reaction sundries runs under the condition of transmembrane pressure 0.04-0.20MPa, the water quality of monitoring membrane module water outlet, when membrane module water outlet COD is less than 100mg/L, discharged wastewater met the national standard.
Further, described Immobilized photosynthetic bacteria filler is prepared as follows: (1) with tetraethoxy and butyl (tetra) titanate for presoma, join in the hydrochloric acid soln of 15 ~ 60mmol/L (preferred 30mmol/L) Sodium dodecylbenzene sulfonate anion surfactant that (concentration of hydrochloric acid is 0.05 ~ 0.2mol/L, preferred 0.1mol/L), 50 ~ 120 DEG C of reaction 10 ~ 36h (preferably 60 DEG C of reaction 15h), after having reacted, reaction solution is centrifugal, solids washed with water, vacuum-drying, obtain SiO
2/ TiO
2complex microsphere; By SiO
2/ TiO
2complex microsphere, at 400 ~ 800 DEG C of temperature lower calcination 4 ~ 8h (preferably 600 DEG C of calcining 6h), obtains SiO
2/ TiO
2composite mesoporous microballoon; By described SiO
2/ TiO
2composite mesoporous microballoon is immersed in methylene dichloride, after ultrasonic disperse, adds chlorsulfonic acid, react under ultrasonic vibration, react 0.5 ~ 3h (preferred 0.5h) under room temperature, after having reacted, centrifugal, solid washing with alcohol, vacuum-drying, obtained sulfonated SiO
2/ TiO
2composite mesoporous microballoon; Described tetraethoxy volumetric usage counts 3 ~ 15ml/g (preferred 3.5ml/g) with Sodium dodecylbenzene sulfonate quality, described butyl (tetra) titanate volumetric usage counts 0.1 ~ 2ml/g (preferred 0.2ml/g) with Sodium dodecylbenzene sulfonate quality, and described chlorsulfonic acid volumetric usage is with SiO
2/ TiO
2composite mesoporous microspheres quality counts 2 ~ 15ml/g (preferred 10ml/g); (2) added by photosynthetic bacteria culture solution in embedding liquid, mixing, makes mixed solution, adopts asepsis injector that mixed solution is injected into sulfonated SiO
2/ TiO
2in suspension prepared by composite mesoporous microballoon water, form the microsphere suspension of injection photosynthetic bacterium; In described photosynthetic bacteria culture solution, wet thallus content is 200 ~ 500g/L (preferred 200g/L), in described embedding liquid, photosynthetic bacterial thallus concentration is 1-10g/L (preferred 5g/L), described embedding liquid is the mixed solution of sodium alginate and polyoxyethylene glycol, and described polyoxyethylene glycol volumetric usage counts 100 ~ 50ml/g (preferred 50ml/g) with sodium alginate quality; Wet thallus and sulfonated SiO in described photosynthetic bacteria culture solution
2/ TiO
2the mass ratio of composite mesoporous microballoon is 1:1-1:10 (preferred 1:3); (3) microsphere suspension of the injection photosynthetic bacterium of step (2) being prepared adds in linking agent, and 0 ~-10 DEG C (preferably-4 DEG C) are crosslinked fixes 2 hours, the Immobilized photosynthetic bacteria filler obtained; The volumetric usage of described linking agent is with sulfonated SiO
2/ TiO
2composite mesoporous microspheres quality counts 200 ~ 500ml/g (preferred 250ml/g), and described linking agent is CaCl
2with the mixing solutions of glutaraldehyde, described glutaraldehyde volumetric usage is with CaCl
2quality counts 50 ~ 100ml/g (preferred 75ml/g).
Further, described Immobilized photosynthetic bacteria concentration is preferably 2.0-10.0g/L.
Further, the condition optimization of wastewater treatment is Immobilized photosynthetic bacteria concentration is 5.0-10.0g/L (most preferably 10g/L), dissolved oxygen concentration is 0.1-1.0mg/L (most preferably 0.5mg/L), temperature is 15-30 DEG C (most preferably 30 DEG C), intensity of illumination is 2500-5000lux (most preferably 3000lux), hydraulic detention time 12-24h (most preferably 20h), transmembrane pressure 0.04-0.10MPa (most preferably 0.04-0.08MPa).
Further, described membrane module is hollow fiber film assembly or plate film assembly, preferably be made up of the open hollow fiber film assembly in external-compression type, curtain, column or one end or plate film assembly, can select microfiltration membrane or ultra-filtration membrane, membrane material is PP, PVDF, PES, PAN, PS and PE etc.
Further, waste water is methylene blue dye wastewater or bright red 4BS waste water from dyestuff, and dye strength is 100-150mg/L, COD is 400-600mg/L.
Photosynthetic bacterium is fixed on porous photocatalytic material by the present invention, thus strengthens the degradation property of photosynthetic bacterium and the ability of anti-shock loading.
PH probe of the present invention, dissolved oxygen meter probe, temperature-sensing probe are for monitoring in real time for the environment in bio-reactor, thus ensure the high-efficiency activated of Immobilized photosynthetic bacteria.Be used for sending and acceptable response device operating working signal when described controllable electric power unit and control converting unit, realized the automatic operating of membrane bioreactor by computer controlling center.
Described micro-hole aerator in bio-reactor, is provided with aeration tube carry out boring aeration, it is connected with air compressor machine, aeration or circular aeration tube centered by dividing by aeration form, strengthened the turbulent extent of bio-reactor inner fluid, strengthen and wash away the shearing of film surface contaminant by aeration.
Immobilized photosynthetic bacteria membrane reaction coupling system of the present invention is applied in the process of refractory organic industrial sewage, as dyeing waste water, paper waste, leather waste water, oily(waste)water etc.
The present invention has the following advantages: (1) the present invention is with the novel sulfonated SiO of high-biocompatibility and photocatalysis performance
2/ TiO
2composite mesoporous microballoon is matrix, and employing entrapping method has prepared the Immobilized photosynthetic bacteria with high light utilization efficiency, high degradation efficiency, the change of resistance to waste water load; (2) sulfonated SiO
2/ TiO
2composite mesoporous microballoon, as the fixation support of bacterium, effectively enhances the transmission of photoelectron between photosynthetic bacterium inside and carrier, significantly improves the degradation property of photosynthetic bacterium; (3) utilize efficient Immobilized photosynthetic bacteria to construct novel membrane bio-reaction system, effectively improve the treatment effect to refractory dyeing waste water, shorten hydraulic detention time in MBR system, reduce the volume of biochemistry pool, reduce running cost; (4) particle bacterium improves the mass transfer effect on film surface dynamic layer structure and surface, is partially formed micro-vortex and turbulent flow, and the centrifugal inertia of micro-vortex can accelerate micro-bubble generation, thus effectively slows down MBR fouling membrane.
(4) accompanying drawing explanation
Fig. 1 is Immobilized photosynthetic bacteria membrane reaction coupling system schematic of the present invention, 1-1 raw water box, 1-2 photosynthetic bacterium bio-reactor, 1-3 controllable electric power unit, 1-4 pneumatic pump, 1-5 light source, 1-6 membrane module, 1-7pH pops one's head in, 1-8 dissolved oxygen meter is popped one's head in, 1-9 temperature-sensing probe, 1-10 controls converting unit, 1-10-1 working signal exports, 1-10-2 monitor signal inputs, 1-10-3 heating signal exports, 1-11 computer controlling center, 1-12 peristaltic pump, 1-13 synthetic glass baffle plate, 1-14 micro-hole aerator, 1-15 vacuum pressure gauge, 1-16 control valve, 1-17 collecting tank, 1-18 reaction tank, 1-19 Immobilized photosynthetic bacteria filler, 1-20 heating rod.
Fig. 2 is photosynthetic bacterium immobilization technology route schematic diagram of the present invention.
Fig. 3 is the sulfonated SiO of the present invention
2/ TiO
2composite mesoporous micro-sphere structure Electronic Speculum figure.
Fig. 4 is the microtexture Electronic Speculum figure of Immobilized photosynthetic bacteria of the present invention.
Fig. 5 is the process waste water design sketch of Immobilized photosynthetic bacteria coupled film bio-reaction system in the embodiment of the present invention and comparative example.
Fig. 6 is that the membrane flux of Immobilized photosynthetic bacteria coupled film bio-reaction system in the embodiment of the present invention and comparative example is with variation diagram working time.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
As shown in Figure 1, the embodiment of the present invention 2, embodiment 3 use Immobilized photosynthetic bacteria membrane reaction coupling system as follows, described Immobilized photosynthetic bacteria membrane reaction coupling system comprises: raw water box 1-1, collecting tank 1-17, controllable electric power unit 1-3, photosynthetic bacterium bio-reactor 1-2, light source and computer controlling center 1-11.Described raw water box 1-1 is communicated with photosynthetic bacterium bio-reactor 1-2 by the pipeline being connected with peristaltic pump 1-12, described light source 1-5 is connected with controllable electric power unit 1-3 and hangs on above photosynthetic bacterium bio-reactor 1-2, and described controllable electric power unit 1-3 is connected with computer controlling center 1-11 by controlling converting unit 1-10, described photosynthetic bacterium bio-reactor 1-2 comprises reaction tank 1-18, Immobilized photosynthetic bacteria filler 1-19, heating rod 1-20, synthetic glass baffle plate 1-13, membrane module 1-6, pH pops one's head in 1-7, dissolved oxygen meter probe 1-8, temperature-sensing probe 1-9 and micro-hole aerator 1-14, described reaction tank inner suspension Immobilized photosynthetic bacteria filler, bottom reaction tank, micro-hole aerator is installed, described micro-hole aerator is connected with controllable electric power unit by the pipeline being connected with pneumatic pump 1-4, reaction tank is separated into heating chamber and membrane module room by described synthetic glass baffle plate, space that can be through is left bottom described synthetic glass baffle plate and reaction tank, described heating chamber is provided with heating rod, described heating rod is connected with controllable electric power unit, described membrane module room is provided with membrane module, described membrane module is by being connected with vacuum pressure gauge 1-15 in turn, peristaltic pump 1-12 is communicated with collecting tank with the pipeline of control valve 1-16, described membrane module room also arranges pH probe, dissolved oxygen meter is popped one's head in, temperature-sensing probe, and be connected with computer controlling center respectively by control converting unit.
Described method of wastewater treatment is: waste water enters the reaction tank that Immobilized photosynthetic bacteria filler is housed by peristaltic pump from raw water box, open light source simultaneously, reaction tank internal fixtion photosynthetic bacterium concentration is 2-20g/L, dissolved oxygen concentration is set as 0.1-2.0mg/L, temperature controls at 15-37 DEG C, intensity of illumination is set as 1000-5000lux, hydraulic detention time controls at 12-36h, the scope of pH is 4.0-8.0, membrane module runs under the condition of transmembrane pressure 0.04-0.20MPa, the water quality of monitoring membrane module water outlet, when membrane module water outlet COD is less than 100mg/L, discharged wastewater met the national standard.
Described light source is visible lamp light source, is by controllable electric power unit control, and the power selection scope of lamp is 50-200w, and lamp source is opened the metabolism growth not being only photosynthetic bacterium and provided energy, and impels the rising of reacting liquid temperature, improves the activity of immobilization bacterium.
Described membrane module is immersion type membrane component, is connected with peristaltic pump, control valve by outlet pipeline, during plant running, controls the unlatching of peristaltic pump by controlling converting unit.
PH probe, dissolved oxygen meter probe and temperature-sensing probe have been installed in Immobilized photosynthetic bacteria bio-reactor, pH, dissolved oxygen content and water temperature in Real-Time Monitoring reactor, by obtained data transmission to control converting unit, and according to data to whole reaction system operational application and the control to actual parameter.In bio-reactor, organic glass baffle plate is installed, strengthens the turbulence of current, delay hydraulic detention time.Microfiltration membrane aeration device is set bottom bio-reactor, be made up of the multiple aeration heads placing different positions, not only effectively improve oxygen transfer efficiency in reactor, thus improve the degradable organic pollutant speed of microorganism, and strengthen mixed solution washing away film surface, alleviate fouling membrane.This micro-hole aerator is connected with air pressure pump by pipeline, and sets the aeration rate of air compressor machine by controllable electric power unit, thus reaches set dissolved oxygen.
Introduce controllable electric power unit in whole reactive system, control converting unit and computer controlling center, wherein controllable electric power unit mainly output services signal, heating signal and control lamp source and air pressure pump, control converting unit primary recipient working signal and monitor signal, signal is transported to computer controlling center the most at last, carry out Data Management Analysis and control, thus realize the automatic operating of membrane bio-reaction system.
As shown in Figure 2, the immobilization technology of photosynthetic bacterium mainly comprises the mesoporous SiO of sulfonic acid funtionalized
2/ TiO
2the embedding on porous particle of the preparation of complex microsphere and photosynthetic bacterium.
Embodiment 1 Immobilized photosynthetic bacteria
Sulfonated SiO
2/ TiO
2the concrete preparation method of composite mesoporous microballoon is: 0.85g Sodium dodecylbenzene sulfonate is dissolved in completely the rare HCl solution of 80ml (concentration of HCl is 0.1mol/L); 3ml tetraethoxy and 0.2ml butyl (tetra) titanate are added in above-mentioned solution, then pours reactor into and leave standstill 15h in 60 DEG C of baking ovens.By centrifugal for the product obtained, dry with deionized water wash final vacuum, the SiO of system
2/ TiO
2complex microsphere.Adopt the tensio-active agent in high-temperature calcination removal duct.By complex microsphere at 600 DEG C of temperature lower calcination 6h, obtained SiO
2/ TiO
2composite mesoporous microballoon.By prepared SiO
2/ TiO
2composite mesoporous microballoon (1.0g) is immersed in 10ml CH completely
2cl
2in, after ultrasonic disperse, 4ml chlorsulfonic acid is added in said mixture, ultrasonic vibration, under room temperature, react 0.5h, ultrasonic condition is power 100w, frequency 53kHz, then centrifugal, solid washing with alcohol, and in vacuum oven, obtain pulverulent solids product, be sulfonated SiO
2/ TiO
2composite mesoporous microballoon (as shown in Figure 3).
Photosynthetic bacterium is Rhodopseudomonas palustris (Rhodopseudomonas palustris), Rhodopseudomonas palustris is inoculated in liquid enrichment culture liquid, put that temperature is 30 DEG C, illuminance is after cultivating 4d under the illumination condition of 3000lux, collect bacterium liquid, 5000rmin
-1centrifugal, discard supernatant liquid, wet thallus aqueous suspension makes photosynthetic bacteria culture solution thalline weight in wet base reach 200gL
-1, 4 DEG C of cryopreservation are for subsequent use.Liquid enrichment culture liquid final concentration consists of: methylene blue 150mg/L, K
2hPO
4400mg/L, KH
2pO
4600mg/L, NH
4cl 1000mg/L, CaCl
2200mg/L, Fe
2sO
4200mg/L, glucose 60g/L, solvent is water, pH nature.
The concrete preparation method of Immobilized photosynthetic bacteria is: be that the photosynthetic bacteria culture solution of 200g/L adds in embedding liquid by wet thallus content, mixing, makes mixed solution; Adopt asepsis injector that mixed solution is injected into sulfonated SiO
2/ TiO
2in suspension prepared by composite mesoporous microballoon water.In described embedding liquid, photosynthetic bacterial thallus concentration is 5.0g/L, and described embedding liquid is the mixed solution of sodium alginate and polyoxyethylene glycol, and described polyoxyethylene glycol volumetric usage counts 50ml/g with sodium alginate quality; Described photosynthetic bacterial thallus weight in wet base and sulfonated SiO
2/ TiO
2the mass ratio of composite mesoporous microballoon is 1:3.
By above-mentioned sulfonated SiO
2/ TiO
2composite mesoporous microballoon adds in linking agent, and-4 DEG C crosslinked fixes 2 hours, with sterilized water washing, is kept in physiological saline, the Immobilized photosynthetic bacteria filler obtained; The volumetric usage of described linking agent is with sulfonated SiO
2/ TiO
2composite mesoporous microspheres quality counts 250ml/g, and described linking agent is CaCl
2with the mixing solutions of glutaraldehyde, described glutaraldehyde volumetric usage is with CaCl
2quality counts 75ml/g.
The microtexture of Immobilized photosynthetic bacteria as shown in Figure 4.
Embodiment 2:
The Immobilized photosynthetic bacteria filler adopting embodiment 1 to prepare, utilizes Immobilized photosynthetic bacteria membrane reaction coupling system of the present invention to process methylene blue dye wastewater, measure the COD of film water outlet and colourity and reactive system run in the change of membrane flux.
The index of methylene blue dye wastewater: dye strength is 150mg/L, COD is 500-800mg/L.
The operational conditions of membrane bioreactor: waste water enters the bio-reactor that Immobilized photosynthetic bacteria (prepared by embodiment 1) is housed (50L) by peristaltic pump from raw water box, open light source simultaneously, carry out the reaction of microbial metabolism decomposing organic matter, dissolved oxygen concentration is set as 0.5mg/L, temperature controls at 30 DEG C, intensity of illumination is set as 3000lux, and hydraulic detention time (HRT) controls to control about 6.0 at 20h, pH.PVDF microfiltration membrane (0.2 μm, the aperture) assembly be immersed in bio-reactor adopts the water outlet of intermittent suction mode, and suction 10min, stops 2min, under transmembrane pressure remains on 0.04-0.08MPa.
Bio-reactor internal fixtion photosynthetic bacterium packing density is 10g/L.
Get 50ml membrane module at regular intervals and go out water sample, detect, analyze its COD and absorbancy.As shown in Figure 5, sulfonated mesoporous microsphere Immobilized photosynthetic bacteria membrane reaction coupling system has higher treatment effect to methylene blue dye wastewater, and water outlet COD is less than 50mg/L, and the clearance of COD and colourity is respectively 99.4% and 88.2%; As shown in Figure 6, the membrane flux that Immobilized photosynthetic bacteria membrane reaction coupling system held is higher, is basically stable at 22.1L/m
2h bar.
Comparative example 1:
Adopt suspension photosynthetic bacterium membrane reaction coupling system to process methylene blue dye wastewater, measure the change of membrane flux during the COD of film water outlet and colourity and reactive system are run.
The index of methylene blue dye wastewater: consistent with embodiment 2.
The operational conditions of membrane bioreactor: consistent with embodiment 2;
In bio-reactor, Immobilized photosynthetic bacteria filler (prepared by embodiment 1) content is 2.5g/L, and dissolved oxygen concentration is 0.5mg/L, and temperature is 30 DEG C, and intensity of illumination is 3000lux.
As shown in Figure 5, suspension photosynthetic bacterium membrane reaction coupling system is respectively 82.8% and 52.6% to the COD of methylene blue dye wastewater and the clearance of colourity, is starkly lower than the treatment effect of Immobilized photosynthetic bacteria membrane reaction coupling system; As shown in Figure 6, the membrane flux in photosynthetic bacterium membrane reaction coupling system stability period is 3.2L/m
2h bar, far below the flux of Immobilized photosynthetic bacteria membrane reaction coupling system.
Comparative example 2:
Adopt traditional Immobilized photosynthetic bacteria membrane reaction coupling system to process methylene blue dye wastewater, measure the change of membrane flux during the COD of film water outlet and colourity and reactive system are run.
The index of methylene blue dye wastewater: consistent with embodiment 2.
The operational conditions of membrane bioreactor: consistent with embodiment 2;
In bio-reactor, Immobilized photosynthetic bacteria filler is the SiO prepared with conventional sol-gel processes
2particle is that carrier adopts entrapping method to prepare Immobilized photosynthetic bacteria, and its immobilized preparation is consistent with embodiment 1, and content is 10g/L, and dissolved oxygen concentration is 0.5mg/L, and temperature is 30 DEG C, and intensity of illumination is 3000lux.SiO
2the preparation of particle: 3ml tetraethoxy is added 25ml aqueous ethanolic solution (ethanol/water volume ratio is 1:3), at room temperature stirs and forms colloidal sol, and then dry at 80 DEG C, institute obtains porous gel and calcines 4h at 400 DEG C, obtains SiO
2particle.
As shown in Figure 5, tradition Immobilized photosynthetic bacteria membrane reaction coupling system is respectively 90.2% and 68.6% to the COD of methylene blue dye wastewater and the clearance of colourity, is starkly lower than the treatment effect of sulfonated mesoporous microsphere Immobilized photosynthetic bacteria membrane reaction coupling system; As shown in Figure 6, the membrane flux in photosynthetic bacterium membrane reaction coupling system stability period is 12.1L/m
2h bar, lower than the flux of sulfonated mesoporous microsphere Immobilized photosynthetic bacteria membrane reaction coupling system.
Embodiment 3:
Embodiment 1 liquid enrichment culture liquid Methylene Blue is replaced with bright red 4BS dyestuff, other operation prepares Immobilized photosynthetic bacteria filler with embodiment 1, utilize Immobilized photosynthetic bacteria membrane reaction coupling system of the present invention to process direct scarlet 4BS waste water from dyestuff, measure the change of membrane flux during the COD of film water outlet and colourity and reactive system are run.
The index of direct scarlet 4BS waste water from dyestuff: dye strength is 100mg/L, COD is 400-600mg/L.
The operational conditions of membrane bioreactor: consistent with embodiment 2;
Bio-reactor internal fixtion photosynthetic bacterium filler (prepared by embodiment 1) concentration is 10g/L, and dissolved oxygen concentration is 0.5mg/L, and temperature is 30 DEG C, and intensity of illumination is 3000lux.
As shown in Figure 5, Immobilized photosynthetic bacteria membrane reaction coupling system has higher treatment effect equally to direct scarlet 4BS waste water from dyestuff, and the clearance of COD and colourity is respectively 99.6% and 89.5%; As shown in Figure 6, Immobilized photosynthetic bacteria membrane reaction coupling system maintains higher membrane flux equally, is basically stable at 26.7L/m
2h bar.
Claims (6)
1. one kind utilizes the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water, it is characterized in that described Immobilized photosynthetic bacteria membrane reaction coupling system comprises raw water box, collecting tank, controllable electric power unit, photosynthetic bacterium bio-reactor, light source and computer controlling center, described raw water box is communicated with photosynthetic bacterium bio-reactor by the pipeline being connected with peristaltic pump, described light source is connected with controllable electric power unit and hangs on above photosynthetic bacterium bio-reactor, and described controllable electric power unit is connected with computer controlling center by controlling converting unit, described photosynthetic bacterium bio-reactor comprises reaction tank, Immobilized photosynthetic bacteria filler, heating rod, synthetic glass baffle plate, membrane module, pH pops one's head in, dissolved oxygen meter is popped one's head in, temperature-sensing probe and micro-hole aerator, described reaction tank inner suspension Immobilized photosynthetic bacteria filler, bottom reaction tank, micro-hole aerator is installed, described micro-hole aerator is connected with controllable electric power unit by the circuit being connected with pneumatic pump, reaction tank is separated into heating chamber and membrane module room by described synthetic glass baffle plate, space that can be through is left bottom described synthetic glass baffle plate and reaction tank, described heating chamber is provided with heating rod, described heating rod is connected with controllable electric power unit, described membrane module room is provided with membrane module, the water outlet of described membrane module by being connected with vacuum pressure gauge in turn, peristaltic pump is communicated with collecting tank with the pipeline of control valve, described membrane module room also arranges pH probe, dissolved oxygen meter probe, temperature-sensing probe, and is connected with computer controlling center respectively by control converting unit, described Immobilized photosynthetic bacteria filler is with sulfonated SiO
2/ TiO
2composite mesoporous microballoon is carrier, adopts freezing entrapping method to be fixed in the carrier by photosynthetic bacterium,
Described method of wastewater treatment is: waste water enters the reaction tank that Immobilized photosynthetic bacteria filler is housed by peristaltic pump from raw water box, open light source simultaneously, reaction tank internal fixtion photosynthetic bacterium concentration is 2-20g/L, dissolved oxygen concentration is set as 0.1-2.0mg/L, temperature controls at 15-37 DEG C, intensity of illumination is set as 1000-5000lux, hydraulic detention time controls at 12-36h, the scope of pH is 4.0-8.0, membrane module runs under the condition of transmembrane pressure 0.04-0.20MPa, the water quality of monitoring membrane module water outlet, when membrane module water outlet COD is less than 100mg/L, discharged wastewater met the national standard.
2. utilize the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water as claimed in claim 1, it is characterized in that described Immobilized photosynthetic bacteria filler is prepared as follows: (1) with tetraethoxy and butyl (tetra) titanate for presoma, join in the hydrochloric acid soln of 15 ~ 60mmol/L Sodium dodecylbenzene sulfonate anion surfactant, 50 ~ 120 DEG C of reaction 10 ~ 36h, after having reacted, reaction solution is centrifugal, solid deionized water wash, vacuum-drying, obtain SiO
2/ TiO
2complex microsphere; By SiO
2/ TiO
2complex microsphere, at 400 ~ 800 DEG C of temperature lower calcination 4 ~ 8h, obtains SiO
2/ TiO
2composite mesoporous microballoon; By described SiO
2/ TiO
2composite mesoporous microballoon is immersed in methylene dichloride, after ultrasonic disperse, adds chlorsulfonic acid, reacts under ultrasonic vibration, reacts 0.5 ~ 3h under room temperature, and after react, centrifugal, solid deionized water wash, vacuum-drying, obtain sulfonated SiO
2/ TiO
2composite mesoporous microballoon; Described tetraethoxy volumetric usage counts 3 ~ 15ml/g with Sodium dodecylbenzene sulfonate quality, and described butyl (tetra) titanate volumetric usage counts 0.1 ~ 2ml/g with Sodium dodecylbenzene sulfonate quality, and described chlorsulfonic acid volumetric usage is with SiO
2/ TiO
2composite mesoporous microspheres quality counts 2 ~ 15ml/g; (2) added by photosynthetic bacteria culture solution in embedding liquid, mixing, makes mixed solution, adopts asepsis injector that mixed solution is injected into sulfonated SiO
2/ TiO
2in suspension prepared by composite mesoporous microballoon water, form the microsphere suspension of injection photosynthetic bacterium; In described photosynthetic bacteria culture solution, wet thallus content is 200 ~ 500g/L, in described embedding liquid, photosynthetic bacterial thallus concentration is 1-10g/L, described embedding liquid is the mixed solution of sodium alginate and polyoxyethylene glycol, and described polyoxyethylene glycol volumetric usage counts 50 ~ 100ml/g with sodium alginate quality; Wet thallus and sulfonated SiO in described photosynthetic bacteria culture solution
2/ TiO
2the mass ratio of composite mesoporous microballoon is 1:1-1:10; (3) microsphere suspension of the injection photosynthetic bacterium of step (2) being prepared adds in linking agent, and 0 ~-10 DEG C crosslinked fixes 2 hours, the Immobilized photosynthetic bacteria filler obtained; The volumetric usage of described linking agent is with sulfonated SiO
2/ TiO
2composite mesoporous microspheres quality counts 200 ~ 500ml/g, and described linking agent is CaCl
2with the mixing solutions of glutaraldehyde, described glutaraldehyde volumetric usage is with CaCl
2quality counts 50 ~ 100ml/g.
3. utilize the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water as claimed in claim 1, it is characterized in that described Immobilized photosynthetic bacteria concentration is 2-10g/L.
4. utilize the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water as claimed in claim 1, it is characterized in that the condition of wastewater treatment be Immobilized photosynthetic bacteria concentration is 5-10g/L, dissolved oxygen concentration is 0.1-1.0mg/L, temperature is 15-30 DEG C, intensity of illumination is 2500-5000lux, hydraulic detention time 12-24h, transmembrane pressure 0.04-0.10MPa.
5. utilize the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water as claimed in claim 1, it is characterized in that described membrane module is hollow fiber film assembly or plate film assembly.
6. utilize the method for Immobilized photosynthetic bacteria membrane reaction coupling system process waste water as claimed in claim 1, it is characterized in that waste water is methylene blue dye wastewater or bright red 4BS waste water from dyestuff, dye strength is 100-150mg/L, COD is 400-600mg/L.
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