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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
photosynthetic bacteria
immobilized
membrane
tio
photosynthetic bacterium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510099925.0A
Other languages
Chinese (zh)
Other versions
CN104743677B (en
Inventor
张国亮
秦磊
范铮
孟琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201510099925.0A priority Critical patent/CN104743677B/en
Publication of CN104743677A publication Critical patent/CN104743677A/en
Application granted granted Critical
Publication of CN104743677B publication Critical patent/CN104743677B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C02F2103/24Nature 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28Nature 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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

A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system process waste water
(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.
CN201510099925.0A 2015-03-06 2015-03-06 A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system to process waste water Active CN104743677B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510099925.0A CN104743677B (en) 2015-03-06 2015-03-06 A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system to process waste water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510099925.0A CN104743677B (en) 2015-03-06 2015-03-06 A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system to process waste water

Publications (2)

Publication Number Publication Date
CN104743677A true CN104743677A (en) 2015-07-01
CN104743677B CN104743677B (en) 2016-08-17

Family

ID=53584048

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510099925.0A Active CN104743677B (en) 2015-03-06 2015-03-06 A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system to process waste water

Country Status (1)

Country Link
CN (1) CN104743677B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105060463A (en) * 2015-08-12 2015-11-18 南宁柯林生物科技有限责任公司 Wastewater treatment method adopting O2 produced by photosynthetic organisms to replace traditional aeration as well as application
CN105327683A (en) * 2015-11-11 2016-02-17 欧一鸿 Carbon nanotube printing and dyeing wastewater treatment complexing agent based on SiO<2>/TiO<2> mesoporous composite microsphere carrier and preparation method
CN105371053A (en) * 2015-12-10 2016-03-02 重庆山岱科技有限责任公司 Motor home sewer purification mechanism
CN106145343A (en) * 2016-09-13 2016-11-23 河海大学 A kind of compound anaerobic membrane bioreactor and application thereof
CN106430831A (en) * 2016-10-28 2017-02-22 同济大学 Bio-microcapsule-ultrafiltration membrane combined process for treating heavy metals and ammonia nitrogen in water
CN107162316A (en) * 2017-05-18 2017-09-15 中国人民大学 Integrated wastewater treatment photosynthetic bacteria membrane bioreactor
CN109207464A (en) * 2017-07-03 2019-01-15 浙江工业大学 A kind of compound immobilization microorganism particles preparation and its application
CN109928515A (en) * 2019-04-20 2019-06-25 无锡吉致电子科技有限公司 It is a kind of without the efficient water cleanser of recycling and its application
CN109928517A (en) * 2019-04-20 2019-06-25 无锡吉致电子科技有限公司 A kind of various dimensions water purifying device and its application
CN111847657A (en) * 2019-04-28 2020-10-30 四川中德盛达环境工程有限公司 Sewage treatment process taking photosynthetic bacteria as biochemical core
CN112939139A (en) * 2021-03-04 2021-06-11 汕头大学 Photocatalysis membrane reactor and sewage treatment system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088893A (en) * 1992-12-31 1994-07-06 山东大学 A kind of core apparatus of cultivating photosynthetic bacterium processing organic waste water
JP2013192465A (en) * 2012-03-16 2013-09-30 Kajima Corp Mixed bacteria and method for wastewater treatment
CN103374561A (en) * 2012-04-13 2013-10-30 南京科盛环保科技有限公司 Preparation and water treatment using method of immobilized nitrifying bacteria
CN104108800A (en) * 2014-04-04 2014-10-22 北京工业大学 Preparation method and application of netted carrier-based sulfur-oxidizing bacteria immobilized fixed bioactive filler

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088893A (en) * 1992-12-31 1994-07-06 山东大学 A kind of core apparatus of cultivating photosynthetic bacterium processing organic waste water
JP2013192465A (en) * 2012-03-16 2013-09-30 Kajima Corp Mixed bacteria and method for wastewater treatment
CN103374561A (en) * 2012-04-13 2013-10-30 南京科盛环保科技有限公司 Preparation and water treatment using method of immobilized nitrifying bacteria
CN104108800A (en) * 2014-04-04 2014-10-22 北京工业大学 Preparation method and application of netted carrier-based sulfur-oxidizing bacteria immobilized fixed bioactive filler

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105060463A (en) * 2015-08-12 2015-11-18 南宁柯林生物科技有限责任公司 Wastewater treatment method adopting O2 produced by photosynthetic organisms to replace traditional aeration as well as application
CN105327683A (en) * 2015-11-11 2016-02-17 欧一鸿 Carbon nanotube printing and dyeing wastewater treatment complexing agent based on SiO<2>/TiO<2> mesoporous composite microsphere carrier and preparation method
CN105371053A (en) * 2015-12-10 2016-03-02 重庆山岱科技有限责任公司 Motor home sewer purification mechanism
CN106145343B (en) * 2016-09-13 2019-08-06 河海大学 A kind of compound anaerobic membrane bioreactor and application thereof
CN106145343A (en) * 2016-09-13 2016-11-23 河海大学 A kind of compound anaerobic membrane bioreactor and application thereof
CN106430831A (en) * 2016-10-28 2017-02-22 同济大学 Bio-microcapsule-ultrafiltration membrane combined process for treating heavy metals and ammonia nitrogen in water
CN107162316A (en) * 2017-05-18 2017-09-15 中国人民大学 Integrated wastewater treatment photosynthetic bacteria membrane bioreactor
CN109207464A (en) * 2017-07-03 2019-01-15 浙江工业大学 A kind of compound immobilization microorganism particles preparation and its application
CN109928515A (en) * 2019-04-20 2019-06-25 无锡吉致电子科技有限公司 It is a kind of without the efficient water cleanser of recycling and its application
CN109928517A (en) * 2019-04-20 2019-06-25 无锡吉致电子科技有限公司 A kind of various dimensions water purifying device and its application
CN109928517B (en) * 2019-04-20 2021-10-26 巴马氧吧生态科技有限公司 Multi-dimensional water body purification system
CN109928515B (en) * 2019-04-20 2022-04-05 德州迈科生物技术有限公司 High-efficiency water purifying agent without recovery and application thereof
CN111847657A (en) * 2019-04-28 2020-10-30 四川中德盛达环境工程有限公司 Sewage treatment process taking photosynthetic bacteria as biochemical core
CN112939139A (en) * 2021-03-04 2021-06-11 汕头大学 Photocatalysis membrane reactor and sewage treatment system

Also Published As

Publication number Publication date
CN104743677B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN104743677B (en) A kind of method utilizing Immobilized photosynthetic bacteria membrane reaction coupling system to process waste water
CN103910434B (en) To exceed standard the membrane type bioreactor of nitrogen phosphorus and treatment process thereof for the treatment of natural pond liquid
CN102976497B (en) Method for treating high-concentration organic waste water by bacilli
CN105692884A (en) Aerobic granule sludge cultivation method based on helotism
CN206126948U (en) Rotation type MABR reactor
CN108996709B (en) A kind of round-the-clock composite photocatalyst collaboration system and preparation method thereof
CN102936080B (en) Photocatalytic/aerobe-combined water treatment device and working method thereof
CN103255123B (en) Method for mycelium pellet to form mixed mycelium pellet by adsorbing photosynthetic bacteria
CN105668935A (en) Novel alga-active sludge coupling reactor and antibiotic removing method
CN204265615U (en) A kind of bioelectric detecting original position clears up the waste disposal plant of mud
CN106145343B (en) A kind of compound anaerobic membrane bioreactor and application thereof
CN104129886B (en) A kind of membrane biological reactor process for VITAMIN pharmacy wastewater treatment
CN108328725B (en) Optical biological sewage treatment system with waveguide enhanced optical transmission
CN101913733B (en) Wastewater treatment process of dimethoate pesticide
CN105036456A (en) Device for degrading organic matters in micro-polluted raw water by two-stage biomembrane-photocatalytic coupled technique
CN203319769U (en) Integrated equipment for treating chemical wastewater by use of immobilized microorganism baffling type packed bed
CN109110928A (en) The cultural method of biomembrane on a kind of biologic packing material
CN111808724B (en) Biological membrane suspension combined type photobioreactor for efficiently purifying biogas slurry by microalgae
CN101367580A (en) Method for accelerating biotransformation of organic matter hard-to-degrade with co-immobilized amboceptor and thalli
CN101182066B (en) Photo-biological reactor for treatment of high-chroma waste water
CN105176962A (en) Method for immobilizing bio-enzyme in ceramic filling material
CN105906155A (en) Wastewater treating process capable of reducing sludge quantity
CN208577510U (en) A kind of microkinetic combined film bioreactor
CN102417241B (en) Optical fluidized bed reactor for organic wastewater treatment
CN201343476Y (en) Combined reclaimed water treatment system

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant