CN104628150B - The method that compound photocatalysis biological adsorption agent processes percolate - Google Patents

The method that compound photocatalysis biological adsorption agent processes percolate Download PDF

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CN104628150B
CN104628150B CN201510030521.6A CN201510030521A CN104628150B CN 104628150 B CN104628150 B CN 104628150B CN 201510030521 A CN201510030521 A CN 201510030521A CN 104628150 B CN104628150 B CN 104628150B
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percolate
adsorption agent
biological adsorption
tio
white
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CN104628150A (en
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胡亮
何益斌
曾光明
陈桂秋
陈安伟
郭志
武海鹏
万佳
于志刚
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Hunan University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a kind of method that compound photocatalysis biological adsorption agent processes percolate, with compound photocatalysis biological adsorption agent as adsorbent, compound photocatalysis biological adsorption agent is added in percolate by the consumption of 20g/L~80g/L weight in wet bases, carry out illumination vibration absorption degradation, separation of solid and liquid after the completion of reaction, filtrate is adjusted to neutrality, the process to percolate is completed.Not only handling process and adsorption plant are simple for method using compound photocatalysis biological adsorption agent process percolate of the invention, it is easy to operate, cost is extremely low, and adsorption capacity is big, adsorption efficiency is high, cleanliness without any pollution, there is good treatment effect to percolate, landfill leachate treatment operating cost can be effectively reduced, be it is a kind of can be with processing method that is widely used, being capable of effective process percolate.

Description

The method that compound photocatalysis biological adsorption agent processes percolate
Technical field
The invention belongs to the biological adsorption process field of waste water, is related to a kind of processing method of percolate;Especially relate to And a kind of method that percolate is processed using compound photocatalysis biological adsorption agent.
Background technology
China starts from 90 year of twentieth century just to landfill percolate research, still lacks to garbage filter up till now Liquid water quality and its Changing Pattern, the system further investigation of leachate treatment technology.Percolate has COD and ammonia nitrogen concentration Height, colourity are big, and bio-refractory content of material is more, toxic, the features such as water quality and quantity amplitude of variation is big, are public in the world at present The sewage disposal technology difficult problem recognized.So, strengthen the research work of this respect, it is special that research is suitable for China's percolate water quality The treatment technology of point is the task of top priority, and this has weight for advancing the rubbish processing to be harmless of China, eliminating solid waste pollution Want meaning.
The landfill leachate treatment of China is mainly pretreatment, main process and the advanced treating skill of percolate in recent years Art, including common materialized pretreatment and common biochemical main process and the high-level oxidation technology for quickly growing in recent years, UF membrane even depth handling process.Photochemical catalysis method effectively can be degraded the organic compound of difficult degradation, improve rubbish and ooze The biodegradability of filtrate, biosorption process are favored by people due to low cost, therefore adopt photochemical catalysis method and life Thing absorption method is combined into a kind of feasible method of percolate, studies compound photocatalysis biological adsorption agent, by combining The advantage of bi-material reaches the purpose for processing percolate.
The content of the invention
The technical problem to be solved is to overcome deficiency of the prior art, there is provided a kind of handling process and absorption Equipment is simple and convenient to operate, adsorption capacity is big, adsorption efficiency is high, production cost is extremely low and the utilization of convenient separation and recovery is combined The method that type photocatalysis biological adsorption agent processes percolate, the method have good treatment effect, energy to percolate Be effectively reduced landfill leachate treatment operating cost, be it is a kind of can with it is widely used, being capable of effective process percolate Method.
To solve above-mentioned technical problem, the technical solution used in the present invention is:There is provided a kind of compound photocatalysis biological suction The method of attached dose of process percolate, it is with compound photocatalysis biological adsorption agent as adsorbent, compound photocatalysis is biological Adsorbent is added to garbage filter by the consumption of 20g/L~80g/L weight in wet bases (weight for claiming in aaerosol solution after filtering) In liquid, vibration absorption degradation under illumination, is carried out, separation of solid and liquid after the completion of reaction adjusts filtrate to neutrality, completes to garbage filter The process of liquid.
Further, aforementioned compound photocatalysis biological adsorption agent is the nitrogen modification TiO with white-rot fungi as carrier2Nanometer Particle and it is calcium alginate embedded white-rot fungi mycelia winding bacterium ball inside.Compound photocatalysis biological adsorption agent is with white rot Fungi viable bacteria mycelia is carrier, and mycelia is wound in bacterium ball, and nitrogen modification TiO is embedded with inside bacterium ball2Nano-particle and calcium alginate, Mycelia and nitrogen are modified TiO as entrapment media by calcium alginate2Nano-particle is closely joined together.
Further, aforementioned compound photocatalysis biological adsorption agent is prepared using following preparation method:
(1) nitrogen is modified into TiO2Nano-particle, sodium alginate are carried out being mixed to get with white-rot fungi spore suspension and mix molten Liquid;
(2) by the mixed solution prepared in step (1) according to volume ratio be 1: 2~4, be dropwise added drop-wise to CaCl2It is molten In liquid, filter after 1~3h of hardening is stood at 20 DEG C~30 DEG C, obtain nitrogen modification TiO2- calcium alginate-white-rot fungi microballoon;
(3) above-mentioned nitrogen is modified into TiO2- calcium alginate-being fixed of white-rot fungi microballoon culture, obtains compound light Catalysis biological adsorbent.
Further, the modification of nitrogen described in aforementioned compound photocatalysis biological adsorption agent TiO2Nano-particle and calcium alginate Mass ratio be 1: 3~5.
Further, the spore concentration of aforementioned white-rot fungi spore suspension is 2.0 × 105Individual/mL~1.0 × 106Individual/ mL;The CaCl2The mass fraction of solution is 2%~4%.
Further, the detailed process of aforementioned Immobilized culture is comprised the following steps:
Nitrogen is modified into TiO2- calcium alginate-white-rot fungi microballoon is added in Kirk culture mediums, at 35 DEG C~39 DEG C, turns Constant-temperature shaking culture 72h~96h under the conditions of fast 120rpm~130rpm, obtains compound photocatalysis biological adsorption agent;Nitrogen is modified TiO2The addition of-calcium alginate-white-rot fungi microballoon is 10g/L~40g/L.
Further, the pH value of aforementioned percolate is 3~8.5.It is furthermore preferred that the pH value of aforementioned percolate is 5.5~6.5.
Further, the initial COD concentration of aforementioned percolate is 100mg/L~600mg/L.
Further, the condition of aforementioned vibration absorption degradation is:Rotating speed is 150rpm~160rpm, and temperature is 25 DEG C~45 DEG C, the time is 72h~96h.It is furthermore preferred that temperature is 35 DEG C~39 DEG C.
Further, abovementioned light intensity is 10Lux~20Lux.
In the preparation method of the compound photocatalysis biological adsorption agent of the present invention, nitrogen modification TiO2Nano-particle and sodium alginate The compound method of mixed liquor is comprised the following steps:
Nitrogen is modified into TiO2Nano-particle is added in the sodium alginate soln that concentration is 30g/L~50g/L, nitrogen modification TiO2Nano-particle addition be 0.01g/mL~0.02g/mL, then under the conditions of 105 DEG C~121 DEG C sterilize 20min~ 30min, finally cools down 60min~120min under sterile conditions, aseptic nitrogen is obtained and modifies TiO2Nano-particle and alginic acid Sodium mixed liquor.
The present invention is processed using compound photocatalysis biological adsorption agent in the method for percolate, illumination vibration absorption drop Incandescent lamp of the light source of solution for 20W~40W;Can also carry out under sunlight simultaneously, because nitrogen is modified TiO2Light Active region expands visible region to from ultraviolet region, as long as so can be smoothed out in the case where there is radiation of visible light.
The present invention innovative point be:
The present invention is processed to percolate using compound photocatalysis biological adsorption agent, and compound photocatalysis is biological Nano-TiO in adsorbent2A kind of typical photochemical catalyst, can in catalytic degradation organic matter under ultraviolet light conditions, but All it is often visible ray in practical application, therefore the application is by nitrogen-doped modified by nano-TiO2Photolytic activity expands visible ray to Area.Meanwhile, nano-TiO2It is easy to run off in use, reclaims difficulty, it is of the invention by nano-TiO2It is supported on calcium alginate, The specific surface area of calcium alginate is general all than larger, can preferably and nano-TiO2With reference to improving its photocatalysis performance.White rot is true Bacterium effectively can be enriched with and absorption organic pollution and heavy metal ion from the aqueous solution, be a kind of generally acknowledged high-performance bio absorption Agent, and widely studied.Immobilized microorganism technology causes white-rot fungi to have higher degraded toxic compounds Ability, can also be effectively improved the mechanical performance of microorganism so as to possess more preferable mechanical strength and reusing, can make Microorganism keeps high concentration by growth and breeding, so as to improve treatment effeciency.
Compared with prior art, it is an advantage of the current invention that:
(1) compound photocatalysis biological adsorption agent of the invention, by nitrogen is modified TiO2It is supported on white-rot fungi viable bacteria On mycelia, photochemical catalyst nano-TiO is combined2With the advantage of biomaterial white-rot fungi;Enormously simplify compound light The preparation technology of catalysis biological adsorbent, can complete immobilization process, immobilization in the growth course of white-rot fungi mycelia Product after culture can be directly used for the process of percolate;And solve nano-TiO2It is easy to run off in use, returns Receive difficult problem.Modified nano-TiO by nitrogen2Photoactive region expand visible region to, be conducive to urging compound light Change biological adsorption agent to be generalized in practical application.Immobilized culture causes microorganism to have the energy of toxic compounds of more strongly degrading Power, can also be effectively improved the mechanical performance of microorganism, so as to improve treatment effeciency.
(2) compound photocatalysis biological adsorption agent of the invention is to collect physics, chemistry and biological adsorption degradation in one The compound-type adsorbent of body, wherein, specifically using white-rot fungi viable bacteria mycelia as biological adsorption degraded composition, and nitrogen is modified TiO2Nano-particle is then embedded in inside mycelium to be further enriched with degradation of contaminant, and calcium alginate is then situated between as immobilization White-rot fungi viable bacteria mycelia and nitrogen are modified TiO by matter2Nano-particle be intimately associated with strengthen whole adsorbent mechanical strength and Stability.
(3) the invention provides it is a kind of using compound photocatalysis biological adsorption agent process percolate method, by Include soluble high-molecular organic matter, insoluble macromolecule organic, macromolecule ammonia nitrogen chemical combination in garbage leachate wastewater Thing, heterologous material, heavy metal and inorganic compound, its constituent are complicated, are a kind of very intractable waste water.In order to have Effect processes percolate, and the present invention improves nitrogen modification TiO in compound adsorbent2The quality of nano-particle and calcium alginate Than so that compound photocatalysis biological adsorption agent is respectively provided with good suction to the total organic carbon and ammonia nitrogen in garbage leachate wastewater Attached degradation effect.By the content for improving calcium alginate in compound adsorbent, be conducive to strengthening the mechanical strength of whole adsorbent And stability;It is prior to be advantageous for strengthening the protective effect to white-rot fungi in compound photocatalysis biological adsorption agent, with Preferably impact of the poisonous and harmful substance to white rot fungal physiology activity in the percolate water sample of reply actual complex.
(4) the invention provides it is a kind of using compound photocatalysis biological adsorption agent process percolate method, no Only handling process and adsorption plant are simple, and easy to operate, cost is extremely low, and adsorption capacity is big, adsorption efficiency is high, cleaning is without dirt Dye, has good treatment effect, can be effectively reduced landfill leachate treatment operating cost to percolate, is that one kind can be with Method that is widely used, being capable of effective process percolate.
Description of the drawings
To make purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the compound photocatalysis biological adsorption agent before process percolate in the embodiment of the present invention 1 at 2000 times Surface mycelium micro-structure diagram under environmental scanning electronic microscope.
Fig. 2 is the electro microscope energy spectrum schematic diagram of compound photocatalysis biological adsorption agent in the embodiment of the present invention 1.
Fig. 3 is the compound photocatalysis biological adsorption agent after process percolate in the embodiment of the present invention 1 at 2000 times Surface mycelium micro-structure diagram under environmental scanning electronic microscope.
Fig. 4 is the compound photocatalysis biological adsorption agent in the embodiment of the present invention 2 in different initial concentration garbage filters Removal effect schematic diagram under the conditions of liquid to TOC.
Fig. 5 is the compound photocatalysis biological adsorption agent in the embodiment of the present invention 2 in different initial concentration garbage filters To NH under the conditions of liquid3The removal effect schematic diagram of-N.
Specific embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but not therefore and Limit the scope of the invention.
Material and instrument employed in following examples be it is commercially available, wherein white-rot fungi be Phanerochaete chrysosporium, It is purchased from China typical culture collection center, preserving number is CCTCC BKMF-1767, Phanerochaete chrysosporium strain transfer preservation On potato plating medium.
Embodiment 1:
A kind of compound photocatalysis biological adsorption agent of the present invention, the compound photocatalysis biological adsorption agent is true with white rot Bacterium viable bacteria mycelia is carrier, and mycelia is wound in bacterium ball, and nitrogen modification TiO is embedded with inside bacterium ball2Nano-particle and calcium alginate, sea Mycelia and nitrogen are modified TiO as entrapment media by calcium alginate2Nano-particle is closely joined together, the nitrogen embedded inside bacterium ball Modification TiO2The mass ratio of nano-particle and calcium alginate is 1: 4 (nitrogen modification TiO2The mass ratio of nano-particle and calcium alginate is When 1: 3~5, can implement).
A kind of preparation method of the compound photocatalysis biological adsorption agent of above-mentioned the present embodiment, comprises the following steps:
(1) sol-gal process prepares nitrogen modification TiO2Nano-particle:0.282g urea is weighed first is placed in 250mL conical flasks In, absolute ethyl alcohol, 8mL ultra-pure waters and the 12mL glacial acetic acid of 40mL are added, magnetic stirrer is opened and is completely dissolved to urea Afterwards, it is designated as solution A.Then the tetrabutyl titanate of 32mL is added in the 500mL conical flasks equipped with 128mL absolute ethyl alcohols, is mixed After closing uniformly, B solution is designated as.Under conditions of magnetic stirrer, solution A is slowly dropped in B solution with syringe, The colloidal sol of homogeneous transparent is obtained after completion of dropping, then to be poured into and obtain gel after 24h being aged at normal temperatures on flat board culture dish.Will Gel is placed in vacuum drying oven, places 4h, obtain xerogel under the conditions of 80 DEG C, will be xerogel grind into powder rearmounted 3h is calcined under the conditions of 500 DEG C in the Muffle furnace, that is, obtains nitrogen modification TiO2Nano-particle.The nitrogen modifies TiO2Nitrogen in nano-particle Molar content be 9.37%.
(2) aseptic nitrogen modifies TiO2The preparation of nano-particle and sodium alginate mixed liquor:Nitrogen is modified into TiO2Nano-particle adds Enter in the sodium alginate soln to concentration for 40g/L, nitrogen modification TiO2Nano-particle addition is 0.01g/mL, then 105 Sterilize under the conditions of DEG C 30min, finally cools down 60min under sterile conditions, aseptic nitrogen is obtained and modifies TiO2Nano-particle and sea The mixed liquor of mosanom.
(3) nitrogen modification TiO2The preparation of-calcium alginate-white-rot fungi microballoon:Aseptically, aseptic nitrogen is modified TiO2The mixed liquor 100mL of nano-particle and sodium alginate and Phanerochaete chrysosporium spore suspension mix by volume at 1: 1, stir Mix uniform, obtain nitrogen modification TiO2The mixed liquor of nano-particle, sodium alginate and Phanerochaete chrysosporium spore suspension, wherein yellow The flat lead fungi spore suspension spore concentration of archespore hair is 1.0 × 106Individual/mL.By nitrogen modification TiO obtained by 200mL2Nano-particle, sea The mixed liquor syringe of mosanom and Phanerochaete chrysosporium spore suspension is dropwise added drop-wise to the aseptic CaCl of 400mL2Solution In, aseptic CaCl2The mass concentration of solution is 3%, obtains nitrogenous modification TiO after standing hardening 2h at room temperature2- calcium alginate- The reactant liquor of white-rot fungi microballoon, after filtration, isolated nitrogen modifies TiO2- calcium alginate-white-rot fungi microballoon.
(4) nitrogen modification TiO2The Immobilized culture of-calcium alginate-white-rot fungi microballoon:Nitrogen is modified into TiO2- calcium alginate- White-rot fungi microballoon is leached from solution, is cleaned repeatedly with aseptic ultra-pure water, nitrogen is modified TiO then2- calcium alginate-white rot Fungi microballoon is transferred in aseptic white-rot fungi liquid Kirk culture mediums, is shifted in every 100mL sterile liquid Kirk culture mediums 2.0g nitrogen modifies TiO2(nitrogen modifies TiO to-calcium alginate-white-rot fungi microballoon2The addition of-calcium alginate-white-rot fungi microballoon For 10g/L~40g/L, can implement), at 37 DEG C, constant-temperature shaking culture 72h under the conditions of rotating speed 120rpm (at 35 DEG C~39 DEG C, Constant-temperature shaking culture 72h~96h under the conditions of rotating speed 120rpm~130rpm, can implement), then the bacterium ball after culture is filtered Go out, aseptic ultra-pure water cleaning is multiple, completes Immobilized culture process, obtains compound photocatalysis biological adsorption agent.
Compound photocatalysis biological adsorption agent obtained above after freeze-drying (is used to process percolate Before), the microstructure of biological adsorption agent is observed under 2000 times of environmental scanning electronic microscope, as shown in Figure 1.As shown in Figure 1, this reality Apply containing abundant white-rot fungi mycelium outside the compound photocatalysis biological adsorption agent of example, whole mycelium is wound in structure Loose bacterium ball, into cellular, with very big specific surface area, this vesicular texture is conducive to contaminant transmission to again to bacterium ball Inside mould assembly photocatalysis biological adsorption agent, and absorption degradation is carried out to pollutant.The coarse whiteness of hyphal surface is marine alga Sour calcium, mycelia particles above shape material are nitrogen modification TiO2Nitrogen is modified TiO by nano-particle, entrapment media calcium alginate2Receive Rice corpuscles and white-rot fungi mycelia are combined closely, and increased the mechanical strength and stability of white-rot fungi mycelia, also enhance white Resistivity of the rotten fungi to toxic pollutant.It is emphasized that the nitrogen modification TiO in the present invention2Nano-particle and marine alga Sour calcium is embedded on white-rot fungi mycelia well, and nitrogen modification TiO2Nano-particle is well dispersed, due to biological suction Attached dose of interior porosity is big, further promotes the absorption and aggregation of pollutant.
Energy spectrum analysis is carried out to the compound photocatalysis biological adsorption agent of the present invention, as shown in Fig. 2 obtaining its unit contained Plain species and its mass percent are as shown in table 1.
Table 1:The compound photocatalysis biological adsorption agent of the present embodiment contains element species and its mass percent
Element Mass percent Atomic percent
C 43.87 71.15
O 18.44 22.45
Na 01.74 01.48
Cl 00.25 00.14
Ca 02.82 01.37
Ti 00.54 00.22
Au 32.34 03.20
As seen from the above table, TiO2Nano-particle has been fixed on white-rot fungi mycelia by calcium alginate well.
Embodiment 2:
A kind of processing method of compound photocatalysis biological adsorption agent to percolate, the compound photocatalysis is biological to inhale Attached dose derives from embodiment 1, comprises the following steps:
(1) prepare COD concentration and be respectively 100mg/L, the percolate of 200mg/L, 400mg/L, 600mg/L is adjusted PH value is respectively charged into the percolate 100mL of above-mentioned concentration in the conical flask of 250mL, goes out under the conditions of 105 DEG C to 6.0 Bacterium 30min.
(2) the compound photocatalysis life in aseptic percolate, in addition embodiment 1 after Immobilized culture Thing adsorbent, addition are the compound photocatalysis biological adsorption agent 4.0g of addition weight in wet base in the aseptic percolates of every 100mL (addition of compound photocatalysis biological adsorption agent be 20g/L~80g/L, can implement), at 37 DEG C, rotating speed 150rpm, 20W Incandescent light vibrates absorption degradation 96h according under the conditions of, and (rotating speed of vibration absorption is 150rpm~160rpm, and temperature is 25 DEG C~45 DEG C, intensity of illumination is 10Lux~20Lux, can be implemented), will separate after the percolate for vibrating adsorption treatment stands Liquid phase and solid phase, adjust liquid phase to neutrality, complete the process to percolate.
Fig. 3 be process percolate after compound photocatalysis biological adsorption agent under 2000 times of environmental scanning electronic microscopes Surface mycelium micro-structure diagram, from the figure 3, it may be seen that after compound photocatalysis biological adsorption agent processes percolate, bacterium ball Mycelia shrinks and attenuates, and bacterium ball inner porosity space becomes big, with very big specific surface area, the pollutant in percolate It is transferred to inside compound photocatalysis biological adsorption agent and is adsorbed degraded.
The TOC concentration and NH in the percolate each sample Jing after processing is determined respectively3- N concentration.
Fig. 4 is compound photocatalysis biological adsorption agent in the present embodiment under the conditions of different initial concentration percolates Removal effect schematic diagram to TOC, as shown in Figure 4, to different initial concentration percolates, compound photocatalysis is biological to inhale Attached dose all has good absorption degradation effect to the TOC in percolate, and last TOC concentration is reduced to 8.0mg/L, 18.3mg/L, 46.3mg/L, 91.2mg/L.
Fig. 5 is compound photocatalysis biological adsorption agent in the present embodiment under the conditions of different initial concentration percolates To NH3The removal effect schematic diagram of-N, as shown in Figure 5, to different initial concentration percolates, compound photocatalysis is biological Adsorbent is to the NH in percolate3- N has good absorption degradation effect, last NH3- N removal efficiency is respectively 68.6%, 59.1%, 53.8%, 48.1%.
Interior figure in Fig. 5 be in the present embodiment compound photocatalysis biological adsorption agent in the scope that process time is 0~12h Interior NH3The removal efficiency of-N.
To the percolate that initial COD concentration is 200mg/L, the TOC in percolate each sample Jing after processing Residual concentration and NH3The measurement result of-N clearances is shown in Table 2.
Table 2:Compound photocatalysis biological adsorption agent is to percolate TOC and NH3- N removal effects
From table 2 and Fig. 4, Fig. 5, change over time, in compound photocatalysis biological adsorption agent absorption degradation mistake Cheng Zhong, trend of the TOC residual concentrations in first increases and then decreases, NH in percolate3- N clearances gradually rise, and are processing NH after 24h3- N clearances have just reached balance.
Embodiment 3:
Processing method of the compound photocatalysis biological adsorption agent of the present embodiment to the percolate of different initial pH values, should Compound photocatalysis biological adsorption agent derives from embodiment 1, comprises the following steps:
(1) percolate of the COD concentration for 200mg/L is prepared, pH value is adjusted and is respectively 3.0,3.5,4.0,4.5, 5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5, the percolate of above-mentioned pH value is respectively charged in the conical flask of 250mL 100mL, sterilize under the conditions of 105 DEG C 30min.
(2) the compound light in the percolate after above-mentioned sterilizing, in addition embodiment 1 after Immobilized culture Catalysis biological adsorbent, addition are the compound photocatalysis biological adsorption of addition weight in wet base in the aseptic percolates of every 100mL Agent 4.0g, at 37 DEG C, rotating speed 150rpm, 20W incandescent lights vibrate absorption degradation 96h according under the conditions of, separate after standing liquid phase and Solid phase, adjusts liquid phase to neutrality, completes the process to percolate.
The TOC concentration and NH in the percolate each sample Jing after processing is determined respectively3- N concentration, percolate TOC and NH3- N is removed and be the results are shown in Table 3.
Table 3:Percolate TOC and NH of the compound photocatalysis biological adsorption agent to different initial pH values3- N removes effect Really
As shown in Table 3, with the continuous rising of percolate pH value, drop in the absorption of compound photocatalysis biological adsorption agent In solution preocess, trend of the TOC clearances in first increases and then decreases in percolate, optimal pH at 6, NH3- N clearances And the trend in first increases and then decreases, optimal pH is at 7.
Embodiment 4:
The present embodiment is processing method of the compound photocatalysis biological adsorption agent of various dose to percolate, and this is multiple Mould assembly photocatalysis biological adsorption agent derives from embodiment 1, comprises the following steps:
(1) percolate of the COD concentration for 200mg/L is prepared, it is 6.0 to adjust pH value, is divided in the conical flask of 250mL Do not load the percolate 100mL of above-mentioned pH value, sterilize under the conditions of 105 DEG C 30min.
(2) the compound light in the percolate after above-mentioned sterilizing, in addition embodiment 1 after Immobilized culture Catalysis biological adsorbent, addition be separately added in the aseptic percolates of every 100mL weight in wet base compound photocatalysis it is biological Adsorbent 2.0g, 3.0g, 4.0g, 5.0g, 6.0g, 7.0g, 8.0g, at 37 DEG C, rotating speed 150rpm, 20W incandescent lamp illumination condition Lower vibration absorption degradation 96h, separates liquid phase and solid phase after standing, adjust liquid phase to neutrality, complete the process to percolate.
The TOC concentration and NH in the percolate each sample Jing after processing is determined respectively3- N concentration, in percolate TOC and NH3- N is removed and be the results are shown in Table 4.
Table 4:The compound photocatalysis biological adsorption agent of various dose is to TOC in percolate and NH3- N removal effects
Dosage (g) 2.0 3.0 4.0 5.0 6.0 7.0 8.0
TOC clearances (%) 31.3 56.2 74.7 75.8 65.8 61.3 58.7
NH3- N clearances (%) 29.4 43.1 57.6 65.3 68.2 71.9 74.6
As shown in Table 4, during absorption degradation, with being continuously increased for compound photocatalysis biological adsorption agent dose, Trend of the TOC clearances in first increases and then decreases in percolate, optimal dose is 5.0g, NH3- N clearances gradually rise.
In sum, compound photocatalysis biological adsorption agent of the invention is degraded for collection physics, chemistry and biological adsorption and is made For the compound-type adsorbent of one, wherein, specifically degraded composition using white-rot fungi viable bacteria mycelia as biological adsorption, and nitrogen Modification TiO2Nano-particle is then embedded in inside mycelium with further rich product degradation of contaminant, and calcium alginate is then as fixed Change medium by white-rot fungi viable bacteria mycelia and nitrogen modification TiO2Nano-particle is intimately associated strong to strengthen the machinery of whole adsorbent Degree and stability.Not only handling process and adsorption plant are simple for the compound photocatalysis biological adsorption agent of the present invention, easy to operate, Cost is extremely low, and adsorption capacity is big, adsorption efficiency is high, cleanliness without any pollution, has good treatment effect, energy to percolate Be effectively reduced landfill leachate treatment operating cost, be one kind can with it is widely used, can effective process percolate it is multiple Mould assembly photocatalysis biological adsorption agent.
The above, is only presently preferred embodiments of the present invention, not makees any pro forma restriction to the present invention.Though So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with those skilled in the art Member, in the case of the Spirit Essence and technical scheme without departing from the present invention, all using in the methods and techniques of the disclosure above Appearance makes many possible variations and modification, or the Equivalent embodiments for being revised as equivalent variations to technical solution of the present invention.Therefore, Every content without departing from technical solution of the present invention, according to the technical spirit of the present invention to made for any of the above embodiments any simple Modification, equivalent, equivalence changes and modification, still fall within the range of technical solution of the present invention protection.

Claims (6)

1. a kind of method that compound photocatalysis biological adsorption agent processes percolate, it is characterised in that urged with compound light Change biological adsorption agent is adsorbent, and compound photocatalysis biological adsorption agent is added to rubbish by the consumption of 40g/L~50g/L weight in wet bases In rubbish percolate, vibration absorption degradation under illumination, is carried out, separation of solid and liquid after the completion of reaction adjusts filtrate to neutrality, completes to rubbish The process of rubbish percolate;The compound photocatalysis biological adsorption agent is the nitrogen modification TiO with white-rot fungi as carrier2Nanoparticle It is sub and calcium alginate embedded inside the bacterium ball of white-rot fungi mycelia winding;Described in the compound photocatalysis biological adsorption agent Nitrogen modifies TiO2The mass ratio of nano-particle and the calcium alginate is 1: 3~5;The pH value of the percolate be 5.0~ 7.5;The initial COD concentration of the percolate is 100mg/L~600mg/L.
2. method according to claim 1, it is characterised in that the compound photocatalysis biological adsorption agent adopts following system Preparation Method is prepared:
(1)Nitrogen is modified into TiO2Nano-particle, sodium alginate and white-rot fungi spore suspension carry out being mixed to get mixed solution;
(2)By step(1)In the mixed solution for preparing be 1: 2~4 according to volume ratio, be dropwise added drop-wise to CaCl2In solution, Filter after 1~3h of hardening is stood at 20 DEG C~30 DEG C, obtain nitrogen modification TiO2- calcium alginate-white-rot fungi microballoon;
(3)The nitrogen is modified into TiO2- calcium alginate-being fixed of white-rot fungi microballoon culture, obtains compound photocatalysis life Thing adsorbent.
3. method according to claim 2, it is characterised in that the spore concentration of the white-rot fungi spore suspension is 2.0 ×105Individual/mL~1.0 × 106Individual/mL;The CaCl2The mass fraction of solution is 2%~4%.
4. method according to claim 2, it is characterised in that the detailed process of the Immobilized culture includes following step Suddenly:
Nitrogen is modified into TiO2- calcium alginate-white-rot fungi microballoon is added in Kirk culture mediums, at 35 DEG C~39 DEG C, rotating speed Constant-temperature shaking culture 72h~96h under the conditions of 120rpm~130rpm, obtains compound photocatalysis biological adsorption agent;The nitrogen is repaiied Decorations TiO2The addition of-calcium alginate-white-rot fungi microballoon is 10g/L~40g/L.
5. the method according to any one of Claims 1 to 4, it is characterised in that the condition of the vibration absorption degradation is: Rotating speed is 150rpm~160rpm, and temperature is 25 DEG C~45 DEG C, and the time is 72h~96h.
6. the method according to any one of Claims 1 to 4, it is characterised in that 10 Lux~20 of intensity of the illumination Lux。
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