Summary of the invention
Technical problem to be solved by this invention overcomes deficiency of the prior art, there is provided a kind for the treatment of process and an adsorption device is simple, easy to operate, loading capacity is large, adsorption efficiency is high, production cost is extremely low and facilitate the method utilizing compound photochemical catalysis biological adsorption agent treating refuse percolate of Separation and Recovery, the method has good treatment effect to percolate, can effectively reduce landfill leachate treatment running cost, be a kind ofly can extensively to adopt, can the method for effective treating refuse percolate.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method providing compound photochemical catalysis biological adsorption agent treating refuse percolate, with compound photochemical catalysis biological adsorption agent for sorbent material, compound photochemical catalysis biological adsorption agent is joined in percolate by the consumption of 20g/L ~ 80g/L weight in wet base (weight claimed after filtering in aaerosol solution), vibration absorption degradation is carried out under illumination, react rear solid-liquid separation, regulate filtrate to neutral, complete the process to percolate.
Further, aforementioned compound photochemical catalysis biological adsorption agent take white-rot fungi as carrier, and nitrogen modifies TiO
2nanoparticle and the calcium alginate embedded bacterium ball inside be wound around white-rot fungi mycelia.Compound photochemical catalysis biological adsorption agent is that mycelia is wound in bacterium ball with white-rot fungi viable bacteria mycelia for carrier, and bacterium ball inside is embedded with nitrogen and modifies TiO
2nanoparticle and alginate calcium, mycelia and nitrogen are modified TiO as entrapment media by alginate calcium
2nanoparticle compact siro spinning technology together.
Further, aforementioned compound photochemical catalysis biological adsorption agent adopts following preparation method to prepare:
(1) nitrogen is modified TiO
2nanoparticle, sodium alginate and white-rot fungi spore suspension carry out being mixed to get mixing solutions;
(2) be 1: 2 ~ 4 by the mixing solutions for preparing in step (1) according to volume ratio, be dropwise added drop-wise to CaCl
2in solution, filter leave standstill sclerosis 1 ~ 3h at 20 DEG C ~ 30 DEG C after, obtain nitrogen and modify TiO
2-alginate calcium-white-rot fungi microballoon;
(3) above-mentioned nitrogen is modified TiO
2-alginate calcium-being fixed of white-rot fungi microballoon is cultivated, and obtains compound photochemical catalysis biological adsorption agent.
Further, nitrogen described in aforementioned compound photochemical catalysis biological adsorption agent modifies TiO
2the mass ratio of nanoparticle and alginate calcium is 1: 3 ~ 5.
Further, the spore concentration of aforementioned white-rot fungi spore suspension is 2.0 × 10
5individual/mL ~ 1.0 × 10
6individual/mL; Described CaCl
2the massfraction of solution is 2% ~ 4%.
Further, the detailed process of aforementioned Immobilized culture comprises the following steps:
Nitrogen is modified TiO
2-alginate calcium-white-rot fungi microballoon adds in Kirk substratum, and at 35 DEG C ~ 39 DEG C, constant-temperature shaking culture 72h ~ 96h under rotating speed 120rpm ~ 130rpm condition, obtains compound photochemical catalysis biological adsorption agent; Nitrogen modifies TiO
2the addition of-alginate calcium-white-rot fungi microballoon is 10g/L ~ 40g/L.
Further, the pH value of aforementioned percolate is 3 ~ 8.5.Preferred, 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, and the time is 72h ~ 96h.Preferred, temperature is 35 DEG C ~ 39 DEG C.
Further, abovementioned light intensity is 10Lux ~ 20Lux.
In the preparation method of the compound photochemical catalysis biological adsorption agent of the present invention, nitrogen modifies TiO
2the compound method of nanoparticle and sodium alginate mixed solution comprises the following steps:
Nitrogen is modified TiO
2it is in the sodium alginate soln of 30g/L ~ 50g/L that nanoparticle joins concentration, and nitrogen modifies TiO
2nanoparticle addition is 0.01g/mL ~ 0.02g/mL, and then sterilizing 20min ~ 30min under 105 DEG C ~ 121 DEG C conditions, finally cools 60min ~ 120min under sterile conditions, and obtained aseptic nitrogen modifies TiO
2nanoparticle and sodium alginate mixed solution.
The present invention utilizes in the method for compound photochemical catalysis biological adsorption agent treating refuse percolate, and the light source of illumination vibration absorption degradation is the incandescent light of 20W ~ 40W; Also can carry out under solar light irradiation, because nitrogen is modified TiO simultaneously
2photoactive region expand visible region to from ultraviolet region, as long as so having under radiation of visible light and can carry out smoothly.
Innovative point of the present invention is:
The present invention adopts compound photochemical catalysis biological adsorption agent to process percolate, nano-TiO in compound photochemical catalysis biological adsorption agent
2be a kind of typical photochemical catalyst, can at catalyzed degradation organism under ultraviolet light conditions, but be all often visible ray in practical application, therefore the application be by nitrogen-doped modified by nano-TiO
2photolytic activity expands visible region to.Meanwhile, nano-TiO
2in use easily run off, reclaim difficulty, the present invention is by nano-TiO
2load is on alginate calcium, and the specific surface area of alginate calcium is general all larger, can good and nano-TiO
2in conjunction with, improve its photocatalysis performance.White-rot fungi can enrichment and be adsorbed with organic pollutants and heavy metal ion from the aqueous solution effectively, is a kind of generally acknowledged high-performance bio sorbent material, and is studied widely.Immobilized microorganism technology makes white-rot fungi have the ability of stronger degraded toxic compounds, effectively can also improve the mechanical property of microorganism, make it possess better physical strength and reusing, microorganism can be made to keep high density by growth and breeding, thus improve processing efficiency.
Compared with prior art, the invention has the advantages that:
(1) compound photochemical catalysis biological adsorption agent of the present invention, by modifying TiO by nitrogen
2load, on white-rot fungi viable bacteria mycelia, combines photochemical catalyst nano-TiO
2with the advantage of biomaterial white-rot fungi; Enormously simplify the preparation technology of compound photochemical catalysis biological adsorption agent, can complete immobilization process in the process of growth of white-rot fungi mycelia, the product after Immobilized culture can be directly used in the process of percolate; And solve nano-TiO
2in use easily run off, reclaim difficult problem.Modified nano-TiO by nitrogen
2photoactive region expand visible region to, be conducive to compound photochemical catalysis biological adsorption agent to be generalized in practical application.Immobilized culture makes microorganism have the ability of toxic compounds of degrading more strongly, effectively can also improve the mechanical property of microorganism, thus improves processing efficiency.
(2) compound photochemical catalysis biological adsorption agent of the present invention is the compound-type adsorbent integrating physics, chemistry and biological adsorption Degradation, wherein, and composition of specifically degrading using white-rot fungi viable bacteria mycelia as biological adsorption, and nitrogen modifies TiO
2it is inner with further enrichment degradation of contaminant that nanoparticle is then embedded in mycelium, and white-rot fungi viable bacteria mycelia and nitrogen are then modified TiO as entrapment media by alginate calcium
2nanoparticle combines the physical strength and the stability that strengthen whole sorbent material closely.
(3) the invention provides a kind of method utilizing compound photochemical catalysis biological adsorption agent treating refuse percolate, owing to including soluble high-molecular organism, insoluble macromolecule organic, polymer ammonia nitriding compound, heterology material, heavy metal and mineral compound in garbage leachate wastewater, its moiety is complicated, is the very unmanageable waste water of one.In order to effective treating refuse percolate, invention increases nitrogen in compound adsorbent and modify TiO
2the mass ratio of nanoparticle and alginate calcium, makes compound photochemical catalysis biological adsorption agent all have good absorption degradation effect to the total organic carbon in garbage leachate wastewater and ammonia nitrogen.By improving the content of alginate calcium in compound adsorbent, be conducive to the physical strength and the stability that strengthen whole sorbent material; The more important thing is and be conducive to strengthening provide protection to white-rot fungi in compound photochemical catalysis biological adsorption agent, with hazardous and noxious substances in the percolate water sample of better tackling actual complex on the impact of white rot fungal physiology activity.
(4) the invention provides a kind of method utilizing compound photochemical catalysis biological adsorption agent treating refuse percolate, not only treatment process and an adsorption device simple, easy to operate, cost is extremely low, and loading capacity is large, adsorption efficiency is high, cleanliness without any pollution, have good treatment effect to percolate, can effectively reduce landfill leachate treatment running cost, be a kind ofly can extensively to adopt, can the method for effective treating refuse percolate.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available, wherein white-rot fungi is Phanerochaete chrysosporium, be purchased from China typical culture collection center, preserving number is CCTCC BKMF-1767, and Phanerochaete chrysosporium strain transfer is deposited on potato plate culture medium.
Embodiment 1:
A kind of compound photochemical catalysis biological adsorption agent of the present invention, this compound photochemical catalysis biological adsorption agent is that mycelia is wound in bacterium ball with white-rot fungi viable bacteria mycelia for carrier, and bacterium ball inside is embedded with nitrogen and modifies TiO
2nanoparticle and alginate calcium, mycelia and nitrogen are modified TiO as entrapment media by alginate calcium
2together, the nitrogen of bacterium ball inside embedding modifies TiO to nanoparticle compact siro spinning technology
2the mass ratio of nanoparticle and alginate calcium is 1: 4 (nitrogen modification TiO
2when the mass ratio of nanoparticle and alginate calcium is 1: 3 ~ 5, all can implement).
A preparation method for the compound photochemical catalysis biological adsorption agent of above-mentioned the present embodiment, comprises the following steps:
(1) sol-gel method prepares nitrogen modification TiO
2nanoparticle: first take 0.282g urea and be placed in 250mL Erlenmeyer flask, adds the dehydrated alcohol of 40mL, 8mL ultrapure water and 12mL Glacial acetic acid, after unlatching magnetic stirrer to urea dissolves completely, is designated as solution A.Then being joined by the tetrabutyl titanate of 32mL is equipped with in the 500mL Erlenmeyer flask of 128mL dehydrated alcohol, after mixing, is designated as B solution.Under the condition of magnetic stirrer, with syringe, solution A is slowly added drop-wise in B solution, after dropwising, obtains the colloidal sol of homogeneous transparent, then to pour on slat chain conveyor ware and obtain gel after ageing 24h at normal temperatures.Gel is placed in vacuum drying oven, under 80 DEG C of conditions, places 4h, obtain xerogel, xerogel grind into powder is placed in retort furnace and calcines 3h under 500 DEG C of conditions, namely obtain nitrogen and modify TiO
2nanoparticle.This nitrogen modifies TiO
2in nanoparticle, the molar content of nitrogen is 9.37%.
(2) aseptic nitrogen modifies TiO
2the preparation of nanoparticle and sodium alginate mixed solution: nitrogen is modified TiO
2it is in the sodium alginate soln of 40g/L that nanoparticle joins concentration, and nitrogen modifies TiO
2nanoparticle addition is 0.01g/mL, and then sterilizing 30min under 105 DEG C of conditions, finally cools 60min under sterile conditions, and obtained aseptic nitrogen modifies TiO
2the mixed solution of nanoparticle and sodium alginate.
(3) nitrogen modifies TiO
2the preparation of-alginate calcium-white-rot fungi microballoon: aseptically, modifies TiO by aseptic nitrogen
2the mixed solution 100mL of nanoparticle and sodium alginate and Phanerochaete chrysosporium spore suspension to mix by volume at 1: 1, stir, obtain nitrogen and modify TiO
2the mixed solution of nanoparticle, sodium alginate and Phanerochaete chrysosporium spore suspension, wherein Phanerochaete chrysosporium spore suspension spore concentration is 1.0 × 10
6individual/mL.200mL gained nitrogen is modified TiO
2the mixed solution syringe of nanoparticle, sodium alginate and Phanerochaete chrysosporium spore suspension is dropwise added drop-wise to the aseptic CaCl of 400mL
2in solution, aseptic CaCl
2the mass concentration of solution is 3%, after left at room temperature sclerosis 2h, obtain nitrogenous modification TiO
2the reaction solution of-alginate calcium-white-rot fungi microballoon, is separated after filtering and obtains nitrogen modification TiO
2-alginate calcium-white-rot fungi microballoon.
(4) nitrogen modifies TiO
2the Immobilized culture of-alginate calcium-white-rot fungi microballoon: nitrogen is modified TiO
2-alginate calcium-white-rot fungi microballoon leaches from solution, cleans repeatedly, then nitrogen is modified TiO with aseptic ultrapure water
2-alginate calcium-white-rot fungi microballoon is transferred in aseptic white-rot fungi liquid Kirk substratum, shifts 2.0g nitrogen and modify TiO in every 100mL sterile liquid Kirk substratum
2(nitrogen modifies TiO to-alginate calcium-white-rot fungi microballoon
2the addition of-alginate calcium-white-rot fungi microballoon is 10g/L ~ 40g/L, all can implement), at 37 DEG C, constant-temperature shaking culture 72h (at 35 DEG C ~ 39 DEG C, constant-temperature shaking culture 72h ~ 96h under rotating speed 120rpm ~ 130rpm condition, all can implement) under rotating speed 120rpm condition, then the bacterium ball after cultivation is leached, aseptic ultrapure water cleaning repeatedly, completes Immobilized culture process, obtains compound photochemical catalysis biological adsorption agent.
By above-mentioned obtained compound photochemical catalysis biological adsorption agent (before percolate) after lyophilize, under the environmental scanning electronic microscope of 2000 times, observe the microtexture of biological adsorption agent, as shown in Figure 1.As shown in Figure 1, the compound photochemical catalysis biological adsorption agent outside of the present embodiment is containing abundant white-rot fungi mycelium, whole mycelium is wound in loosely organized bacterium ball, bacterium ball becomes vesicular, there is very large specific surface area, it is inner to compound photochemical catalysis biological adsorption agent that this cell texture is conducive to contaminant transmission, and carry out absorption degradation to pollutent.The coarse white mass of hyphal surface is alginate calcium, and the particulate material above mycelia is that nitrogen modifies TiO
2nanoparticle, nitrogen is modified TiO by entrapment media alginate calcium
2nanoparticle and white-rot fungi mycelia are combined closely, and add physical strength and the stability of white-rot fungi mycelia, also enhance the resistivity of white-rot fungi to toxic pollutant.It is emphasized that the nitrogen in the present invention modifies TiO
2nanoparticle and alginate calcium are embedded on white-rot fungi mycelia all well, and nitrogen modifies TiO
2nanoparticle dispersion is good, because biological adsorption agent interior porosity is large, further promotes absorption and the gathering of pollutent.
Energy spectrum analysis is carried out to compound photochemical catalysis biological adsorption agent of the present invention, as shown in Figure 2, obtain its element kind contained and mass percent as shown in table 1.
Table 1: the compound photochemical catalysis biological adsorption agent of the present embodiment contains element kind and mass percent thereof
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, TiO
2nanoparticle has well been fixed on white-rot fungi mycelia by alginate calcium.
Embodiment 2:
Compound photochemical catalysis biological adsorption agent is to a treatment process for percolate, and this compound photochemical catalysis biological adsorption agent 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, adjust ph to 6.0, in the Erlenmeyer flask of 250mL, be respectively charged into the percolate 100mL of above-mentioned concentration, sterilizing 30min under 105 DEG C of conditions.
(2) in aseptic percolate, add the compound photochemical catalysis biological adsorption agent in embodiment 1 after Immobilized culture, addition is add the compound photochemical catalysis biological adsorption agent 4.0g of weight in wet base in the aseptic percolate of every 100mL (addition of compound photochemical catalysis biological adsorption agent is 20g/L ~ 80g/L, all can implement), at 37 DEG C, rotating speed 150rpm, vibrating under 20W incandescent light illumination condition, (rotating speed of vibration absorption is 150rpm ~ 160rpm to absorption degradation 96h, temperature is 25 DEG C ~ 45 DEG C, intensity of illumination is 10Lux ~ 20Lux, all can implement), liquid phase and solid phase is separated by after the percolate of adsorption treatment of vibrating leaves standstill, regulate liquid phase to neutral, complete the process to percolate.
Fig. 3 is the surperficial mycelium micro-structure diagram of compound photochemical catalysis biological adsorption agent under 2000 times of environmental scanning electronic microscopes after treating refuse percolate, as shown in Figure 3, after compound photochemical catalysis biological adsorption agent treating refuse percolate, the mycelia of bacterium ball shrinks and attenuates, bacterium ball inner porosity space becomes large, have very large specific surface area, the contaminant transmission in percolate is inner by absorption degradation to compound photochemical catalysis biological adsorption agent.
Measure the TOC concentration in percolate each sample after treatment and NH respectively
3-N concentration.
Fig. 4 is the removal effect schematic diagram of compound photochemical catalysis biological adsorption agent to TOC under different starting point concentration percolate conditions in the present embodiment, as shown in Figure 4, to different starting point concentration percolates, compound photochemical catalysis biological adsorption agent all has good absorption degradation effect to the TOC in percolate, last TOC concentration is reduced to 8.0mg/L respectively, 18.3mg/L, 46.3mg/L, 91.2mg/L.
Fig. 5 be in the present embodiment compound photochemical catalysis biological adsorption agent under different starting point concentration percolate conditions to NH
3the removal effect schematic diagram of-N, as shown in Figure 5, to different starting point concentration percolates, compound photochemical catalysis biological adsorption agent is to the NH in percolate
3-N has good absorption degradation effect, last NH
3-N removal efficiency is respectively 68.6%, and 59.1%, 53.8%, 48.1%.
Interior figure in Fig. 5 is compound photochemical catalysis biological adsorption agent NH in the scope that the treatment time is 0 ~ 12h in the present embodiment
3the removal efficiency of-N.
Be the percolate of 200mg/L to initial COD concentration, the TOC residual concentration in percolate each sample after treatment and NH
3the measurement result of-N clearance is in table 2.
Table 2: compound photochemical catalysis biological adsorption agent is to percolate TOC and NH
3-N removal effect
From table 2 and Fig. 4, Fig. 5, along with the change of time, in compound photochemical catalysis biological adsorption agent absorption degradation process, in percolate, TOC residual concentration is the trend of first increases and then decreases, NH
3-N clearance raises gradually, NH after process 24h
3-N clearance just reaches balance.
Embodiment 3:
The present embodiment compound photochemical catalysis biological adsorption agent is to the treatment process of the percolate of different initial pH value, and this compound photochemical catalysis biological adsorption agent derives from embodiment 1, comprises the following steps:
(1) preparing COD concentration is the percolate of 200mg/L, and adjust ph 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, in the Erlenmeyer flask of 250mL, be respectively charged into the percolate 100mL of above-mentioned pH value, sterilizing 30min under 105 DEG C of conditions.
(2) in the percolate after above-mentioned sterilizing, add the compound photochemical catalysis biological adsorption agent in embodiment 1 after Immobilized culture, addition is the compound photochemical catalysis biological adsorption agent 4.0g adding weight in wet base in the aseptic percolate of every 100mL, at 37 DEG C, vibrate under rotating speed 150rpm, 20W incandescent light illumination condition absorption degradation 96h, is separated liquid phase and solid phase after leaving standstill, regulate liquid phase to neutral, complete the process to percolate.
Measure the TOC concentration in percolate each sample after treatment and NH respectively
3-N concentration, percolate TOC and NH
3-N removes and the results are shown in Table 3.
Table 3: compound photochemical catalysis biological adsorption agent is to percolate TOC and NH of different initial pH value
3-N removal effect
As shown in Table 3, along with the continuous rising of percolate pH value, in compound photochemical catalysis biological adsorption agent absorption degradation process, in percolate, TOC clearance is the trend of first increases and then decreases, optimal ph at 6 places, NH
3-N clearance is also the trend in first increases and then decreases, and optimal ph is at 7 places.
Embodiment 4:
The present embodiment be the compound photochemical catalysis biological adsorption agent of various dose to the treatment process of percolate, this compound photochemical catalysis biological adsorption agent derives from embodiment 1, comprises the following steps:
(1) preparing COD concentration is the percolate of 200mg/L, and adjust ph is 6.0, is respectively charged into the percolate 100mL of above-mentioned pH value in the Erlenmeyer flask of 250mL, sterilizing 30min under 105 DEG C of conditions.
(2) in the percolate after above-mentioned sterilizing, add the compound photochemical catalysis biological adsorption agent in embodiment 1 after Immobilized culture, addition is the compound photochemical catalysis biological adsorption agent 2.0g adding weight in wet base in the aseptic percolate of every 100mL respectively, 3.0g, 4.0g, 5.0g, 6.0g, 7.0g, 8.0g, at 37 DEG C, vibrate under rotating speed 150rpm, 20W incandescent light illumination condition absorption degradation 96h, is separated liquid phase and solid phase after leaving standstill, regulate liquid phase to neutral, complete the process to percolate.
Measure the TOC concentration in percolate each sample after treatment and NH respectively
3-N concentration, TOC and NH in percolate
3-N removes and the results are shown in Table 4.
Table 4: the compound photochemical catalysis biological adsorption agent of various dose is to TOC and NH in percolate
3-N removal effect
Dosage (g) |
2.0 |
3.0 |
4.0 |
5.0 |
6.0 |
7.0 |
8.0 |
TOC clearance (%) |
31.3 |
56.2 |
74.7 |
75.8 |
65.8 |
61.3 |
58.7 |
NH
3-N clearance (%)
|
29.4 |
43.1 |
57.6 |
65.3 |
68.2 |
71.9 |
74.6 |
As shown in Table 4, in absorption degradation process, along with the continuous increase of compound photochemical catalysis biological adsorption agent dose, in percolate, TOC clearance is the trend of first increases and then decreases, and optimal dose is 5.0g, NH
3-N clearance raises gradually.
In sum, compound photochemical catalysis biological adsorption agent of the present invention is the compound-type adsorbent integrating physics, chemistry and biological adsorption Degradation, wherein, and composition of specifically degrading using white-rot fungi viable bacteria mycelia as biological adsorption, and nitrogen modifies TiO
2it is inner with further rich long-pending degradation of contaminant that nanoparticle is then embedded in mycelium, and white-rot fungi viable bacteria mycelia and nitrogen are then modified TiO as entrapment media by alginate calcium
2nanoparticle combines the physical strength and the stability that strengthen whole sorbent material closely.Compound photochemical catalysis biological adsorption agent of the present invention not only treatment process and an adsorption device simple, easy to operate, cost is extremely low, and loading capacity is large, adsorption efficiency is high, cleanliness without any pollution, good treatment effect is had to percolate, can effectively reduce landfill leachate treatment running cost, be one can extensively adopt, can the effective compound photochemical catalysis biological adsorption agent for the treatment of refuse percolate.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from spirit of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.