CN102616912B - Method for adsorbing lead in wastewater by using composite magnetic biological adsorbent - Google Patents
Method for adsorbing lead in wastewater by using composite magnetic biological adsorbent Download PDFInfo
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Abstract
The invention discloses a method for adsorbing lead in wastewater by using a composite magnetic biological adsorbent. The method comprises the following steps of: adding 15-60 g/L of the composite magnetic biological adsorbent by wet weight into lead-contained industrial waste water with a pH value ranging from 2 to 6.5 and a concentration being 10-500 mg/L; oscillating and adsorbing the mixture at a temperature of 30-35 DEG C for more than 8 hours; then separating the adsorbent from the wastewater; and adjusting the wastewater to be neutral to discharge. The composite magnetic biological adsorbent uses white-rot fungus living mycelium as a carrier; the mycelium is wound into a pellet; Fe3O4 nanometer particles and calcium alginate are embedded inside the pellet; and the calcium alginate serving as an immobilization medium is used for tightly connecting the mycelium with the Fe3O4 nanometer particles. The method provided by the invention has the advantages of large adsorption amount, high adsorption efficiency, simpleness and convenience for operation, low cost, high recycle rate, cleanliness, no pollution and the like.
Description
Technical field
The invention belongs to the biological adsorption process field of waste water, relate in particular to a kind of method of compound biological adsorbent absorption heavy metal in waste water.
Background technology
Along with the quickening of urbanization process and developing rapidly of industrial or agricultural, China's most cities all exists comparatively serious water pollution problems.A large amount of undressed municipal wastess, trade effluent and sanitary sewage and atmospheric fallout constantly enter in the water body, heavy metal content in water body suspended substance and the settling is sharply raise, oneself becomes global problem of environmental pollution heavy metal pollution of water body, and is extremely urgent to the improvement of heavy metal-polluted water.
Lead waste water between various electrically-operated platform trucks, dressing-works, petroleum chemical plant etc., in these industrial and mining enterprises' production management process, the waste water that produces is not treated or process and thoroughly just do not enter in the water body, land pollutant enters water body or enrichment in aquatic organism, arrive in the human body by food chain again, and then cause lead poisoning.In addition, contained lead also is the main source of Lead contamination in the water body in plumbous zinc ore, nonferrous metals ore tailings water, beneficiation wastewater, the waste residue.Ion exchange method, chemical precipitation method, electrolytic process, liquid-film method and absorption method are generally adopted in plumbous removal in the water at present.Wherein, that absorption method possesses is easy and simple to handle, process effective, the recyclable heavy metal of low concentration heavy metal water, can not produce the advantage such as secondary pollution, now is widely used in the wastewater treatment.
Whiterot fungi (
P. chysosporium) effectively enrichment and Adsorption of Heavy Metal Ions from the aqueous solution, also can further reclaim heavy metal ion, be a kind of generally acknowledged high-performance bio sorbent material, and studied widely.In traditional biosorption process treating processes, biomass cells generally is in unbound state, very easily runs off from reactor and along with pending liquid is discharged from, and it is difficult to reclaim and by Reusability by solid-liquid separation method.In addition, the pending waste water often toxicity to cell is very large, and its activity of biomass cells that is under the unbound state is difficult to keep, thereby causes the gradually decline of processing efficiency.
Microbial immobilized technology also can effectively be improved the mechanical property of microorganism so that microorganism has the ability of the toxic compounds of degrading more strongly, makes it possess better physical strength and reusing.The stability of microorganism strengthens, and has created relatively preferably growing environment to microorganism in pending waste water, can make it keep high density by growth and breeding, thereby improves speed and the efficient of processing; Even when the processing load is higher, can not cause the phenomenon of deviating from of microorganism cells yet, process load and is easy to control.How to develop better and use microbial immobilized technology to carry out the processing of heavy metal wastewater thereby, just becoming an emerging research field.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of adsorptive capacity is large, adsorption efficiency is high, simple to operation, cost is low, repeating utilization factor is high and the method for utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water of cleanliness without any pollution.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, may further comprise the steps: it is 2～6.5 that described compound magnetic biological adsorption agent is joined pH value scope by the consumption of 15～60g/L weight in wet base, concentration is in the lead-containing industrial wastewater of 10 mg/L～500 mg/L, more than 30 ℃～35 ℃ lower vibration absorption 8h, then from described lead-containing industrial wastewater, isolate compound magnetic biological adsorption agent, the lead-containing industrial wastewater that leaches after the separation is adjusted to neutral rear discharging, finishes the processing to lead-containing industrial wastewater;
Described compound magnetic biological adsorption agent be with whiterot fungi (
P. chysosporium) the viable bacteria mycelia is carrier, described mycelia is wound in the bacterium ball, and described bacterium ball inside is embedded with Fe
3O
4Nanoparticle and alginate calcium, described alginate calcium as entrapment media with described mycelia and Fe
3O
4Nanoparticle closely links together.
The compound magnetic biological adsorption agent of the invention described above is the compound-type adsorbent that collection physics, a chemistry and biological adsorption act on one, wherein, specifically with whiterot fungi viable bacteria mycelia as the biological adsorption agent composition, and Fe
3O
4Nanoparticle then is embedded in mycelium inside with further enrichment pollutent, alginate calcium then as entrapment media with whiterot fungi viable bacteria mycelia and Fe
3O
4Nanoparticle is closely in conjunction with physical strength and stability to strengthen whole sorbent material.
Compound magnetic biological adsorption agent of the present invention can be used for processing lead-containing industrial wastewater, when compound magnetic biological adsorption agent of the present invention is used for processing lead-containing industrial wastewater, the pH value scope of lead-containing industrial wastewater should be controlled in 2～6.5 the scope, and the scope of this pH value is determined by following test.Compound magnetic biological adsorption agent of the present invention is joined in the lead-containing industrial wastewater of 50 mL by 1.5 g weight in wet bases, and the Pb In Exhausted Water ionic concn is controlled at 100 mg/L, utilizes the HNO of 0.5 M
3Regulate pH in 2～6.5 scope with NaOH solution, constant temperature oscillation adsorbs 12 h under 30 ℃, 150 rpm, leach sorbent material, get supernatant liquor and measure the concentration of residue Pb (II), and analyze accordingly the adsorption efficiency (measurement result see the following form 1) of this compound magnetic biological adsorption agent under different pH values.By descending as seen from Table 1, when compound magnetic biological adsorption agent of the present invention is used for processing lead-containing industrial wastewater, not only significantly improved the adsorption efficiency of whiterot fungi to Pb (II), also show better stability, when the pH value is 4～6.5 scope, its adsorption efficiency remains at more than 80%, is higher than loose whiterot fungi far away, and optimal adsorption pH value is 5.0.
Table 1: under condition of different pH to the adsorption efficiency of Pb (II)
| The pH value | 2 | 3 | 4 | 5 | 6 | 6.5 |
| Whiterot fungi | 4.36% | 23.16% | 34.32% | 37.56% | 21.92% | 19.96% |
| Compound magnetic biological adsorption agent | 63.2% | 73.26% | 82.84% | 95.03% | 91.44% | 86.92% |
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, the Fe of the inner embedding of described bacterium ball
3O
4The mass ratio of nanoparticle and alginate calcium is preferably 1: (0.1～1.2).
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, the time of described vibration absorption is preferably 8h～12h.The preferred time of vibration absorption is determined by following test: adding compound magnetic biological adsorption agent of the present invention to plumbum ion concentration by 1.5 g weight in wet bases is that 50 mg/L, pH value are in 5 the lead waste water, constant temperature oscillation adsorbs 24 h under 35 ℃, 150 rpm, measure the compound magnetic biological adsorption agent of different time sections to the adsorption efficiency of lead ion by following time sampling, the result is as shown in table 2 below, behind the absorption 8h, absorption reaches balance substantially.With respect to traditional biological adsorption agent, the adsorption time of compound magnetic biological adsorption agent of the present invention is than very fast, and better adsorption time is 8h～12h.
Table 2: under different adsorption time conditions to the adsorption efficiency of Pb (II)
| Adsorption time (h) | 1 | 2 | 4 | 6 | 8 | 10 | 12 | 24 |
| Adsorption efficiency (%) | 54.49 | 61.03 | 80.07 | 89.97 | 91.87 | 92.06 | 92.27 | 92.81 |
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, plumbum ion concentration is preferably 10 mg/L～200 mg/L(and utilizes method of the present invention to process the trade effluent that contains lead concentration≤200 mg/L in the described lead-containing industrial wastewater, and cost performance is optimum).
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, described method also preferably includes the operating process of sorbent material desorption cycle, this operating process specifically may further comprise the steps: will carry out desorb by isolated compound magnetic biological adsorption agent from described lead-containing industrial wastewater, with the hydrochloric acid of 0.1～0.5 M as strippant, measure lead concentration in the stripping liquid at 30 ℃～35 ℃ lower vibration desorb 30min～60min(), leach this compound magnetic biological adsorption agent after the desorb, ultrapure water cleans, and then its circulation is joined Adsorption of Lead in the pending lead-containing industrial wastewater.The reusing of the compound magnetic biological adsorption agent of the present invention can be determined by following test: as strippant the compound magnetic biological adsorption agent after adsorbing is carried out desorb with 0.1～0.5 M hydrochloric acid, 35 ℃ of lower vibration desorb 30min～60min, measure concentration plumbous in the stripping liquid, leach sorbent material, ultrapure water cleans, and then it is joined 50 mL Pb (II) concentration is 100mg/L, the pH value is in 5 the trade effluent, at 35 ℃, constant temperature oscillation absorption 8h under 150 rpm, repeat this absorption-desorption process 9 times, verify its reusing, the results are shown in following table 3.The data of following table 3 show, after 8 absorption-desorption cyclical operations, this compound magnetic biological adsorption agent still remains on more than 90% to containing adsorption rate plumbous in the lead solution (concentration is 100 mg/L), this shows that compound magnetic biological adsorption agent of the present invention has good reusing, still keep higher adsorption efficiency through repeating after 8 absorption-desorption processes, in the treating processes that is used for lead-containing industrial wastewater, can effectively recycle, to reduce running cost.
Table 3: under absorption-desorption circulation to adsorption efficiency and the desorption efficiency of Pb (II)
| |
1 | 2 | 3 | 4 | 5 | … | 8 | 9 |
| Adsorption efficiency (%) | 94.14 | 92.81 | 92.08 | 91.89 | 91.82 | … | 90.32 | 89.74 |
| Desorption efficiency (%) | 59.98 | 57.17 | 54.14 | 53.59 | 51.51 | … | 49.16 | 48.81 |
In the above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, the preparation method of described compound magnetic biological adsorption agent preferably includes following steps:
Under the aseptic condition, at aseptic Fe
3O
4The spore suspension of the described whiterot fungi of inoculation in particle and the sodium alginate mixed solution, inoculum size in every milliliter of mixed solution is 0.2mL～1.0mL, get mixing solutions after fully mixing, the described mixing solutions of 1 volume dropwise is added drop-wise to the aseptic CaCl of 4～10 volumes
2(the described mixing solutions of preferably getting 4mL～5mL dropwise is added drop-wise to the aseptic CaCl of 20mL～40mL in the solution
2In the solution), after leaving standstill 1h～4h under the room temperature, obtain containing Fe
3O
4The reaction solution of-alginate calcium-whiterot fungi microballoon is again to described Fe
3O
4-alginate calcium-being fixed of whiterot fungi microballoon cultivation obtains compound magnetic biological adsorption agent after cultivation is finished.
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, described aseptic Fe
3O
4The compound method of particle and sodium alginate mixed solution preferably includes following steps:
With Fe
3O
4Nanoparticle joins in the sodium alginate soln that concentration is 20 g/L～60 g/L, described Fe
3O
4The addition of nanoparticle is 0.05 g/mL～0.20 g/mL, and the 30min～60min that then sterilizes under 105 ℃～115 ℃ conditions cools off 60min～90min at last under aseptic condition, make aseptic Fe
3O
4Particle and sodium alginate mixed solution.
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, the spore concentration of the spore suspension of described whiterot fungi is preferably 1.0 * 10
6Individual/mL～2.0 * 10
6Individual/mL; Described aseptic CaCl
2The concentration of solution is preferably 0.1M～0.2M.
The above-mentioned method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, the detailed process that described immobilization is cultivated preferably includes following steps:
With described Fe
3O
4-alginate calcium-whiterot fungi microballoon leaches from described reaction solution, and aseptic ultrapure water cleans repeatedly (3～5 times get final product), then with Fe
3O
4In the whiterot fungi liquid Kirk substratum that-alginate calcium-whiterot fungi microballoon is transferred to, shift 2.5g～4.5g Fe in the described liquid Kirk of the every 50ml～100ml substratum
3O
4-alginate calcium-whiterot fungi microballoon, constant-temperature shaking culture is 4～5 days under 35 ℃～37 ℃, 120 rpm～150 rpm conditions, and the bacterium ball after then will cultivating leaches, and the ultrapure water flushing is (3～5 times get final product) repeatedly, finish the immobilization culturing process.
Undertaken finding after microexamination is analyzed by the compound magnetic biological adsorption agent that a large amount of employing preferred process of the present invention are made, compound magnetic biological adsorption agent of the present invention is observed under 1000 times environmental scanning electronic microscope has special microtexture, the outside of the compound magnetic biological adsorption agent of the present invention contains abundant whiterot fungi mycelium, mycelium is white in color, well-grown, whole mycelium is wound in loosely organized bacterium ball, the bacterium ball is vesicular, specific surface area is large, and contain a large amount of little spaces, so that Pb (II) is transferred to compound magnetic biological adsorption agent inside, be rich in carboxyl on the hyphal cell wall, hydroxyl, amino, phosphoryl, the multiple functional group such as carbonyl, these functional groups have the ability of bonding lead ion, and good surface adsorption effect is arranged; The entrapment media alginate calcium is then with whiterot fungi mycelia and Fe
3O
4The close combination of nanoparticle has increased physical strength and the stability of whiterot fungi mycelia; What be worth especially proposition is Fe among the present invention
3O
4It is inner that nanoparticle and alginate calcium all are embedded in whiterot fungi bacterium ball well, and Fe
3O
4The nanoparticle good dispersion because the sorbent material interior porosity is large, has further promoted absorption and the gathering of Pb (II), has effectively improved the problem that the inner absorption of whiterot fungi bacterium ball is restricted, and has strengthened the internal transmission adsorption mechanism of sorbent material.
Compared with prior art, the invention has the advantages that:
(1) the present invention has reformed the structure of compound magnetic biological adsorption agent, and than traditional immobilized biological adsorbent, its, compound magnetic biological adsorption agent of the present invention is the Fe of and enrichment pollutent adsorbable in the inner embedding of bacterium ball
3O
4Nanoparticle has effectively strengthened the internal transmission adsorption mechanism of compound magnetic biological adsorption agent, has reduced the toxicity of pollutent to microorganism; The whiterot fungi on compound magnetic biological adsorption agent surface then contains a large amount of adsorption sites, the heavy metal ion in the energy active adsorption water; In addition, by adopting the bacterium bag to bury Fe
3O
4The structure formation of nanoparticle and alginate calcium, physical strength and the stability of compound magnetic biological adsorption agent are strengthened greatly, and the singularity of this microtexture and stability are so that the present invention becomes a kind of compound-type adsorbent that physics, chemistry and biological adsorption act on one that collects;
(2) compound magnetic biological adsorption agent of the present invention is for the treatment of lead-containing industrial wastewater the time, not only treatment process and an adsorption device are simple, easy to operate, cost is extremely low, and loading capacity is large, rate of adsorption is fast, repeating utilization factor is high, and cleanliness without any pollution, lead waste water to lower concentration (for example 1～100 ppm) has good treatment effect, can effectively reduce wastewater treatment running cost, be a kind of can extensively adopt, efficient plumbous compound magnetic biological adsorption agent in the removal heavy metal pollutant effluents;
(3) in the preferred technical scheme of the present invention, greatly simplified the preparation technology of compound magnetic biological adsorption agent, shortened the immobilization time, in the process of growth of whiterot fungi mycelia, can finish immobilization process, product after immobilization is cultivated can be directly used in plumbous absorption, has avoided the collection of bacterium powder and the operation of complexity such as milling; As seen, compound magnetic biological adsorption agent of the present invention is not only made simply, and easy to use, prepares compound magnetic biological adsorption agent by the operating procedure of proportioning raw materials and low cost, portable scientifically and rationally, and using for mass-producing provides prerequisite.
Description of drawings
Fig. 1 is the surperficial mycelium micro-structure diagram of compound magnetic biological adsorption agent under 1000 times of environmental scanning electronic microscopes in the embodiment of the invention 1.
Fig. 2 is the internal microstructure figure of compound magnetic biological adsorption agent under 1000 times of environmental scanning electronic microscopes in the embodiment of the invention 1.
Fig. 3 is the design sketch that compound magnetic biological adsorption agent adsorbs lead ion in the different concns lead waste water in the embodiment of the invention 2.
Embodiment
The invention will be further described below in conjunction with Figure of description and specific embodiment.
Embodiment 1:
A kind of method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water may further comprise the steps:
Get lead-containing industrial wastewater 1L, the Pb of this waste water (II) content is about 300mg/L, with waste water by the acid-alkali accommodation pond regulate the pH value to 5(2～6.5 all can) after, in reactive tank, add the 60g(weight in wet base) compound magnetic biological adsorption agent of the present invention, be that 35 ℃ (30 ℃～35 ℃ all can), rotating speed be under the 150 rpm conditions in temperature, vibration absorption 8h, then direct filtration, compound magnetic biological adsorption agent after separation water outlet and the absorption, the lead-containing industrial wastewater that leaches after the separation is adjusted to neutral rear discharging, finishes the processing to lead-containing industrial wastewater.
Measure the lead that is not adsorbed with atomic absorption spectrophotometry, plumbous clearance reaches 89.24%(and sees table the contrast of removing plumbous effect in 4), biological adsorption agent after the use can be recycled by parsing, concrete operations comprise: will carry out desorb by isolated compound magnetic biological adsorption agent from lead-containing industrial wastewater, with the hydrochloric acid of 0.1～0.5 M as strippant, at 35 ℃ of lower vibration desorb 30min～60min, leach this compound magnetic biological adsorption agent after the desorb, ultrapure water cleans, and then its circulation is joined Adsorption of Lead in the pending lead-containing industrial wastewater; After 8 absorption-desorption circulations, this compound magnetic biological adsorption agent still remains on more than 90% to containing adsorption rate plumbous in the lead solution (Pb (II) concentration is 100 mg/L), as seen, compound magnetic biological adsorption agent of the present invention has good reusing, can be effective to the processing of lead waste water.
Table 4: processing efficiency and loading capacity contrast that different sorbent materials are processed lead waste water
| Sorbent material | Adsorption efficiency | Loading capacity |
| Fe 3O 4Nanoparticle | 30.69% | 46.04 mg/g |
| Fe 3O 4-calcium alginate microsphere | 38.95% | 58.43 mg/g |
| Fixed white rot bacterium not P. chysosporium | 25.06% | 37.59 mg/g |
| Calcium-alginate-immobilized whiterot fungi P. chysosporium | 42.46% | 63.69 mg/g |
| Fe 3O 4-alginate calcium-whiterot fungi P. chrysosporium | 89.24% | 133.86 mg/g |
The preparation method of the compound magnetic biological adsorption agent of present embodiment may further comprise the steps:
(1) aseptic Fe
3O
4The preparation of particle and sodium alginate mixed solution: with 0.20g Fe
3O
4Nanoparticle joins in the sodium alginate soln that 2mL concentration is 40g/L, stirs, and the 30min that then sterilizes under 105 ℃ of conditions cools off 80min at last under aseptic condition, make aseptic Fe
3O
4Particle and sodium alginate mixed solution;
(2) Fe
3O
4The preparation of-alginate calcium-whiterot fungi microballoon: under the aseptic condition, inoculation 0.4mL spore concentration is 2.0 * 10
6The aseptic Fe that the whiterot fungi spore suspension of individual/mL makes to 2mL above-mentioned steps (1)
3O
4In particle and the sodium alginate mixed solution, get mixing solutions after fully mixing, utilize the medical aseptic syringe that this mixing solutions dropwise is added drop-wise to the 20mL volumetric molar concentration and be the aseptic CaCl of 0.2M
2In the solution, obtain containing Fe after leaving standstill 4h under the room temperature
3O
4The reaction solution of-alginate calcium-whiterot fungi microballoon;
(3) immobilization is cultivated: after the immobilization process of above-mentioned steps (2) is finished, with Fe
3O
4-alginate calcium-whiterot fungi microballoon leaches from reaction solution, and with the Fe of aseptic ultrapure water to making
3O
4-alginate calcium-whiterot fungi microballoon washs 3 times, then with 3.0g Fe
3O
4-alginate calcium-whiterot fungi microballoon is transferred in the 50mL whiterot fungi liquid Kirk substratum, and constant-temperature shaking culture is 4 days under 37 ℃, 150rpm condition, and the bacterium ball after cultivating is leached, and ultrapure water flushing 3 times makes the compound magnetic biological adsorption agent of present embodiment.
The microtexture of the compound magnetic biological adsorption agent that the observation present embodiment makes under 1000 times environmental scanning electronic microscope, the outside of the compound magnetic biological adsorption agent of discovery present embodiment contains abundant whiterot fungi mycelium, and (mycelium is white in color, well-grown), whole mycelium is wound in loosely organized bacterium ball, the bacterium ball is vesicular, huge specific surface area is arranged, and contain a large amount of little spaces (referring to Fig. 1), so that Pb (II) is transferred to compound magnetic biological adsorption agent inside, be rich in carboxyl on the hyphal cell wall, hydroxyl, amino, phosphoryl, the multiple functional group such as carbonyl, these functional groups have the ability of bonding lead ion, and good surface adsorption effect is arranged; The entrapment media alginate calcium is then with whiterot fungi mycelia and Fe
3O
4The close combination of nanoparticle has increased physical strength and the stability of whiterot fungi mycelia; What be worth especially proposition is Fe among the present invention
3O
4It is inner that nanoparticle and alginate calcium all are embedded in whiterot fungi bacterium ball well, and Fe
3O
4Nanoparticle good dispersion (referring to Fig. 2), because the sorbent material interior porosity is large, further promote absorption and the gathering of Pb (II), effectively improved the problem that the inner absorption of whiterot fungi bacterium ball is restricted, strengthened the internal transmission adsorption mechanism of sorbent material.Therefore, the compound magnetic biological adsorption agent of using in the present embodiment be with whiterot fungi (
P. chysosporium) the viable bacteria mycelia is carrier, mycelia is wound in the bacterium ball, and bacterium ball inside is embedded with Fe
3O
4Nanoparticle and alginate calcium, described alginate calcium as entrapment media with described mycelia and Fe
3O
4Nanoparticle closely links together.The Fe of the inner embedding of bacterium ball
3O
4The mass ratio of nanoparticle and alginate calcium is 1: 0.4.
Embodiment 2:
With among the embodiment 1 preparation compound magnetic biological adsorption agent by 60 g/L(weight in wet bases) join in the lead-containing industrial wastewater (Pb (II) concentration 10～500 mg/L) of different concns, the pH value of lead-containing industrial wastewater all is adjusted to 5, vibration absorption under 35 ℃, 150 rpm conditions, behind 8 h upon adsorption, direct filtration, isolate compound magnetic biological adsorption agent from lead-containing industrial wastewater, the lead-containing industrial wastewater that leaches is adjusted to neutral rear discharging.
Utilize flame atomic absorption spectrophotometer to measure the lead ion that is not adsorbed in the solution, this compound magnetic biological adsorption agent in the different concns lead waste water to the adsorption effect of lead as shown in Figure 3.As seen from Figure 3, method of the present invention reaches 90.18% to the clearance of the lead waste water of 10 mg/L, Pb (II) residual volume is 0.82 mg/L after the absorption, (total lead＜1.0mg/L), namely compound magnetic biological adsorption agent of the present invention can be effective to the removal of determination of lead in waste water to reach the national standard of the highest permission emission concentration of first kind pollutent; Be that the clearance of trade effluent of 50mg/L～200mg/L is all more than 94% to lead concentration, but remaining lead concentration surpasses 1.0mg/L, do not reach emission standard, but according to our test, when the concentration of Pb in the lead-containing industrial wastewater (II) surpasses 200mg/L, can process by the usage quantity that increases this compound magnetic biological adsorption agent.
Claims (8)
1. method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water, may further comprise the steps: described compound magnetic biological adsorption agent is joined by the consumption of 15～60g/L weight in wet base pH value scope is 2～6.5, concentration is in the lead-containing industrial wastewater of 10 mg/L～500 mg/L, more than 30 ℃～35 ℃ lower vibration absorption 8h, then from described lead-containing industrial wastewater, isolate compound magnetic biological adsorption agent, the lead-containing industrial wastewater that leaches after the separation is adjusted to neutral rear discharging, finishes the processing to lead-containing industrial wastewater;
Described compound magnetic biological adsorption agent be with whiterot fungi (
P. chysosporium) the viable bacteria mycelia is carrier, described mycelia is wound in the bacterium ball, and described bacterium ball inside is embedded with Fe
3O
4Nanoparticle and alginate calcium, described alginate calcium as entrapment media with described mycelia and Fe
3O
4Nanoparticle closely links together;
The preparation method of described compound magnetic biological adsorption agent may further comprise the steps: under the aseptic condition, at aseptic Fe
3O
4The spore suspension of the described whiterot fungi of inoculation in particle and the sodium alginate mixed solution, inoculum size in every milliliter of mixed solution is 0.2mL～1.0mL, get mixing solutions after fully mixing, the described mixing solutions of 1 volume dropwise is added drop-wise to the aseptic CaCl of 4～10 volumes
2In the solution, after leaving standstill 1h～4h under the room temperature, obtain containing Fe
3O
4The reaction solution of-alginate calcium-whiterot fungi microballoon is again to described Fe
3O
4-alginate calcium-being fixed of whiterot fungi microballoon cultivation obtains compound magnetic biological adsorption agent after cultivation is finished.
2. the method for utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1 is characterized in that: the Fe of the inner embedding of described bacterium ball
3O
4The mass ratio of nanoparticle and alginate calcium is 1: (0.1～1.2).
3. the method for utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1, it is characterized in that: the time of described vibration absorption is 8h～12h.
4. the method for utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1, it is characterized in that: plumbum ion concentration is 10 mg/L～500 mg/L in the described lead-containing industrial wastewater.
5. the method for utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1, it is characterized in that, described method also comprises the operating process of sorbent material desorption cycle, this operating process specifically may further comprise the steps: will carry out desorb by isolated compound magnetic biological adsorption agent from described lead-containing industrial wastewater, with the hydrochloric acid of 0.1～0.5 M as strippant, at 30 ℃～35 ℃ lower vibration desorb 30min～60min, leach this compound magnetic biological adsorption agent after the desorb, ultrapure water cleans, and then its circulation is joined Adsorption of Lead in the pending lead-containing industrial wastewater.
6. each described method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water is characterized in that described aseptic Fe according to claim 1～5
3O
4The compound method of particle and sodium alginate mixed solution may further comprise the steps:
With Fe
3O
4Nanoparticle joins in the sodium alginate soln that concentration is 20 g/L～60 g/L, described Fe
3O
4The addition of nanoparticle is 0.05 g/mL～0.20 g/mL, and the 30min～60min that then sterilizes under 105 ℃～115 ℃ conditions cools off 60min～90min at last under aseptic condition, make aseptic Fe
3O
4Particle and sodium alginate mixed solution.
7. each described method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1～5, it is characterized in that: the spore concentration of the spore suspension of described whiterot fungi is 1.0 * 10
6Individual/mL～2.0 * 10
6Individual/mL; Described aseptic CaCl
2The concentration of solution is 0.1M～0.2M.
8. each described method of utilizing compound magnetic biological adsorption agent absorption Pb In Exhausted Water according to claim 1～5 is characterized in that the detailed process that described immobilization is cultivated may further comprise the steps:
With described Fe
3O
4-alginate calcium-whiterot fungi microballoon leaches from described reaction solution, and aseptic ultrapure water cleans repeatedly, then with Fe
3O
4In the whiterot fungi liquid Kirk substratum that-alginate calcium-whiterot fungi microballoon is transferred to, shift 2.5g～4.5g Fe in the described liquid Kirk of the every 50ml～100ml substratum
3O
4-alginate calcium-whiterot fungi microballoon, constant-temperature shaking culture is 4～5 days under 35 ℃～37 ℃, 120 rpm～150 rpm conditions, and the bacterium ball after then will cultivating leaches, and ultrapure water washes repeatedly, finishes the immobilization culturing process.
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| CN108865154A (en) * | 2018-06-11 | 2018-11-23 | 佛山皖阳生物科技有限公司 | A kind of cadmium soil remediation biological agent |
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| CN109225163A (en) * | 2018-11-14 | 2019-01-18 | 浙江海洋大学 | A kind of method of cadmium in compound magnetic microalgae biological adsorption agent and its absorption waste water |
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