Gram-bacteria is utilized to dispose of sewage the method for middle heavy metal
Technical field
The present invention relates to a kind for the treatment of process containing heavy metal ion sewage, particularly relate to a kind of method utilizing gram-bacteria to adsorb set heavy metal, belong to purification of water quality and field of environment protection.
Background technology
Along with developing rapidly of China's industrial or agricultural, the quantity discharged of heavy metal ion-containing waste water is in increasing trend year by year, and all kinds of heavy metal in waste water content is constantly increasing on the one hand, and heavy metal kind also becomes increasingly sophisticated simultaneously.Consider that heavy metal is to the chronicity of the harm that human body and environment cause and seriousness on the other hand, country is also more and more stricter to the harmless treatment standard of heavy metal-containing waste water.Therefore, how economy, efficiently removal heavy metal ions in wastewater have become current very urgent task.
Traditional heavy metal treatment process due to its processing efficiency lower, and costly, process problem is single, easily cause again the shortcomings such as secondary pollution just gradually eliminate by new treatment process.
For the waste water comprising complicated heavy metal ion, the integrated conduct method that multiple purification techniques combines comes into one's own just day by day.Traditional purification means comprise charcoal absorption, organism complexing etc., a kind of recently method utilizing graphene oxide to remove heavy metal ion in water, although it can realize the adsorption cleaning to some heavy metal ion, but there is adsorbable heavy metal ion kind, limited amount, after process, Graphene reclaims the shortcoming of inconvenience.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing gram-bacteria to adsorb set heavy metal ions in sewage, it can realize the adsorption cleaning to the sewage containing several different heavy metal ion, and process efficient, quick, simple, pollution-free, thus overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme:
Utilize gram-bacteria to adsorb a method for set heavy metal ions in sewage, step comprises:
The gram-bacteria adopted selects Gram-negative bacteria; its cell walls of its cell walls forms primarily of peptidoglycan, protein and lipid; the main functional group that can combine with metal ion in these components comprises carboxyl, phosphoryl, hydroxyl, sulfate group, amino and amide group etc., and wherein the atom such as nitrogen, oxygen, sulphur can provide lone-pair electron and metallic ion coordination complexing.The bacterial strain specifically selected is A.nidulans bacterium or Rhodopseudomonas palustris (Rhodopseudomonaspalustris) or Spherical red antibacterial.
Bacterial classification has access to nitrogen substratum after nitrogen-free agar slant activation, at 28-30 DEG C, shaking culture 5d under 120r/min condition, this is cultivated bacterium liquid by 20% inoculum size access without in nitrogen breeze substratum, at 28-30 DEG C, shaking culture 5d under 120r/min condition, obtain gram-bacteria-fly ash composite material used.Add deionized water again, make the aqueous solution of the gram-bacteria-fly ash composite material of concentration 2-6g/L.
There is nitrogen substratum: sucrose 10.0g, yeast extract paste 0.3g, (NH
4)
2sO
40.5g, CaCO
30.5g, MgSO
47H
2o1g, K
2hPO
41.0g, l.0L, pH value is 7.0-7.5 to distilled water.
Nitrogen-free agar: sucrose 5.0g, CaCO
30.1g, MgSO
47H
2o0.5g, FeCl
36H
2o1mg, Na
2hPO
412H
2o5.0g, l.0L, pH value is 7.0-7.5 to distilled water.
Without nitrogen breeze substratum: the first level flour coal ash adding 15g/L in nitrogen-free agar.Chemical reagent used is analytical pure.
Then, the aqueous solution of this gram-bacteria-fly ash composite material is added in the sewage containing heavy metal ion, through fully, be uniformly mixed to form mixed solution, leave standstill and reach adsorption equilibrium in more than 72 hours.
Next, centrifugal treating is carried out to reaction system, rotating speed 5000r/min, time 15min.Get supernatant liquid after centrifugal, drain after qualified after testing; Get the turbid liquid of bottom, stand-by.
In the inventive solutions, described heavy metal ion is selected from Zn
2+, Cd
2+, Cu
2+, Cr
3+and Pb
2+in any one or a few, the concentration of described heavy metal ion is 10mg/L-100mg/L.
The method utilizing gram-bacteria to adsorb set heavy metal ions in sewage of the present invention's proposition is a kind of novel method being suitable for processing complicated effluent containing heavy metal ions.
Micro heavy ion is only needed, general≤0.1mg/L in microorganism normal growth.But in the environment that some heavy metal ion contents are high, also find that there is microorganism growth.Such as, in the earth (Cu content reaches 68000mg/L) and water (Cu content reaches 100mg/L) of the very high muskeg of some copper (cu) content, fungal growth is still had; In the mineralic acid containing arsenic, antimony, although their concentration substantially exceeds the toxigenous level of biology, also still existed by the microflora be made up of algae, fungi, protozoon and bacterium etc.When heavy metal and compound thereof use as sterilant or sterilizing agent, overdose often, while obtaining effectiveness, has also caused the resistance of microorganism to each metal ion species.The adsorbable metal ion of microorganism also in cell surface accumulation, even can reach more than 90% of dry cell weight.The absorption of microorganism can be divided into non-specific absorption, if certain micro-organisms is to the absorption of copper, cadmium, zinc, nickel; And specificity absorption, as certain micro-organisms depends on cellular energy metabolism, to the absorption of thallium and accumulation etc.
The composition of flyash and character flyash are the solid waste that Hazards in Power Plant is discharged.Its main component is SiO
2, A1
2o
3, CaO, Fe
2o
3deng, simultaneously also containing other material a small amount of.Flyash is made up of the particulate with different structure and form, and wherein great majority are glass spheres, and the particle diameter of single powder coal ash particle is about 5 ~ 300 μm, average geometric particle diameter 40 μm.Flyash has vesicular structure, and porosity is generally 60%-75%, and specific surface area is generally at 2500 ~ 5000cm
2/ g, has stronger adsorptive power.
In gram-bacteria-fly ash composite material, bacterium heavy metal ion has adsorption, this comprises the absorption of bacterium surface heavy metal ion, the flocculation of Extracellular polymers heavy metal ion, and the complexing action of exocellular polysaccharide and organic acidic material heavy metal ion.Except bacterium is to except the absorption of ion, flyash itself is also good sorbent material, and energy absorbed portion heavy metal ion, therefore both combinations make adsorption effect strengthen.Gram-bacteria-fly ash composite material to the adsorption rate of 5 kinds of ions all higher than bacterial adsorption, especially to Pb
2+adsorption rate reaches more than 97%.To Pb
2+adsorption effect is superior is because bacterium is to Pb
2+selective adsorption.This characteristic makes the present invention can targetedly for the treatment of containing Pb
2+waste water.
Waste water after gram-bacteria-fly ash composite material process is after centrifugal, and supernatant liquor as clear as crystal, this illustrates that the settleability of matrix material is better than single bacterial adsorption.Because the specific surface area of flyash is large, adsorption efficiency is high, is suitable for processing the sewage containing contents of many kinds of heavy metal ion.Compared with the sewage water treatment method of the single component such as gac, organic complexing agent of prior art, technical scheme of the present invention is except having the features such as simple, green non-pollution, also have and once can process contents of many kinds of heavy metal ion, process heavy metal ion kind is many, clearance 90% with first-class advantage; The present invention simultaneously can also effectively process some precious metals, as platinum, gold etc.And the gram-bacteria-flyash of Adsorption of Heavy Metal Ions can be used for producing the material of construction such as cement, ceramic tile, the free heavy metal ion of occurring in nature is solidified.
Take off the turbid liquid of layer, be placed in drainage trap, this drainage trap comprises the membrane module in a direct insertion groove, and this membrane module is made up of polyethylene hollow fiber microfiltration membrane, membrane pore size 0.1 μm, film silk internal diameter 0.27mm, film silk external diameter 0.42mm, membrane area 2m
2, an air bell is set below membrane module, plays water quality mixing effect.Membrane module has water pump pipe, and the water flowed out through going out water pump pipe directly discharges, and this water meets emission standard after testing.Described microfiltration membrane is produced by MIT.
The water ratio of the turbid liquid of the lower floor in drainage trap, lower than after 40%, takes out membrane module, is taken out by residue and mix with ceramic raw material, after shaping, fire ceramic tile.
Embodiment
Embodiment 1
Utilize gram-bacteria to adsorb a method for set heavy metal ions in sewage, step comprises:
The bacterial strain selected is A.nidulans bacterium.Bacterial classification has access to nitrogen substratum after nitrogen-free agar slant activation, at 28-30 DEG C, shaking culture 5d under 120r/min condition, this is cultivated bacterium liquid by 20% inoculum size access without in nitrogen breeze substratum, at 28-30 DEG C, shaking culture 5d under 120r/min condition, obtain gram-bacteria-fly ash composite material used.Add deionized water again, make the aqueous solution of the gram-bacteria-fly ash composite material of concentration 2-6g/L.
There is nitrogen substratum: sucrose 10.0g, yeast extract paste 0.3g, (NH
4)
2sO
40.5g, CaCO
30.5g, MgSO
47H
2o1g, K
2hPO
41.0g, l.0L, pH value is 7.0-7.5 to distilled water.
Nitrogen-free agar: sucrose 5.0g, CaCO
30.1g, MgSO
47H
2o0.5g, FeCl
36H
2o1mg, Na
2hPO
412H
2o5.0g, l.0L, pH value is 7.0-7.5 to distilled water.
Without nitrogen breeze substratum: the first level flour coal ash adding 15g/L in nitrogen-free agar.Chemical reagent used is analytical pure.
Then, what the aqueous solution of this gram-bacteria-fly ash composite material is joined 1L contains Fe
3+, Cu
2+, Cr
2+ionic concn be in the sewage of 20mg/L, after stirring at room temperature process 1h leave standstill 72h, reach adsorption equilibrium, realize dirty water purification.Centrifugal treating is carried out to reaction system, rotating speed 5000r/min, time 15min.Get supernatant liquid after centrifugal, detect each heavy metal ion content with atomic absorption spectrum, find that clearance can reach more than 99.5%.
Embodiment 2
The bacterial strain selected is Rhodopseudomonas palustris (Rhodopseudomonaspalustris).The aqueous solution of this gram-bacteria-fly ash composite material is joined 1L, containing Fe
3+, Ni
2+, Cu
2+each ionic concn is in the sewage of 50mg/L, leaves standstill 72h, reach adsorption equilibrium, realize dirty water purification after stirring at room temperature process 1h.The other the same as in Example 1.Get the supernatant liquor atomic absorption spectrum after process and detect each heavy metal ion content, find Fe
3+the clearance of ion is 98.7%, Ni
2+the clearance of ion is 99.3%, Cu
2+the clearance of ion is 97.4%.
Embodiment 3
The bacterial strain selected is Spherical red antibacterial.The aqueous solution of this gram-bacteria-fly ash composite material is joined 1L, containing Au
3+ionic concn is in the sewage of 50mg/L, leaves standstill 72h, reach adsorption equilibrium, realize dirty water purification after stirring at room temperature process 1h.The other the same as in Example 1.Get the supernatant liquor atomic absorption spectrum after process and detect Au
3+ion content, finds Au
3+ion remaval rate can reach 99%.
Embodiment 4
The bacterial strain selected is A.nidulans bacterium.The aqueous solution of this gram-bacteria-fly ash composite material is joined 1L, containing Au
3+, Pb
2+, Cr
2+each ionic concn is in the sewage of 100mg/L, leaves standstill 120h, reach adsorption equilibrium, realize dirty water purification after stirring at room temperature process 1h.The other the same as in Example 1.Get the supernatant liquor atomic absorption spectrum after process and detect each heavy metal ion content, find Au
3+the clearance of ion is 90.7%, Pb
2+the clearance of ion is 91.3%, Cr
2+the clearance of ion is 90.4%.
Embodiment 5
Take off the turbid liquid of layer, be placed in drainage trap, this drainage trap comprises the membrane module in a direct insertion groove, and this membrane module is made up of polyethylene hollow fiber microfiltration membrane, membrane pore size 0.1 μm, film silk internal diameter 0.27mm, film silk external diameter 0.42mm, membrane area 2m
2, an air bell is set below membrane module, plays water quality mixing effect.Membrane module has water pump pipe, and the water flowed out through going out water pump pipe meets emission standard.Described microfiltration membrane is produced by MIT.
The water ratio of the turbid liquid of the lower floor in drainage trap is lower than after 40%, take out membrane module, residue is taken out, then by weight, get this residue 1 and sandstone 3, dolomite 4, high-calcium fly ass 1.5, phosphatic rock 12, asbestos 8, colemanite 0.8, quartz sand 30, nanometer silicon carbide fiber 4, starch 15, six ring stone 15, nano titanium oxide 0.5, alkali treatment modifying clay 20, stand-by;
The preparation method of described alkali treatment modifying clay is as follows: 1:3:2 takes kaolin, wilkinite, palygorskite clay in mass ratio, adds water to solid content about 30% and mixes, being placed in strong magnetic field circumstance and removing Ferromagnetic Impurities; The Ca (OH) of additional described one of clay raw materials gross weight 0.5 times again
2, mix, put into plumbago crucible and heat 2 hours at the temperature of 110 DEG C and use stainless steel stirring rod to stir, then be washed with distilled water to neutrality, dry, 300 DEG C of calcining 30min, pulverize, cross 240 mesh sieves, stand-by.
Above-mentioned raw materials is mixed, adds softening agent and binding agent, stir, then make the particle that particle diameter is 2mm.Then send into forming machine compression moulding under 80MPa, then the adobe suppressed being delivered in dry kiln and being dried to water content is 1.5%;
By the adobe of drying with the ramp to 1350 DEG C of 15 DEG C/min, insulation 2h, then be cooled to 880 DEG C with the speed of 5 DEG C/min, insulation 2h, 510 DEG C are cooled to again with the speed of 4 DEG C/min, insulation 1h, then with the ramp to 1160 DEG C of 8 DEG C/min, insulation 2.5h, 680 DEG C are cooled to again with the speed of 5 DEG C/min, insulation 1.5h, naturally cools to normal temperature, through edging, packs and obtain ceramic tile finished product.
Should be understood that, the present invention can represent with other the specific form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, the above embodiment of the present invention can only be thought explanation of the present invention and can not limit the present invention, claim of the present invention indicates scope of the present invention, any change in the spirit and implication of claim, all should think to comprise within the scope of the claims.