Background technology:
How administering heavy metal polluted waste water is the outstanding problem that current environmental protection work faces.At present aspect the heavy metal wastewater thereby of handling lower concentration, mainly contain chemical precipitation method, ion exchange method, chemistry redox method, reverse osmosis method, ultra-filtration method, active carbon absorption technology etc., its cost height, low, the generation secondary pollution of efficient, a little less than the regenerative power, regeneration back adsorptive power does not have obvious raising.Biosorption process particularly aspect the heavy metal wastewater thereby of handling lower concentration, has very wide prospect as a kind of emerging treatment technology.Compare with traditional treatment method (chemical precipitation method, ion exchange method, chemistry redox method, reverse osmosis method, ultra-filtration method, active carbon absorption technology etc.), the biosorption process cost is low, efficient is high, do not produce secondary pollution, regenerative power is strong, and regeneration back adsorptive power does not have obvious reduction.
Radicula byssoidea shows the ability of very strong absorption heavy metal.The mycelium of Auricularia polytricha (Mout) Sacc. (Auriculariapolytricha), Phanerochaete chrysosporium (Phanerochaete chrysosporiu), red suede lid bolete (Gomphidiusvi scidus), rivet mushroom (Gomphidius viscidus), bush mycorrhizal fungi (Glomus mosseae) etc. all can be removed the heavy metal in the aqueous solution effectively.The industrial fermentation waste material black-koji mould filament of inactivation has very strong adsorptive power to the nickel in the aqueous solution, calcium, iron and chromium.Agricultural waste materials, especially rich cellulose, have very strong biological adsorptive power.Rice bran, stalk, wheat bran, wheat husk, Pericarppium arachidis hypogaeae, soybean peel, Exocarpium cocois (Cocos nucifera L), nut-shell, cotton seed hulls, useless tealeaves, corn cob, bagasse, Pericarpium Mali pumilae, beet pulp, Sunflower Receptacle stem, cotton straw etc. are all attempted being used to adsorb heavy metal.
Edible fungus industrial production has become the direction of China's mushroom industry development.The Edible Fungus's Industrialized Production in China kind mainly is white gold needle mushroom (Flammulina velutiper) at present, and its turnout accounts for more than 60% of all edible fungus industrial products.5 tons white gold needle mushroom factory of a daily output just can produce the useless bacterium of about 5-6 ton every day and wrap, and quantum of output is huge.Therefore, the processing of useless bacterium bag is a problem of needing solution badly.At present, the needle mushroom batch production is produced useless bacterium bag and is mainly used to do fertilizer, fodder additives, biogas fermentation raw material or is used for planting other mushroom again, does not see the report used as the heavy metal ion biological adsorption agent.
Batch production is produced needle mushroom and is only gone out a damp mushroom, these the culture material of cotton seed hulls, wheat bran and corn cob in the useless bacterium bag after comprising fermentation, also contain a large amount of golden mushroom myceliums, specific surface area is huge, but the functional group of containing multiple bonding heavy metal ion, these all make it become possibility as biological adsorption agent.
The new purposes of the useless bacterium bag of exploitation Biosorbent for heavy metals to handle heavy metal-containing waste water, is " treatment of wastes with processes of wastes against one another ", " turning waste into wealth ", and the recycling that wraps for the processing and the useless bacterium of heavy metal-containing waste water provides new approach.This measure has taken into account environment and economic benefit, will have broad application prospects!
Summary of the invention:
The object of the present invention is to provide a kind of cost low, the adsorption efficiency height, technology is simple, and the easy to operate useless bacterium bag that utilizes the needle mushroom batch production to produce is removed the method for heavy metal ion in the aqueous solution.
Purpose of the present invention can reach by following measure: a kind of method of utilizing the needle mushroom batch production to produce heavy metal ion in the useless bacterium bag removal aqueous solution is characterized in that comprising the steps:
(1), useless bacterium bag nature that the needle mushroom batch production is produced dries, after put into 55~65 ℃ loft drier and dry to constant weight;
(2), the useless bacterium bag that will dry pulverizes the back and crosses standard sieve, the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent;
(3), above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; After pack in the triangular pyramidal bottle that fills heavy metal solution, biological adsorption agent consumption 6~10g/L at 23~27 ℃, places constant temperature oscillator vibration absorption 3~5h under 100~150r/min condition.
In order further to realize purpose of the present invention, the useless bacterium bag that described needle mushroom batch production is produced is meant by cotton seed hulls, wheat bran, corn cob according to 1: 1: 1 ratio, add the water mixing by material-water ratio 1: 1.2~1.5 and make substratum, pack, normal pressure moist heat sterilization 10-12h is cooled to room temperature, inoculation needle mushroom bacterial classification, the bacterium and the first damp fruiting process through 35~45 days, the useless bacterium bag of depleted after the needle mushroom of gathering.
The present invention can produce following positively effect compared with the prior art:
1, batch production production needle mushroom only goes out a damp mushroom, these culture materials of cotton seed hulls, wheat bran and corn cob in the useless bacterium bag after comprising fermentation, also contain a large amount of golden mushroom myceliums, useless bacterium bag specific surface area is huge, but the functional group of containing multiple bonding heavy metal ion, the adsorption efficiency height, the cadmium of 8~12mg/L and plumbous clearance reach more than 95% in testing the aqueous solution; Clearance to the manganese of 40~60mg/L, nickel, copper, zinc is respectively 80~85%, 65~70%, 70~75%, 75~80%.
2, useless bacterium bag biological adsorption agent is produced in the needle mushroom batch production, the adsorption efficiency height, and technology is simple, and is easy to operate, and cost is low.
3, this method has promptly been widened the range of choice of biological adsorption agent, has made full use of the agriculture production waste again---and useless bacterium bag is produced in the needle mushroom batch production, is " treatment of wastes with processes of wastes against one another ", " turning waste into wealth ".This measure has taken into account environment and economic benefit, will have broad application prospects!
Embodiment:
Below the specific embodiment of the present invention is elaborated:
Raw material is prepared: the needle mushroom batch production is produced useless bacterium bag from Shandong Province highly dense curry favour moral agricultural-food company limited, be meant by cotton seed hulls, wheat bran, corn cob according to 1: 1: 1 ratio, add the water mixing by material-water ratio 1: 1.2~1.5 and make substratum, pack, normal pressure moist heat sterilization 10-12h is cooled to room temperature, inoculation needle mushroom bacterial classification, the bacterium and the first damp fruiting process through 35~45 days, the useless bacterium bag of depleted after the needle mushroom of gathering.From the useless bacterium bag of the needle mushroom of other producer, also can adopt as long as the culture material composition is the same.
Embodiment 1:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.3g waste bacterium bag grain packed into to be filled in the 150ml triangular pyramidal bottle of 50ml, pH=6,10mg/LCd (NO3) 24H2O solution, and promptly the sorbent material consumption is 6g/L, 23 ℃, places constant temperature oscillator vibration absorption 4h under the 120r/min condition.Afterwards, high speed centrifugation is got supernatant liquor, Cd in the supernatant liquor
2+Concentration measure with flame atomic absorption spectrophotometer (GBC932-AA).Useless bacterium bag biological adsorption agent is to Cd
2+Clearance Re calculate by following formula:
In the formula, R
eClearance for heavy metal ion; C
0Initial concentration (mg/L) for heavy metal ion in the solution; C
eConcentration (mg/L) for heavy metal ion in the supernatant liquor after the adsorption equilibrium.
As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production reaches 96.5% to the clearance of the cadmium of 10mg/L in the aqueous solution.
Embodiment 2:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.4g waste bacterium bag grain packed into fill 50ml, pH=5,10mg/L Pb (NO
3)
2In the 150ml triangular pyramidal bottle of solution, promptly the sorbent material consumption is 8g/L, 25 ℃, places constant temperature oscillator vibration absorption 3h under the 120r/min condition.Afterwards, high speed centrifugation is got supernatant liquor, Pb in the supernatant liquor
2+Concentration measure with flame atomic absorption spectrophotometer (GBC932-AA).Useless bacterium bag biological adsorption agent is to Pb
2+Clearance R
eCalculate by following formula:
In the formula, R
eClearance for heavy metal ion; C
0Initial concentration (mg/L) for heavy metal ion in the solution; C
eConcentration (mg/L) for heavy metal ion in the supernatant liquor after the adsorption equilibrium.
As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production can reach 95.9% to the clearance of the lead of 10mg/L in the aqueous solution.
Embodiment 3:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.5g waste bacterium bag grain packed into fill 50ml, pH=5,50mg/L MnSO
4H
2In the 150ml triangular pyramidal bottle of O solution, promptly the sorbent material consumption is 10g/L, 25 ℃, places constant temperature oscillator vibration absorption 5h under the 120r/min condition.Afterwards, high speed centrifugation is got supernatant liquor, Mn in the supernatant liquor
2+Concentration measure with flame atomic absorption spectrophotometer (GBC932-AA).Useless bacterium bag biological adsorption agent is to Mn
2+Clearance R
eCalculate by following formula:
In the formula, R
eClearance for heavy metal ion; C
0Initial concentration (mg/L) for heavy metal ion in the solution; C
eConcentration (mg/L) for heavy metal ion in the supernatant liquor after the adsorption equilibrium.
As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production is 81.2% to the clearance of the manganese of 50mg/L in the aqueous solution.
Embodiment 4:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.4g waste bacterium bag grain packed into fill 50ml, pH=5,50mg/L NiSO
46H
2In the 150ml triangular pyramidal bottle of O solution, promptly the sorbent material consumption is 8g/L, 27 ℃, place constant temperature oscillator vibration absorption 4h under the 120r/min condition, and each handles triplicate.Afterwards, high speed centrifugation is got supernatant liquor, Ni in the supernatant liquor
2+Concentration measure with flame atomic absorption spectrophotometer (GBC932-AA).Useless bacterium bag biological adsorption agent is to Ni
2+Clearance R
eCalculate by following formula:
In the formula, R
eClearance for heavy metal ion; C
0Initial concentration (mg/L) for heavy metal ion in the solution; C
eConcentration (mg/L) for heavy metal ion in the supernatant liquor after the adsorption equilibrium.As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production is 68.7% to the clearance of the nickel of 50mg/L in the aqueous solution.
Embodiment 5:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is loaded in the valve bag as biological adsorption agent.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.45g waste bacterium bag grain packed into fill 50ml, pH=5,50mg/L CuSO
45H
2In the 150ml triangular pyramidal bottle of O solution, promptly the sorbent material consumption is 9g/L, 25 ℃, place constant temperature oscillator vibration absorption 4h under the 120r/min condition, and each handles triplicate.Afterwards, high speed centrifugation is got supernatant liquor, Cu in the supernatant liquor
2+Concentration measure with flame atomic absorption spectrophotometer (GBC932-AA).Useless bacterium bag biological adsorption agent is to Cu
2+Clearance R
eCalculate by following formula:
In the formula, Re is the clearance of heavy metal ion; C0 is the initial concentration (mg/L) of heavy metal ion in the solution; Ce is the concentration (mg/L) of heavy metal ion in the supernatant liquor after the adsorption equilibrium.
As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production is 72.3% to the clearance of the copper of 50mg/L in the aqueous solution.
Embodiment 6:
1, the needle mushroom batch production is produced useless bacterium bag and dries naturally earlier, after put into 55~65 ℃ loft drier and dry to constant weight;
2, the useless bacterium bag that will dry is pulverized the back and is crossed standard sieve, and the particle that obtains 425~600 μ m is done
For biological adsorption agent is loaded in the valve bag.
3, above-mentioned biological adsorption agent is put into 55~65 ℃ of loft drier and dried by the fire 20~30h; The 0.35g waste bacterium bag grain packed into fill in the 150ml triangular pyramidal bottle of 50ml, pH=5,50mg/L ZnSO47H2O solution, be that the sorbent material consumption is 7g/L, 25 ℃, place constant temperature oscillator vibration absorption 4h under the 120r/min condition, each handles triplicate.Afterwards, high speed centrifugation is got supernatant liquor, and the concentration of Zn2+ is measured with flame atomic absorption spectrophotometer (GBC932-AA) in the supernatant liquor.Useless bacterium bag biological adsorption agent calculates by following formula the clearance Re of Zn2+:
In the formula, R
eClearance for heavy metal ion; C
0Initial concentration (mg/L) for heavy metal ion in the solution; C
eConcentration (mg/L) for heavy metal ion in the supernatant liquor after the adsorption equilibrium.As calculated, heavy metal ion biological adsorption agent provided by the invention---the useless bacterium bag of needle mushroom batch production production is 76.3% to the clearance of the zinc of 50mg/L in the aqueous solution.