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CN102139934A - Method for removing heavy metal ions from aqueous solution by utilizing waste bacterial packets from industrial production of flammulina velutipes - Google Patents

Method for removing heavy metal ions from aqueous solution by utilizing waste bacterial packets from industrial production of flammulina velutipes Download PDF

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Publication number
CN102139934A
CN102139934A CN2011100276234A CN201110027623A CN102139934A CN 102139934 A CN102139934 A CN 102139934A CN 2011100276234 A CN2011100276234 A CN 2011100276234A CN 201110027623 A CN201110027623 A CN 201110027623A CN 102139934 A CN102139934 A CN 102139934A
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heavy metal
flammulina velutipes
aqueous solution
bacterium bag
waste
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CN102139934B (en
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李维焕
程显好
高兴喜
马天云
图力古尔
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Ludong University
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Ludong University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

本发明涉及了一种利用金针菇工厂化生产废菌包去除水溶液中重金属离子的方法,其特征在于将金针菇工厂化生产废弃的菌包自然晒干,后烘至恒重;粉碎后过筛得425~600μm的颗粒作为生物吸附剂;称取一定量的生物吸附剂装入盛有重金属溶液的三角锥形瓶中,生物吸附剂用量为6~10g/L,在23~27℃,100~150r/min条件下置于恒温振荡器中振荡吸附3~5h,该吸附剂对水溶液中8~12mg/L的镉和铅的去除率达95以上;对40~60mg/L的锰、镍、铜、锌的去除率分别为80~85%、65~70%、70~75%、75~80%。本发明的生物吸附剂具有成本低,吸附效率高,工艺简单,操作方便的优点,将有广阔的应用前景。The invention relates to a method for removing heavy metal ions in an aqueous solution by utilizing the waste bacterial packs produced by the industrial production of Flammulina velutipes, which is characterized in that the discarded bacterial packs of Flammulina velutipes are naturally dried, and then baked to constant weight; after being crushed, sieved to obtain 425 Particles of ~600μm are used as biosorbent; weigh a certain amount of biosorbent and put it into a conical flask filled with heavy metal solution. Placed in a constant temperature oscillator for oscillating adsorption for 3-5 hours under the condition of /min, the removal rate of the adsorbent for 8-12mg/L cadmium and lead in aqueous solution is above 95; for 40-60mg/L manganese, nickel, copper , Zinc removal rates were 80-85%, 65-70%, 70-75%, 75-80%. The biosorbent of the invention has the advantages of low cost, high adsorption efficiency, simple process and convenient operation, and will have broad application prospects.

Description

A kind of method of utilizing the needle mushroom batch production to produce heavy metal ion in the useless bacterium bag removal aqueous solution
Technical field:
The present invention relates to a kind of method of utilizing biomaterial to remove heavy metal ion in the aqueous solution, be specifically related to a kind of method of utilizing useless bacterium bag in the needle mushroom batch production production process to remove heavy metal ion such as cadmium in the aqueous solution, lead, manganese, nickel, copper, zinc as biological adsorption agent.
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:
R e = ( C 0 - C i ) C 0 × 100 %
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:
R e = ( C 0 - C i ) C 0 × 100 %
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:
R e = ( C 0 - C i ) C 0 × 100 %
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:
R e = ( C 0 - C i ) C 0 × 100 %
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:
R e = ( C 0 - C i ) C 0 × 100 %
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+:
R e = ( C 0 - C i ) C 0 × 100 %
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.

Claims (2)

1.一种利用金针菇工厂化生产废菌包去除水溶液中重金属离子的方法,其特征在于包括如下步骤:1. a method utilizing Flammulina velutipes factory production waste bacteria bag to remove heavy metal ions in aqueous solution, is characterized in that comprising the steps: (1)、将金针菇工厂化生产的废菌包自然晒干,后放入55~65℃的干燥箱中烘至恒重;(1), naturally dry the waste bacteria bag produced by the factory production of Flammulina velutipes, and then put it into a drying oven at 55-65° C. to dry to constant weight; (2)、将烘干的废菌包粉碎后过标准筛,获得425~600μm的颗粒作为生物吸附剂装于自封袋中;(2), crush the dried waste bacteria bag and pass it through a standard sieve to obtain 425-600 μm particles as biosorbents and put them in ziplock bags; (3)、将上述生物吸附剂放入55~65℃干燥箱中烘20~30h;后装入盛有重金属溶液的三角锥形瓶中,生物吸附剂用量6~10g/L,在23~27℃,100~150r/min条件下置于恒温振荡器中振荡吸附3~5h。(3), put the above-mentioned biosorbent into a drying oven at 55-65° C. for 20-30 hours; then put it into a triangular conical flask filled with heavy metal solution, the amount of biosorbent is 6-10 g/L, and the Place in a constant temperature oscillator at 27°C, 100-150r/min, and oscillate for 3-5 hours. 2.根据权利要求1所述的一种利用金针菇工厂化生产废菌包去除水溶液中重金属离子的方法,其特征在于所述的金针菇工厂化生产的废菌包是指由棉籽壳、麸皮、玉米芯按照1∶1∶1比例,按料水比1∶1.2~1.5加水混匀制成培养基,装袋,常压湿热灭菌10-12h,冷却至室温,接种金针菇菌种,经35~45天的发菌及第一潮出菇过程,采收金针菇后废弃的废菌包。2. a kind of method according to claim 1 utilizes the waste bacterium bag of industrial production of Flammulina velutipes to remove heavy metal ion in the aqueous solution, it is characterized in that the waste bacterium bag of described Flammulina velutipes industrial production refers to by cottonseed hull, bran, The corn cob is mixed according to the ratio of 1:1:1, and water is added according to the material-water ratio of 1:1.2~1.5 to make a culture medium, bagged, sterilized by moist heat at normal pressure for 10-12h, cooled to room temperature, inoculated with Flammulina velutipes strains, after 35 ~ 45 days of mushrooming and first tide fruiting process, discarded waste mushroom bags after harvesting Flammulina velutipes.
CN201110027623A 2011-01-21 2011-01-21 A method for removing heavy metal ions in aqueous solution by utilizing the industrial production waste bacteria bag of Flammulina velutipes Expired - Fee Related CN102139934B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521193A (en) * 2013-10-25 2014-01-22 鲁东大学 Method for improving adsorption capacity of enoki mushroom industrialized production waste bacteria bags to heavy metals
CN107088399A (en) * 2017-05-25 2017-08-25 东北农业大学 A kind of preparation method and applications of germ bran biological carbon adsorbent
CN108046854A (en) * 2018-01-06 2018-05-18 天津大学 Mushroom bran for heavy metal adsorption-bacterial manure fermentation recycles coupling device and method

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JP2002018484A (en) * 2000-07-10 2002-01-22 Idemitsu Kosan Co Ltd Treatment method for wastewater containing hardly decomposable substances
CN1541510A (en) * 2003-04-28 2004-11-03 上海浦东天厨菇业有限公司 Culture medium formula of factory run golden mushroom and its preparation process
CN1657429A (en) * 2005-01-28 2005-08-24 湖南大学 Method for removing cadmium-containing industrial wastewater by using mushroom culture medium waste

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002018484A (en) * 2000-07-10 2002-01-22 Idemitsu Kosan Co Ltd Treatment method for wastewater containing hardly decomposable substances
CN1541510A (en) * 2003-04-28 2004-11-03 上海浦东天厨菇业有限公司 Culture medium formula of factory run golden mushroom and its preparation process
CN1657429A (en) * 2005-01-28 2005-08-24 湖南大学 Method for removing cadmium-containing industrial wastewater by using mushroom culture medium waste

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521193A (en) * 2013-10-25 2014-01-22 鲁东大学 Method for improving adsorption capacity of enoki mushroom industrialized production waste bacteria bags to heavy metals
CN107088399A (en) * 2017-05-25 2017-08-25 东北农业大学 A kind of preparation method and applications of germ bran biological carbon adsorbent
CN108046854A (en) * 2018-01-06 2018-05-18 天津大学 Mushroom bran for heavy metal adsorption-bacterial manure fermentation recycles coupling device and method

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