CN104014314A - Bio-adsorbent, preparation method and application - Google Patents

Bio-adsorbent, preparation method and application Download PDF

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Publication number
CN104014314A
CN104014314A CN201410249226.5A CN201410249226A CN104014314A CN 104014314 A CN104014314 A CN 104014314A CN 201410249226 A CN201410249226 A CN 201410249226A CN 104014314 A CN104014314 A CN 104014314A
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adsorption agent
biological adsorption
powder
sodium alginate
preparation
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CN201410249226.5A
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CN104014314B (en
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徐卫华
谢浩
刘云国
简浩
顾岩岭
王达菲
谭小飞
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Hunan University
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Hunan University
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Abstract

The invention belongs to the field of environmental pollution control, and particularly relates to a bio-adsorbent, a preparation method and application. The bio-adsorbent comprises magnetic particles, penicillium simplicissimum powder and sodium alginate, wherein the sodium alginate covers the penicillium simplicissimum powder and the penicillium simplicissimum covers the magnetic particles. The preparation method of the bio-adsorbent specifically comprises the following steps: adding the penicillium simplicissimum powder and the magnetic particles into the sodium alginate solution, and agitating the mixture to obtain a mixed solution; and dropwise adding the mixed solution into a calcium chloride solution to obtain the bio-adsorbent. The penicillium simplicissimum powder and the magnetic particles are used as the adsorbent, sodium alginate is used as an embedding carrier, and the penicillium simplicissimum powder, the magnetic particles and sodium alginate supplement one another, so that heavy metal and/or organic pollutants in water can be effectively removed. The bio-adsorbent has the advantages of high removal efficiency, wide adaptability, strong selectivity, simplicity in operation, low raw material cost, renewability and the like.

Description

A kind of biological adsorption agent, preparation method and purposes
Technical field
The invention belongs to environmental pollution improvement field, be specifically related to a kind of biological adsorption agent, preparation method and purposes.
Background technology
At present, along with industrial expansion, the waste gas, the waste water that in coking, oil refining, petrochemical industry, fertilizer and pesticide, manufacture plastics, fuel combustion process, produce enter in environment, cause the combined pollution of heavy metal and organic pollution, cause the day by day severe of production, living environment, people are extremely urgent for the improvement demand of metal and Organic Pollution.
The method of processing at present heavy metal or organic wastewater mainly contains: chemical precipitation and charcoal absorption, ion-exchange and ozone oxidation, electrochemical treatments, reverse osmosis membrane technology, distillation, electrodialysis etc., these processing methods have obtained good effect to a certain extent, but ubiquity secondary pollution, removal heavy metal or organic pollution that simultaneously can only be single can not be removed two kinds of pollutants simultaneously.
Biological adsorption is a kind of means of as adsorbent, water body being processed by organism or derivatives thereof.Biological method for organic matter degradation mainly adopts bacterial degradation at present, and because bacterium is to heavy metal sensitive, therefore, for existing, the water treatment effect of heavy metal pollution and the dual pollution of organic pollution is unsatisfactory.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of to Heavy Metals in Waters ion and/or organic pollutant removal rate is high, applicability is wide, selective strong, simple to operate, cost of material is low, reproducible biological adsorption agent and its production and use.
For solving the problems of the technologies described above, the invention provides a kind of biological adsorption agent, biological adsorption agent comprises magnetic particle, simple Penicillium notatum powder, sodium alginate, and sodium alginate is coated on simple Penicillium notatum powder, and simple Penicillium notatum powder is coated on magnetic particle.In biological adsorption agent, the mass ratio of magnetic particle, simple Penicillium notatum powder, sodium alginate is 1: 5: 20.Magnetic particle is preferably ferriferrous oxide nano-particle; Ferriferrous oxide nano-particle passes through Fe 2+/ Fe 3+mixed solution be greater than at pH with ammonia spirit under 9 condition and react and obtain.
The present invention also provides a kind of preparation method of biological adsorption agent, comprises the steps,
S1: simple Penicillium notatum powder and magnetic particle are joined in sodium alginate soln, stir and obtain mixed liquor;
S2: mixed liquor is added drop-wise to and obtains biological adsorption agent in calcium chloride solution.
Further, S2 step also comprises separating step, and biological adsorption agent is standing, filters and obtains filter residue, by residue washing, the dry biological adsorption agent sterling that obtains.Mixed liquor is preferably by peristaltic pump and capillary and is added drop-wise in calcium chloride solution.The concentration of calcium chloride is preferably 0.1~0.5mol/L.
As the total technical conceive of the present invention, the present invention also provides biological adsorption agent that the preparation method of aforementioned biological adsorption agent or aforementioned biological adsorption agent prepares in the purposes of removing Heavy Metals in Waters ion and/or organic pollution, comprise the steps: biological adsorption agent to join in the water body that contains heavy metal ion and/or organic pollution, at pH, be 5, temperature is 35 ℃~40 ℃, rotating speed is the 48h that vibrates under the condition of 150rpm, separation.
Creativeness of the present invention is:
Biological adsorption agent provided by the invention comprises simple Penicillium notatum powder, magnetic particle and sodium alginate.There is the functional group of Adsorption of Heavy Metal Ions in letter Penicillium notatum flour cell wall surface, in the situation that magnetic particle exists, has strengthened the absorption of simple Penicillium notatum powder to heavy metal, has unit specific area large, and adsorption efficiency is high, simple operation and other advantages.Sodium alginate is as embedding carrier, in its molecular structure, there is carboxyl, there is the characteristics such as hydrophily is strong, soft, cheap, stable in properties, be suitable for the good embedding carrier as simple Penicillium notatum powder, sodium alginate can generate insoluble alginates in heavy metal solution simultaneously, can further improve the adsorption efficiency of heavy metal, and be convenient to the separation of biological adsorption agent and the parsing of heavy metal and/or organic pollution.
The invention has the beneficial effects as follows:
(1) biological adsorption agent provided by the invention comprises simple Penicillium notatum powder, magnetic particle and sodium alginate, three kinds of compositions complement each other, making that biological adsorption agent is higher to the adsorption efficiency of heavy metal and/or organic pollution, resolution factor is stronger, is a kind of good regenerable sorbent.Initial in water body is 50 ± 0.02mg/l containing cadmium concentration, with biological adsorption agent of the present invention, at pH, is 5, and temperature is that after processing 48h under the condition of 35 ℃~40 ℃, concentration is reduced to 6.125mg/l, and clearance reaches 87.75%; In water body, initial phenol concentration is 25mg/l, with biological adsorption agent of the present invention, at pH, is 5, and temperature is that after processing 48h under the condition of 35 ℃~40 ℃, concentration is reduced to 1.322mg/l, and clearance reaches 94.71%.After filtering biological adsorbent, with 100ml, the hydrochloric acid solution of 1mol/l is in 37 ℃, and the desorb 24h that vibrates under 150rpm condition, reaches 91.34% to the desorption efficiency of cadmium, and Pyrogentisinic Acid's desorption efficiency reaches 92.13%.
(2) biological adsorption agent provided by the invention, adopts ferriferrous oxide nano-particle as magnetic particle, better to the heavy metal adsorption effect in water body.
(3) preparation method of biological adsorption agent provided by the invention, the mixed solution of simple Penicillium notatum powder, magnetic particle and sodium alginate is added drop-wise in calcium chloride solution, make sodium alginate that simple Penicillium notatum powder and magnetic particle embedding are got up to form embedding thing, and precipitate, be convenient to the separation of biological adsorption agent.Aforesaid mixed liquor is added drop-wise in described calcium chloride solution by peristaltic pump and capillary simultaneously, makes the embedding thing particle diameter of formation more even.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.
Fig. 1 is the structural representation of biological adsorption agent of the present invention.
Fig. 2 is the photo of biological adsorption agent of the present invention under electron microscope.
Fig. 3 is the exterior view of biological adsorption agent of the present invention under electron microscope.
Fig. 4 is preparation and the purposes method flow diagram of biological adsorption agent of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The simple Penicillium notatum powder (Penicillium simplicissimum) adopting in following examples, derive from Chinese industrial microorganism fungus kind preservation center (China Center of Industrial Culture Collection, CICC), CICC is numbered 40667.
Embodiment 1
Referring to Fig. 1: as the preferred embodiments of the present invention, a kind of biological adsorption agent is provided, comprise magnetic particle 01, simple Penicillium notatum powder 02, sodium alginate 03, wherein the mass ratio of magnetic particle 01, simple mould 02, sodium alginate 03 is 1: 5: 20, sodium alginate 03 is coated on simple mould 02, and simple mould 02 is coated on magnetic particle 01.
Wherein magnetic particle 01 is Fe 3o 4nano particle.
Embodiment 1 is only the preferred embodiments of the present invention, and the mass ratio of magnetic particle 01, simple Penicillium notatum powder 02, sodium alginate 03 is not limited in 1: 5: 20 in the present invention, and three's quality all can be implemented under any ratio.
Fig. 2 is the biological adsorption agent of embodiment 1 shape under electron microscope.Fig. 3 is the biological adsorption agent of embodiment 1 surface texture under electron microscope.
Embodiment 2
As shown in Figure 4, biological adsorption agent preparation method of the present invention specifically comprises the steps:
1) preparation of simple Penicillium notatum powder 02: by fluid nutrient medium (aforementioned liquids medium component is as shown in table 1) sterilizing 20min under 115 ℃ of conditions, be then cooled to room temperature under aseptic condition.Simple mould thalline is inoculated in aforementioned sterilizing cooling fluid nutrient medium, in shaken cultivation case, take temperature as 28 ℃, rotating speed is 150r/min shaken cultivation 48h.After shaken cultivation finishes, the simple mould in the growth period of taking the logarithm filters with silk, gets deionized water washing 3 times for filter residue, then scrapes the cell of staying on silk, clays into power and obtain simple Penicillium notatum powder 02 after freeze drying.
Table 1 Liquid Culture based component
2) Fe 3o 4the preparation of particle solution: the FeSO that takes 11.1208g 47H 2the FeCl of O and 10.8116g 36H 2o, is dissolved in respectively in 1L ultra-pure water, the Fe that the molar concentration that is made into Fe is 0.04mol/L 2+/ Fe 3+mixed solution one.At Fe 2+/ Fe 3+mixed solution one in drip a small amount of H +, prevent Fe 2+and Fe 3+be hydrolyzed.Get 200ml, the NH of concentration 100ml/L 3h 2o joins in there-necked flask, stirs NH 3h 2o.Get the Fe of 200ml 2+/ Fe 3+mixed solution one join NH 3h 2in O, rapid stirring, then regulates pH value with the NaOH of 0.1M, makes pH value be greater than 9 and obtains mixed solution two (in the present embodiment, the pH of solution two is 9.2).Mixed solution two is reacted to 1h at normal temperatures, then with ultra-pure water, repeatedly rinse to neutrality, obtain tri-iron tetroxide (Fe 3o 4) nano particle.In 500ml ultra-pure water, add Fe 3o 4nano particle, is settled to 500ml, obtains Fe 3o 4nano-particle solution.
3) preparation of biological adsorption agent: the Fe that is 6.7mg/ml by the cryodesiccated simple Penicillium notatum powder 01 of 0.5g and 15ml concentration 3o 4nano-particle solution joins 50mL, mass concentration is in sodium alginate 03 solution of 4% (sodium alginate that is about to 4g is dissolved in the water of 100mL), obtains mixed liquor.Aforementioned mixed liquor is fully stirred, then the capillary that is 2mm with peristaltic pump and aperture is added drop-wise to by mixed liquor the CaCl that concentration is 0.25mol/L 2in solution, form embedding thing.By after aforementioned embedding thing standing over night, cross leaching filter residue.By aforementioned filter residue deionized water rinsing, dry up and obtain biological adsorption agent.
CaCl in embodiment 2 2the concentration of solution is preferably 0.25mol/L, in the present invention CaCl 2the concentration of solution all can be implemented between 0.1~0.5mol/L.
Embodiment 3
1) biological adsorption agent absorption: the biological adsorption agent of 1.37g embodiment 1 (biological adsorption agent of 1.37g is 0.1g 65 ℃ of dried constant weights) is joined to 100ml, the Cd that concentration is 50mg/L 2+, in the phenol composite solution that concentration is 25mg/L, at pH, be 5, temperature is 35 ℃~40 ℃, oscillation treatment 48h under the condition that rotating speed is 150rpm, Cd 2+concentration is reduced to 6.125mg/L, and phenol concentration is reduced to 1.322mg/L, and clearance is respectively 87.75%, 94.71%.Filtering biological adsorbent, by biological adsorption agent 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, desorb 24h under the oscillating condition that rotating speed is 150rpm, to Cd 2+desorption efficiency reach 91.34%, Pyrogentisinic Acid's desorption efficiency reaches 92.13%.
Embodiment 4
1.37g biological adsorption agent (biological adsorption agent of 1.37g is 0.1g 65 ℃ of dried constant weights) is joined to 100ml, concentration is in 25mg/L phenol solution, at pH, be 5, temperature is 35 ℃~40 ℃, rotating speed is oscillation treatment 48h under the condition of 150rpm, phenol concentration is reduced to 9.616mg/L, and the clearance of phenol reaches 61.53%.Filtering biological adsorbent, by biological adsorption agent 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, desorb 24h under the oscillating condition that rotating speed is 150rpm, the desorption efficiency of phenol reaches 85.87%.
Embodiment 5
1.37g biological adsorption agent (biological adsorption agent of 1.37g is 0.1g 65 ℃ of dried constant weights) is joined to 100ml, the cadmium (Cd that concentration is 50mg/L 2+) in solution, at pH, be 5, temperature is 35 ℃~40 ℃, oscillation treatment 48h under the condition that rotating speed is 150rpm, Cd 2+cd in solution 2+concentration is reduced to 4.743mg/L, Cd 2+clearance reaches 90.51%.Filtering biological adsorbent, by biological adsorption agent 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, desorb 24h under the oscillating condition that rotating speed is 150rpm, Cd 2+desorption efficiency reach 88.53%.
Embodiment 6
1.37g biological adsorption agent (biological adsorption agent of 1.37g is 0.1g 65 ℃ of dried constant weights) is joined to 100ml, the Pb that concentration is 50mg/L 2+in solution, at pH, be 5, temperature is 35 ℃~40 ℃, oscillation treatment 48h under the condition that rotating speed is 150rpm, Pb 2+pb in solution 2+concentration is reduced to 11.84mg/l, Pb 2+clearance reaches 76.32%.Filtering biological adsorbent, by biological adsorption agent 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, desorb 24h under the oscillating condition that rotating speed is 150rpm, Pb 2+desorption efficiency reach 89.32%.
Embodiment 7
1.37g biological adsorption agent (biological adsorption agent of 1.37g is 0.1g 65 ℃ of dried constant weights) is joined to 100ml, the Cr that concentration is 50mg/L 6+in solution, at pH, be 5, temperature is 35 ℃~40 ℃, oscillation treatment 48h under the condition that rotating speed is 150rpm, Cr 6+cr in solution 6+concentration is reduced to 9.25mg/l, Cr 6+clearance reaches 81.5%.Filtering biological adsorbent, by biological adsorption agent 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, desorb 24h under the oscillating condition that rotating speed is 150rpm, Cr 6+desorption efficiency reach 94.56%.
Comparative example 1
The simple Penicillium notatum powder that 0.1g is dried to constant weight joins 100ml, the Cd that concentration is 50mg/L 2+, concentration is in 25mg/L phenol composite solution, at pH, is 5, temperature is 35 ℃~40 ℃, oscillation treatment 48h under the condition that rotating speed is 150rpm, Cd 2+concentration is reduced to 12.385mg/L, and phenol concentration is reduced to 4.821mg/L, and clearance is respectively 75.23%, 80.72%.Filter simple Penicillium notatum powder, by simple Penicillium notatum powder 100ml, the hydrochloric acid solution that concentration is 1mol/L is 37 ℃ in temperature, and desorb 24h under the oscillating condition that rotating speed is 150rpm, to Cd 2+desorption efficiency reach 88.64%, Pyrogentisinic Acid's desorption efficiency reaches 85.48%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various modifications and variations.Within every the spirit and principles in the present invention, any modification of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.

Claims (10)

1. a biological adsorption agent, is characterized in that, comprises magnetic particle, simple Penicillium notatum powder, sodium alginate, and described sodium alginate is coated on described simple Penicillium notatum powder, and described simple Penicillium notatum powder is coated on described magnetic particle.
2. biological adsorption agent according to claim 1, is characterized in that, in described biological adsorption agent, the mass ratio of magnetic particle, simple Penicillium notatum powder, sodium alginate is 1: 5: 20.
3. biological adsorption agent according to claim 1 and 2, is characterized in that, described magnetic particle is ferriferrous oxide nano-particle.
4. biological adsorption agent according to claim 3, is characterized in that, described ferriferrous oxide nano-particle passes through Fe 2+/ Fe 3+mixed solution be greater than at pH with ammonia spirit under 9 condition and react and obtain.
5. a preparation method for the biological adsorption agent described in any one in claim 1 to 4, is characterized in that, comprises the steps:
S1: simple Penicillium notatum powder and magnetic particle are joined in sodium alginate soln, stir and obtain mixed liquor;
S2: described mixed liquor is added drop-wise to and obtains described biological adsorption agent in calcium chloride solution.
6. preparation method according to claim 5, is characterized in that, described S2 also comprises separating step: described biological adsorption agent is standing, and filter and obtain filter residue, by described residue washing, the dry biological adsorption agent sterling that obtains.
7. according to the preparation method described in claim 5 or 6, it is characterized in that, described in described S2, mixed liquor is added drop-wise in described calcium chloride solution by peristaltic pump and capillary.
8. according to the preparation method described in claim 5 or 6, it is characterized in that, the concentration of described calcium chloride is 0.1~0.5mol/L.
9. the biological adsorption agent that a biological adsorption agent as described in any one in claim 1 to 4 or the preparation method as described in any one in claim 5 to 8 prepare is in the purposes of removing Heavy Metals in Waters ion and/or organic pollution.
10. purposes according to claim 9, is characterized in that, comprises the steps: described biological adsorption agent to join in the water body that contains heavy metal ion and/or organic pollution, at pH, be 5, temperature is 35 ℃~40 ℃, the 48h that vibrates under the condition that rotating speed is 150rpm, separation.
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Cited By (7)

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CN105294263A (en) * 2015-10-30 2016-02-03 全椒县琪悦家庭农场 Nitrogen-fixing microorganism compound fertilizer and preparation method thereof
CN108176370A (en) * 2017-12-22 2018-06-19 苏州纳贝通环境科技有限公司 A kind of preparation method of magnetic gel heavy metal absorbent
CN108503039A (en) * 2018-03-15 2018-09-07 湖南大学 A method of utilizing Penicillium notatum magnetic nanometer composite material degradation Atrazine
CN110639476A (en) * 2019-08-20 2020-01-03 华南农业大学 Heavy metal adsorbent based on alkaline residue recycling and preparation method and application thereof
CN110902849A (en) * 2020-02-10 2020-03-24 广州赛太特生物医学科技有限公司 Method for treating industrial wastewater by using biological adsorbent
CN111729624A (en) * 2020-07-08 2020-10-02 江苏科技大学 Preparation and application method of biogel for environmental remediation
CN112745858A (en) * 2020-12-15 2021-05-04 广东华南环保产业技术研究院有限公司 Persistent organic pollutant contaminated site repairing agent and preparation method thereof

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CN101314123A (en) * 2008-07-17 2008-12-03 湖南大学 Magnetic biological adsorption agent and preparation method thereof
CN102151551A (en) * 2011-01-25 2011-08-17 湖南大学 Heavy metal biological absorbent, preparation method thereof and application in treating cadmium-containing wastewater
CN102614839A (en) * 2012-04-10 2012-08-01 湖南大学 Compound magnetic biological adsorbent and preparation method for same

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US6416671B1 (en) * 1993-06-08 2002-07-09 Cortex Biochem, Inc. Methods for removing hazardous organic molecules from liquid waste
CN101314123A (en) * 2008-07-17 2008-12-03 湖南大学 Magnetic biological adsorption agent and preparation method thereof
CN102151551A (en) * 2011-01-25 2011-08-17 湖南大学 Heavy metal biological absorbent, preparation method thereof and application in treating cadmium-containing wastewater
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105294263A (en) * 2015-10-30 2016-02-03 全椒县琪悦家庭农场 Nitrogen-fixing microorganism compound fertilizer and preparation method thereof
CN108176370A (en) * 2017-12-22 2018-06-19 苏州纳贝通环境科技有限公司 A kind of preparation method of magnetic gel heavy metal absorbent
CN108503039A (en) * 2018-03-15 2018-09-07 湖南大学 A method of utilizing Penicillium notatum magnetic nanometer composite material degradation Atrazine
CN110639476A (en) * 2019-08-20 2020-01-03 华南农业大学 Heavy metal adsorbent based on alkaline residue recycling and preparation method and application thereof
CN110902849A (en) * 2020-02-10 2020-03-24 广州赛太特生物医学科技有限公司 Method for treating industrial wastewater by using biological adsorbent
CN111729624A (en) * 2020-07-08 2020-10-02 江苏科技大学 Preparation and application method of biogel for environmental remediation
CN112745858A (en) * 2020-12-15 2021-05-04 广东华南环保产业技术研究院有限公司 Persistent organic pollutant contaminated site repairing agent and preparation method thereof

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