CN102921388A - Heavy metal biological adsorbent and preparation method thereof - Google Patents
Heavy metal biological adsorbent and preparation method thereof Download PDFInfo
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- CN102921388A CN102921388A CN2012104489624A CN201210448962A CN102921388A CN 102921388 A CN102921388 A CN 102921388A CN 2012104489624 A CN2012104489624 A CN 2012104489624A CN 201210448962 A CN201210448962 A CN 201210448962A CN 102921388 A CN102921388 A CN 102921388A
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Abstract
The invention discloses a heavy metal biological adsorbent and a preparation method of the heavy metal biological adsorbent. The biological adsorbent takes boletes as main ingredients and is prepared in the following steps that the boletes of various types and parts are selected, cleaned, separated, dried, smashed, sieved and the like. The biological adsorbent can be used for specific adsorption of heavy metal in various media, and is simple and fast in technology, low in equipment requirement and cost, simple and convenient to use, and high in adsorption efficiency.
Description
Technical field
The invention belongs to the heavy metal absorbent field, be specifically related to a kind of Biosorbent for heavy metals that is mainly consisted of by macro fungi.
Background technology
Along with the impact of industrial expansion and mankind's activity, the situation of heavy metal pollution becomes increasingly serious.Each heavy metal species that the processes such as metal smelt, mining, wastewater from chemical industry and combustion of fossil fuel that are accompanied by produce enters atmosphere, water and soil.Different from organic pollution, heavy metal can not directly be degraded to nontoxic material by biology under field conditions (factors) and thoroughly be eliminated, even the heavy metal that has can form the combining form of indissoluble in soil, in case but soil environment changes, a part of heavy metal can again discharge again and geobiont is caused murder by poisoning.Heavy metal pollution has the feature of disguise, irreversibility and chronicity, is a kind of chronic pollution of the property accumulated.
Biological prosthetic heavy metal-polluted dyeing technique is as rapid rising in recent years and study more a kind of method, have be easy to implement, small investment and the advantage little to environmental perturbation.Bolete is as a kind of Applying Ectomycorrhizal Fungi, the ability that itself has very strong accumulation heavy metal, show that not only heavy metal concentration is very high in the soil somatomedin, be also included within when heavy metal concentration is low in the medium that the concentration of heavy metal also can exceed the soil manyfold in the mycelium.Scholars begin to propose to utilize bolete to the high accumulation ability of heavy metal, the bolete mycelium that is fit to the contaminated area growth is inoculated in the heavy metal hyperaccumulative plant, the cogeneration system that utilizes bolete and plant to form carries out the heavy-metal contaminated soil reparation, the normal growth of plant not only can be ensured, the heavy metal pollution remediation efficiency can also be improved.But the method is mainly used in soil remediation, can't effectively repair contaminated other media, and need to plant bolete, exists complicated operation, time cycle long, repairs the problems such as speed is low.In addition, also there are some that the bolete mycelium is carried out cultured in vitro, and by its suction-operated to heavy metal, remove the heavy metal in the water.The method need to be carried out the cultured in vitro of long period to obtain enough mycelium, also has complicated operation, and cost is high, the problems such as length consuming time.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of making simple, fast, easy to use, cost is low and applicable to the Biosorbent for heavy metals of medium.
The invention provides a kind of novel Biosorbent for heavy metals, its active ingredient is made of the bolete powder.
As optimal way, bolete powder diameter of the present invention is the 50-200 micron.
As optimal way, bolete of the present invention is selected any one in black suede lid bolete, cepe or the light brown suede lid bolete, and selects black suede lid bolete best for the adsorption effect of lead or cadmium.
As optimal way, bolete of the present invention is selected at least one part in cap, tube or three parts of stem of bolete.
As optimal way, according to the difference of the kind of the heavy metal of required absorption, the powder at three positions of described three kinds of boletes is mixed according to different ratios.
As optimal way, when being used for the absorption of lead or cadmium, bolete powder of the present invention is made by the cap of black suede lid bolete.
As optimal way, bolete powder of the present invention is pressed into cake.Concrete grammar adds a small amount of polyvinyl alcohol and makes binding agent for getting the bolete powder, mixes to be placed in the mould, adopts hand-operated hydraulic press 10 seconds of pressurize under 0.5 MPa, and sample is withdrawed from from mould.
As optimal way, bolete powder of the present invention is supported on and makes the bead adsorbent on the carrier.The weight proportion of the component that described bead adsorbent contains is: 7 parts of polyvinyl alcohol, 2 parts of sodium alginates, 1 part in calcium chloride, 4 parts in bacterium powder.As optimal way, also can sieve described bead adsorbent, choose the bead of diameter in 1-5 mm scope as adsorbent.
In addition, Biosorbent for heavy metals of the present invention can also select the edible bolete commodity to add man-hour discarded part as the raw material of making the bolete powder.
The present invention also provides a kind of preparation method of Biosorbent for heavy metals, may further comprise the steps:
(1) cleans: the bolete that gathers is cleaned with deionized water;
(2) drying: the sample after will cleaning places thermostatic drying chamber, dries to constant weight under 50 ± 2 ℃;
(3) pulverize: place after cooling pulverizer to pulverize, be made into dry bacterium powder;
(4) sieve: with sub-sieve the bacterium powder is carried out grain size grading.
As optimal way, in the preparation method of Biosorbent for heavy metals of the present invention.Can also be after cleaning step first cap, three parts of tube and stem to bolete separate, and then each several part is carried out respectively drying, pulverizes and sieves, obtain the bacterium powder of different piece, mix as required more at last.
As optimal way, also comprise following operation after the step of sieving in the preparation method of Biosorbent for heavy metals of the present invention:
Polyvinyl alcohol and sodium alginate are placed water, after heating is stirred to dissolving, be cooled to 45-50 ℃, add bolete bacterium powder, mix, make bacterium algae matter; Then described bacterium algae matter is joined CaCl
2In the solution, constantly stir and make bacterium algae adsorbent bead, leave standstill and clean with distilled water after fixing 24 hours, under 50 ± 2 ℃, dry to constant weight.
Adsorbance and adsorption rate computing formula:
Q=(
C i –
C f )
V/
M Formula 1
E=(
C i –
C f )/C
i * 100% formula 2
Q-unit mass adsorbent (dry weight) is to metal biosorption amount (mg/g);
E-Metal biosorption rate (%);
CiGOLD FROM PLATING SOLUTION belongs to the initial concentration (mg/L) of ion before the-absorption;
CfGOLD FROM PLATING SOLUTION belongs to the equilibrium concentration (mg/L) of ion after the-absorption;
VThe volume of-solution (mL);
MThe dry weight of-adsorbent (mg).
The resolution factor computing formula:
D=QM/C
1V
1 Formula 3
D-resolution factor;
Q-unit mass adsorbent (dry weight) is to metal biosorption amount (mg/g);
MThe dry weight (mg) of the adsorbent that adds during-absorption;
C
1GOLD FROM PLATING SOLUTION belongs to the mass concentration of ion after the-desorption;
V
1-strippant volume.
Beneficial effect of the present invention:
(1) the present invention is owing to adopt the powder of bolete, only need to simply clean, the steps such as drying, crushing screening, manufacture craft is simple, quick, equipment requirement is low, with low cost, and can add man-hour discarded part as the raw material of making the bolete powder by selecting the edible bolete commodity, further reduce cost.
(2) adsorbent of the present invention only need to mix adsorbent in use with the medium that contains heavy metal, make it adsorb a period of time after, adsorbent separated with medium get final product, do not need bolete is planted or cultured in vitro, easy to use, simple to operate.
(3) adsorbent of the present invention is applicable to the different media such as soil, water, air.For example this adsorbent is placed have certain permeability container again with the medium contact that contains heavy metal, also can directly adsorb with water or contact with air.
(4) adsorbent of the present invention is applicable to the various heavy such as cadmium, copper, zinc, manganese, chromium, lead, has the wide spectrum characterization of adsorption, but its adsorption efficiency to various ions has again certain otherness, can carry out specific adsorption to some metal ions, be particularly suited for lead or the cadmium larger to toxicity.
(5) adsorbent of the present invention can select the different parts of different types of bolete as adsorbent for the difference that is adsorbed metal, improves adsorption effect.
(6) adsorbent of the present invention can also be at CaCl after use
2, HNO
3, MgCl
2, H
2SO
4, HCl, Na
2CO
3, NaHCO
3, NH
4Carry out desorb under the effect of the strippants such as Cl, heavy metal is reclaimed, adsorbent can reuse, also can be as crops fertilizer after parsing after repeatedly using.
(7) adsorbent of the present invention can be fixed on and be made into bead on the carrier, increases the balling-up of bead, mechanical strength, and acid resistance makes that adsorbent is easier to be separated with the aqueous solution, uses more conveniently, and range of application is wider, easier reusing.
Description of drawings
Fig. 1 is that the bolete powder at variety classes and position is to the adsorbance schematic diagram of lead.
Fig. 2 is that the bolete powder at variety classes and position is to the adsorbance schematic diagram of cadmium.
Fig. 3 is the preparation flow figure of bolete powder in the Biosorbent for heavy metals of the present invention.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
(1) preparation of bacterium powder
Get black suede lid bolete, clean with deionized water; Place thermostatic drying chamber, under 50 ± 2 ℃, dry to constant weight; Place after cooling pulverizer to pulverize, be made into the bacterium powder of corresponding drying; Gained bacterium powder sieved through 80 orders, 100 orders, 120 orders, 150 orders and 300 purpose sub-sieves successively carry out grain size grading, obtain 4 kinds of absorbent powders that particle diameter is respectively 150-200 μ m, 125-150 μ m, 100-125 μ m and 50-100 μ m.
(2) adsorption test
Get the clean tool plug triangular flask of 4 250 mL, the lead solution that 25 mL concentration are 100mg/L (the plumbous standard liquid GSB 04-1742-2004 dilution of 1000 mg/L that provided by national non-ferrous metal and electronic material Institute of Analysis 10 times obtain) is provided for each, take by weighing respectively the above-mentioned bolete powder of 500 mg and join (the bolete powder of every bottle of a kind of particle size range of correspondence) in the triangular flask, other gets the clean tool plug triangular flask of 4 250 mL, the cadmium solution that 25 mL concentration are 100 mg/L (the cadmium standard liquid GSB 04-1721-2004 dilution of 1000 mg/L that provided by national non-ferrous metal and electronic material Institute of Analysis 10 times obtain) is provided for each, taking by weighing respectively 500 mg bolete powder joins in the triangular flask, after shaking up gently, above-mentioned 8 triangular flasks are placed at room temperature adsorbed on the isothermal vibration machine 1 hour.
With solution filter, measure the concentration of remaining heavy metal ion in the filtrate with atomic absorption spectrophotometer after the absorption
C f , mensuration is prepared the initial concentration of metal ion in plumbous and the cadmium solution simultaneously
C i , each is processed and all establishes three repetitions.And the adsorbance and the adsorption rate that adopt formula 1 and formula 2 to calculate separately.
The result shows: particle diameter is that the adsorption effect of two kinds of bolete powder of 125-150 μ m and 100-125 μ m is best.
Embodiment 2
Getting among the embodiment 1 the preparation particle diameter and be bolete powder 500 mg of 150-200 μ m and polyethylene solution that 200 μ L concentration are 5 mg/mL mixes, placing the cross section is circular mould, adopt hand-operated hydraulic press 10 seconds of pressurize under 0.5 MPa, sample is withdrawed from from mould, obtain the adsorbent cake.
Get 2 as stated above the adsorbent cakes of preparation to place respectively 25 mL concentration be lead solution and the cadmium solution of 100 mg/L, adsorb after 1 hour, take out the adsorbent cake, with the concentration of remaining heavy metal ion in the atomic absorption spectrophotometer mensuration filtrate
C f , mensuration is prepared the initial concentration of metal ion in plumbous and the cadmium solution simultaneously
C i , each is processed and all establishes three repetitions.And the adsorbance and the adsorption rate that adopt formula 1 and formula 2 to calculate separately.
The result shows: the adsorbent cake is respectively 81% and 62% to the adsorption rate of plumbous and cadmium.
Get black suede lid bolete, clean with deionized water; Place thermostatic drying chamber, under 50 ± 2 ℃, dry to constant weight; Place after cooling pulverizer to pulverize, be made into the bacterium powder of corresponding drying; Respectively gained bacterium powder being sieved with 80 orders and 300 purpose sub-sieves successively, to obtain particle diameter be 50-200 μ m absorbent powder.Adopting the method identical with the adsorption test among the embodiment 1 to record its adsorbance to lead is 4.3 mg/g, and adsorption rate is 86%; Adsorbance to cadmium is 2.2 mg/g, and adsorption rate is 44%.
Get the bolete discarded object, clean with deionized water; Place thermostatic drying chamber, under 50 ± 2 ℃, dry to constant weight; Place after cooling pulverizer to pulverize, be made into the bacterium powder of corresponding drying; Respectively gained bacterium powder being sieved with 80 orders and 300 purpose sub-sieves successively, to obtain particle diameter be 50-200 μ m absorbent powder.Adopting the method identical with adsorption test among the embodiment 1 to record its adsorbance to lead is 4.0 mg/g, and adsorption rate is 80%; Adsorbance to cadmium is 2.0 mg/g, and adsorption rate is 40%.
Embodiment 5The desorption test
Get and after concussion absorption, filter the two kinds of bolete filter residues (respectively adsorbance cadmium and lead) that obtain among the embodiment 3, joining respectively 50 mL concentration is in the HCl strippant solution of 0.1 mol/L, concussion desorb 4 hours, measure respectively cadmium and plumbous mass concentration in the solution with Atomic Absorption Spectrometer, adopt formula 3 to calculate desorption efficiency.
The adsorbent that obtains with desorption repeats above-mentioned adsorption test, calculates adsorption rate.
The result shows that cadmium and plumbous desorption efficiency are respectively 80% and 85%, are respectively the adsorption rate of plumbous and cadmium when the adsorbent after the desorb adsorbs again: 85% and 43%, illustrate that these bolete powder can reuse by desorption.
Get 7 g polyvinyl alcohol and 2 g sodium alginates place 100 mL water, after heating is stirred to dissolving, be cooled to 45-50 ℃, add the bolete bacterium powder of preparation among the 4 g embodiment 3, mix, make bacterium algae matter; Then above-mentioned bacterium algae matter is joined 100 mL mass body volume concentrations and is 1% CaCl
2In the solution, constantly stir and make bacterium algae adsorbent bead, leave standstill and clean with distilled water after fixing 24 hours, under 50 ± 2 ℃, dry to constant weight, obtain bolete adsorbent bead, the bead adsorbent of gained is sieved, choose the bead of diameter in 1-5 mm scope as adsorbent.
Get two parts of above-mentioned diameters at 1-5 mm scope bolete adsorbent bead, every part of 2 g, placing respectively 25 mL concentration is lead solution and the cadmium solution of 100 mg/L, after shaking up gently, at room temperature adsorbs on the isothermal vibration machine 1 hour.
With solution filter, measure the concentration of remaining heavy metal ion in the filtrate with atomic absorption spectrophotometer after the absorption
C f , mensuration is prepared the initial concentration of metal ion in plumbous and the cadmium solution simultaneously
C i , each is processed and all establishes three repetitions.And the adsorbance and the adsorption rate that adopt formula 1 and formula 2 to calculate separately.
Two kinds of adsorbent beads that obtain after filtering are joined respectively in the HCl strippant solution that 50 mL concentration are 0.1 mol/L, and concussion desorb 4 hours is measured respectively cadmium and plumbous mass concentration in the solution with Atomic Absorption Spectrometer, adopts formula 3 to calculate desorption efficiency.
The adsorbent bead that obtains with desorption repeats above-mentioned adsorption test, calculates adsorption rate.
The result shows: when described bolete adsorbent bead adsorbs for the first time the adsorption rate of plumbous and cadmium is respectively 81% and 42%, and the desorption efficiency 78% and 83% of lead and cadmium, the adsorption rate when the adsorbing for the second time is respectively 80% and 41%.Illustrate that this adsorbent bead has good adsorption effect and can reuse.
Embodiment 7 different bolete kinds and different parts thereof are to the comparison of plumbous and cadmium adsorption capacity
Choose black suede lid bolete, cepe and three kinds of boletes of light brown suede lid bolete, clean with deionized water respectively; Respectively cap, three parts of tube and stem of three kinds of boletes are separated; Place thermostatic drying chamber, under 50 ± 2 ℃, dry to constant weight; Place respectively pulverizer to pulverize each several part after cooling, be made into the bacterium powder of corresponding drying; Respectively gained bacterium powder is sieved with 120 order sub-sieves and obtain absorbent powder (totally 9 kinds).
Get the clean tool plug triangular flask of 9 250 mL, the lead solution that 25 mL concentration are 100 mg/L (the plumbous standard liquid GSB 04-1742-2004 dilution of 1000 mg/L that provided by national non-ferrous metal and electronic material Institute of Analysis 10 times obtain) is provided for each, respectively take by weighing 500 mg bolete powder and join (every bottle of a kind of bolete powder of correspondence in the triangular flask, and carry out mark), other gets the clean tool plug triangular flask of 9 250 mL, the cadmium solution that 25 mL concentration are 100 mg/L (the cadmium standard liquid GSB 04-1721-2004 dilution of 1000 mg/L that provided by national non-ferrous metal and electronic material Institute of Analysis 10 times obtain) is provided for each, respectively take by weighing 500 mg bolete powder and join (every bottle of a kind of bolete powder of correspondence in the triangular flask, and carry out mark), after shaking up gently, above-mentioned 18 triangular flasks are placed at room temperature adsorbed on the isothermal vibration machine 1 hour.
With solution filter, with solution filter, measure the concentration of remaining heavy metal ion in the filtrate with atomic absorption spectrophotometer after the usefulness absorption after the absorption
C f , mensuration is prepared the initial concentration of metal ion in plumbous and the cadmium solution simultaneously
C i , each is processed and all establishes three repetitions.And the adsorbance and the adsorption rate that adopt formula 1 and formula 2 to calculate separately.
The result is as depicted in figs. 1 and 2: different bolete kinds and position have certain otherness to the adsorbance of plumbous and cadmium, all are adsorbance and the adsorption rates that the cap of black suede lid bolete has maximum for these two kinds of metals.In actual use, can also according to the difference of the heavy metal of required absorption, in different ratios above-mentioned 9 kinds of bolete powder be mixed, to reach the optimal adsorption effect.
Claims (10)
1. Biosorbent for heavy metals, it is characterized in that: described biological adsorption agent contains the bolete powder.
2. Biosorbent for heavy metals as claimed in claim 1, it is characterized in that: the particle diameter of described bolete powder is the 50-200 micron.
3. Biosorbent for heavy metals as claimed in claim 1 is characterized in that: described bolete is in black suede lid bolete, cepe or the light brown suede lid bolete any one.
4. Biosorbent for heavy metals as claimed in claim 1, it is characterized in that: at least one part in the cap that described bolete powder is bolete, tube or three parts of stem obtains after crushed.
5. such as any one described Biosorbent for heavy metals among the claim 1-4, it is characterized in that: described bolete powder is pressed into cake.
6. such as any one described Biosorbent for heavy metals among the claim 1-4, it is characterized in that: described bolete powder is supported on and makes the bead adsorbent on the carrier.
7. Biosorbent for heavy metals as claimed in claim 6, it is characterized in that: the weight proportion of the component that described bead adsorbent contains is: 7 parts of polyvinyl alcohol, 2 parts of sodium alginates, 1 part in calcium chloride, 4 parts in bolete powder.
8. preparation method of Biosorbent for heavy metals as claimed in claim 1 is characterized in that may further comprise the steps:
(1) cleans: the bolete that gathers is cleaned with deionized water;
(2) drying: the sample after will cleaning places thermostatic drying chamber, dries to constant weight under 50 ± 2 ℃;
(3) pulverize: place after cooling pulverizer to pulverize, be made into dry bacterium powder;
(4) sieve: with sub-sieve the bacterium powder is carried out grain size grading.
9. the preparation method of Biosorbent for heavy metals as claimed in claim 8 is characterized in that may further comprise the steps:
(1) cleans: the bolete that gathers is cleaned with deionized water;
(2) separate: cap, three parts of tube and stem of liver bacterium are separated;
(3) drying: the each several part sample of gained is placed respectively thermostatic drying chamber, under 50 ± 2 ℃, dry to constant weight;
(4) pulverize: place after cooling pulverizer to pulverize, be made into dry bacterium powder;
(5) sieve: with sub-sieve the bacterium powder is carried out grain size grading.
10. the preparation method of Biosorbent for heavy metals as claimed in claim 8 or 9 is characterized in that: also comprise following operation after the described step of sieving:
Polyvinyl alcohol and sodium alginate are placed water, after heating is stirred to dissolving, be cooled to 45-50 ℃, add bolete bacterium powder, mix, make bacterium algae matter; Then described bacterium algae matter is joined CaCl
2In the solution, constantly stir and make bacterium algae adsorbent bead, clean with distilled water after leaving standstill, fix 24 hours, under 50 ± 2 ℃, dry to constant weight.
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| CN106520573A (en) * | 2016-11-14 | 2017-03-22 | 周宇 | Preparation method of fungal inoculant for improving soil heavy metal pollution |
| CN106622167A (en) * | 2016-11-28 | 2017-05-10 | 韩山师范学院 | Heavy metal adsorption immobilized biological adsorbent and preparation method and application thereof |
| CN112457856A (en) * | 2020-09-21 | 2021-03-09 | 山东碧泉环境工程技术有限公司 | Heavy metal solidification stabilizer based on biomass polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106492762A (en) * | 2016-11-04 | 2017-03-15 | 河南工程学院 | A kind of biological adsorption agent for process containing cadmium ion waste water |
| CN106492762B (en) * | 2016-11-04 | 2018-11-06 | 河南工程学院 | A kind of biological adsorption agent for handling the waste water containing cadmium ion |
| CN106520573A (en) * | 2016-11-14 | 2017-03-22 | 周宇 | Preparation method of fungal inoculant for improving soil heavy metal pollution |
| CN106520573B (en) * | 2016-11-14 | 2019-12-13 | 周宇 | preparation method of fungal inoculant for improving soil heavy metal pollution |
| CN106622167A (en) * | 2016-11-28 | 2017-05-10 | 韩山师范学院 | Heavy metal adsorption immobilized biological adsorbent and preparation method and application thereof |
| CN112457856A (en) * | 2020-09-21 | 2021-03-09 | 山东碧泉环境工程技术有限公司 | Heavy metal solidification stabilizer based on biomass polymer and preparation method thereof |
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Inventor after: Zhang Dan Inventor after: Li Wei Inventor after: Zhang Yu Inventor after: Li Bin Inventor before: Zhang Dan Inventor before: Li Wei Inventor before: Zhang Yu |
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Effective date of registration: 20170301 Address after: 610041 Chengdu City, Wuhou District province people's road, No. four, No. 9, No. Patentee after: Chinese Academy of Sciences Patentee after: Chengdu Institute of mountain hazards and environment Patentee after: Sichuan Province Company of China National Tobacco Coporation Address before: 610041 Chengdu City, Wuhou District province people's road, No. four, No. 9, No. Patentee before: Chinese Academy of Sciences Patentee before: Chengdu Institute of mountain hazards and environment |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150812 Termination date: 20191112 |
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| CF01 | Termination of patent right due to non-payment of annual fee |