CN101829545A - Heavy metal biological adsorbent using eggshell membrane as matrix and preparation method thereof - Google Patents
Heavy metal biological adsorbent using eggshell membrane as matrix and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heavy metal biological adsorbent using an eggshell membrane as a matrix and a preparation method thereof. The heavy metal biological adsorbent adopts chitosan as an immobilized carrier and eggshell membrane powder as a basis material, and comprises the following components in part by weight: 10 to 13 parts of the eggshell membrane powder, 20 to 30 parts of the chitosan of which the deacetylation degree is 86.9 percent, and a minute amount of gelatinous substance of a complex which contains sodium and potassium and is formed in the preparation process. The particle size of the biological adsorbent is 2 to 3 millimeters. The method comprises the steps of performing vacuum freeze drying and mechanical disintegration on a fresh eggshell membrane (a fibrous membrane between an eggshell and egg white), and then embedding the eggshell membrane with chitosan glue solution to obtain the biological adsorbent for adsorbing heavy metals. The biological adsorbent can be used for treating waste water containing the heavy metals of nickel, cobalt, cadmium, copper, lead and the like of which the concentration is lower than 100 mg/L, and the adsorption rate achieves 42 to 98 percent.
Description
Technical field
The invention belongs to the biological adsorption agent field, relate to a kind of method that adopts chitosan imbedded egg shell membrane powder to prepare the agent of absorption Biosorption of Heavy Metals.This biological adsorption agent is a primary raw material with membranes of fowl eggshells (the fibrous film between eggshell and albumen), is suitable for handling the waste water that contains the heavy metals such as nickel, cobalt, cadmium, copper and lead of concentration below 100mg/L.
Background technology
Because heavy metal wastewater thereby is big to natural environment harm, generally attach great importance to the processing of this type of waste water both at home and abroad, work out multiple improvement technology.By to its improvement, with poisonous be converted into nontoxic, will be harmful to and be converted into harmlessly, and reclaim wherein precious metal, the waste water after purifying is recycled, eliminate and reduce the discharge capacity of heavy metal.Along with plating, the fast development of electronics industry and the raising day by day of environmental requirement, at present, this type of industry has gradually adopted process for cleanly preparing, overall control and recycling economy to integrate the stage, and resource recycling and closed cycle are the main flow directions of heavy metal containing wastewater treatment development.How eliminating the harm of heavy metal and reclaiming precious metal in the waste water effectively is face in the current environmental protection work one very distinct issues.Handle in the waste water that heavy metal is general to adopt traditional physico-chemical process, when the heavy metal concentration in the water lower (100mg/L below), not only clearance is low, and has complex process, complex operation, operating cost height, generation secondary pollution problems.
Biological adsorption technology is as the technology of heavy metal in the emerging removal waste water, has that the raw material source is abundant, cost is low, adsorption plant is simple, easy to operate a, advantage such as secondary pollution is few, more and more is subjected to people's attention.
Membranes of fowl eggshells (the fibrous film between eggshell and albumen) is based on keratin, the compound protein that combines with mucopolysaccharide, the soluble high-molecular compound that wherein contains compositions such as N-acetylglucosamine galactolipin, glucuronic acid, hyaluronic acid, chondroitin sulfate (N-acetylglucosamine galactolipin, glucuronic acid, hyaluronic acid, chondroitin sulfate are the mucopolysaccharide material, are the basic substances that constitutes cell), amino acid.These main functional groups that can combine with metal in forming have carboxyl, phosphoryl, hydroxyl, sulfuric acid ester base, amino and amide groups etc., and they have the binding site of the different heavy metals of absorption, and the part heavy metal is had extremely strong adsorption effect.The heavy metal that is adsorbed can be inhaled by other ions, integrated agent or acidolysis.
The birds, beasts and eggs shell always is taken as refuse and abandons.According to a preliminary estimate, just there are tons up to a hundred in Beijing every month only egg shell abandoned of each food factory, egg product processing factory, and untimely processing can serious environment pollution.And it utilize potentiality very big.The raw material source of egg shell membrane biological adsorption agent is abundant, and cost is low, and not only adsorption plant is simple, and is easy to operate, and has speed height, big, the good selective of adsorbance.Aspect processing, with general chemical method just can desorb the heavy metal of absorption, and reclaimed, and the adsorbent after the desorb also can reuse, the precious metal in the waste water is also reclaimed in the harm of elimination heavy metal effectively, is the green project that economic environmental protection is laid equal stress on.
Shortcomings such as membranes of fowl eggshells is as biological adsorption agent, and it is soft perishable are brought very big inconvenience to adsorption operations, therefore egg shell membrane are carried out mechanical performance and the chemical stability that processing means such as chemical modification and immobilization improve egg shell membrane.Investment is a kind of simple method for immobilizing cell, and this method is simple to operate, cell can be locked in the specific macromolecule network structure.This structure can allow substrate infiltration and product diffusion closely to being enough to prevent the cell seepage, and the pair cell activity influence is less, and the intensity of the immobilized cell of making is higher, is the method the most widely of research at present.The chitosan gel rubber of mesh-like structure has that mechanical strength height, physicochemical property are stable, flow speed stability and the big essential characteristic of adsorption capacity, but long term storage can be sterilized with conventional method.
Summary of the invention
One of purpose of the present invention provides a kind of Biosorbent for heavy metals, described Biosorbent for heavy metals includes the shitosan and the trace impurity of deacetylation 86.9% of egg shell membrane powder, 20～30 weight portions of 10～13 weight portions, this trace impurity is the gelatinous mass that contains the complex of sodium, potassium, is to produce in the preparation process.The particle diameter of described biological adsorption agent is 2～3mm.Described biological adsorption agent can be handled contain nickel, cobalt, cadmium, copper and the plumbous heavy metal wastewater thereby of concentration below 100mg/L, adsorption rate reaches 42～98%, for the heavy metal wastewater thereby of low concentration (100mg/L following) provides a kind of novel environment friendly effective water treatment agent.
Another object of the present invention is to propose a kind of method of utilizing chitosan imbedded egg shell membrane powder to prepare the agent of absorption Biosorption of Heavy Metals, and this preparation method carries out carrying out the agent of embedding acquisition absorption Biosorption of Heavy Metals with the shitosan glue after vacuum freeze drying, the mechanical crushing to fresh egg shell membrane.
The method that the present invention prepares the agent of absorption Biosorption of Heavy Metals has following preparation steps:
The first step: preserved egg shell membrane powder
The birds, beasts and eggs shell that reclaims, the preliminary cleaning is immersed in 24h in the water (also available 2% watery hydrochloric acid soaks 2h), separating husk, film, collection membrane then;
Is that 1～20Pa, temperature are in-56～-40 ℃ the environment behind dry 24～48h with the fresh-laid egg shell membrane collected at pressure, adopts the mechanical crushing mode to make the dried egg shell membrane powder that particle diameter is 40～80 μ m, stand-by;
Second step: preparation embedding treatment liquid
Add 20g sodium pyrophosphate, 40g potassium oxalate in every liter of deionized water, stir, make embedding treatment liquid;
The 3rd step: preparation shitosan glue
Every liter of concentration is the shitosan that adds 20～30g, 80～200 orders, deacetylation 86.9% in 1% the acetic acid solution, stirs, and makes the shitosan glue;
The 4th step: preparation embedding body
Add 10～13g in every liter of shitosan glue and do the egg shell membrane powder, stir, form suspension, adopt ultrasonic cell disruptor to pulverize 15min and make the embedding body;
The 5th step: investment is produced biological adsorption agent
Connecting syringe needle with peristaltic pump slowly splashes into the embedding body in the embedding treatment liquid, form the adsorbent bead, rest in the embedding treatment liquid and solidify 30min, filter, deionized water rinsing 1～5 time is making the biological adsorption agent that particle diameter is 2～3mm behind the freeze drying 24h under-56～-40 ℃ of conditions.
The invention has the advantages that:
(1) adsorption rate of adsorbent provided by the invention reaches 42～98%, for the heavy metal wastewater thereby of low concentration (100mg/L following) provides a kind of novel environment friendly effective water treatment agent;
(2) adsorbent provided by the invention is the little spherical shape of rule, and it is little and even to have a particle diameter, and specific area is big, the advantage of advantages of good adsorption effect;
(3) under the adsorbent normal temperature provided by the invention better adsorption capability is arranged promptly, wide to the pH value scope of application, adsorption operations is simple;
(4) adsorbent provided by the invention all has adsorption effect preferably for various heavy waste water;
(5) after the adsorbents adsorb heavy metal provided by the invention, heavy metal is reclaimed in available general chemical method desorb, and adsorbent can reuse, and can not produce secondary pollution;
(6) the matrix material membranes of fowl eggshells source of the present invention's employing is abundant, and cost is low;
(7) the carrier material shitosan of the present invention's employing has very high affinity and retentiveness to water, good biocompatibility, and to biological nontoxic, mass-transfer performance is good, and can not produce secondary pollution, the adsorbent mechanical strength height that makes;
(8) the present invention adopts vacuum freeze-drying method, and membranes of fowl eggshells is freezed at low temperatures, makes wherein moisture by the solid-state gaseous state that is directly sublimed under vacuum state, dehydrates.Whole dry run is carried out under low temperature, low pressure, and moisture directly distils, and membranes of fowl eggshells is not subjected to surface tension effects, its institutional framework and mode of appearance are preserved preferably, do not have surperficial sclerosis problem, and it inner forms the spongy of porous, help improving adsorption capacity;
(9) the present invention adopts the embedding mode, and the egg shell membrane powder is fixed in the chitin carrier, and the preparation method is simple to operate, does not relate to high temperature deactivation, and is less to the influence of egg shell membrane cytoactive;
(10) equipment needed thereby is simple in the preparation of adsorbent process provided by the invention, and operating process is controlled easily.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
The absorption Biosorption of Heavy Metals agent of the chitosan imbedded egg shell membrane powder of employing provided by the invention, described biological adsorption agent includes the gelatinous mass that the trace that forms in the shitosan of deacetylation 86.9% of egg shell membrane powder, 20～30 weight portions of 10～13 weight portions and the preparation process contains the complex of sodium, potassium, and the particle diameter of described biological adsorption agent is 2～3mm.
The present invention is a kind of preparation method who adopts the Biosorbent for heavy metals of chitosan imbedded egg shell membrane powder, and the concrete operations step is as follows:
The first step: preserved egg shell membrane powder
The egg shell that reclaims after preliminary the cleaning, is immersed in 24h in the water (also available 2% watery hydrochloric acid soaks 2h), separating husk, film, collection membrane;
Is that 1～20Pa temperature is in-56～-40 ℃ the environment behind dry 24～48h with the fresh-laid egg shell membrane collected at pressure, adopts the food processor mechanical crushing, makes particle diameter and is the dried egg shell membrane powder of 40～80 μ m, stand-by;
The freeze drying instrument selects for use moral sky, Beijing to help development in science and technology Co., Ltd, the FD-1PF freeze drier;
Second step: preparation embedding treatment liquid
Add 20g sodium pyrophosphate, 40g potassium oxalate in every liter of deionized water, stir, make embedding treatment liquid;
The 3rd step: preparation shitosan glue
Every liter of concentration is the shitosan that adds 20～30g, 80～200 orders, deacetylation 86.9% in 1% the acetic acid solution, stirs, and makes the shitosan glue;
The 4th step: preparation embedding body
Get the dried egg shell membrane powder that the first step makes, join the 3rd and go on foot in the shitosan glue that makes, stir, form suspension, adopt ultrasonic cell disruptor to pulverize 15min and make the embedding body; Add 10～13g in every liter of shitosan glue and do the egg shell membrane powder.
The 5th step: investment is produced biological adsorption agent
Connecting embedding body that syringe needle made for the 4th step with peristaltic pump slowly splashes in the embedding treatment liquid that second step made, form the adsorbent bead, rest in the embedding treatment liquid (second step made) and solidify 30min, filter, deionized water rinsing is making the biological adsorption agent that particle diameter is 2～3mm behind the freeze drying 24h under-56～-40 ℃ of conditions;
Peristaltic pump instrument selection Cole-Parmer Instrument Company, model 7554-85.
The present invention enriches in used biological sorbing material birds, beasts and eggs shell source, and cost is low, and not only adsorption plant is simple, and is easy to operate, and has speed height, big, the good selective of adsorbance.Method is simple for mechanical crushing, and cost is low, and grain diameter is more even, helps the moulding of adsorbent and can improve the absorption property of adsorbent.The carrier material shitosan that adopts is a kind of natural macromolecular material, because the existence of polar group, shitosan has very high affinity and retentiveness to water, good biocompatibility, to biological nontoxic, mass-transfer performance is good, and can not produce secondary pollution, the adsorbent mechanical strength height that makes.Egg shell membrane adopts vacuum freeze drying in the above-mentioned first step, and moisture is directly by solid-state distillation, and dry back adsorbent internal organizational structure and mode of appearance maintain the original state, and do not have surperficial sclerosis problem, help absorption;
When the embedding treatment liquid of producing in described second step is used to handle the embedding body, formation contains the gelatinous mass (this gelatinous mass exists as the trace impurity composition) of the complex of sodium, potassium in the bead biological adsorption agent for preparing, be used for realizing the egg shell membrane powder is embedded in gelatinous mass, improve solidification effect;
Adopt the purpose of the acetate preparation shitosan glue of dilution to be to make shitosan to become liquid state rapidly in described the 3rd step, be beneficial to the embedding of egg shell membrane powder with biocompatibility;
The biological adsorption agent spheroid that makes through this method is regular little spherical shape, it is little and even to have particle diameter, and specific area is big, advantages of good adsorption effect, to characteristics such as the pH value scope of application are wide, be suitable for handling the waste water that contains heavy metals such as low concentration (100mg/L is following) nickel, cobalt, cadmium, copper and lead.Adsorbent after the absorption can reclaim heavy metal with general chemical method desorb, and adsorbent can reuse, and can not produce secondary pollution.
In order to verify the absorption property of the biological adsorption agent spheroid that the present invention makes, estimate adsorption effect by adsorbance and adsorption rate, desorption efficiency is estimated desorption effect, and concrete computational methods are as follows:
Equilibrium adsorption capacity
Adsorption rate
Desorption efficiency
In the formula, q is an equilibrium adsorption capacity, the mg/L of unit; C
0Be the initial concentration of heavy metal, the mg/L of unit; C
eThe concentration of heavy metal during for adsorption equilibrium, the mg/L of unit; C
iBe the concentration of heavy metal in the stripping liquid, the mg/L of unit, stripping liquid are meant that concentration is hydrochloric acid or the salpeter solution of 1mol/L; V is the volume that contains the solution of heavy metal, the L of unit; W is the quality of biological adsorption agent spheroid, the g of unit.
Embodiment 1:Absorption and desorb to Cd, Co, Cu, Ni, Pb under the condition of different pH.
The first step: preserved egg shell membrane powder
The egg shell that reclaims after preliminary the cleaning, is immersed in 24h in the water, separating husk, film, collection membrane;
Adopt the freeze drying instrument, is 1～20Pa, cryogenic temperature-56～-40 ℃ with the fresh-laid egg shell membrane at pressure, drying time 24h condition under carry out freeze drying, adopt the food processor mechanical crushing then, make particle diameter and be the dried egg shell membrane powder of 40～80 μ m, stand-by;
Described freeze drying instrument selects for use moral sky, Beijing to help development in science and technology Co., Ltd, the FD-1PF freeze drier.
Second step: preparation embedding treatment liquid
Add 20g sodium pyrophosphate, 40g potassium oxalate in every liter of deionized water, stir, make embedding treatment liquid;
The 3rd step: preparation shitosan glue
Every liter of concentration is the shitosan that adds 20g, 80～200 orders, deacetylation 86.9% in 1% the acetic acid solution, stirs, and makes the shitosan glue;
The 4th step: preparation embedding body
Add 13g in every liter of shitosan glue and do the egg shell membrane powder, stir, form suspension, adopt ultrasonic cell disruptor to pulverize 15min and make the embedding body;
The 5th step: investment is produced biological adsorption agent
Connecting syringe needle with peristaltic pump slowly splashes into the embedding body in the embedding treatment liquid, form the adsorbent bead, rest in the embedding treatment liquid and solidify 30min, filter, deionized water rinsing, at pressure is 1～20Pa, cryogenic temperature-56～-40 ℃, drying time 24h condition under make the biological adsorption agent that particle diameter is 2～3mm after the freeze drying;
Described peristaltic pump is selected Cole-Parmer Instrument Company, model 7554-85 for use.
Take by weighing the Cd (NO of 100mL finite concentration (seeing Table 1) respectively
3)
2, CoCl
2, Cu (NO
3)
2, NiSO
4, PbCl
2Heavy metal solution adds in the conical flask, each 3 bottles of every kind of solution, and its pH is respectively 5,6,7 (hydrochloric acid and sodium hydroxide solution with 0.1mol/L are regulated), and the conical flask number only amounts to 3 * 5=15.In each conical flask, add 0.1g biological adsorption agent bead respectively and seal the taper bottleneck, heavy metal solution vacuum filtration after getting certain volume absorption after 25 ℃ of concussion absorption 4h reach balance in constant temperature water bath case concussion case, adopt inductively coupled plasma atomic emission spectrometer (PerkinElmer Instr Ltd., model: Optima 2100/5000) to measure the wherein concentration of heavy metal.
Measure through parallel laboratory test, obtain following result:
The adsorption effect of table 1 Biosorbent for heavy metals
PH＝5
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| ??C 0 | ??135.3 | ??123.8 | ??110.2 | ??128.7 | ??120.2 |
| ??C e | ??27.15 | ??86.77 | ??57.67 | ??90.03 | ??90.06 |
| ??η | ??79.93％ | ??29.91％ | ??47.67％ | ??42.18％ | ??25.07％ |
| ??q(mg/g) | ??108.15 | ??37.03 | ??52.53 | ??54.29 | ??30.14 |
PH＝6
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| ??C 0 | ??135.3 | ??123.8 | ??110.2 | ??128.7 | ??120.2 |
| ??C e | ??27.64 | ??83.38 | ??58.38 | ??74.41 | ??2.774 |
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| ??η | ??79.57％ | ??32.65％ | ??47.02％ | ??42.18％ | ??97.69％ |
| ??q(mg/g) | ??107.66 | ??40.42 | ??51.82 | ??54.29 | ??117.426 |
PH＝7
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| ??C 0 | ??66.77 | ??103.6 | ??97.62 | ??98.01 | ??86.47 |
| ??C e | ??8.923 | ??15.3 | ??88.02 | ??74.41 | ??14.97 |
| ??η | ??86.64％ | ??85.23％ | ??9.83％ | ??24.08％ | ??82.69％ |
| ??q(mg/g) | ??57.847 | ??88.3 | ??9.6 | ??23.6 | ??71.5 |
(5) absorption-desorption circulation
Compound concentration is that the hydrochloric acid solution of 1mol/L is as strippant.To reach the adsorbent deionized water rinsing after the adsorption equilibrium, remove the free heavy metal in surface, add again in the 50mL strippant,, after the desorb solution be filtered, measure after the desorb heavy metal concentration in the stripping liquid 25 ℃ of vibration desorbs 5 hours down.Adsorbent after the desorb is soaked in the 10min that regenerates in the sodium hydroxide solution of 1mol/L, enters next sorption cycle through deionized water rinsing then.
Measure through parallel laboratory test, obtain following result:
The hydrochloric acid solution desorption effect of table 2 1mol/L is analyzed
PH＝5
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| Theoretical desorb concentration (mg/g) | ??108.15 | ??37.03 | ??52.53 | ??28.67 | ??30.14 |
| Actual resolved concentration (mg/g) | ??51.2 | ??19.69 | ??37.09 | ??21.44 | ??25.39 |
PH＝6
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| Theoretical desorb concentration (mg/g) | ??107.66 | ??40.42 | ??51.82 | ??54.29 | ??117.426 |
| Actual resolved concentration (mg/g) | ??46.52 | ??23.14 | ??41.23 | ??22.38 | ??18.03 |
PH＝7
| ??Cd | ??Co | ??Cu | ??Ni | ??Pb | |
| Theoretical desorb concentration (mg/g) | ??57.847 | ??88.3 | ??9.6 | ??23.6 | ??71.5 |
| Actual resolved concentration (mg/g) | ??39.45 | ??55.35 | ??7.7 | ??17.3 | ??65.05 |
It is as follows to reach a conclusion by experiment:
Increase with the adsorbent dosage, the egg shell membrane biological adsorption agent constantly raises to the adsorption rate of heavy metal.The egg shell membrane biological adsorption agent is to Cd, Co, Cu, Ni, Pb five heavy metal species all have suction-operated, wherein again with adsorption effect the best to Cd, measure through parallel laboratory test, be respectively 5,6,7 o'clock at PH, the egg shell membrane adsorbent has reached 108.15mg/g respectively to the adsorbance of Cd, 107.66mg/g, 57.847mg/g.
The HCl that adopts 1mol/L is as strippant, and the egg shell membrane biological adsorption agent can repeat absorption-desorption circulation 1～3 time, and the heavy metal after the desorb can muriatic form reclaim.
Embodiment 2:
The first step: preserved egg shell membrane powder
The egg shell that reclaims after preliminary the cleaning, soaks 2h, separating husk, film, collection membrane with 2% watery hydrochloric acid;
The fresh-laid egg shell membrane is carried out freeze drying handle, treatment conditions are: pressure is 1～20Pa, cryogenic temperature-56～-40 ℃, and drying time, 48h adopted the food processor mechanical crushing then, made particle diameter and was the dried egg shell membrane powder of 40～80 μ m, and is stand-by.
Second step: preparation embedding treatment liquid
Add the 20g sodium pyrophosphate in every liter of deionized water, the 40g sodium oxalate stirs, and makes embedding treatment liquid.
The 3rd step: preparation shitosan glue
Every liter of concentration is the shitosan that adds 30g, 200 orders, deacetylation 86.9% in 1% the acetic acid solution, stirs, and makes the shitosan glue.
The 4th step: preparation embedding body
Add 10g in every liter of shitosan glue and do the egg shell membrane powder, stir, form suspension, adopt ultrasonic cell disruptor to pulverize 15min and make the embedding body.
The 5th step: investment is produced biological adsorption agent
Connecting syringe needle with peristaltic pump slowly splashes into the embedding body in the embedding treatment liquid, form the adsorbent bead, rest in the embedding treatment liquid and solidify 30min, filter, deionized water rinsing, at pressure is 1～20Pa, cryogenic temperature-56～-40 ℃, drying time 48h condition under freeze drying under the condition, make the biological adsorption agent that particle diameter is 2～3mm.
Adopt method similarly to Example 1 that heavy metal solution is carried out heavy metal absorption, this biological adsorption agent is to Cd
2+, Co
2+, Cu
2+, Pb
2+Adsorption rate reach 75.54%, 98.56%, 97.36%, 98.21% respectively.
In sum, with shitosan as carrier fixedly the adsorbent profile of egg shell membrane powder preparation to be particle diameter be the coccoid of 2～3mm rule, used fixation support shitosan is natural macromolecular material, the adsorbent preparation manipulation is simple, with low cost, and can not cause secondary pollution, effective to the heavy metal containing wastewater treatment of low concentration, having wide should have prospect and use value preferably.For the processing and the recycling of low-concentration heavy metal in surface treatment industry and other industrial wastewaters provides a kind of simple and effective method, simultaneously the resource of this zero cost of egg shell membrane is made full use of, and has opened up a kind of process for fixation of effective biological sorbing material---chitosan-immobilized.For the industrial applications of biological adsorption agent lays the foundation, realize the new breakthrough of environmental pollution improvement's aspect biotechnology.
Claims (5)
1. Biosorbent for heavy metals that utilizes egg shell membrane as matrix, it is characterized in that: described biological adsorption agent includes the trace impurity that forms in the shitosan of deacetylation 86.9% of egg shell membrane powder, 20～30 weight portions of 10～13 weight portions and the preparation process, the particle diameter of described biological adsorption agent is 2～3mm, and described trace impurity is the gelatinous mass that contains the complex of sodium, potassium.
2. according to the described Biosorbent for heavy metals of claim 1, it is characterized in that: described biological adsorption agent can be handled contain nickel, cobalt, cadmium, copper and the plumbous heavy metal wastewater thereby of concentration below 100mg/L, and adsorption rate reaches 42～98%.
3. according to the described Biosorbent for heavy metals of claim 1, it is characterized in that: the particle diameter of described egg shell membrane powder is 40～80 μ m.
4. one kind prepares the method for utilizing egg shell membrane as the Biosorbent for heavy metals of matrix as claimed in claim 1, it is characterized in that having following preparation steps:
The first step: preserved egg shell membrane powder;
Reclaim the birds, beasts and eggs shell, the preliminary cleaning soaked separating husk, film, collection membrane then;
Is that 1～20Pa, temperature are freeze drying 24～48h in-56～-40 ℃ the environment with the fresh-laid egg shell membrane at pressure, adopts food processor mechanical crushing mode to make the dried egg shell membrane powder that particle diameter is 40～80 μ m then, stand-by;
Second step: preparation embedding treatment liquid;
Add 20g sodium pyrophosphate, 40g potassium oxalate in every liter of deionized water, stir, make embedding treatment liquid;
The 3rd step: preparation shitosan glue;
Every liter of concentration is the shitosan that adds 20～30g, 80～200 orders, deacetylation 86.9% in 1% the acetic acid solution, stirs, and makes the shitosan glue;
The 4th step: preparation embedding body;
Go on foot dried egg shell membrane powder 10～13g that the adding first step makes in the shitosan glue that makes at every liter the 3rd, stir, form suspension, adopt ultrasonic cell disruptor to pulverize 15min and make the embedding body;
The 5th step: investment is produced biological adsorption agent;
With peristaltic pump connection syringe needle the 4th embedding body that goes on foot preparation slowly being splashed into second goes on foot in the embedding treatment liquid that makes, form the adsorbent bead, leave standstill and solidify 30min, filter, deionized water rinsing 1～5 time is making the biological adsorption agent that particle diameter is 2～3mm behind the freeze drying 24h under-56～-40 ℃ of conditions.
5. preparation method according to claim 4 is characterized in that: the mode of separating husk, film is that the birds, beasts and eggs shell is immersed in 24h in the water in the step 1, perhaps soaks 2h with 2% watery hydrochloric acid.
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