CN103349967B - Method for preparing magnetic blueberry-pomace material adsorbing heavy metal ions and application of magnetic blueberry-pomace material in removal equipment - Google Patents
Method for preparing magnetic blueberry-pomace material adsorbing heavy metal ions and application of magnetic blueberry-pomace material in removal equipment Download PDFInfo
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- CN103349967B CN103349967B CN201310316983.5A CN201310316983A CN103349967B CN 103349967 B CN103349967 B CN 103349967B CN 201310316983 A CN201310316983 A CN 201310316983A CN 103349967 B CN103349967 B CN 103349967B
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Abstract
The invention discloses a method for preparing magnetic blueberry-pomace material adsorbing heavy metal ions and an application of the magnetic blueberry-pomace material in removal equipment, relates to the preparation and the application of materials adsorbing heavy metal ions, and aims to solve the problem that the preparation of the present ferromagnetic adsorbing material has a narrow selection range of raw materials and is high in cost. The method comprises the follow steps: (1) ferromagnetic particles are prepared; (2) blueberry pomace, the ferromagnetic particles and ethanol solution are mixed, then the mixture is added with a cross-linking agent and then is subjected to stirring, filtering, washing and drying to obtain magnetic blueberry pomace particles. Thus, the preparation of the magnetic blueberry-pomace material is completed. The application of the magnetic blueberry-pomace material in the removal equipment is as follows: after back to warm, groundwater to-be-treated enters a precipitation and adsorption treatment pool and then is added with the magnetic blueberry pomace particles; after being treated, the groundwater is discharged. The invention broadens the application range of functional monomers for preparing the adsorbing material, further creates a new thinking as the application for absorbing and removing heavy metal ions in the groundwater, and saves the disposal cost of the blueberry pomace during the production process of blueberries. The method has the advantages that the application is easy to operate; the cost is low; when the magnetic blueberry-pomace material is used for treating the heavy metal ions in the groundwater, the treatment cost is low and the treatment effect is high.
Description
Technical field
The present invention relates to the preparation method of Adsorption of Heavy Metal Ions material and the application in eliminating equipment.
Background technology
Heavy metal pollution refers to the environmental pollution caused by heavy metal and compound thereof.Heavy metal contaminants is difficult to degraded in the environment, can at animal and plant cylinder accumulation, and by food chain progressively enrichment, concentration energy hundreds of millions of even millions of times of ground increases, and finally enters human body and works the mischief, and is one of maximum pollutant of harm humans.At present, the a large amount of surface water and groundwater body of China stands the pollution of heavy metal ion, the impact of heavy metal element in water body on health is increasing, closely bound up with our life, favourable or the harmful kind not only depending on metal of metal in water body, physicochemical property, but also depend on the concentration of metal and the valence state of existence and form, in surface water and groundwater body, the harm of heavy metal pollution to population health is many-sided, multi-level, the method of now main process heavy metal pollution mainly contains: extraction, Coagulation Method, oxidation-reduction method, neutralisation, hyperfiltration and ion-exchange-resin process etc.These separation methods can obtain good separating effect within the scope of metal ion higher concentration, but all not ideal enough to its separating effect of wastewater treatment of low-concentration metallic ion.Current absorption method mainly removes one of underwater gold using method belonging to ion, the application of absorption method and sorbing material has good effect when possessing the aqueous solution containing low-concentration heavy metal ions of the outstanding advantages, particularly process such as simple to operate, with low cost and treating capacity is large.
Blue poison has strong anti-oxidative activity, current more with health care research mainly for absorption of human body, use on a large scale in food, drinks beverage and health products trade, domestic blueberry industry is flourish, blueberry product form is varied, and wherein the relevant enterprise of blueberry production is various, in process of production, directly discarded a large amount of blueberry roughing and unprocessed discarded pomace can be produced, if will be all a kind of waste to whole blueberry industry.
Present stage prepares in magnetic bio sorbing material, functional monomer is the important source material of preparation this kind of material, require that the unsaturated double-bond of energy copolymerzation with cross-linking is contained in one end of functional monomer, the other end then containing can with the reactive group of template molecule or ions binding, polysaccharose substance boiomacromolecule is also started to be used as the function monomer of polymerism, for the preparation of the functional monomer of adsorbability polymer, the unsaturated double-bond of one end equally containing energy copolymerzation with cross-linking of functional monomer, the other end is then containing the coordinating group that can be combined with metal ion.
At present, the polysaccharide of application, has nature to synthesize and Prof. Du Yucang, Prof. Du Yucang polysaccharide cost is higher, and efficiency is low, and most preparation process all directly adopts occurring in nature polysaccharide biological substance, but mainly concentrate on algae and protein, also have the shitosan one class material of synthesis
Summary of the invention
The present invention seeks to solve and there is containing the preparation of ferromagnetic sorptive material the problem that raw material range of choice is narrow and cost is high now, and the preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material and the application in eliminating equipment are provided.
The preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material, realizes according to the following steps:
One, in the there-necked flask containing protochloride molysite and iron chloride salt mixed solution, add ammoniacal liquor, constant temperature 70 DEG C stirs 4 ~ 6 hours, filters, and distilled water washs, and then vacuum drying 24 ~ 32 hours at 40 ~ 50 DEG C, obtains ferromagnetic particle;
Two, by blueberry pomace, ferromagnetic particle and volumetric concentration be 60% ~ 70% ethanolic solution 1:(0.2 ~ 0.3 in mass ratio): (1.5 ~ 2.5) mix, then crosslinking agent is added, to stir after 2 ~ 3 hours static one day, filtering precipitate, vacuum cooled drying 24 ~ 36 hours at latter 15 ~ 20 DEG C of washing, obtain magnetic blueberry pomace particle, namely complete the preparation of magnetic blueberry pomace Adsorption of Heavy Metal Ions material;
Wherein the thing mass ratio of step one ferrous ions, iron ion, hydroxide ion is 1:1:6;
In step 2, crosslinking agent is acrylate or trimethyl propane;
In step 2, the mass ratio of blueberry pomace and crosslinking agent is 1:(0.1 ~ 0.2).
The application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment of above-mentioned preparation: realize according to the following steps: water pump suction 20 cubic metres of pending underground water enter precipitation and to rise again pond, hydraulic detention time is 6 ~ 12 hours, then precipitation adsorption treatment pond is entered through water pump, 5kg magnetic blueberry pomace particle is added in precipitation adsorption treatment pond, hydraulic detention time is 10 ~ 12 hours, then discharges through outlet pipe.
The present invention effectively uses blueberry resource, by the method that the blueberry pomace resource that production is discarded combines with magnetic bio sorbing material, prepare the sorbing material of environmentally safe, utilization ratio is high, energy consumption is low removal heavy metal, used for contaminated underground water body.
Utilize the glycosidic bond of blueberry and ferromagnetic particle to form magnetic corpuscular ball sorptive material in the present invention, then utilize the anti-oxidation characteristics of blueberry itself and ferromagnetic particle jointly form absorption to the heavy metal ion of body of groundwater and remove.
The present invention's application blueberry pomace is as high molecular polymerization raw material in sorbing material, still belong to the first time, not only containing polysaccharose substance in blueberry pomace, the anthocyanidin wherein had and be rich in abundant vitamin, protein and cellulose, not only can play a role in health care to human body, and possess the physical characteristic that sorbing material should have.
This natural small berry pomace of the present invention's application blueberry pomace is as the raw material Adsorption of Heavy Metals particle of adsorpting polymerization functional monomer, open up and prepared the sorptive material functional monomer scope of application, new approaches have been started in application as the heavy metal ion in Adsorption underground water especially, and have saved pomace obsolescence cost in blueberry production process.
In the present invention, blueberry pomace is due to broken and aspherical particle, polysaccharide in its blueberries and cellulose fully expose, the polysaccharide wherein contained can be cross-linked and embed ferromagnetic particle material by glycosidic bond, when processing the underground water by heavy metal pollution, the ferromagnetic particle of its absorption accelerates the suction-operated of polysaccharide, cellulose, protein heavy metal, so application blueberry pomace has the effect of getting twice the result with half the effort.
The application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment prepared by the present invention, the groundwater treatment device structure adopted is simple, application operating is convenient, with low cost, heavy metal ion in process underground water, disposal cost is low, treatment effect is good, for the treatment of the underground water of heavy metal superelevation in V class standard, the clearance of its Pb ion is up to 99.1%, the clearance of Cu ion is up to 80.07%, the clearance of Zn ion is up to 89.69%, in view of national underground standards of water quality GB/T14848-93, its index from superelevation on V class, become and be less than IV class.
Accompanying drawing explanation
The equipment schematic diagram that Fig. 1 uses for the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment prepared in the present invention, wherein 1 precipitates pond of rising again, 2 precipitation adsorption treatment ponds, 3 thermometers, 4 outlet pipes, 5 water pumps, 6 water pumps, 7 screen packs.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the preparation method of present embodiment magnetic blueberry pomace Adsorption of Heavy Metal Ions material, realizes according to the following steps:
One, in the there-necked flask containing protochloride molysite and iron chloride salt mixed solution, add ammoniacal liquor, constant temperature 70 DEG C stirs 4 ~ 6 hours, filters, and distilled water washs, and then vacuum drying 24 ~ 32 hours at 40 ~ 50 DEG C, obtains ferromagnetic particle;
Two, by blueberry pomace, ferromagnetic particle and volumetric concentration be 60% ~ 70% ethanolic solution 1:(0.2 ~ 0.3 in mass ratio): (1.5 ~ 2.5) mix, then crosslinking agent is added, to stir after 2 ~ 3 hours static one day, filtering precipitate, vacuum cooled drying 24 ~ 36 hours at latter 15 ~ 20 DEG C of washing, obtain magnetic blueberry pomace particle, namely complete the preparation of magnetic blueberry pomace Adsorption of Heavy Metal Ions material;
Wherein the thing mass ratio of step one ferrous ions, iron ion, hydroxide ion is 1:1:6;
In step 2, crosslinking agent is acrylate or trimethyl propane;
In step 2, the mass ratio of blueberry pomace and crosslinking agent is 1:(0.1 ~ 0.2).
Detailed description of the invention two: present embodiment and detailed description of the invention one stir 5 hours unlike constant temperature in step one 70 DEG C, filters, and distilled water washs, then vacuum drying 28 hours at 45 DEG C.Other step and parameter identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike in step 2 by blueberry pomace, ferromagnetic particle and volumetric concentration be 65% ethanolic solution in mass ratio 1:0.25:2 mix.Other step and parameter identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are 1:0.15 unlike the mass ratio of blueberry pomace in step 2 and crosslinking agent.Other step and parameter identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike stirring in step 2 after 2.5 hours static one day, filtering precipitate, dry 28 hours of vacuum cooled at washing latter 28 DEG C.Other step and parameter identical with one of detailed description of the invention one to four.
Detailed description of the invention six: composition graphs 1, the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment of preparation in detailed description of the invention one: realize according to the following steps: water pump 5 suction 20 cubic metres of pending underground water enter precipitation and to rise again pond 1, hydraulic detention time is 6 ~ 12 hours, then precipitation adsorption treatment pond 2 is entered through water pump 6,5kg magnetic blueberry pomace particle is added in precipitation adsorption treatment pond 2, hydraulic detention time is 10 ~ 12 hours, then discharges through outlet pipe 4.
Precipitating pond 1 object of rising again in present embodiment is make temperature lower ground descend water body to rise again.
In present embodiment, precipitation adsorption treatment pond 2 object carries out adsorbing and precipitating.
Detailed description of the invention seven: present embodiment and detailed description of the invention six to be risen again pond 1 unlike entering precipitation, and hydraulic detention time is 10 hours.Other step and parameter identical with detailed description of the invention six.
Detailed description of the invention eight: present embodiment and detailed description of the invention six or seven are unlike precipitation adsorption treatment pond 2, and hydraulic detention time is 11 hours.Other step and parameter identical with detailed description of the invention six or seven.
Embodiment:
The preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material, realizes according to the following steps:
One, in the there-necked flask containing protochloride molysite and iron chloride salt mixed solution, add ammoniacal liquor, constant temperature 70 DEG C stirs 5 hours, filters, and distilled water washs, and then vacuum drying 28 hours at 45 DEG C, obtains ferromagnetic particle;
Two, by blueberry pomace, ferromagnetic particle and volumetric concentration be 60% ~ 70% ethanolic solution in mass ratio 1:0.25:2 mixing, then crosslinking agent is added, to stir after 2.5 hours static one day, filtering precipitate, dry 28 hours of vacuum cooled at washing latter 18 DEG C, obtain magnetic blueberry pomace particle, namely complete the preparation of magnetic blueberry pomace Adsorption of Heavy Metal Ions material;
Wherein the thing mass ratio of step one ferrous ions, iron ion, hydroxide ion is 1:1:6;
In step 2, crosslinking agent is acrylate;
In step 2, the mass ratio of blueberry pomace and crosslinking agent is 1:0.15.
Composition graphs 1, the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment of above-mentioned preparation: realize according to the following steps: water pump 5 suction 20 cubic metres of pending underground water enter precipitation and to rise again pond 1, hydraulic detention time is 10 hours, then precipitation adsorption treatment pond 2 is entered through water pump 6,5kg magnetic blueberry pomace particle is added in precipitation adsorption treatment pond 2, hydraulic detention time is 11 hours, then discharges through outlet pipe 4.
Pending underground water in the present embodiment, Pb ion concentration 8.53mg/L after testing, Cu ion concentration 5.56mg/L, Zn ion concentration 11.45mg/L, after treatment its Pb ion concentration 0.07mg/L, Cu ion concentration 1.07mg/L, Zn ion concentration 1.18mg/L, clearance is respectively 99.1%, 80.07%, 89.69%, in view of national underground standards of water quality GB/T14848-93, its index from superelevation, becomes and is less than IV class on V class.
Claims (6)
1. the preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material, is characterized in that it realizes according to the following steps:
One, in the there-necked flask containing protochloride molysite and iron chloride salt mixed solution, add ammoniacal liquor, constant temperature 70 DEG C stirs 4 ~ 6 hours, filters, and distilled water washs, and then vacuum drying 24 ~ 32 hours at 40 ~ 50 DEG C, obtains ferromagnetic particle;
Two, by blueberry pomace, ferromagnetic particle and volumetric concentration be 60% ~ 70% ethanolic solution 1:(0.2 ~ 0.3 in mass ratio): (1.5 ~ 2.5) mix, then crosslinking agent is added, to stir after 2 ~ 3 hours static one day, filtering precipitate, vacuum cooled drying 24 ~ 36 hours at latter 15 ~ 20 DEG C of washing, obtain magnetic blueberry pomace particle, namely complete the preparation of magnetic blueberry pomace Adsorption of Heavy Metal Ions material;
Wherein the thing mass ratio of step one ferrous ions, iron ion, hydroxide ion is 1:1:6;
In step 2, crosslinking agent is acrylate or trimethyl propane;
In step 2, the mass ratio of blueberry pomace and crosslinking agent is 1:0.15.
2. the preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material according to claim 1, to it is characterized in that in step one that constant temperature 70 DEG C stirs 5 hours, filter, distilled water washs, then vacuum drying 28 hours at 45 DEG C.
3. the preparation method of magnetic blueberry pomace Adsorption of Heavy Metal Ions material according to claim 1 and 2, it is characterized in that in step 2 by blueberry pomace, ferromagnetic particle and volumetric concentration be 65% ethanolic solution in mass ratio 1:0.25:2 mixing.
4. the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment prepared by claim 1, it is characterized in that it realizes according to the following steps: water pump (5) suction 20 cubic metres of pending underground water enter precipitation and to rise again pond (1), hydraulic detention time is 6 ~ 12 hours, then precipitation adsorption treatment pond (2) is entered through water pump (6), 5kg magnetic blueberry pomace particle is added in precipitation adsorption treatment pond (2), hydraulic detention time is 10 ~ 12 hours, then discharges through outlet pipe (4).
5. the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material according to claim 4 in eliminating equipment, it is characterized in that entering precipitation and to rise again pond (1), hydraulic detention time is 10 hours.
6. the application of magnetic blueberry pomace Adsorption of Heavy Metal Ions material in eliminating equipment according to claim 4 or 5, it is characterized in that precipitation adsorption treatment pond (2), hydraulic detention time is 11 hours.
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| CN201310316983.5A CN103349967B (en) | 2013-07-25 | 2013-07-25 | Method for preparing magnetic blueberry-pomace material adsorbing heavy metal ions and application of magnetic blueberry-pomace material in removal equipment |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085661A1 (en) * | 1982-02-02 | 1983-08-10 | Gelinnovation Handelsaktiebolag | Metal ion adsorbent |
| CN101928085A (en) * | 2009-12-17 | 2010-12-29 | 昆明理工大学 | Micro-electrolysis method for lead and zinc smelting waste water |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085661A1 (en) * | 1982-02-02 | 1983-08-10 | Gelinnovation Handelsaktiebolag | Metal ion adsorbent |
| CN101928085A (en) * | 2009-12-17 | 2010-12-29 | 昆明理工大学 | Micro-electrolysis method for lead and zinc smelting waste water |
Non-Patent Citations (2)
| Title |
|---|
| "磁性交联壳聚糖对稀土金属离子的吸附性能";李继平等;《中国稀土学报》;20020630;第20卷(第3期);第1.3-1.4节 * |
| Silke Schiewer et al.."Pectin-rich fruit wastes as biosorbents for heavy metal removal:Equilibrium and kinetics".《Bioresource Technology》.2007,第99卷 * |
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