CN103170313A - Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment - Google Patents
Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment Download PDFInfo
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- CN103170313A CN103170313A CN2013101059582A CN201310105958A CN103170313A CN 103170313 A CN103170313 A CN 103170313A CN 2013101059582 A CN2013101059582 A CN 2013101059582A CN 201310105958 A CN201310105958 A CN 201310105958A CN 103170313 A CN103170313 A CN 103170313A
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Abstract
The invention discloses a heavy metal modified bioadsorbent and a preparation method thereof as well as an application of the heavy metal modified bioadsorbent in tungsten-containing waste water treatment. The heavy metal modified bioadsorbent is formed by alga or fruit residue sequentially subjected to saponification, saponification crosslinking, graft copolymerization, sulfenyl complexation and xanthation modification treatment. The preparation method of the heavy metal modified bioadsorbent takes certain amount of fruit residue waste or algae as a raw material and comprises the following steps of: cleaning, drying, levigating and sieving, sequentially carrying out saponification, saponification crosslinking, graft copolymerization, sulfenyl complexation and xanthation modification treatment, and then adding active groups adsorbing metal ions into orange peel, so that the aim of improving adsorption capacity of the heavy metal modified bioadsorbent is achieved. The invention also correspondingly provides a method for treating the tungsten-containing waste water by utilizing the heavy metal modified bioadsorbent. The heavy metal modified bioadsorbent has good adsorption effect and is simple to operate, easy to implement, low in cost and high in efficiency.
Description
Technical field
The present invention relates to microbe application field and field of waste water treatment, be specially heavy metal modification biological adsorbent and preparation method thereof and the application in processing tungstenic waste water.
Background technology
Tungsten belongs to rare metal, has high-melting-point, and the characteristics of high rigidity are widely used in the every field such as metallurgy, machinery, oil, mine, electronics and Aero-Space.Particularly after 18 Great Councils, each tungsten smelting enterprise is faced with the enterprise transformation upgrading, eliminates environmental protection enterprise not up to standard and factory building, and develop pollution-free metallurgical technology aspect, its special advantage is arranged.During with the alkali Decomposition of Tungsten, heavy metal ion in mineral etc. are also in company with advancing in people's coarse sodium tungstate, advance people's waste water with the rear liquid of its exchange when the ion-exchange purification of tungsten in, when washing exchange column subsequently from resin after with strippant, tungsten being freed, can produce a large amount of heavy metal ion-containing waste waters, at present APT manufacturer returns to leach to this type of waste water more and utilizes, and result causes the heavy metal in waste water impurity content to raise, and directly affects the purity of APT and the processability of follow-up tungsten-bast alloy new material.Therefore the Novel impurity-cleaning reagent of efficient, the cleaning of developmental research, inexpensive easy reuse is extremely urgent.
At present, existing researcher uses the fruit residues such as citrus pulp, pomace, persimmon powder to come heavy metal ion in Adsorption water, and is doing a lot of work aspect the chemical modification of fruit residue.The materials such as a large amount of pectin that the fruit residue is rich in, tannin can adsorb the heavy metal ion in solution.Algae is a kind of plant that heavy metal ion is had good enrichment, can be widely used among the processing of the improvement in heavy metal pollution waters and trade effluent, can also be used for reclaiming valuable metal ions.But directly adopt the fruit residue as adsorbent have that adsorption capacity is little, the shortcoming such as unstable properties, adsorption equilibrium are difficult to reach, be mainly due to water soluble ingredient wherein, non-pectin, the tannin composition is more and the exposed cause such as less of active group; In addition, contain pectic substance as a kind of natural adsorbent, the heavy metal ion in adsorbent solution to a certain degree, but the strong aquation of pectin hinders its direct application, therefore must carry out chemical modification to it and process.To further studies show that of biological adsorption, the fruit residue is carried out chemical modification, the activity of pectin and tannin is improved, the ability of Adsorption of Heavy Metals strengthens; Pomace is carried out crosslinking Treatment, can weaken the hydration characteristic of pectin, improve it to the absorption property of heavy metal.
Summary of the invention
Technical problem solved by the invention is: for the deficiency of prior art existence, a kind of heavy metal modification biological adsorbent of high adsorption capacity is provided, correspondingly provide a kind of method for preparing this heavy metal modification biological adsorbent, a kind of method of this heavy metal modification biological sorbent treatment tungstenic waste water also is provided.The present invention with biological adsorption agents such as algae and fruit residues as matrix material, take the waste water of tungsten smelting enterprise and polluted water region as destination object, take Coordinative Chemistry, molecular structure theory, adsorption theory as guidance, take chemical modification as means, " cut the garment according to the figure " and design active group, the high-performance bio adsorbent that synthesizes high-adsorption-capacity realizes that biological adsorption agent efficiently utilizes, heavy metal polluted waste water purifies and the purpose of heavy metal recycling multi-efficiency.
Technical problem solved by the invention realizes by the following technical solutions:
One heavy metal species modification biological adsorbent, by, graft copolymerization crosslinked through saponification, saponification successively, sulfenyl coordinates and the xanthogenation modification after algae or fruit residue form.
The present invention provides a kind of method for preparing heavy metal modification biological adsorbent accordingly, comprises the following steps:
Take the fruit residue waste material of certain mass or algae as raw material, through cleaning, oven dry, levigate and sieve after,, graft copolymerization crosslinked through saponification, saponification successively, sulfenyl coordinate and the xanthogenation modification, introduce the active group of adsorbing metal ions again in orange peel, thereby reach the target that improves its adsorption capacity.
The present invention also provides the method for utilizing above-mentioned heavy metal modification biological sorbent treatment tungstenic waste water accordingly, comprises the following steps:
Adopt single bottle to reach the continuous dual mode of post absorption in batches and study, preparation contains the model solution of various heavy metal ion, comprise arsenic, cadmium, lead, copper, zinc etc., adopt single bottle of constant temperature oscillation method to measure heavy metal ion adsorbed static behavior, comprise the dynamics etc. of selective, the absorption that affects rule (as the competitive Adsorption of pH, initial concentration, adsorbent consumption, temperature, time of contact, coexisting ion etc.), absorption of load capacity, adsorption conditions; Dynamic column adsorption process mensuration drafting adsorbent adsorbs the elution curve of various heavy metal ion in exchange column, understand the feature of Adsorption Dynamic behavior; Desorption process adopts the solution of different systems and variable concentrations to carry out backwash, and heavy metal ion is shifted from adsorbent, investigates the desorption ability of biological adsorption agent and the enrichment behavior of heavy metal ion.
Innovative point of the present invention
(1) innovation biological adsorption agent preparation technology forms heavy metal wastewater thereby biological adsorption new method
Take aqueous solution metal ion as destination object, the biological adsorption agents such as algae, fruit residue are carried out chemical modification design and specific aim processing, obtain the high-performance bio adsorbent of high-adsorption-capacity.The method is that heavy metal wastewater thereby is administered new method, possesses raw material sources extensive, and with low cost, effect is good, and is simple to operate, and can not produce the advantage of secondary pollution.
(2) by the modified adsorbent application study, realize resource circulation utilization
Adopting raw material is common algae and discarded fruit residue of south, and raw material is cheap and easy to get, turns waste into wealth, and processes the heavy metal ion-containing waste water of Ganzhou tungsten smelting enterprise, administers the heavy metal pollution in waters, Ganzhou, and the treatment of wastes with processes of wastes against one another realizes resource circulation utilization.
Compared with prior art, the present invention has the following advantages:
The present invention with algae and fruit residue as raw material, at first adopt simple chemical method to carry out modification to it, change its surface texture and surface-active number of functional groups, then add and carry out the metal biosorption process in the tungsten smelting wastewater, filter after adsorption process, filter residue is used for recycling metal wherein, and waste water reaches emission request through processing.This treatment technology has that process is simply controlled, automaticity is high, metal recovery rate is high, supplementary product onsumption is few, technological process is short, equipment is simple, production efficiency is high, and the processing procedure cost is low.This technology mainly is divided into the modifying process of biological adsorption agent and the sewage disposal process of modification biological adsorbent.Modifying process is divided into gas-phase modification and liquid phase modification, be mainly the liquid phase modification herein, according to different demands, modification can be carried out in different modifying agents and different liquid phase environment, then pass through filtration drying, can obtain the modified adsorbent of required microstructure and active group.Then adsorbent is added and stir vibration, then filtered and recycled metal ion wherein in sewage.This method has suitable advantage, and whole process stabilization is controlled, the modified adsorbent advantages of good adsorption effect.Compare with other conventional methods, this method has the following advantages:
1) wide adaptability can operate under different pH, temperature and process.The modification biological adsorbent has very strong adaptability, can carry out adsorption of metal ions in waste water under various environment, and stability is strong, for wastewater treatment, good application is arranged.
2) selective high, can be from solution Adsorption of Heavy Metal Ions and be not subjected to the interference of alkali metal ion.Except wide adaptability, the surface active groups of modification biological adsorbent has very high selective for the absorption of heavy metal ion, can not be subject to the impact of other foreign ions, thereby facilitate the subsequent recovery utilization of metal ion.
3) the concentration of metal ions impact is little.The modification biological adsorbent for the metal biosorption principle be its surperficial active group to metal biosorption power, so no matter in waste water concentration of metal ions what are, modified adsorbent all can have very good effect.
4) power of regeneration is strong, step is simple, and after regeneration, adsorption capacity is without obvious reduction.The power of regeneration of active bio adsorbent of adsorbing metal ion is strong, and regeneration step is simple, easy operating, and repeatedly repetitive cycling is used.
5) modification biological adsorbent technology and equipment interoperability thereof are high, are fit to process multiple solution, and adaptability to raw material is wide, realize product diversification by adjusting reaction condition, and manufacturing cost is than traditional handicraft decrease, and industrialization prospect is good.
The specific embodiment
In order to make technological means of the present invention, creation characteristic, workflow, using method reach purpose and effect is easy to understand, below further set forth the present invention.
Take the reaction mechanism of orange peel Adsorption of Heavy Metal Ions as example, concrete technology path is: take the natural orange peel waste material of certain mass as raw material, through cleaning, oven dry, levigate and sieve after,, graft copolymerization crosslinked through saponification, saponification successively, sulfenyl coordinates and the xanthogenation modification after, introduce the active group of adsorbing metal ions again in orange peel, thereby can improve its adsorption capacity.In the absorbent preparation process, constituent structure and modification sign adopts the Instrumental Analysis such as infrared spectrum, ultraviolet spectra, nuclear magnetic resonance to carry out, and the effects of ion behavior adopts the solution equilibria analysis to carry out in conjunction with plasma spectrum, infrared spectrum analysis etc.; Binding soln character and metal ion architectural feature are wherein adjusted the pending solution of following adopted biological adsorption agent; Follow-up fixed mixing ratio according to adsorbent and pending solution can be added suitable catalyst, adopts single bottle of constant temperature oscillation method or dynamic column absorption method to carry out adsorption test.
Need in process of the test its adsorption equilibrium and adsorption process dynamics research, can adopt atomic absorption spectrum etc. to belong to ion concentration and change to deduce and draw by measuring GOLD FROM PLATING SOLUTION, adopt single bottle of constant temperature oscillation method to measure heavy metal ion adsorbed static behavior, comprise the dynamics etc. of selective, the absorption that affects rule (as the competitive Adsorption of pH, initial concentration, adsorbent consumption, temperature, time of contact, coexisting ion etc.), absorption of load capacity, adsorption conditions; Dynamic column adsorption process mensuration drafting adsorbent adsorbs the elution curve of various heavy metal ion in exchange column, understand the feature of Adsorption Dynamic behavior; Desorption process adopts the solution of different systems and variable concentrations to carry out backwash, heavy metal ion is shifted from adsorbent, with the desorption ability of understanding biological adsorption agent and the enrichment behavior of heavy metal ion; By adsorption process balance and dynamics research, carry out summarizes, draw the technical regulation parameter of applicable industrial applications.
This project is intended the parameters in whole technology path is carried out quantitative assay, to heavy metal treatment effect in solution, determines optimal parameter according to the biological adsorption agent for preparing.In addition, carry out the influence factors such as adsorption equilibrium, adsorption dynamics adsorption kinetics, adsorption capacity, adsorption mechanism, adsorptive selectivity and many metallic solutions system for whole process and carry out scrutiny, and with various analysis of modernization means, different phase absorption behavior in process is carried out phenetic analysis, comprise metal analytic ability and enrichment behavior etc. under its solution composition, coexisting ion architectural feature, elution curve, different system and concentration.
Above demonstration and described basic principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (3)
1. a heavy metal species modification biological adsorbent is characterized in that: by, graft copolymerization crosslinked through saponification, saponification successively, sulfenyl coordinates and the xanthogenation modification after algae or fruit residue form.
2. method for preparing heavy metal modification biological adsorbent as claimed in claim 1 comprises the following steps:
Take the fruit residue waste material of certain mass or algae as raw material, through cleaning, oven dry, levigate and sieve after,, graft copolymerization crosslinked through saponification, saponification successively, sulfenyl coordinate and the xanthogenation modification, then introduce the active group of adsorbing metal ions in the orange peel.
3. method of utilizing the heavy metal modification biological sorbent treatment tungstenic waste water of heavy metal modification biological adsorbent as claimed in claim 1 or preparation method as claimed in claim 2 preparation comprises the following steps:
Adopt single bottle to reach the continuous dual mode of post absorption in batches and study, preparation contains the model solution of various heavy metal ion, comprise arsenic, cadmium, lead, copper, zinc etc., adopt single bottle of constant temperature oscillation method to measure heavy metal ion adsorbed static behavior, comprise the dynamics etc. of selective, the absorption that affects rule, absorption of load capacity, adsorption conditions; Dynamic column adsorption process mensuration drafting adsorbent adsorbs the elution curve of various heavy metal ion in exchange column, understand the feature of Adsorption Dynamic behavior; Desorption process adopts the solution of different systems and variable concentrations to carry out backwash, and heavy metal ion is shifted from adsorbent, investigates the desorption ability of biological adsorption agent and the enrichment behavior of heavy metal ion.
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Cited By (4)
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| CN104573273A (en) * | 2015-01-27 | 2015-04-29 | 江西理工大学 | Building method of modified bioadsorbent structure-activity relationship model and application thereof |
| CN104710014A (en) * | 2015-03-23 | 2015-06-17 | 泰山医学院 | Method for adsorbing heavy metal ion chromium in water by using modified Ascophyllum Nodosum |
| CN107986498A (en) * | 2017-12-20 | 2018-05-04 | 北京科技大学 | The method of sulphion in a kind of precipitation-biological adsorption combination removing waste water |
| CN113413887A (en) * | 2021-07-04 | 2021-09-21 | 南昌大学 | Compound lead ion adsorbent m-phenylenediamine polymerized pectin microspheres and preparation method thereof |
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| JP2000237741A (en) * | 1999-02-16 | 2000-09-05 | Katsutoshi Inoue | Separation method of lead ion using orange squeezed juice residue |
| CN101837282A (en) * | 2010-02-02 | 2010-09-22 | 中南大学 | Biological adsorbent for adsorbing heavy metal ions and preparation method and application thereof |
| CN102059099A (en) * | 2010-12-10 | 2011-05-18 | 中南大学 | Biological adsorbent for waste water treatment and preparation method thereof |
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| JP2000237741A (en) * | 1999-02-16 | 2000-09-05 | Katsutoshi Inoue | Separation method of lead ion using orange squeezed juice residue |
| CN101837282A (en) * | 2010-02-02 | 2010-09-22 | 中南大学 | Biological adsorbent for adsorbing heavy metal ions and preparation method and application thereof |
| CN102059099A (en) * | 2010-12-10 | 2011-05-18 | 中南大学 | Biological adsorbent for waste water treatment and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104573273A (en) * | 2015-01-27 | 2015-04-29 | 江西理工大学 | Building method of modified bioadsorbent structure-activity relationship model and application thereof |
| CN104573273B (en) * | 2015-01-27 | 2017-05-24 | 江西理工大学 | Building method of modified bioadsorbent structure-activity relationship model and application thereof |
| CN104710014A (en) * | 2015-03-23 | 2015-06-17 | 泰山医学院 | Method for adsorbing heavy metal ion chromium in water by using modified Ascophyllum Nodosum |
| CN107986498A (en) * | 2017-12-20 | 2018-05-04 | 北京科技大学 | The method of sulphion in a kind of precipitation-biological adsorption combination removing waste water |
| CN113413887A (en) * | 2021-07-04 | 2021-09-21 | 南昌大学 | Compound lead ion adsorbent m-phenylenediamine polymerized pectin microspheres and preparation method thereof |
| CN113413887B (en) * | 2021-07-04 | 2022-09-23 | 南昌大学 | Compound lead ion adsorbent m-phenylenediamine polymerized pectin microspheres and preparation method thereof |
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Application publication date: 20130626 |