CN101607191B - Liner for separating metal ions and preparation method thereof - Google Patents
Liner for separating metal ions and preparation method thereof Download PDFInfo
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- CN101607191B CN101607191B CN2008100391599A CN200810039159A CN101607191B CN 101607191 B CN101607191 B CN 101607191B CN 2008100391599 A CN2008100391599 A CN 2008100391599A CN 200810039159 A CN200810039159 A CN 200810039159A CN 101607191 B CN101607191 B CN 101607191B
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- zeolite
- courage body
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Abstract
The invention relates to a liner for separating metal ions, which is characterized in that: the liner consists of the following compositions in percentage by weight: 50 to 100 percent of polymer resin, 0 to 25 percent of active carbon and 0 to 25 percent of zeolite; the polymer resin, the active carbon and the zeolite are all processed; and the polymer resin is any one of polyester resin, epoxy resin and pseudoceramide copolymer resin. The invention solves the problem that an inorganic ion exchange adsorbent is difficult to form and has high solution loss and poor fluidity and permeability, and utilizes characteristics of organic ion exchange resin to generate a novel liner for separating the metal ions; and the liner has the advantages of good adsorption selectivity, quick exchange speed, high adsorption capacity, less solution loss, capability of being recycled, and low cost.
Description
Technical field:
The present invention relates to the technical field of separation of metal ions material, specifically utilize the characteristic of metal ion, design a kind of absorption or ion exchange principle of adopting and extract separation of metal ions courage body of metal ion and preparation method thereof, relate in particular to the processing method of courage body material wherein.
Background technology:
New adsorption and separation material is all being explored in countries in the world at present, the direct single high pure metal ion of separation and Extraction from be rich in metal, alkali metal, alkaline-earth metal plasma liquid.But existing adsorption and separation material, organic ion exchanger resin and inorganic ions exchange and adsorbent in function, efficient, cost and suitability for industrialized production, all can't reach requirement.
Summary of the invention:
The object of the present invention is to provide a kind of courage body that is used for separation of metal ions and preparation method thereof, this courage body has the advantages that adsorptive selectivity, exchange velocity are comparatively fast preferably, adsorption capacity is bigger.
Technical scheme of the present invention is achieved in that a kind of courage body that is used for separation of metal ions, it is characterized in that: described courage body is made up of macromolecule resin, active carbon and zeolite, their percentage by weight is, macromolecule resin 50-100%, active carbon 0-25%, zeolite 0-25%, macromolecule resin, active carbon, zeolite are all treated, macromolecule resin be mylar, epoxy resin, and vinegar amine copolymer resin in any one.
A kind of courage preparation that is used for separation of metal ions is characterized in that: described courage preparation may further comprise the steps:
A, activated carbon, zeolite are carried out 350-550 ℃ heat treated respectively, be to form the high surface courage body material with porous crack or many irregular surfaces structure in 5-20 hour heat time heating time; B, be mylar, epoxy resin, and vinegar amine copolymer resin with water-fast macromolecule resin, being heated to 45-135 ℃, heat time heating time respectively is 1-48 hour, then with the nitric acid of 0.1M-0.5M dilution, and the acid of 0.1M-0.5M dilution salt wash processing, the high surface courage body material that makes macromolecule resin material formation have porous crack or many irregular surfaces structure according to the mixed acid that the volume ratio of 0-10: 1-10 mixes; C, will wash the high surface courage body material macromolecule resin after handling, high surface courage body material activity charcoal and the zeolite after the heat treated mixes with organic solvent respectively separately, be dispersed in respectively and form nonpolar organic facies between organic solvent fluid; D, polar liquid phase added in the nonpolar organic facies of each self-forming and carry out the Hybrid Heating reaction respectively, heating-up temperature is 50-135 ℃, time 1-26 hour, is processed into the high surface area material of organic or inorganic respectively; E, the high surface area material that will add the organic or inorganic that is processed into respectively after the thermal response adopt water or methyl alcohol respectively, clean at 10～60 ℃; The high surface area material of f, the organic or inorganic after will cleaning respectively adopts hot blast to carry out drying respectively, and baking temperature is 40-80 ℃, and be 1-24 hour drying time; G, be that the ratio of high surface area material macromolecule resin 50-100%, active carbon 0-25%, zeolite 0-25% is carried out filling in matrix, can produce separation of metal ions courage body then according to percentage by weight.
The present invention is processed into high surface courage body material with activated carbon, zeolite, water insoluble macromolecule resin in brief, be dispersed in respectively between organic solvent fluid and form a nonpolar organic facies, but and with comprise that polar liquid phase that the functional group, alcohol compound and the water that possess addition reaction is formed produces Hybrid Heating and reacts.To react back material cleaning, drying, and select the desirable characteristics material to mix to scale, can produce the separation of metal ions courage body of novelty.
The invention solves inorganic ions exchange and adsorbent, difficult forming, molten damage height, flowability is poor, permeability is not good, and utilize the characteristic of organic ion exchanger resin, produce a kind of novel separation of metal ions courage body, have the good adsorption selectivity, exchange velocity is fast, adsorption capacity is big, it is little, reusable hold to decrease, cost is cheap relatively.
Description of drawings:
Fig. 1 is a schematic flow sheet of the present invention
Fig. 2 is a courage body material processed schematic diagram
Fig. 3 is nonpolar organic synthesis schematic diagram
Fig. 4 is the synthetic schematic diagram of polar liquid phase
Fig. 5 is Hybrid Heating reaction schematic diagram
The specific embodiment:
The invention will be further described below in conjunction with drawings and Examples.
A kind of courage body that is used for separation of metal ions, it is characterized in that: described courage body is made up of macromolecule resin, active carbon and zeolite, their percentage by weight is, macromolecule resin 50-100%, active carbon 0-25%, zeolite 0-25%, macromolecule resin, active carbon, zeolite are all treated, macromolecule resin be mylar, epoxy resin, and vinegar amine copolymer resin in any one or wherein any combination of 2-3 kind.
A kind of courage preparation that is used for separation of metal ions is characterized in that: described courage preparation may further comprise the steps:
A, activated carbon, zeolite are carried out 350-550 ℃ heat treated respectively, be to form the high surface courage body material with porous crack or many irregular surfaces structure in 5-20 hour heat time heating time; B, be mylar, epoxy resin, and vinegar amine copolymer resin with water-fast macromolecule resin, being heated to 45-135 ℃, heat time heating time respectively is 1-48 hour, then with the nitric acid of 0.1M-0.5M dilution, and the acid of 0.1M-0.5M dilution salt wash processing, the high surface courage body material that formation has porous crack or many irregular surfaces structure according to the mixed acid that the volume ratio of 0-10: 1-10 mixes; C, will wash the high surface courage body material macromolecule resin after handling, high surface courage body material activity charcoal and the zeolite after the heat treated mixes with organic solvent respectively separately, be dispersed in respectively and form nonpolar organic facies between organic solvent fluid; D, polar liquid phase added respectively in the nonpolar organic facies of each self-forming and carry out the Hybrid Heating reaction, heating-up temperature is 50-135 ℃, time 1-26 hour, is processed into the high surface area material of organic or inorganic respectively; E, the high surface area material that will add the organic or inorganic that is processed into respectively after the thermal response adopt water or methyl alcohol respectively, clean at 10～60 ℃ and remove remaining salt and unreacted reactant; The high surface area material of f, the organic or inorganic after will cleaning respectively adopts hot blast to carry out drying respectively, and baking temperature is 40-80 ℃, and be 1-24 hour drying time; G, be that the ratio of high surface area material macromolecule resin 51-99%, active carbon 1-25%, zeolite 1-25% is carried out filling in matrix, can produce separation of metal ions courage body then according to percentage by weight.All belong to prior art about matrix and filling, matrix is the container body that carries out separation of metal ions, but the container body is a kind of closed container of demolition, installation, and volume is 0.001～10 cubic metre.Filling is according to the required time of staying of different metal solution, with the high surface area material of different organic or inorganics in above-mentioned ratio, carry out filling with layering or the mode that mixes, the filling step is: earlier the container body is taken apart, loaded and enter the container body with the inorganic high surface area material of the organic high surface area material one deck of one deck, regularly arranged mode, or organic high surface area material and inorganic high surface area material are mixed filling enter the container body, make separation of metal ions courage body.
Beginning 1, the material 2 of courage body is made in selection earlier, is divided into two big groups.Be a group and be a group with activated carbon 2.11, zeolite 2.12 with mylar 2.21, epoxy resin 2.22, vinegar amine copolymer resin 2.23.With two big group materials, be processed into high surface courage body material 3 respectively, be dispersed in again and form a nonpolar organic facies 4 between organic solvent 4.0 liquid; With polar liquid phase 5: comprise functional group 5.1, alcohol compound 5.2, the water 5.3 that possesses addition reaction but wherein form, add in the nonpolar organic facies 4 and continue in adding thermal response 6.After the reaction material is cleaned 7, dry 8, to handle the macromolecule resin material of back according to necessary requirement: mylar 8.21, epoxy resin 8.22, vinegar amine copolymer resin 8.23, with activated carbon 8.11, and zeolite 8.12, according to 50-100%: 0-25%: 0-25% part by weight lamination or evenly hybrid mode filling 9, the novel separation of metal ions courage body that is formed.High surface courage body material is meant that the ratio of total surface area/volume of this courage body material greater than more than 3 times, stirs with 10～2000rpm, polar liquid phase is added continue to be heated to 50～135 ℃, 1～26 hour time in the nonpolar organic facies.Organic solvent described in the present invention means Ethyl formate, methyl acetate, ethyl acetate, methyl iso-butyl ketone (MIBK), cyclohexanone, tetrahydrochysene Furans, arsenic pyridine, methyl Dimethyl formamide, dimethyl ethanamide, three cyclic ethers, Fourth Ring ether and other ethers, carrene, dichloroethanes, chloroform, selection is wherein a kind of or any combination of at least two kinds.Described polar liquid phase is made up of functional group, alcohol compound, water, and their mol ratio is 1-10: 1-2: 0-2, functional group, alcohol compound, water are mixed and stirs mixing time 1-30 minute; The functional group means one or both the random mixing in toluene sulphur vinegar chlorine or the methyl sulphur vinegar chlorine; Alcohol compound means the random mixing of a kind of in ethylene glycol, propane diols, butanediol, pentanediol, glyceryl alcohol, unit or polyalcohol or the polyhydric phenols or at least two kinds.During concrete enforcement, the mixing plant of use is 100～1000rpm.When cleaning, as adopting methyl alcohol, the purity of methyl alcohol is 70%～100%.
Innovation of the present invention mainly is that the processing of the organic or inorganic material of making the courage body and these courage body materials are applicable to the proportioning that constitutes the courage body when separating the concentrating metals ion in the different hybrid metal solution, uses principle of the present invention and advantage to be:
Utilize affinitys different between metal ion, associativity and element distribution sorting, make ion and other kind ion isolation in the metal ion liquid, reach effectively and purpose fast with different materials.The present invention has avoided the molten loss rate height of inorganic nature adsorption material, flowability is poor, permeability is not good and difficult forming,, problems such as exchange velocity slow, adsorption capacity little, utilization rate low, cost height poor with organic ion exchanger resin adsorptive selectivity.More adopt the highly enriched property and the close property of the organic material resistance to compression characteristics of inorganic nature adsorption material, produce a kind of separation of metal ions courage body of novelty again.
Provide specific embodiment below
Embodiment A, utilize the present invention to make to be useful in and separate the courage body that concentrates copper ion in the hybrid metal solution.It is courage body material that present embodiment is selected with zeolite and mylar, zeolite is heated to 400～425 ℃, 8 hours time earlier, mylar is heated to 75～85 ℃, 6～8 hours time, then with after the 0.25M Xi salt acid flushing, be dispersed in the methyl iso-butyl ketone (MIBK) of 2 times of volumes, the solvent that the tetrahydrochysene Furans is constituted, constitute nonpolar phase; Polarity mutually in, with toluene sulphur vinegar chlorine is the functional group, the selection pentanediol is an alcohol radical, with the functional group: alcohol radical: the mole ratio of water=2: 1: 1 is mixed, add in the nonpolar phase and stir with 200～300rpm, continue to be heated to 92～98 ℃, the reaction of 16～20 hours time formation Hybrid Heating, reaction back is with 70% purity washed with methanol and 45 ℃ of dryings after 4 hours, the courage body is with mylar: the ratio of zeolite=10: 1 is mixed, form the courage body of separating copper ion in the hybrid metal solution, have the effect that primary first-order equation can form 12～20 times of concentrated copper ions.
Embodiment B, utilize the present invention to make to be useful in and separate the courage body that concentrates zinc, nickel ion in the hybrid metal solution that contains organic matter.It is courage body material that present embodiment is selected with active carbon and vinegar amine copolymer resin, it is standby that active carbon is heated to 525～550 ℃, 4 hours time earlier, vinegar amine copolymer resin is heated to 65～80 ℃, 3～4 hours time, then with after 0.25M Xi salt acid/rare nitric acid flushing of one to one, be dispersed in the arsenic pyridine of 2.5 times of volumes and the solvent that three cyclic ethers are constituted, constitute nonpolar phase.Polarity mutually in, with methyl sulphur vinegar chlorine is the functional group, selecting propane diols and benzoglycols is alcohol radical, with the functional group: alcohol radical: the mole ratio of water=2: 2: 0.5 is mixed, add in the nonpolar phase and stir with 80～120rpm, continue to be heated to 78～85 ℃, 24～26 hours time formed the Hybrid Heating reaction, reaction back water and methyl alcohol (weight ratio 1: 1) cleaning and 50 ℃ of dryings are after 5 hours, the courage body mixes with the ratio of vinegar amine copolymer portions of resin active carbon=25: 3, formation is useful in separation of Zinc in the hybrid metal solution that contains organic matter, the courage body of nickel ion, can effectively reduce organic property material in conjunction with zinc, interference when nickel ion separates can reach the effect that concentrates 12 times of object ions simultaneously.
Embodiment C, utilize the present invention to make to be useful in hybrid metal and the nonmetallic ion solution, separating the courage body that concentrates zinc, nickel ion. it is courage body material that present embodiment is selected with active carbon, zeolite and mylar, it is standby that active carbon is heated to 525～550 ℃ earlier, zeolite is heated to 4～5 hours 425～450 ℃ of times, mylar is heated to 70～85 ℃, 2～3 hours time, after using 5: 1 0.15M Xi salt acid/rare nitric acid flushing then, be dispersed in the solvent that the dimethyl ethanamide and the cyclohexanone of 3.5 times of volumes constituted, constitute nonpolar phase.Polarity mutually in, with toluene sulphur vinegar chlorine is the functional group, selecting propane diols and glycerine is alcohol radical, with the functional group: alcohol radical: the mole ratio of water=2: 2: 1 is mixed, add in the nonpolar phase and stir with 100～120rpm, continue to be heated to 65～85 ℃, 20～24 hours time formed the Hybrid Heating reaction, the water cleaning of reaction back and 50 ℃ of dryings are after 5 hours, the courage body is with mylar: active carbon: the ratio of zeolite=30: 3: 2 is mixed, formation is useful in hybrid metal and the nonmetallic ion solution, separate and concentrate zinc, the courage body of nickel ion can effectively avoid nonmetallic ion to disturb zinc, the nickel ion separating effect can reach the purpose that concentrates 12 times of object ions simultaneously.
Claims (6)
1. courage body that is used for separation of metal ions, it is characterized in that: described courage body is made up of macromolecule resin, active carbon and zeolite, their percentage by weight is, macromolecule resin 51-99%, active carbon 1-25%, zeolite 1-25%, their component sum is 100%, macromolecule resin, active carbon, zeolite are all treated, macromolecule resin be mylar, epoxy resin, and vinegar amine copolymer resin in any one or wherein any combination of 2-3 kind.
2. courage preparation that is used for separation of metal ions, it is characterized in that: described courage preparation may further comprise the steps:
A, activated carbon, zeolite are carried out 350-550 ℃ heat treated respectively, be to form the high surface courage body material with porous crack or many irregular surfaces structure in 5-20 hour heat time heating time; B, be mylar, epoxy resin, and vinegar amine copolymer resin with water-fast macromolecule resin, being heated to 45-135 ℃, heat time heating time respectively is 1-48 hour, then with the nitric acid of 0.1M-0.5M dilution, and the acid of 0.1M-0.5M dilution salt wash processing, the high surface courage body material that makes macromolecule resin material formation have porous crack or many irregular surfaces structure according to the mixed acid that the volume ratio of 0-10: 1-10 mixes; C, will wash the high surface courage body material macromolecule resin after handling, high surface courage body material activity charcoal and the zeolite after the heat treated mixes with organic solvent respectively separately, be dispersed in respectively and form nonpolar organic facies between organic solvent fluid; D, polar liquid phase added in the nonpolar organic facies of each self-forming and carry out the Hybrid Heating reaction respectively, heating-up temperature is 50-135 ℃, time 1-26 hour, is processed into the high surface area material of organic or inorganic respectively; E, the high surface area material that will add the organic or inorganic that is processed into respectively after the thermal response adopt water or methyl alcohol more respectively, clean at 10～60 ℃; The high surface area material of f, the organic or inorganic after will cleaning respectively adopts hot blast to carry out drying respectively, and baking temperature is 40-80 ℃, and be 1-24 hour drying time; G, be that the ratio of high surface area material macromolecule resin 50-100%, active carbon 0-25%, zeolite 0-25% is carried out filling in matrix, can produce separation of metal ions courage body then according to percentage by weight.
3. courage preparation that is used for separation of metal ions, it is characterized in that: described courage preparation may further comprise the steps:
A, activated carbon, zeolite are carried out 350-550 ℃ heat treated respectively, be to form the high surface courage body material with porous crack or many irregular surfaces structure in 5-20 hour heat time heating time; B, be mylar, epoxy resin, and vinegar amine copolymer resin with water-fast macromolecule resin, being heated to 45-135 ℃, heat time heating time respectively is 1-48 hour, then with the nitric acid of 0.1M-0.5M dilution, and the acid of 0.1M-0.5M dilution salt wash processing, the high surface courage body material that formation has porous crack or many irregular surfaces structure according to the mixed acid that the volume ratio of 0-10: 1-10 mixes; C, will wash the high surface courage body material macromolecule resin after handling, high surface courage body material activity charcoal and the zeolite after the heat treated mixes with organic solvent respectively separately, be dispersed in respectively and form nonpolar organic facies between organic solvent fluid; D, polar liquid phase added respectively in the nonpolar organic facies of each self-forming and carry out the Hybrid Heating reaction, heating-up temperature is 50-135 ℃, time 1-26 hour, is processed into the high surface area material of organic or inorganic respectively; E, the high surface area material that will add the organic or inorganic that is processed into respectively after the thermal response adopt water or methyl alcohol respectively, clean at 10～60 ℃ and remove remaining salt and unreacted reactant; The high surface area material of f, the organic or inorganic after will cleaning respectively adopts hot blast to carry out drying respectively, and baking temperature is 40-80 ℃, and be 1-24 hour drying time; G, according to percentage by weight be then, the ratio of high surface area material macromolecule resin 51-99%, active carbon 1-25%, zeolite 1-25%, their component sum is 100%, carries out filling in matrix, can produce separation of metal ions courage body.
4. by claim 2 or 3 described a kind of courage preparations that are used for separation of metal ions, it is characterized in that: described organic solvent means Ethyl formate, methyl acetate, ethyl acetate, methyl iso-butyl ketone (MIBK), cyclohexanone, oxolane, methyl Dimethyl formamide, dimethyl ethanamide, three cyclic ethers, Fourth Ring ether and other ethers, carrene, dichloroethanes, chloroform, selection is wherein a kind of or any combination of at least two kinds.
5. by claim 2 or 3 described a kind of courage preparations that are used for separation of metal ions, it is characterized in that: described polar liquid phase is made up of functional group, alcohol compound, water, their mol ratio is 1-10: 1-2: 0-2, functional group, alcohol compound, water are mixed and stir mixing time 1-30 minute; The functional group means one or both the random mixing in toluene sulphur vinegar chlorine or the methyl sulphur vinegar chlorine; Alcohol compound means the random mixing of a kind of in ethylene glycol, propane diols, butanediol, pentanediol, the glyceryl alcohol or at least two kinds.
6. by claim 2 or 3 described a kind of courage preparations that are used for separation of metal ions, it is characterized in that: described polar liquid phase is made up of functional group, alcohol compound, water, their mol ratio is 1-10: 1-2: 0-2, functional group, alcohol compound, water are mixed and stir mixing time 1-30 minute; The functional group means one or both the random mixing in toluene sulphur vinegar chlorine or the methyl sulphur vinegar chlorine; Alcohol compound means the random mixing of a kind of in unit or polyalcohol or the polyhydric phenols or at least two kinds.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100391599A CN101607191B (en) | 2008-06-18 | 2008-06-18 | Liner for separating metal ions and preparation method thereof |
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| CN2008100391599A CN101607191B (en) | 2008-06-18 | 2008-06-18 | Liner for separating metal ions and preparation method thereof |
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| CN101607191A CN101607191A (en) | 2009-12-23 |
| CN101607191B true CN101607191B (en) | 2011-08-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103585987A (en) * | 2013-10-17 | 2014-02-19 | 青岛昊源环境工程技术有限公司 | Environment-friendly adsorbing material for removing cations in industrial wastewater |
| CN104190159B (en) * | 2014-08-27 | 2016-03-30 | 江苏永尚能源科技有限公司 | Filter the preparation method of filter material |
| CN104194268A (en) * | 2014-08-27 | 2014-12-10 | 江苏永尚能源科技有限公司 | Filter material |
| CN116764449B (en) * | 2023-08-21 | 2023-11-17 | 西安金沃泰环保科技有限公司 | Resin material for benzene series waste gas treatment and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478807A (en) * | 2002-08-30 | 2004-03-03 | 中国船舶重工集团公司第七研究院第七 | Chelate resin and its synthesis method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478807A (en) * | 2002-08-30 | 2004-03-03 | 中国船舶重工集团公司第七研究院第七 | Chelate resin and its synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| 张剑波等.离子交换树脂对有机废水中铜离子的吸附.《水处理技术》.2001,第27卷(第1期),29-32. * |
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