CN101905146A - Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions - Google Patents
Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions Download PDFInfo
- Publication number
- CN101905146A CN101905146A CN 201010241146 CN201010241146A CN101905146A CN 101905146 A CN101905146 A CN 101905146A CN 201010241146 CN201010241146 CN 201010241146 CN 201010241146 A CN201010241146 A CN 201010241146A CN 101905146 A CN101905146 A CN 101905146A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- polyethylene polyamine
- solvent
- adsorption material
- heavy metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of absorbing materials of heavy metal and relates to silica gel-polyethylene polyamine and a polyhydroxy chelate absorbing material, an amine carboxyl chelate absorbing material and a pyridine chelate absorbing material prepared from the silica gel-polyethylene polyamine. In the structural formula of the silica gel-polyethylene polyamine, n value is 1 to 10. An amine group, a polyhydroxy group, an amine carboxyl group and a pyridine group in the absorbing material generate a chemical complexation action with heavy metal ions in a water solution, thereby takes a specificity absorbing function on the heavy metal ions. The invention has the characteristics of high absorbing selectivity, high absorbing capacity, easy regeneration, recycling and low transformation expansion rate in the absorbing-desorbing process.
Description
Technical field
The invention belongs to heavy metal sorbing material technical field, relate to a kind of silica gel-polyethylene polyamine and preparation method thereof, also relate to the polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and the pyridine chelate adsorption material that make by silica gel-polyethylene polyamine.
Background technology
Often there is heavy metal ion in the water body,,, therefore it need be removed from water body because these heavy metal ion can pollute as lead, cadmium, mercury, chromium, copper, nickel, zinc etc.At present more to the technical scheme that is present in removal of heavy metal ions, separation or enriching and recovering in the water body, mainly as follows:
The chemicals purified treatment is as precipitation-flocculence, handle not thorough, processing procedure has also been introduced other impurity, its handling properties also only is that the heavy metal ion in the water body is transferred in the sediment, be not with the recycling purpose that reaches resource of its enriching and recovering, formed harmful new solid waste on the contrary again.
The complexometric extraction rule causes operating cost to increase because may have the dissolving of extractant in the extraction process and carry secretly and be lost to water, also may cause new pollution because of the potential toxicity of extractant simultaneously.
Ion exchange resin adsorption treatment method, present organic backbone resin such as polystyrene or polyacrylic resin exist that exchange velocity is slow, moisture content is high, need expend shortcoming such as a large amount of petrochemical industry resources during preparation, and the cyclic stress that produces of the intrinsic periodic expansion of exchange process-contraction and cause resin matrix fracture phenomena to occur, thereby cause service life short.
U.S. Pat P5695882, USP6576590B2 and USP5997748 disclose with polymine, polyvinylamine and PAH and have prepared silica gel-polyamine compound, prepare heavy metal ion adsorbing material on the basis of silica gel-polyamine compound.But there is following defective in above-mentioned patent: these three kinds of polyamine of (1) polymine, polyvinylamine and PAH are because molecular weight is bigger, silica gel itself is again high polymer, two kinds of locomotivities of high polymer own are poor, thereby cause kinetics poor performance in the grafting process, graft reaction time length and percent grafting not high; (2) gelation appears in the process of grafting of above-mentioned three kinds of polyamine easily, only rests on laboratory scale, still can not carry out suitability for industrialized production; (3) above-mentioned three kinds of polyamine cost an arm and a leg and cause the preparation cost height of silica gel-polyamine compound, have also seriously limited it in industrial large-scale production and application.
Summary of the invention
The object of the present invention is to provide big silica gel-polyethylene polyamine of a kind of adsorbance and preparation method thereof, the polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and the pyridine chelate adsorption material that are made by silica gel-polyethylene polyamine also are provided simultaneously, and these chelate adsorption materials have the specific adsorption effect to heavy metal ion.
The present invention is by the following technical solutions:
Silica gel-polyethylene polyamine, its structural formula is:
Wherein the n value is 1-10.
The method for preparing silica gel-polyethylene polyamine, may further comprise the steps: add halogen propyl group silica gel and polyethylene polyamine in the solvent jointly, the weight ratio of halogen propyl group silica gel and polyethylene polyamine is 1: 0.2～3, the consumption of solvent is 3～30 times of halogen propyl group silica gel weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains silica gel-polyethylene polyamine; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
Silica gel-polyethylene polyamine is in the application of absorbing heavy metal ions.
A kind of polyhydroxy chelate adsorption material that makes by silica gel-polyethylene polyamine, its structural formula is:
Wherein the n value is 1-10.
The method for preparing the polyhydroxy chelate adsorption material, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding glycidol or 3-chloro-1, the 2-propane diols, silica gel-polyethylene polyamine and glycidol or 3-chloro-1, the weight ratio of 2-propane diols is 1: 0.3～3, the consumption of solvent is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains the polyhydroxy chelate adsorption material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
A kind of amine carboxyl chelate adsorption material that makes by silica gel-polyethylene polyamine, its structural formula is:
Wherein the n value is 1-10.
The method for preparing amine carboxyl chelate adsorption material, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding monoxone, bromoacetic acid, sodium chloroacetate, bromoacetic acid sodium, potassium chloroacetate or bromoacetic acid potassium, silica gel-polyethylene polyamine and monoxone, bromoacetic acid, sodium chloroacetate, bromoacetic acid sodium, the weight ratio of potassium chloroacetate or bromoacetic acid potassium is 1: 0.3～3, solvent load is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains amine carboxyl chelating type heavy metal ion adsorbing material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
The pyridine chelate adsorption material that a kind of silica gel-polyethylene polyamine makes, its structural formula is:
Wherein the n value is 1-10.
The method for preparing the pyridine chelate adsorption material, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding PMC, bromo methyl cycloheptapyridine, chloromethyl pyridine hydrochloride or bromo methyl cycloheptapyridine hydrochloride, silica gel-polyethylene polyamine and PMC, bromo methyl cycloheptapyridine, the weight ratio of chloromethyl pyridine hydrochloride or bromo methyl cycloheptapyridine hydrochloride is 1: 0.3～3, the consumption of solvent is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains the pyridine chelate adsorption material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
The polyethylene polyamine molecular formula that adopts among the present invention is: H
2N-(CH
2CH
2NH)
nH, n=1～10.For example the n value is 1 o'clock, and the material of the actual representative of polyethylene polyamine is an ethylenediamine; The n value is 5 o'clock, and the material of the actual representative of polyethylene polyamine is a penten, and can select n in the preparation heavy metal ion adsorbing material process for use is a kind of amine of a certain particular value or the mixture of forming more than 2 kinds.
The preparation method of the halogen propyl group silica gel that adopts among the present invention: 10 weight portion silica-gel carriers are added in 20～200 weight portion organic solvents, add 3～30 weight portion organo silane coupling agents again, reaction temperature is that normal temperature is between the organic solvent boiling point, confined reaction 10～50 hours, use organic solvent washing then, 20～50 ℃ of vacuum drying obtain halogen propyl group silica gel to constant weight.Organic solvent is one or more in methyl alcohol or ethanol, toluene, ether, acetone, the hexane; Organo silane coupling agent is γ-halogen propyl trimethoxy silicane or γ-halogen propyl-triethoxysilicane, γ-halogen propyltrichlorosilan, and halogen wherein is chlorine or bromine, iodine; The specific area of silica-gel carrier is 200～1500m
2/ g, aperture 1～100nm, pore volume 0.4～2mL/g.
The structural formula of halogen propyl group silica gel is
R is Cl or Br.
Silica gel-the polyethylene polyamine that the present invention relates to, polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and a series of heavy metal ion adsorbing materials of pyridine chelate adsorption material and preparation method thereof, these heavy metal ion adsorbing materials are to be basic framework with silica gel, obtain silica gel-polyethylene polyamine composite by the functional graft reaction, this composite is the heavy metal ion adsorbing material of amido chelating type.Thereby but on the basis of silica gel-polyethylene polyamine also the preparation of a series of functional groups of grafting have polyhydroxy chelating type, amine carboxyl chelating type, the pyridine chelating type heavy metal ion adsorbing material of high selectivity and high-adsorption-capacity.Heavy metal ion generation chemical complexing effect in amido in the sorbing material, polyhydroxy, amine carboxyl, pyridine radicals and the aqueous solution, thus heavy metal ion is played the specific adsorption effect.
The a series of heavy metal ion series of silica gel-polyethylene polyamine involved in the present invention, polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and pyridine chelate adsorption material sorbing material is used and is mainly reflected in following several aspect: the one, and the processing of municipal wastewater, industrial wastewater, can remove and reclaim the heavy metal ion of trace in the water body even trace, thereby make heavy metal concentration and total amount in the water body reach the pollutant control discharge standard that State Environmental Protection Administration stipulates; The 2nd, be applied to the improvement and the resource aspect of hydrometallurgy and lean ore/mine tailing, thereby heavy metal heavy metal ion is wherein carried out enrichment, separates and reclaimed; The 3rd, in the preparation of drinking pure water and industrial clean water, and removal, separation or the enriching and recovering of the heavy metal ion that relates in the processes such as food, pharmaceutical production.
The present invention mainly comprises the synthetic of silica gel-polyethylene polyamine composite in the preparation, and functional group is in the load of composite material surface, silica gel-polyethylene polyamine, the polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and a series of heavy metal ion adsorbing materials of pyridine chelate adsorption material have the reaction condition gentleness in entire synthesis process, initial raw material silica gel and polyethylene polyamine are cheap and easy to get, the adsorption function group is with the stable carrier surface, silica gel-polyethylene polyamine and follow-up polyhydroxy of grafting on of mode of chemical bonding, the amine carboxyl, it is big that the pyridine functional group has the grafting amount, the characteristics that adsorptive selectivity and adsorption capacity are high.
Silica gel-polyethylene polyamine of the present invention, polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and a series of heavy metal ion adsorbing materials of pyridine chelate adsorption material can adopt batch process in use, promptly adding adsorbent in the container that fills heavy metal ion solution adsorbs, also can adopt the column continuous process, sorbing material is loaded on ion exchange column, heavy metal ion solution is adsorbed by exchange column.
The repeated use capable of circulation of a series of heavy metal ion series sorbing material of silica gel-polyethylene polyamine involved in the present invention, polyhydroxy chelate adsorption material, amine carboxyl chelate adsorption material and pyridine chelate adsorption material, mainly under acid condition, adsorbed heavy metal ion is carried out wash-out regeneration with hydrochloric acid or sulfuric acid, the adsorption capacity of sorbing material does not have obvious decline after 10 regeneration cycle, and expansion rate transition of adsorption-desorption process was low when circular regeneration used.
The specific embodiment
Embodiment 1
Get specific area 1500m
2The silica-gel carrier 20g of/g, average pore size 1nm, pore volume 0.4ml/g, add in the 40g ethanol, add 6g γ-r-chloropropyl trimethoxyl silane again, normal-temperature reaction is 10 hours in closed system, then with toluene and the washing of hexane mixed solvent, to remove excessive unreacted γ-r-chloropropyl trimethoxyl silane, to constant weight, promptly obtain chloropropyl silica gel after 20 ℃ of vacuum drying
20g chloropropyl silica gel is added in the 60g water, add 6g penten (molecular weight is 275) then and mix, 50 ℃ were reacted 50 hours, filtered, and washed filter cake then with water, and filtration cakes torrefaction obtains silica gel-penten composite, and its structural formula is:
This composite is the heavy metal ion adsorbing material of amido chelating type, can adsorb the copper in the solution, nickel ion.
Get the amido chelate adsorption material silica gel-penten 0.1g of present embodiment, add and contain 500ppm Cu
2+Solution 100ml, intermittent oscillation absorption was adopted Cu in the solution of aas determination absorption back after 4 hours
2+Concentration be 462ppm, silica gel-penten that present embodiment is described is to Cu
2+Adsorption capacity be about 0.6mmol/g.
The regeneration of the described amido chelate adsorption material silica gel of present embodiment-penten is soaked 10h with mass concentration 3%HCl solution, with distilled water sorbing material is carried out drip washing then, and being neutralized to pH with the ammoniacal liquor of mass concentration 1% again is 6～7, regeneration ending.Sorbing material can enter the next circulation of using.
Embodiment 2
Getting the silica gel that embodiment one makes-penten 25g adds in the 75g methyl alcohol, add 10g glycidol or 3-chloro-1 again, the 2-propane diols, 50 ℃ of reactions 50 hours, filter, use the methanol wash filter cake then, filtration cakes torrefaction obtains flaxen polyhydroxy chelate adsorption material, and its structural formula is:
Get the polyhydroxy chelate adsorption material 0.1g of present embodiment, add the solution 100ml that contains boric acid 500ppm, after the intermittent oscillation absorption 4 hours, adopting the concentration of solution mesoboric acid before and after the titration measuring absorption, is the 1.0mmol/g sorbing material to the adsorption capacity of boric acid.
Regneration of adsorbent material method of the present invention is identical with embodiment one.
Embodiment 3
Get specific area 200m
2The silica-gel carrier 20g of/g, average pore size 100nm, pore volume 2ml/g, add in the 400g toluene, add γ-bromopropyl trichlorosilane again, normal-temperature reaction is 50 hours in closed system, use hexane wash then, to remove excessive unreacted γ-bromopropyl trichlorosilane, to constant weight, promptly obtain bromopropyl silica gel after 50 ℃ of vacuum drying
20g bromopropyl silica gel is added in the 600g ethanol, mix with 60g ten ethylidene undecylamines then, 80 ℃ were reacted 10 hours, filter, with the mixed solvent washing leaching cake that ethanol and ether are formed, filtration cakes torrefaction obtains silica gel-ten ethylidene undecylamine composite, and its structural formula is:
20g silica gel-ten ethylidene undecylamine the composite that makes is previously added in the 60g acetone, and then adding 15g sodium chloroacetate, 50 ℃ of reactions 50 hours, filter, use the ethanol washing leaching cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of amine carboxyl chelating type, and its structural formula is:
Get the amine carboxyl chelate adsorption material 0.1g of present embodiment, add and contain Cu
2+Among the solution 100ml of 500ppm, intermittent oscillation absorption was adopted Cu in the solution of aas determination absorption back after 4 hours
2+Concentration be 448ppm, illustrate that amine carboxyl chelate adsorption material that present embodiment makes is to Cu
2+Adsorption capacity be about 0.8mmol/g.
Get the amine carboxyl chelate adsorption material 0.1g of present embodiment, add and contain Ni
2+Among the solution 100ml of 500ppm, intermittent oscillation absorption was adopted Ni in the solution of aas determination absorption back after 4 hours
2+Concentration be 470ppm, illustrate that amine carboxyl chelate adsorption material that present embodiment makes is to Ni
2+Adsorption capacity be about 0.5mmol/g.
The regeneration of the described amine carboxyl of present embodiment chelate adsorption material is soaked 10h with mass concentration 3%HCl solution, with distilled water sorbing material is carried out drip washing then, and regeneration ending, sorbing material can enter the next circulation of using.
Embodiment 4
Getting the silica gel-ten ethylidene undecylamine composite 25g that embodiment three makes adds in the 250g ethanol, add 50g3-chloro-1 again, the 2-propane diols, 70 ℃ were reacted 30 hours, filter, use the ethanol washing leaching cake then, filtration cakes torrefaction obtains flaxen polyhydroxy chelate adsorption material, and its structural formula is:
Embodiment 5
Get specific area 250m
2The silica-gel carrier 20g of/g, average pore size 13nm, pore volume 1ml/g, add in the 50g ether, add 12g γ-chloropropyl trichloro-silane again, normal-temperature reaction is 20 hours in closed system, use toluene wash then, to remove excessive unreacted γ-chloropropyl trichloro-silane, to constant weight, promptly obtain chloropropyl silica gel after 40 ℃ of vacuum drying
20g chloropropyl silica gel is added in the 200g ether, mix with the 30g ethylenediamine then, 70 ℃ were reacted 30 hours, filter, the mixed solvent washing leaching cake that water, methyl alcohol, ethanol and ether are formed, filtration cakes torrefaction obtains silica gel-ethylenediamine composite, and its structural formula is:
20g silica gel-ethylenediamine composite is added in the 60g ether, and then add the 25g PMC, 60 ℃ of reactions 25 hours, filter, use the ether washing leaching cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of pyridine chelating type, and its structural formula is:
Get the pyridine chelate adsorption material 0.1g of present embodiment, add and contain Cu
2+, Fe
3+And Al
3+The solution 100ml of each 500ppm, intermittent oscillation absorption was adopted Cu in the solution of aas determination absorption back after 4 hours
2+, Fe
3+And Al
3+The concentration of ion is respectively 475ppm, 500ppm and 500ppm, and the pyridine chelate adsorption material that present embodiment is described is to Cu
2+Adsorption capacity be 0.4mmol/g, to Fe
3+And Al
3+Then absorption hardly.
The renovation process of the pyridine chelate adsorption material of present embodiment is identical with embodiment one.
Embodiment 6
Get the silica gel that embodiment five makes-ethylenediamine composite 25g and add in the 750g acetone, add the 75g glycidol again, 80 ℃ of reactions 10 hours, filter, use the ether washing leaching cake then, filtration cakes torrefaction obtains flaxen polyhydroxy chelate adsorption material, and its structural formula is:
Embodiment 7
Get the silica gel that embodiment one makes-penten 20g and add in the 200g methyl alcohol, add 6g bromoacetic acid sodium again, 70 ℃ of reactions 30 hours, filter, use the ethanol washing leaching cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of amine carboxyl chelating type, and its structural formula is:
Embodiment 8
Get the silica gel that embodiment five makes-ethylenediamine composite 20g and add in the 600g acetone, add the 60g monoxone again, 80 ℃ of reactions 10 hours, filter, use the ethanol washing leaching cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of amine carboxyl chelating type, and its structural formula is:
Embodiment 9
Getting the silica gel-ten ethylidene undecylamine composite 20g that embodiment three makes adds in the 200g methyl alcohol, add the 6g bromo methyl cycloheptapyridine again, 50 ℃ were reacted 50 hours, and used the ethanol washing leaching cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of pyridine chelating type, and its structural formula is:
Embodiment 10
Getting the silica gel that embodiment one makes-penten 20g adds in the 600g acetone, add the 60g chloromethyl pyridine hydrochloride again, 80 ℃ were reacted 10 hours, and used the methanol wash filter cake then, filtration cakes torrefaction obtains the heavy metal ion adsorbing material of pyridine chelating type, and its structural formula is:
Claims (9)
1. silica gel-polyethylene polyamine, its structural formula is:
Wherein the n value is 1-10.
2. the preparation method of the described silica gel-polyethylene polyamine of claim 1, may further comprise the steps: add halogen propyl group silica gel and polyethylene polyamine in the solvent jointly, the weight ratio of halogen propyl group silica gel and polyethylene polyamine is 1: 0.2～3, the consumption of solvent is 3～30 times of halogen propyl group silica gel weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains silica gel-polyethylene polyamine; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
3. the described silica gel-polyethylene polyamine of claim 1 is in the application of absorbing heavy metal ions.
4. polyhydroxy chelate adsorption material that makes by the described silica gel-polyethylene polyamine of claim 1, its structural formula is:
Wherein the n value is 1-10.
5. the preparation method of the described polyhydroxy chelate adsorption material of claim 4, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding glycidol or 3-chloro-1, the 2-propane diols, silica gel-polyethylene polyamine and glycidol or 3-chloro-1, the weight ratio of 2-propane diols is 1: 0.3～3, the consumption of solvent is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains the polyhydroxy chelate adsorption material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
6. amine carboxyl chelate adsorption material that makes by the described silica gel-polyethylene polyamine of claim 1, its structural formula is:
Wherein the n value is 1-10.
7. the preparation method of the described amine carboxyl of claim 6 chelate adsorption material, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding monoxone, bromoacetic acid, sodium chloroacetate, bromoacetic acid sodium, potassium chloroacetate or bromoacetic acid potassium, silica gel-polyethylene polyamine and monoxone, bromoacetic acid, sodium chloroacetate, bromoacetic acid sodium, the weight ratio of potassium chloroacetate or bromoacetic acid potassium is 1: 0.3～3, solvent load is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains amine carboxyl chelating type heavy metal ion adsorbing material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
8. pyridine chelate adsorption material that makes by the described silica gel-polyethylene polyamine of claim 1, its structural formula is:
Wherein the n value is 1-10.
9. the preparation method of the described pyridine chelate adsorption material of claim 8, may further comprise the steps: silica gel-polyethylene polyamine is added in the solvent, and then adding PMC, bromo methyl cycloheptapyridine, chloromethyl pyridine hydrochloride or bromo methyl cycloheptapyridine hydrochloride, silica gel-polyethylene polyamine and PMC, bromo methyl cycloheptapyridine, the weight ratio of chloromethyl pyridine hydrochloride or bromo methyl cycloheptapyridine hydrochloride is 1: 0.3～3, the consumption of solvent is 3～30 times of silica gel-polyethylene polyamine weight, reacted 10～50 hours down at 50～80 ℃, filter, use the solvent wash filter cake then, filtration cakes torrefaction obtains the pyridine chelate adsorption material; Described solvent is one or more in water or methyl alcohol, ethanol, ether or the acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010241146 CN101905146A (en) | 2010-07-30 | 2010-07-30 | Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010241146 CN101905146A (en) | 2010-07-30 | 2010-07-30 | Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101905146A true CN101905146A (en) | 2010-12-08 |
Family
ID=43260820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010241146 Pending CN101905146A (en) | 2010-07-30 | 2010-07-30 | Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101905146A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671642A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN102671643A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine and pyridine difunctional group composite adsorbing material loaded on silica gel and preparation method thereof |
| CN102814166A (en) * | 2011-06-08 | 2012-12-12 | 工信华鑫科技有限公司 | Preparation method of copper ion special-purposed adsorption material |
| CN103554514A (en) * | 2013-10-30 | 2014-02-05 | 江苏上田环境修复有限公司 | Chelating agent for recovering heavy metal-contaminated soil, and preparation and usage methods thereof |
| CN104745814A (en) * | 2015-03-25 | 2015-07-01 | 苏州鼎驰金属材料有限公司 | Method for adsorbing and recovering metal ions in solution by modified silica gel of propanethiol containing substituent groups |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695882A (en) * | 1995-08-17 | 1997-12-09 | The University Of Montana | System for extracting soluble heavy metals from liquid solutions |
| US20020139753A1 (en) * | 2001-02-01 | 2002-10-03 | Edward Rosenberg | Materials and methods for the separation of copper ions and ferric iron in liquid solutions |
| CN101642700A (en) * | 2009-09-03 | 2010-02-10 | 嘉应学院 | Preparation method of boron adsorbent |
-
2010
- 2010-07-30 CN CN 201010241146 patent/CN101905146A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695882A (en) * | 1995-08-17 | 1997-12-09 | The University Of Montana | System for extracting soluble heavy metals from liquid solutions |
| US20020139753A1 (en) * | 2001-02-01 | 2002-10-03 | Edward Rosenberg | Materials and methods for the separation of copper ions and ferric iron in liquid solutions |
| CN101642700A (en) * | 2009-09-03 | 2010-02-10 | 嘉应学院 | Preparation method of boron adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 《华东工学院学报》 19920229 杨绪杰等 硅胶表面螯合剂吸附重金属离子 1－9 , 第2期 2 * |
| 《郑州大学学报》 20100331 范忠雷等 乙二胺接枝硅胶的合成研究 1－9 第31卷, 第2期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814166A (en) * | 2011-06-08 | 2012-12-12 | 工信华鑫科技有限公司 | Preparation method of copper ion special-purposed adsorption material |
| CN102671642A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN102671643A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine and pyridine difunctional group composite adsorbing material loaded on silica gel and preparation method thereof |
| CN102671642B (en) * | 2012-05-28 | 2013-07-10 | 陕西水木油田技术服务有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN102671643B (en) * | 2012-05-28 | 2013-11-13 | 陕西水木油田技术服务有限公司 | Polyamine and pyridine difunctional group composite adsorbing material loaded on silica gel and preparation method thereof |
| CN103554514A (en) * | 2013-10-30 | 2014-02-05 | 江苏上田环境修复有限公司 | Chelating agent for recovering heavy metal-contaminated soil, and preparation and usage methods thereof |
| CN104745814A (en) * | 2015-03-25 | 2015-07-01 | 苏州鼎驰金属材料有限公司 | Method for adsorbing and recovering metal ions in solution by modified silica gel of propanethiol containing substituent groups |
| CN104745814B (en) * | 2015-03-25 | 2017-03-15 | 苏州鼎驰金属材料有限公司 | The method that adsorption recovery is carried out to metal ion in solution with the modified silica-gel containing substituent propanethiol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yao et al. | Thiol-rich, porous carbon for the efficient capture of silver: Understanding the relationship between the surface groups and transformation pathways of silver | |
| CN105107467B (en) | One kind utilizes preparation of rear modification MIL 101 (Cr) adsorbent and application thereof | |
| CN101759809B (en) | Method for preparing dithiocarbamate-based modified porous starch | |
| CN105498726B (en) | A kind of high Adsorption of Heavy Metals ion chelating agent of the structure containing dithiocar-bamate and preparation method thereof | |
| CN101701042B (en) | Carboxymethyl chitosan thiourea resin and preparation method and application thereof | |
| Xiong et al. | Selective recovery of Ag (I) coordination anion from simulate nickel electrolyte using corn stalk based adsorbent modified by ammonia–thiosemicarbazide | |
| CN103285837A (en) | Preparation method of adsorption material with high selectivity on different heavy metal ions | |
| Wu et al. | A new porous magnetic chitosan modified by melamine for fast and efficient adsorption of Cu (II) ions | |
| JP6079113B2 (en) | Palladium separating agent, and production method and use thereof | |
| CN102350225B (en) | PVDF (Polyvinylidene Fluoride) hybridized flat film for absorbing heavy metal ions | |
| CN106824113B (en) | Preparation and application of imidazole ionic liquid modified chitosan adsorbent | |
| CN101905146A (en) | Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions | |
| CN105771885A (en) | Preparation method of modified zeolite and application of modified zeolite in arsenic-bearing waste water | |
| CN103055816A (en) | Novel class of calixarene crown ether bond-type silicon-based adsorption materials and preparation method thereof | |
| CN113214480A (en) | Synthesis method and adsorption application of cationic framework material | |
| Huang et al. | Efficient and selective capture of uranium by polyethyleneimine-modified chitosan composite microspheres from radioactive nuclear waste | |
| CN103301890B (en) | A kind of selective strong basic anion-exchange resin and preparation method thereof | |
| CN103272572A (en) | Preparation method capable of absorbing Ca<2+> material from magnesium sulfate waste water | |
| CN105817210A (en) | Method for preparing alkalescent ion exchange fibers | |
| CN111019147A (en) | Metal organic framework adsorbent, one-step preparation method and application thereof | |
| Wang et al. | Adsorption of Pb2+ and Cu2+ in wastewater by lignosulfonate adsorbent prepared from corn straw | |
| CN102863579B (en) | Barbituric acid chelating resin and preparation method and application thereof | |
| CN104549172B (en) | Method for preparing sulfydryl-modified chitosan short hole microspheres | |
| CN105294890A (en) | Method for recycling silver ion from sewer sludge by using novel chelate resin | |
| CN109610166B (en) | Chelate fiber, preparation method thereof and application thereof in preparing Au in electronic waste3+Application of separation and enrichment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101208 |