CN102060995A - Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin - Google Patents
Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin Download PDFInfo
- Publication number
- CN102060995A CN102060995A CN 201010552070 CN201010552070A CN102060995A CN 102060995 A CN102060995 A CN 102060995A CN 201010552070 CN201010552070 CN 201010552070 CN 201010552070 A CN201010552070 A CN 201010552070A CN 102060995 A CN102060995 A CN 102060995A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- reaction
- dithiocar
- bamate
- obtains
- 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.)
- Granted
Links
Abstract
The invention relates to a method for preparing heavy metal chelating resin, in particular to a method for preparing silica gel supported dithiocarbamate heavy metal chelating resin and adsorption of heavy metals such as lead, cadmium, copper, mercury and the like by the resin. The method comprises the following steps of: reacting carbon disulfide with a polyamine compound to generate a dithiocarbamate compound; and grafting the dithiocarbamate compound onto the surface of silicon dioxide, wherein a halogen group is modified on the surface of the silicon dioxide. By the method, the adsorption capacity of dithiocarbamate chelating resin is effectively improved; and the problem that silica gel is dissolved due to too high alkalinity of a reaction system (pH value is more than 11), or the dithiocarbamate compound cannot be generated through reaction due to too low alkalinity (the pH value is less than 10) when a dithiocarbamate functional group is prepared by reacting the silica gel with the carbon disulfide in the conventional synthetic route is solved, wherein an amino group is modified on the surface of the silica gel.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal chelate resin, particularly a kind of silica gel load dithiocar-bamate heavy metal chelate resin preparation method and to the absorption of heavy metals such as lead, cadmium, copper, mercury.
Background technology
Heavy metal is difficult in environment by metabolism because toxicity is big, and is not only serious to water pollution easily by biomagnification and biological amplification is arranged, also serious threat human and animal's existence.At the water body of heavy metal contamination, adoptable treatment technology has chemical precipitation, reverse osmosis, electrowinning, ion-exchange and absorption method etc.In these methods, absorption method has the characteristics of high efficiency, easy and simple to handle, environmentally safe and is subjected to paying close attention to widely.Resin is a kind of as sorbing material, has the preparation of being easy to, adsorptive capacity height, advantage such as reusable.
The dithiocarbamate(s) organism can form the very high inner complex of stability constant with many heavy metal ion, extremely strong to the sequestering power of heavy metal ion such as mercury, lead, cadmium, copper especially, and not with basic metal and alkaline-earth metal chelating, so it is widely used in from environment removing and the enriching heavy metal ion.The dithiocar-bamate resin of bibliographical information adopts polyvinyl chloride more, polystyrene, polyethers, the hydrophobicity skeletons such as polymkeric substance that contain polyamines polyene, when can causing sequestrant to use in the aqueous solution, this is difficult to by the solvent quick humidification, ion is obstructed in the sequestrant internal divergence, rate of adsorption and efficient (B.Mathew have been reduced, V.N.R.Pillai, Divinylhcnzene crosslinkedpolyacrylamide-supported dithocarbamates as metal complexing agents, Polymer Bulled.1991,26:603-610A; Denizlia, K.Kesenci, Dithiocarbamate-incorporated monosizepolystyrene microspheres for selective removal of mercury ions, Reactive ﹠amp; FunctionalPolymers.2000,44:235-243).Therefore, the absorption that this resinoid is used for the water body heavy metal has been subjected to certain restriction.
Inorganic/the organic materials that with silica gel is matrix is one of focus of current research, this be since silica gel except having excellent mechanical intensity and higher chemical stability, thermostability, also having outstanding characteristics is exactly that its surface is contained abundant silicon hydroxyl and made the silica gel matrix have good hydrophilicity, has improved the absorption property of resin greatly.The synthetic method of the silica gel load dithiocar-bamate resin of bibliographical information is mainly the grafting method, promptly earlier at silica gel finishing amino group, again under alkaline condition, make amino the reaction generate the dithiocar-bamate (K.A.Venkatesan of functional group with dithiocarbonic anhydride, T.G.Srinivasan, Removal of complexed mercury from aqueous solutionsusing dithiocarbamate grafted on silica gel, Sep.Sci.Technol.2002,37:1417-1429; K.Dimos, P.Stathi, M.A.Karakassides, Synthesis and characterization of hybrid MCM-41materials for heavy metal adsorption, Microporous Mesoporous.Mater.2009,126:65-71).We discover, adopt this synthetic route that the pH value of reaction system is had strict requirement, and alkalescence too high (the pH value is greater than 11) can make the silica gel dissolving, and alkalescence low excessively (the pH value is lower than 10) almost can not be reacted and be generated dithiocar-bamate functional group.The aminocompound with the dithiocarbonic anhydride reaction of bibliographical information mostly is the polyamine substance of small molecular weight, as quadrol, diethylenetriamine, triethylene tetramine etc., adopt the synthetic dithiocar-bamate number of functional groups that obtains of these materials not high, cause the low (M.E.Mahmoud of resin adsorptive capacity, Selective solid phase extraction ofmercury (II) by silica gel-immobilized-dithiocarbamate derivatives, Anal.Chim.Acta.1999,398:297-304; S.G.Renaudin, R.Schneiderb, A.Walcarius, Synthesis of newdithiocarbamate-based organosilanes for grafting on silica, Tetrahedron Lett.2007,48:2113-2116).
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of silica gel load dithiocar-bamate heavy metal chelate resin, can effectively improve the adsorptive capacity of dithiocar-bamate resin, also overcome state too harsh in the existing processing method to a certain extent the pH requirement.
Technical scheme of the present invention is: the present invention adopts and makes polyamine compounds and dithiocarbonic anhydride at OH earlier
-Concentration is to generate dithiocar-bamate under the highly basic condition of 350～500g/L, again the dithiocar-bamate that generates is grafted to the silica gel surface that halogen atom is modified.
Described polyamine compounds comprises a kind of in triethylene tetramine, matter average molecular weight 1000～10000 polymines or matter average molecular weight 1000～10000 polypropylene amines.
What adopt in the silica gel process that halogen atom is modified is 80～140 ℃ of inert organic solvents, system temperatures with activated silica gel and halogen atom-containing silane coupling agent, nitrogen atmosphere down reaction obtains, and described inert organic solvents is a kind of in hexanaphthene, heptane, toluene, the dimethylbenzene.
Most preferred reaction conditions is that reaction pH value is 8～11 in the process of grafting, and temperature of reaction is 55～65 ℃, and the reaction times is 5～10 hours.
Method of the present invention is with the preparation synthetic route of silica gel load dithiocar-bamate heavy metal chelate resin, redesign through the contriver, thereby can effectively improve the adsorptive capacity of resin, when having avoided the silica gel of finishing amino group in the existing synthetic route and dithiocarbonic anhydride prepared in reaction dithiocar-bamate functional group simultaneously, because of reaction system alkalescence too high (the pH value is greater than 11) causes the silica gel dissolving, or alkalescence low excessively (the pH value is lower than 10) can not be reacted generation dithiocar-bamate compound.
The preparation method of a kind of silica gel load dithiocar-bamate heavy metal chelate resin of the present invention, concrete steps are:
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml inert organic solvents that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 80～140 ℃; 80ml inert organic solvents and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 80～140 ℃ of system temperatures, the nitrogen atmosphere 24～48h that refluxes in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polyamine compounds and 100ml anhydrous methanol and join in the 500ml three-necked bottle mechanical stirring under the ice bath.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12～24h.Suction filtration obtained the solid state product after reaction was finished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the dithiocar-bamate compound.
(4) get the dithiocar-bamate compound 10g that step (3) obtains and in the 500ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8～11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 40～60 ℃, mechanical stirring reaction 5～10h.Suction filtration obtained solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
The described inert organic solvents of step (2) comprises a kind of in hexanaphthene, heptane, toluene, the dimethylbenzene.
The described polyamine compounds of step (3) comprises triethylene tetramine, polymine (matter average molecular weight 1000, the 50wt.% aqueous solution, the rich chemical industry company limited of Hubei match) a kind of or in the polypropylene amine (matter average molecular weight 3000, the 50wt.% aqueous solution, the rich chemical industry company limited of Hubei match).
Advantage of the present invention and positively effect are, the inventive method provides a kind of loading capacity big (metal ions M (II) adsorptive capacity can reach 0.4mmol/g, has improved 2～3 times than the adsorptive capacity of the dithiocar-bamate resin of existing silica gel load), physical strength is good, dynamic performance is good silica gel load dithiocar-bamate heavy metal chelate resin and preparation method thereof.The product for preparing by present method, not only effectively improved the adsorptive capacity of dithiocar-bamate resin, when also having overcome the silica gel of finishing amino group in the existing synthetic route and dithiocarbonic anhydride prepared in reaction dithiocar-bamate functional group, because of reaction system alkalescence too high (the pH value is greater than 11) causes the silica gel dissolving, or alkalescence low excessively (the pH value is lower than 10) can not be reacted generation dithiocar-bamate compound.
Embodiment
Following embodiment is intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1 adopts the different inert organic solvent to prepare silica gel load dithiocar-bamate resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, 150ml hexanaphthene, heptane, toluene or the dimethylbenzene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 80～140 ℃; 80ml hexanaphthene, heptane, toluene or dimethylbenzene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keep 80～140 ℃ of system temperatures, the nitrogen atmosphere 24～48h that refluxes in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 24h.Suction filtration obtained the solid state product after reaction was finished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the dithiocar-bamate compound.
(4) get the dithiocar-bamate compound 10g that step (3) obtains and in the 500ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH=11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 10h.Suction filtration obtained solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
Table 1 adopts the silica gel load dithiocar-bamate resin of different inert organic solvent preparation and the relation of heavy metal ion adsorbed amount
Embodiment 2 adopts different polyamine compounds to prepare silica gel load dithiocar-bamate resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml triethylene tetramine, polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) or polypropylene amine (matter average molecular weight 3000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12～24h.Suction filtration obtained the solid state product after reaction was finished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the dithiocar-bamate compound.
(4) get the dithiocar-bamate compound 10g that step (3) obtains and in the 250ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH=11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 10h.Suction filtration obtained solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
Table 2 adopts the silica gel load dithiocar-bamate resin of polyamine compounds preparation and the relation of heavy metal ion adsorbed amount
The different pH value preparation of embodiment 3 control reaction systems silica gel load dithiocar-bamate resin
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution) and join in the 500ml three-necked bottle mechanical stirring under the ice bath with the 100ml anhydrous methanol.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol.Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 24h.Suction filtration obtained the solid state product after reaction was finished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the dithiocar-bamate compound.
(4) get the dithiocar-bamate compound 10g that step (3) obtains and in the 250ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8～11.Add the silanized silica gel that 10g step (2) obtains, be warming up to 60 ℃, mechanical stirring reaction 5～10h.Suction filtration obtained solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
The silica gel load dithiocar-bamate resin of the different pH value preparations of table 3 control reaction system and the relation of heavy metal ion adsorbed amount
Comparative Examples 1
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/LHNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get silanized silica gel and the 100ml anhydrous methanol that 10g step (2) obtains and join in the 250ml three-necked bottle, heat temperature raising to 60 ℃.Add the 20ml triethylene tetramine, react 24h under the mechanical stirring.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum-drying 12h, obtains amido modified silica gel.
(4) get amido modified silica gel 10g and the 100ml deionized water that step (3) obtains and place the 500ml three-necked bottle, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 9～12 under the mechanical stirring.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol, dropwise drips under the ice bath to three-necked bottle, continues to stir, and treats that dithiocarbonic anhydride-methanol solution dropwises, and is warming up to 60 ℃ of reaction 24h.Use 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution regulation system pH value 9～12 in the reaction process.Suction filtration got solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this solid product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
The different pH values of table 4 are triethylene tetramine modified silica-gel and the silica gel load dithiocar-bamate resin of dithiocarbonic anhydride prepared in reaction and the relation of heavy metal ion adsorbed amount down
Comparative Examples 2
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in the entire reaction course.Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel.
(3) get silanized silica gel and the 100ml anhydrous methanol that 10g step (2) obtains and join in the 250ml three-necked bottle, heat temperature raising to 60 ℃.Add 20ml polymine (matter average molecular weight 1000, the 50wt.% aqueous solution), react 24h under the mechanical stirring.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum-drying 12h, obtains amido modified silica gel.
(4) get amido modified silica gel 10g and the 100ml deionized water that step (3) obtains and place the 500ml three-necked bottle, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 9～12 under the mechanical stirring.Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol, dropwise drips under the ice bath to three-necked bottle, continues to stir, and treats that dithiocarbonic anhydride-methanol solution dropwises, and is warming up to 60 ℃ of reaction 24h.Use 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution regulation system pH value 9～12 in the reaction process.Suction filtration got solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this solid product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin.
The different pH values of table 5 are polyethylene imine beautify silica gel and the silica gel load dithiocar-bamate resin of dithiocarbonic anhydride prepared in reaction and the relation of heavy metal ion adsorbed amount down
Claims (5)
1. the preparation method of a silica gel load dithiocar-bamate heavy metal chelate resin, at first with polyamine compounds and dithiocarbonic anhydride at OH
-Concentration is to generate dithiocar-bamate under the highly basic condition of 350～500g/L, again the dithiocar-bamate that generates is grafted to the silica gel surface that halogen atom is modified.
2. preparation method according to claim 1, described polyamine compounds comprises a kind of in triethylene tetramine, matter average molecular weight 1000～10000 polymines or matter average molecular weight 1000～10000 polypropylene amines.
3. preparation method according to claim 1, what adopt in the silica gel process that halogen atom is modified is 80～140 ℃ of inert organic solvents, system temperatures with activated silica gel and halogen atom-containing silane coupling agent, nitrogen atmosphere down reaction obtains, and described inert organic solvents is a kind of in hexanaphthene, heptane, toluene, the dimethylbenzene.
4. according to each described preparation method of claim 1-3, the reaction conditions in the process of grafting is that the pH value is 8～11, and temperature of reaction is 55～65 ℃, and the reaction times is 5～10 hours.
5. preparation method according to claim 1 may further comprise the steps:
(1) gets the 30g chromatogram and fill out post silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of following mechanical stirring 6h, reaction back suction filtration gets solid product, uses deionized water and methanol wash to neutral successively it, and drying at room temperature 12h obtains activated silica gel;
(2) get activated silica gel, the 150ml inert organic solvents that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical stirring, the oil bath heating makes reaction system be warming up to 80～140 ℃; 80ml inert organic solvents and dropwise splash into three-necked bottle after 20ml γ-the chloropropyl triethyl silicane mixes keeps 80～140 ℃ of system temperatures, the nitrogen atmosphere 24～48h that refluxes in the entire reaction course; Suction filtration obtained solid product after reaction was finished, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum-drying 12h, obtains silanized silica gel;
(3) get 20ml polyamine compounds and 100ml anhydrous methanol and join in the 500ml three-necked bottle mechanical stirring under the ice bath.Get sodium hydroxide 30g and be dissolved in the 100ml deionized water, the stirring and dissolving postcooling is to room temperature; Other gets 50ml dithiocarbonic anhydride and is dissolved in 100ml methyl alcohol; Sodium hydroxide solution and dithiocarbonic anhydride-methanol solution dropwise joins in the three-necked bottle simultaneously, and the dropping process continues to stir, and uses ice bath to keep temperature of reaction system below 5 ℃.Reactant dropwises the back system and is warming up to 40 ℃, continues reaction 12～24h; Suction filtration obtained the solid state product after reaction was finished, and this product is washed the back in 50 ℃ of vacuum-drying 12h with anhydrous methanol, obtained the dithiocar-bamate compound;
(4) get the dithiocar-bamate compound 10g that step (3) obtains and in the 500ml three-necked bottle, be dissolved in the 200ml deionized water, dropwise add 10wt.% sulphuric acid soln or 10wt.% sodium hydroxide solution conditioned reaction body pH value 8～11; Add the silanized silica gel that 10g step (2) obtains, be warming up to 40～60 ℃, mechanical stirring reaction 5～10h; Suction filtration obtained solid product after reaction was finished, and used deionized water and methanol wash to neutral successively this product, in 50 ℃ of vacuum-drying 12h, obtained silica gel load dithiocar-bamate resin;
The described inert organic solvents of step (2) comprises a kind of in hexanaphthene, heptane, toluene, the dimethylbenzene;
The described polyamine compounds of step (3) comprises a kind of in triethylene tetramine, polymine or the polypropylene amine; What described polymine adopted is to be matter average molecular weight 1000, the 50wt.% aqueous solution, and what described polypropylene amine adopted is matter average molecular weight 3000, the 50wt.% aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010552070XA CN102060995B (en) | 2010-11-19 | 2010-11-19 | Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010552070XA CN102060995B (en) | 2010-11-19 | 2010-11-19 | Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102060995A true CN102060995A (en) | 2011-05-18 |
| CN102060995B CN102060995B (en) | 2012-06-06 |
Family
ID=43996512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010552070XA Expired - Fee Related CN102060995B (en) | 2010-11-19 | 2010-11-19 | Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102060995B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407099A (en) * | 2011-09-08 | 2012-04-11 | 中南大学 | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal |
| CN102441367A (en) * | 2011-09-08 | 2012-05-09 | 中南大学 | Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal |
| CN102649998A (en) * | 2012-05-28 | 2012-08-29 | 陕西安圣美贸易发展有限公司 | Method for separating and enriching copper, cadmium and zinc in copper and cadmium sediment |
| CN102814058A (en) * | 2012-09-17 | 2012-12-12 | 工信华鑫科技有限公司 | Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material |
| CN103012228A (en) * | 2012-11-30 | 2013-04-03 | 西北农林科技大学 | Method for separating and purifying astaxanthin by silver ion chelating chromatographic column |
| CN103801270A (en) * | 2012-11-14 | 2014-05-21 | 长沙飞达矿冶技术有限公司 | Environmental material for treating wastewater containing complicated heavy metal and production technology of environmental material |
| CN103933940A (en) * | 2014-04-25 | 2014-07-23 | 西安科技大学 | Method for preparing coal-based composite chelating agent from triethylene tetramine as raw material |
| CN104549152A (en) * | 2015-01-12 | 2015-04-29 | 云南银发绿色环保产业股份有限公司 | Preparation method of soil heavy-metal stabilizer |
| CN104891615A (en) * | 2015-05-27 | 2015-09-09 | 福建洋屿环保科技股份有限公司 | Flocculating agent and preparation method thereof |
| CN105413660A (en) * | 2015-12-17 | 2016-03-23 | 山东大学 | Nanosilicon dioxide structure-based high-heavy metal ion adsorption chelating agent and preparation method thereof |
| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN107199018A (en) * | 2016-03-18 | 2017-09-26 | 绿琪（北京）生物科技有限公司 | A kind of dithiocarbamates chelating agent modified graphene oxide and preparation method thereof |
| CN108212225A (en) * | 2018-03-15 | 2018-06-29 | 李宾 | A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof |
| CN111704907A (en) * | 2020-06-15 | 2020-09-25 | 河南大学 | Heavy metal passivator and preparation method and application thereof |
| CN112897671A (en) * | 2021-01-19 | 2021-06-04 | 西南科技大学 | Heavy metal ion capturing material and preparation method thereof |
| CN113318706A (en) * | 2021-04-10 | 2021-08-31 | 江苏乐尔环境科技股份有限公司 | Preparation method of nano hollow-structure heavy metal chelating agent |
| CN113856637A (en) * | 2021-11-01 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method and application of chelate adsorption filler |
| CN114132960A (en) * | 2021-12-21 | 2022-03-04 | 湖北亚星电子材料有限公司 | Preparation method for purifying titanium dioxide by composite solid phase column |
| CN114477275A (en) * | 2022-03-08 | 2022-05-13 | 天津泽希新材料有限公司 | Preparation method of novel spherical barium titanate |
| CN114477275B (en) * | 2022-03-08 | 2024-05-14 | 天津泽希新材料有限公司 | Preparation method of spherical barium titanate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004095018A1 (en) * | 2003-04-24 | 2004-11-04 | Daicel Chemical Industries, Ltd. | Separating agent for optical isomer |
| WO2006032843A1 (en) * | 2004-09-22 | 2006-03-30 | Bp Chemicals Limited | Silica support, heteropolyacid catalyst produced therefrom and ester synthesis using the silica supported heteropolyacid catalyst |
| CN101215250A (en) * | 2007-12-28 | 2008-07-09 | 上海电力学院 | Chelating agent containing double DTC group and preparation method thereof |
| CN101759809A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing dithiocarbamate-based modified porous starch |
-
2010
- 2010-11-19 CN CN201010552070XA patent/CN102060995B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004095018A1 (en) * | 2003-04-24 | 2004-11-04 | Daicel Chemical Industries, Ltd. | Separating agent for optical isomer |
| WO2006032843A1 (en) * | 2004-09-22 | 2006-03-30 | Bp Chemicals Limited | Silica support, heteropolyacid catalyst produced therefrom and ester synthesis using the silica supported heteropolyacid catalyst |
| CN101215250A (en) * | 2007-12-28 | 2008-07-09 | 上海电力学院 | Chelating agent containing double DTC group and preparation method thereof |
| CN101759809A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing dithiocarbamate-based modified porous starch |
Non-Patent Citations (1)
| Title |
|---|
| 《中国化学会第十五届全国化学热力学和热分析化学学术会议论文摘要》 20100821 白蓝等 硅胶负载新型二硫代氨基甲酸盐螯合树脂的制备方法 241 1 , * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441367B (en) * | 2011-09-08 | 2013-10-23 | 中南大学 | Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal |
| CN102441367A (en) * | 2011-09-08 | 2012-05-09 | 中南大学 | Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal |
| CN102407099A (en) * | 2011-09-08 | 2012-04-11 | 中南大学 | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal |
| CN102407099B (en) * | 2011-09-08 | 2013-05-08 | 中南大学 | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal |
| CN102649998A (en) * | 2012-05-28 | 2012-08-29 | 陕西安圣美贸易发展有限公司 | Method for separating and enriching copper, cadmium and zinc in copper and cadmium sediment |
| CN102649998B (en) * | 2012-05-28 | 2013-08-28 | 陕西水木油田技术服务有限公司 | Method for separating and enriching copper, cadmium and zinc in copper and cadmium sediment |
| CN102814058A (en) * | 2012-09-17 | 2012-12-12 | 工信华鑫科技有限公司 | Method for implementing nickel-magnesium separation, enrichment and purification by using heavy metal adsorbing material |
| CN103801270B (en) * | 2012-11-14 | 2016-03-30 | 长沙飞达矿冶技术有限公司 | For the treatment of the environment-friendly materials and the production technology thereof that contain complicated heavy metal wastewater thereby |
| CN103801270A (en) * | 2012-11-14 | 2014-05-21 | 长沙飞达矿冶技术有限公司 | Environmental material for treating wastewater containing complicated heavy metal and production technology of environmental material |
| CN103012228B (en) * | 2012-11-30 | 2014-07-02 | 西北农林科技大学 | Method for separating and purifying astaxanthin by silver ion chelating chromatographic column |
| CN103012228A (en) * | 2012-11-30 | 2013-04-03 | 西北农林科技大学 | Method for separating and purifying astaxanthin by silver ion chelating chromatographic column |
| CN103933940B (en) * | 2014-04-25 | 2016-07-06 | 西安科技大学 | A kind of preparation method of the coal-based association complex being raw material with triethylene tetramine |
| CN103933940A (en) * | 2014-04-25 | 2014-07-23 | 西安科技大学 | Method for preparing coal-based composite chelating agent from triethylene tetramine as raw material |
| CN104549152A (en) * | 2015-01-12 | 2015-04-29 | 云南银发绿色环保产业股份有限公司 | Preparation method of soil heavy-metal stabilizer |
| CN104891615A (en) * | 2015-05-27 | 2015-09-09 | 福建洋屿环保科技股份有限公司 | Flocculating agent and preparation method thereof |
| CN105413660B (en) * | 2015-12-17 | 2018-05-22 | 山东大学 | A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof |
| CN105413660A (en) * | 2015-12-17 | 2016-03-23 | 山东大学 | Nanosilicon dioxide structure-based high-heavy metal ion adsorption chelating agent and preparation method thereof |
| CN107199018A (en) * | 2016-03-18 | 2017-09-26 | 绿琪（北京）生物科技有限公司 | A kind of dithiocarbamates chelating agent modified graphene oxide and preparation method thereof |
| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN108212225A (en) * | 2018-03-15 | 2018-06-29 | 李宾 | A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof |
| CN111704907B (en) * | 2020-06-15 | 2021-07-16 | 河南大学 | Heavy metal passivator and preparation method and application thereof |
| CN111704907A (en) * | 2020-06-15 | 2020-09-25 | 河南大学 | Heavy metal passivator and preparation method and application thereof |
| CN112897671A (en) * | 2021-01-19 | 2021-06-04 | 西南科技大学 | Heavy metal ion capturing material and preparation method thereof |
| CN113318706A (en) * | 2021-04-10 | 2021-08-31 | 江苏乐尔环境科技股份有限公司 | Preparation method of nano hollow-structure heavy metal chelating agent |
| CN113856637A (en) * | 2021-11-01 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method and application of chelate adsorption filler |
| CN113856637B (en) * | 2021-11-01 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method and application of chelate adsorption filler |
| CN114132960A (en) * | 2021-12-21 | 2022-03-04 | 湖北亚星电子材料有限公司 | Preparation method for purifying titanium dioxide by composite solid phase column |
| CN114477275A (en) * | 2022-03-08 | 2022-05-13 | 天津泽希新材料有限公司 | Preparation method of novel spherical barium titanate |
| CN114477275B (en) * | 2022-03-08 | 2024-05-14 | 天津泽希新材料有限公司 | Preparation method of spherical barium titanate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102060995B (en) | 2012-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102060995B (en) | Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin | |
| WO2016187796A1 (en) | Preparation method and use of heavy metal ion adsorbent | |
| CN102441367B (en) | Preparation method for silica gel-loaded aminomethylpyridine chelating resin for deep copper removal | |
| CN102407099B (en) | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal | |
| CN112679731B (en) | Covalent organic framework material containing sulfonic acid group and preparation and application thereof | |
| CN104059167B (en) | A kind of preparation method and applications of polyamine compounds modified magnetic chitosan | |
| CN104353424B (en) | Amine-containing functional mesoporous material and application thereof to separation of rhenium and molybdenum | |
| CN106378105A (en) | Preparation method of magnetic chitosan compound adsorbent | |
| CN106111088B (en) | A kind of preparation method of silica/cationic-type polyacrylamide hybrid sorbents | |
| CN109205748A (en) | A kind of flocculant and preparation method for heavy metal-polluted water process | |
| CN105126790A (en) | Synthesis and application method of composite function resin for selectively removing nitrate and phosphate at same time | |
| CN106984137B (en) | CO absorption device capable of realizing rapid phase separation2Preparation and use method of polyamino acid ionic liquid type phase separation absorbent | |
| CN104525158A (en) | Heavy metal ion adsorbent and preparation method thereof | |
| CN105498719A (en) | Two-ion modified biologicalal adsorbent and preparation method thereof | |
| CN102863579B (en) | Barbituric acid chelating resin and preparation method and application thereof | |
| CN113372523B (en) | Transition metal ion modified sulfonic acid covalent organic framework material and preparation and application thereof | |
| CN114735795A (en) | Sodium alginate-diatomite composite magnetic flocculant and preparation method thereof | |
| CN104130440A (en) | Preparation method for iron ion imprinted polymer | |
| CN106732345A (en) | A kind of composite adsorbing material for heavy metal containing wastewater treatment and preparation method thereof | |
| CN116809034B (en) | Preparation method of dephosphorizing agent based on rare earth modified gangue | |
| CN107952419B (en) | Renewable adsorption material for rapidly adsorbing and removing organic micropollutants in water and preparation method thereof | |
| CN106582577B (en) | Preparation method and application of attapulgite/polymer porous millimeter-scale pellets | |
| CN113304730A (en) | Preparation method of special adsorbent for cobalt recovery in waste ternary batteries | |
| CN103755004A (en) | Strong acid resin composite material of load zero-valence composite metal, preparation method and application thereof | |
| CN113351187B (en) | Heavy metal ion imprinted hydrogel ball and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120606 Termination date: 20161119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |