CN105367699A - Arsenic macroreticular adsorption resin and preparation method and application thereof - Google Patents
Arsenic macroreticular adsorption resin and preparation method and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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Abstract
The invention provides a preparation method of arsenic macroreticular adsorption resin. The preparation method includes the steps that (1) a water solution of polyvinyl alcohol and sodium chloride serves as the water phase, a methylene blue solution is added, a mixed solution of styrene dissolved with BPO and divinyl benzene and a pore-foaming agent serves as the oil phase, macroporous crosslinked polystyrene is obtained through a suspension polymerization method, the pore-foaming agent is recycled, drying is conducted, and a white ball is obtained; 2, firstly, the white ball is expanded with chloromethylation solvent, then a catalyst is added, a chloromethylation reaction is conducted, washing and drying are conducted, and a chloromethylated bead is obtained; 3, amination reagent is added to the chloromethylated bead for amination, then the chloromethylated bead is cleaned and treated with hydrochloric acid, and an amination chloride type ball is obtained; 4, the amination chloride type ball is soaked with a hydrochloric acid ferric chloride solution, treated with liquid caustic soda and washed with water, and the resin is obtained. By means of the method, the resin is particularly applicable to arsenic removal; besides, the preparation method is simple, easy to implement, convenient to operate, equipment and a feeding method in the prior art can be continued, and the preparation method is suitable for application and popularization.
Description
Technical field
The present invention relates to a kind of resin, particularly relate to a kind of macroporous type arsenic polymeric adsorbent and its preparation method and application.
Background technology
Polymeric adsorbent is a kind of to be adsorbed as feature, to have the resin sorbent of porous three dimensional structure.It is a kind of porous resin that the recent years of new development in field of polymer technology is got up, and is widely used in wastewater treatment, medicament isolation andpurification, as the filler of the carrier of chemical reaction catalyst, gas chromatographic analysis and gel permeation chromatography molecular-weight gradation post.Be characterized in regenerating easily, can Reusability.
At present, being applied to by polymeric adsorbent in arsenic removal, is feasible.Wherein, CN103232091A discloses a kind of method that macroporous resin removes arsenic in water body, comprise the steps: macroporous resin pre-treatment, the solution of zirconium-containing compound carries out coprecipitation method load process, with the macroporous resin after load, adsorption treatment is carried out to the water body that trivalent arsenic or pentavalent arsenic content are 10-5000 μ g/L, total arsenic content can be down to 10 below μ g/L, resin regeneration can be carried out with sodium hydroxide, the regeneration rate of resin reaches more than 95%, the method arsenic removal efficiency is high, technological operation is simple, is easy to industrialization; CN102633930A discloses a kind of synthesis preparation method of arsenic removal resin, comprises and in mass ratio divinylbenzene, vinyl cyanide, primary isoamyl alcohol mixing and stirring is obtained organic phase; Be dissolved in deionized water with cerous sulfate, configure the certain density aqueous solution, add the polyvinyl alcohol of certain mass ratio, stir to obtain solution; Urea is dissolved in deionized water, is configured to urea saturated solution, add in solution by volume, stir to obtain aqueous phase; Organic phase is added in aqueous phase in mass ratio, is stirred to droplet diameter distribution within the specific limits, adds BP, intensification, isothermal reaction, isothermal curing a few hours, after filtration, obtain solid particulate; Particle is placed in after sodium hydroxide solution soaks several hours, loads resin column, with sodium hydroxide+clorox mixed solution drip washing to effluent liquid clear, filter and be product; This product is high to the arsenic-selective in the aqueous solution, and loading capacity is large, is easy to regeneration, concentrated for arsenic concentrating in regenerated liquid can be carried out industry recycling, not by secondary pollution.
In fact, in actual Synthesis and applications process, those skilled in the art find, the phenomenon that preparation method is complicated and effect is not good still exists, and therefore, a kind of preparation method is simple, the resin that effect of removing arsenic is good, remain this area in the urgent need to.
Summary of the invention
Based on above-mentioned background, the invention provides a kind of macroporous type arsenic polymeric adsorbent and its preparation method and application.Improved preparation method, makes described macroporous type arsenic polymeric adsorbent be applied in arsenic removal especially applicable, the more important thing is, this preparation method is simple, easy to operate, and equipment of the prior art and charging process can be continued to use, be suitable for promotion and application.
Technical scheme of the present invention comprises a kind of preparation method of macroporous type arsenic polymeric adsorbent, it is characterized in that, comprising:
Step 1: using the aqueous solution of polyvinyl alcohol and sodium-chlor as aqueous phase, and add methylene blue solution as aqueous phase stopper, to be dissolved with the vinylbenzene of BPO and Vinylstyrene mixed solution and pore-creating agent as oil phase, macroporous cross-linked polystyrene is obtained by suspension polymerization, reclaim pore-creating agent, dry and obtain Archon;
Step 2: first by described Archon chloromethylation solvent expansion, then add catalyzer and carry out chloromethylation, obtains chlorine ball after washing drying;
Step 3: add amination reagent and carry out amination in described chlorine ball, then carries out cleaning and obtains amination chlorine type ball with HCl treatment;
Step 4: the immersion of described amination chlorine type ball warp persalt ferric chloride Solution, and by liquid caustic soda process, washing obtains described macroporous type arsenic polymeric adsorbent.
Preferably, the skeleton degree of crosslinking of described macroporous cross-linked polystyrene is 5%-20%.
Preferably, described pore-creating agent be selected from comprise in toluene, the direct-connected alkane of C9-C18, isopropylcarbinol, the cinnamic good solvent of primary isoamyl alcohol or cinnamic poor solvent any one or a few; Its usage quantity is the 20%-60% of the total mass of vinylbenzene and Vinylstyrene, is preferably 40%-60%.
Preferably, the method for described recovery pore-creating agent comprises any one or a few the combination in extraction, steam spray, underpressure distillation.
Preferably, described chloromethylation solvent is chloromethyl ether and/or chlorsulfonic acid.
Preferably, described amination reagent is Trimethylamine 99 and/or dimethylethanolamine.
In one embodiment of the invention, in described step 1, described aqueous phase and oil phase mix under agitation, be warming up to 70-80 DEG C (being preferably 75 DEG C), be incubated 4-5 hour (being preferably 4 hours), be then warming up to 90-100 DEG C (being preferably 95 DEG C), be incubated 5-7 hour (being preferably 6 hours), reclaim pore-creating agent, and described macroporous cross-linked polystyrene is dried with hot water and cold water washing successively.
In another one embodiment of the present invention, in described step 2, first by described Archon chloromethylation solvent expansion 2-3 hour (being preferably 2 hours), then catalyzer is added, be warming up to 45-55 DEG C (being preferably 48 DEG C), be incubated 10-15 hour (being preferably 12 hours), washing is dry.
Preferably, described catalyzer is zinc chloride and/or iron(ic) chloride.
In one embodiment of the invention, in described step 3, in described chlorine ball, add amination reagent, stir under 35-45 DEG C of (being preferably 38 DEG C) condition 5-8 hour (being preferably 6 hours), then clean, and obtain amination chlorine type ball with HCl treatment.
Preferably, described state add amination reagent in chlorine ball before, first add water, add liquid caustic soda again, finally add described amination reagent, wherein, described alkali lye is preferably sodium hydroxide solution, be more preferably the sodium hydroxide solution that mass percent is 20%-50%, be more preferably the sodium hydroxide solution that mass percent is 30%; More preferably, described HCl treatment is adjust ph is acid, is preferably 1-4, is more preferably 2-3, is more preferably 2; Preferably, after HCl treatment, be washed to neutrality and obtain described amination chlorine type ball.
In an embodiment of the present invention, in described step 4, add chlorination of hydrochloric acid ferrous solution, be warming up to 40-55 DEG C (being preferably 45 DEG C), insulation 2-3 hour, adds liquid caustic soda after draining described chlorination of hydrochloric acid ferrous solution again, is warming up to 70-100 DEG C (being preferably 80 DEG C), be incubated 10-15 hour (being preferably 12-13 hour), be washed to neutrality and obtain described macroporous type arsenic polymeric adsorbent.
Preferably, described alkali lye is preferably sodium hydroxide solution, is more preferably the sodium hydroxide solution that mass percent is 20%-50%, is more preferably the sodium hydroxide solution that mass percent is 30%.
In an embodiment of the present invention, about the restriction of consumption, in step 1, wherein, in oil phase, the mass ratio of described vinylbenzene and Vinylstyrene is 2-4:1, is preferably 2.5-3.5:1; The consumption of described BPO is the 0.8-2.5% of the total mass of described vinylbenzene and Vinylstyrene, is preferably 1%; The consumption of described pore-creating agent is the 20%-60% of the total mass of vinylbenzene and Vinylstyrene, is preferably 40%-60%.Further, in aqueous phase, described methylene blue solution is massfraction is 0.1% methylene blue solution, and preferably, the massfraction of every 1L aqueous phase interpolation 0.1-1.0ml is the methylene blue solution of 0.1%; The weight ratio of described polyvinyl alcohol and sodium-chlor is 1:5-20, is preferably 1:10-15, and further, the quality of its aqueous solution is 10-40 times of the gross weight of described polyvinyl alcohol and sodium-chlor, is preferably 15-30 doubly.
In step 3, described state add amination reagent in chlorine ball before, first add the 2-3 water doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene, add the liquid caustic soda of the 2%-10% of the total mass being equivalent to described vinylbenzene and Vinylstyrene again, finally add the 1-2 amination reagent doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene.Wherein, described alkali lye is preferably sodium hydroxide solution, is more preferably the sodium hydroxide solution that mass percent is 20%-50%, is more preferably the sodium hydroxide solution that mass percent is 30%.
In step 4, add the 2-3 chlorination of hydrochloric acid ferrous solution doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene; Wherein, in described chlorination of hydrochloric acid ferrous solution, the concentration of iron(ic) chloride is 300-800g/L.
Technical scheme of the present invention also comprises a kind of preparation method described above and prepares macroporous type arsenic polymeric adsorbent, it is characterized in that, containing iron ion complex compound.
Technical scheme of the present invention also comprises the application of a kind of macroporous type arsenic polymeric adsorbent described above in arsenic removal.
Wherein, the saturated adsorption capacity of described macroporous type arsenic polymeric adsorbent to arsenic ranges up to 180mgg
-1above.
In described preparation method provided by the invention, in aqueous phase, adding methylene blue solution as aqueous phase stopper is committed step, and this is related to the effect of suspension polymerization, is especially important for the Archon that can obtain uniform pore diameter.Adopt first by described Archon chloromethylation solvent expansion, then add the step that catalyzer carries out chloromethylation, be also necessary, this makes chloromethylation more even.Certainly, the component concentration of various material is also the key in preparation method, especially vinylbenzene and Vinylstyrene adding proportion, can effectively regulate the degree of crosslinking of Archon in claimed range because control divinylbenzene ratio, in addition, the consumption of pore-creating agent is also crucial selection.The temperature of reaction of suspension polymerization have employed the mode of staged insulation reaction, and relative and prior art, effect is better.The more important thing is, by the immersion of chlorination of hydrochloric acid ferrous solution and the process of liquid caustic soda, make containing a large amount of iron ion complex compounds in described resin, make described macroporous type arsenic polymeric adsorbent when being applied to arsenic removal, it ranges up to 180mgg to the saturated adsorption capacity of arsenic
-1above.Certainly, preparation method provided by the invention, as an overall technical architecture, each step and details aspect all connect each other, and it the object of the invention is very necessary for realization.
Embodiment
The invention provides a kind of preparation method of macroporous type arsenic polymeric adsorbent, it is characterized in that, comprising:
Step 1: using the aqueous solution of polyvinyl alcohol and sodium-chlor as aqueous phase, and add methylene blue solution as aqueous phase stopper, to be dissolved with the vinylbenzene of BPO and Vinylstyrene mixed solution and pore-creating agent as oil phase, macroporous cross-linked polystyrene is obtained by suspension polymerization, reclaim pore-creating agent, dry and obtain Archon;
Step 2: first by described Archon chloromethylation solvent expansion, then add catalyzer and carry out chloromethylation, obtains chlorine ball after washing drying;
Step 3: add amination reagent and carry out amination in described chlorine ball, then carries out cleaning and obtains amination chlorine type ball with HCl treatment;
Step 4: the immersion of described amination chlorine type ball warp persalt ferric chloride Solution, and by liquid caustic soda process, washing obtains described macroporous type arsenic polymeric adsorbent.
Preferably, the skeleton degree of crosslinking of described macroporous cross-linked polystyrene is 5%-20%.
Preferably, described pore-creating agent be selected from comprise in toluene, the direct-connected alkane of C9-C18, isopropylcarbinol, the cinnamic good solvent of primary isoamyl alcohol or cinnamic poor solvent any one or a few; Its usage quantity is the 20%-60% of the total mass of vinylbenzene and Vinylstyrene, is preferably 40%-60%.
Preferably, the method for described recovery pore-creating agent comprises any one or a few the combination in extraction, steam spray, underpressure distillation.
Preferably, described chloromethylation solvent is chloromethyl ether and/or chlorsulfonic acid.
Preferably, described amination reagent is Trimethylamine 99 and/or dimethylethanolamine.
In one embodiment of the invention, in described step 1, described aqueous phase and oil phase mix under agitation, be warming up to 70-80 DEG C (being preferably 75 DEG C), be incubated 4-5 hour (being preferably 4 hours), be then warming up to 90-100 DEG C (being preferably 95 DEG C), be incubated 5-7 hour (being preferably 6 hours), reclaim pore-creating agent, and described macroporous cross-linked polystyrene is dried with hot water and cold water washing successively.
In another one embodiment of the present invention, in described step 2, first by described Archon chloromethylation solvent expansion 2-3 hour (being preferably 2 hours), then catalyzer is added, be warming up to 45-55 DEG C (being preferably 48 DEG C), be incubated 10-15 hour (being preferably 12 hours), washing is dry.
Preferably, described catalyzer is zinc chloride and/or iron(ic) chloride.
In one embodiment of the invention, in described step 3, in described chlorine ball, add amination reagent, stir under 35-45 DEG C of (being preferably 38 DEG C) condition 5-8 hour (being preferably 6 hours), then clean, and obtain amination chlorine type ball with HCl treatment.
Preferably, described state add amination reagent in chlorine ball before, first add water, add liquid caustic soda again, finally add described amination reagent, wherein, described alkali lye is preferably sodium hydroxide solution, be more preferably the sodium hydroxide solution that mass percent is 20%-50%, be more preferably the sodium hydroxide solution that mass percent is 30%; More preferably, described HCl treatment is adjust ph is acid, is preferably 1-4, is more preferably 2-3, is more preferably 2; Preferably, after HCl treatment, be washed to neutrality and obtain described amination chlorine type ball.
In an embodiment of the present invention, in described step 4, add chlorination of hydrochloric acid ferrous solution, be warming up to 40-55 DEG C (being preferably 45 DEG C), insulation 2-3 hour, adds liquid caustic soda after draining described chlorination of hydrochloric acid ferrous solution again, is warming up to 70-100 DEG C (being preferably 80 DEG C), be incubated 10-15 hour (being preferably 12-13 hour), be washed to neutrality and obtain described macroporous type arsenic polymeric adsorbent.
Preferably, described alkali lye is preferably sodium hydroxide solution, is more preferably the sodium hydroxide solution that mass percent is 20%-50%, is more preferably the sodium hydroxide solution that mass percent is 30%.
In an embodiment of the present invention, about the restriction of consumption, in step 1, wherein, in oil phase, the mass ratio of described vinylbenzene and Vinylstyrene is 2-4:1, is preferably 2.5-3.5:1; The consumption of described BPO is the 0.8-2.5% of the total mass of described vinylbenzene and Vinylstyrene, is preferably 1%; The consumption of described pore-creating agent is the 20%-60% of the total mass of vinylbenzene and Vinylstyrene, is preferably 40%-60%.Further, in aqueous phase, described methylene blue solution is massfraction is 0.1% methylene blue solution, and preferably, the massfraction of every 1L aqueous phase interpolation 0.1-1.0ml is the methylene blue solution of 0.1%; The weight ratio of described polyvinyl alcohol and sodium-chlor is 1:5-20, is preferably 1:10-15, and further, the quality of its aqueous solution is 10-40 times of the gross weight of described polyvinyl alcohol and sodium-chlor, is preferably 15-30 doubly.
In step 3, described state add amination reagent in chlorine ball before, first add the 2-3 water doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene, add the liquid caustic soda of the 2%-10% of the total mass being equivalent to described vinylbenzene and Vinylstyrene again, finally add the 1-2 amination reagent doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene.Wherein, described alkali lye is preferably sodium hydroxide solution, is more preferably the sodium hydroxide solution that mass percent is 20%-50%, is more preferably the sodium hydroxide solution that mass percent is 30%.
In step 4, add the 2-3 chlorination of hydrochloric acid ferrous solution doubly of the total mass being equivalent to described vinylbenzene and Vinylstyrene; Wherein, in described chlorination of hydrochloric acid ferrous solution, the concentration of iron(ic) chloride is 300-800g/L.
Present invention also offers a kind of preparation method described above and prepare macroporous type arsenic polymeric adsorbent, it is characterized in that, containing iron ion complex compound.
Present invention also offers the application of a kind of macroporous type arsenic polymeric adsorbent described above in arsenic removal.
Wherein, the saturated adsorption capacity of described macroporous type arsenic polymeric adsorbent to arsenic ranges up to 180mgg
-1above.
According to technique scheme, now with the following Examples, technical scheme of the present invention is explained further and illustrates.
Embodiment 1
5g polyvinyl alcohol and 60g sodium-chlor are added in the there-necked flask that 1000ml pure water is housed and dissolves, and to add 5 massfractions be 0.1% methylene blue solution, 375g vinylbenzene and 125g Vinylstyrene is added as monomer phase in beaker, again monomer mutually in add and account for the BPO that monomer total mass is 1%, by control divinylbenzene monomer mutually in ratio regulate making large-pore white balls used degree of crosslinking, add 300g isopropylcarbinol again as pore-creating agent, stirring is opened after oil phase and aqueous phase mixing, rotating speed is adjusted to 100r/min, oil bath is warming up to 75 DEG C of insulation 4h, then 95 DEG C are warming up to, pore-creating agent is reclaimed in underpressure distillation, hot water and cold water washing are used successively to polymer microballoon, dry, expand the making large-pore white balls used chloromethyl ether of synthesis 2h, adds appropriate zinc chloride and be warming up to 48 DEG C, and insulation 12h cleans up reaction product water and drying, add 1000ml water, 20ml concentration is the liquid caustic soda of 30%, 500ml trimethylamine aqueous solution, is warming up to 38 DEG C of insulations 6 hours, and products therefrom washes with water totally, and being adjusted to ph with 100ml hydrochloric acid is 2, then washes with water to neutrality, add the chlorination of hydrochloric acid ferrous solution 1000ml being dissolved with 500g iron(ic) chloride, 45 DEG C are incubated 2 hours, drain chlorination of hydrochloric acid ferrous solution, add the liquid caustic soda of 30%, and 80 DEG C are incubated 12 hours, products in water are washed till neutrality, obtain described macroporous type arsenic polymeric adsorbent.
Embodiment 2
5g polyvinyl alcohol and 60g sodium-chlor are added in the there-necked flask that 1000ml pure water is housed and dissolves, and to add 5 massfractions be 0.1% methylene blue solution, 375g vinylbenzene and 125g Vinylstyrene is added as monomer phase in beaker, again monomer mutually in add and account for the BPO that monomer total mass is 1%, by control divinylbenzene monomer mutually in ratio regulate making large-pore white balls used degree of crosslinking, add the direct-connected alkane of 300gC9-C18 again as pore-creating agent, stirring is opened after oil phase and aqueous phase mixing, rotating speed is adjusted to 100r/min, oil bath is warming up to 75 DEG C of insulation 4h, then 95 DEG C are warming up to, pore-creating agent is reclaimed in underpressure distillation, hot water and cold water washing are used successively to polymer microballoon, dry, expand the making large-pore white balls used chloromethyl ether of synthesis 2h, adds appropriate zinc chloride and be warming up to 48 DEG C, and insulation 12h cleans up reaction product water and drying, add 1000ml water, 20ml concentration is the liquid caustic soda of 30%, 500ml trimethylamine aqueous solution, is warming up to 38 DEG C of insulations 6 hours, and products therefrom washes with water totally, and being adjusted to ph with 100ml hydrochloric acid is 2, then washes with water to neutrality, add the chlorination of hydrochloric acid ferrous solution 1000ml being dissolved with 500g iron(ic) chloride, 45 DEG C are incubated 2 hours, drain chlorination of hydrochloric acid ferrous solution, add the liquid caustic soda of 30%, and 80 DEG C are incubated 12 hours, products in water are washed till neutrality, obtain described macroporous type arsenic polymeric adsorbent.
Embodiment 3
5g polyvinyl alcohol and 60g sodium-chlor are added in the there-necked flask that 1000ml pure water is housed and dissolves, and to add 5 massfractions be 0.1% methylene blue solution, 375g vinylbenzene and 125g Vinylstyrene is added as monomer phase in beaker, again monomer mutually in add and account for the BPO that monomer total mass is 1%, by control divinylbenzene monomer mutually in ratio regulate making large-pore white balls used degree of crosslinking, add 300g primary isoamyl alcohol again as pore-creating agent, stirring is opened after oil phase and aqueous phase mixing, rotating speed is adjusted to 100r/min, oil bath is warming up to 75 DEG C of insulation 4h, then 95 DEG C are warming up to, pore-creating agent is reclaimed in underpressure distillation, hot water and cold water washing are used successively to polymer microballoon, dry, expand the making large-pore white balls used chloromethyl ether of synthesis 2h, adds appropriate zinc chloride and be warming up to 48 DEG C, and insulation 12h cleans up reaction product water and drying, add 1000ml water, 20ml concentration is the liquid caustic soda of 30%, 500ml trimethylamine aqueous solution, is warming up to 38 DEG C of insulations 6 hours, and products therefrom washes with water totally, and being adjusted to ph with 100ml hydrochloric acid is 2, then washes with water to neutrality, add the chlorination of hydrochloric acid ferrous solution 1000ml being dissolved with 500g iron(ic) chloride, 45 DEG C are incubated 2 hours, drain chlorination of hydrochloric acid ferrous solution, add the liquid caustic soda of 30%, and 80 DEG C are incubated 12 hours, products in water are washed till neutrality, obtain described macroporous type arsenic polymeric adsorbent.
Application Example 1
Containing As (III) amount for 5g/L, pH value are that the arsenic solution 400mL of 5.0 is in 1000mL beaker, add the resin tree 10g that embodiment 1 obtains, fully stir at 30 DEG C of temperature, carry out exchange adsorption test, obtain resin under different time to the exchange adsorption amount of As (III), with the prolongation of experimental period, the exchange adsorption amount of As (III) constantly increases.After proceeding to 120min, exchange adsorption amount no longer increases, and namely reaction tends to balance, and experimentally result calculates, and the saturated adsorption capacity of resin to As (III) is 182mgg under this condition
-1.
Application Example 2
Containing As (III) amount for 5g/L, pH value are that the arsenic solution 400mL of 5.0 is in 1000mL beaker, add the resin 10g that embodiment 2 obtains, fully stir at 30 DEG C of temperature, carry out exchange adsorption test, obtain resin under different time to the exchange adsorption amount of As (III), with the prolongation of experimental period, the exchange adsorption amount of As (III) constantly increases.After proceeding to 120min, exchange adsorption amount no longer increases, and namely reaction tends to balance, and experimentally result calculates, and the saturated adsorption capacity of resin to As (III) is 180mgg under this condition
-1.
Application Example 3
Containing As (III) amount for 5g/L, pH value are that the arsenic solution 400mL of 5.0 is in 1000mL beaker, add the resin 10g that embodiment 3 obtains, fully stir at 30 DEG C of temperature, carry out exchange adsorption test, obtain resin under different time to the exchange adsorption amount of As (III), with the prolongation of experimental period, the exchange adsorption amount of As (III) constantly increases.After proceeding to 120min, exchange adsorption amount no longer increases, and namely reaction tends to balance, and experimentally result calculates, and the saturated adsorption capacity of resin to As (III) is 188mgg under this condition
-1.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (10)
1. a preparation method for macroporous type arsenic polymeric adsorbent, is characterized in that, comprising:
Step 1: using the aqueous solution of polyvinyl alcohol and sodium-chlor as aqueous phase, and add methylene blue solution as aqueous phase stopper, to be dissolved with the vinylbenzene of BPO and Vinylstyrene mixed solution and pore-creating agent as oil phase, macroporous cross-linked polystyrene is obtained by suspension polymerization, reclaim pore-creating agent, dry and obtain Archon;
Step 2: first by described Archon chloromethylation solvent expansion, then add catalyzer and carry out chloromethylation, obtains chlorine ball after washing drying;
Step 3: add amination reagent and carry out amination in described chlorine ball, then carries out cleaning and obtains amination chlorine type ball with HCl treatment;
Step 4: the immersion of described amination chlorine type ball warp persalt ferric chloride Solution, and by liquid caustic soda process, washing obtains described macroporous type arsenic polymeric adsorbent.
2. preparation method according to claim 1, is characterized in that, the skeleton degree of crosslinking of described macroporous cross-linked polystyrene is 5%-20%.
3. preparation method according to claim 1, is characterized in that, described pore-creating agent be selected from comprise in toluene, the direct-connected alkane of C9-C18, isopropylcarbinol, the cinnamic good solvent of primary isoamyl alcohol or cinnamic poor solvent any one or a few; Its usage quantity is the 20%-60% of the total mass of vinylbenzene and Vinylstyrene.
4. preparation method according to claim 1, is characterized in that, described amination reagent is Trimethylamine 99 and/or dimethylethanolamine.
5. preparation method according to claim 1, it is characterized in that, in described step 1, described aqueous phase and oil phase mix under agitation, are warming up to 70-80 DEG C, insulation 4-5 hour, then 90-100 DEG C is warming up to, insulation 5-7 hour, reclaims pore-creating agent, and dries with hot water and cold water washing successively described macroporous cross-linked polystyrene.
6. preparation method according to claim 1, is characterized in that, in described step 2, first by described Archon chloromethylation solvent expansion 2-3 hour, then adds catalyzer, is warming up to 45-55 DEG C, and insulation 10-15 hour, washing is dry.
7. preparation method according to claim 1, is characterized in that, in described step 3, adds amination reagent, stir 5-8 hour, then clean under 35-45 DEG C of condition in described chlorine ball, and obtain amination chlorine type ball with HCl treatment.
8. preparation method according to claim 7, is characterized in that, described state add amination reagent in chlorine ball before, first add water, then add liquid caustic soda, finally add described amination reagent, wherein, the sodium hydroxide solution of described alkali lye to be mass percent be 20%-50%; Described HCl treatment is adjust ph is 1-4; After excellent HCl treatment, be washed to neutrality and obtain described amination chlorine type ball.
9. preparation method according to claim 1, it is characterized in that, in described step 4, add chlorination of hydrochloric acid ferrous solution, be warming up to 40-55 DEG C, insulation 2-3 hour, liquid caustic soda is added again after draining described chlorination of hydrochloric acid ferrous solution, be warming up to 70-100 DEG C, insulation 10-15 hour, is washed to neutrality and obtains described macroporous type arsenic polymeric adsorbent; Wherein, the sodium hydroxide solution of described alkali lye to be mass percent be 20%-50%.
10. for preparing as the preparation method in claim 1-9 as described in any one obtains a macroporous type arsenic polymeric adsorbent, it is characterized in that, containing iron ion complex compound.
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