Summary of the invention
The present invention is intended to overcome the defective that above-mentioned prior art exists, and strong-base anion-exchange resin and preparation method thereof in a kind of large pore anion of tertiary-amino-containing is provided.This ion exchange resin is made by one-step method; Technology is simple and direct; And prepared macroporous anion exchange resin can be used for separation, purifying and the recovery of various heavy complex anions such as cadmium, lead, zinc, copper, and the processing that contains above-mentioned heavy metal ion industrial wastewater.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
The macroporous anion exchange resin of tertiary-amino-containing is characterized in that the weight portion of raw material consists of:
Oil phase
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 40-60 part
The 3rd monomer 8-20 part
Crosslinking agent 30-50 part
Pore-foaming agent 50-120 part
Initator 1-4 part
Water
Distilled water 600-800 part
Salt 120-160 part
Suspension protective agent 10-20 part
Oxygen scavenger 1-3 part
Preferred weight portion is:
Oil phase
Dimethylaminoethyl acrylate methyl ammonia ethyl ester 45-55 part
The 3rd monomer 10-15 part
Crosslinking agent 35-45 part
Pore-foaming agent 80-120 part
Initator 1-2 part
Water
Distilled water 600-700 part
Salt 120-140 part
Suspension protective agent 10-12 part
Oxygen scavenger 1-2 part
Said the 3rd monomer is acrylonitrile, methyl acrylate or hydroxyethyl methacrylate etc.
Said crosslinking agent is divinylbenzene, methacrylate glycol ester, allyl methacrylate or triallyl isocyanurate etc.
Said pore-foaming agent is toluene, xylenes, 200# gasoline or isooctanol etc.
Said initator is azodiisobutyronitrile or dibenzoyl peroxide.
Said salt is industrial NaCl, KCl or Na
2SO
4Deng.
Said suspension protective agent is industrial gelatine or industrial polyvinyl alcohol etc.
Said oxygen scavenger is a methylene blue etc.
The preparation method of tertiary-amino-containing macroporous anion exchange resin according to the invention comprises following processing step:
The preparation of a, oil phase: accurately take by weighing dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylonitrile, crosslinking agent, pore-foaming agent, initator, fully stir the miscible oil phase that gets;
The preparation of b, water: in container, add distilled water, NaCl, suspension protective agent and oxygen scavenger, be heated to 50 ℃ of abundant mixings and get water;
C, oil phase mix with water: the temperature of step b water is risen to 60 ℃; Pour the oil phase of step a into, start stirring, be dispersed into the pearl body of 0.40-2.00mm to oil phase; Temperature with reaction system rises to 65-70 ℃ again, and the granularity of adjustment polymer dispersion reaches 0.20-1.20mm;
The curing of d, polymer dispersion: the temperature of step c polymer dispersion system is risen to 72-75 ℃; Make the polymer dispersion polymerization, behind the solidified forming, be incubated 1-2 hour; Temperature with polymerization reaction system rises to 80 ℃, 85 ℃, 90 ℃, 95 ℃ successively then, and is incubated 2-3 hour respectively;
The formation of e, resin bead body: the temperature of steps d polymerization reaction system is reduced to 30-50 ℃, leach the resin bead body;
The processing of f, resin: earlier with the resin bead body of running water washing step e 3-5 time; Use steam distillation device boiling 2-3h then; To remove unreacted pore-foaming agent; Wash with 5-8 times of industrial alcohol of resin volume again,, obtain product with 2 1N HCl, 3 1N NaOH alternate treatment at last to remove unconverted monomer and oligomer.
The present invention adopts macromolecule suspension condensation polymerization technology from the macromolecule design principle, is basic polymer raw with dimethylaminoethyl acrylate methyl ammonia ethyl ester, divinylbenzene etc., with high concentration NaCl, KCl or Na
2SO
4The aqueous solution is decentralized medium, is the suspension protective agent with polyvinyl alcohol or gelatin, is pore-foaming agent with toluene, xylenes, gasoline and isooctanol etc., promptly synthesizes pearl tertiary-amino-containing macroporous anion exchange resin through the one-step polymerization reaction, and technology is simple, and cost is not high.
The present invention adopts high concentration NaCl, KCl or Na
2SO
4The aqueous solution is the suspended dispersed medium; Polyvinyl alcohol etc. are for disperseing protectant suspension polymerization system; Efficiently solve the loss of monomer in the copolymerization process; Suspension polymerization system is carried out effective protection, guaranteed the quality of tertiary-amino-containing macroporous anion exchange resin product, improved the yield of product.
The specific embodiment
Embodiment 1
A kind of macroporous anion exchange resin of tertiary-amino-containing is characterized in that the weight portion of raw material consists of:
Oil phase
50 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters
10 parts of acrylonitrile
40 parts of divinylbenzenes
100 parts of toluene
2 parts of azodiisobutyronitriles
Water
800 parts of distilled water
160 parts of NaCl
12 parts of industrial gelatines
2 parts of methylene blues
Embodiment 2
A kind of macroporous anion exchange resin of tertiary-amino-containing is characterized in that the weight portion of raw material consists of:
Oil phase
40 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters
20 parts of methyl acrylates
40 parts of methacrylate glycol esters
120 parts of xylenes
2 parts of dibenzoyl peroxides
Water
700 parts of distilled water
140 parts of KCl
(1788) 10 parts of polyvinyl alcohol
2 parts of methylene blues
Embodiment 3
A kind of macroporous anion exchange resin of tertiary-amino-containing is characterized in that the weight portion of raw material consists of:
Oil phase
40 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters
20 parts of acrylonitrile
40 parts of allyl methacrylates
80 parts in 200# gasoline
2 parts of benzoyl peroxides
Water
800 parts of distilled water
Na
2SO
4130 parts
15 parts in gelatin
2 parts of methylene blues
Embodiment 4
A kind of macroporous anion exchange resin of tertiary-amino-containing is characterized in that the weight portion of raw material consists of:
Oil phase
40 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters
40 parts of divinylbenzenes
20 parts of hydroxyethyl methacrylates
100 parts of diethylbenzene
3 parts of dibenzoyl peroxides
Water
800 parts of distilled water
Na
2SO
4160 parts
16 parts in gelatin
4 parts of methylene blues
Embodiment 5
A kind of preparation method of tertiary-amino-containing macroporous anion exchange resin comprises following processing step:
The preparation of a, oil phase: take by weighing 50 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters, 10 parts of acrylonitrile, 40 parts of divinylbenzenes, 100 parts of toluene, 2 parts of dibenzoyl peroxides, fully stir the miscible oil phase that gets;
The preparation of b, water: in container, add 2 parts of 800 parts of distilled water, 140 parts of NaCl, 16 parts in gelatin and methylene blues, be heated to 50 ℃ of abundant mixings and get water;
C, oil phase mix with water: the temperature of step b water is risen to 60 ℃; Pour the oil phase of step a into, start stirring, be dispersed into the pearl body of 0.40-2.00mm to oil phase; Temperature with reaction system rises to 65-70 ℃ again, the granularity 0.20-1.20mm of adjustment polymer dispersion;
The curing of d, polymer dispersion: the temperature of step c polymer dispersion system is risen to 72-75 ℃; Make the polymer dispersion polymerization, behind the solidified forming, be incubated 1-2 hour; Temperature with polymerization reaction system rises to 80 ℃, 85 ℃, 90 ℃, 95 ℃ successively then, and is incubated 2-3 hour respectively;
The formation of e, resin bead body: the temperature of steps d polymerization reaction system is reduced to 30-50 ℃, leach the resin bead body;
The processing of f, resin: earlier with the resin bead body of running water washing step e 3-5 time; Use steam distillation device boiling 2-3h then; To remove unreacted pore-foaming agent; Wash with industrial alcohol again,, obtain product with 2 1N HCl, 3 1N NaOH alternate treatment at last to remove unconverted monomer and oligomer.
Embodiment 6
A kind of preparation method of tertiary-amino-containing macroporous anion exchange resin comprises following processing step:
The preparation of a, oil phase: take by weighing 40 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters, 40 parts of methacrylate glycol esters, 20 parts of methyl acrylates, 120 parts of xylenes, 2 parts of azodiisobutyronitriles, fully stir the miscible oil phase that gets;
The preparation of b, water: in container, add 2 parts of 800 parts of distilled water, 160 parts of KCl, 12 parts of polyvinyl alcohol and methylene blues, be heated to 50 ℃ of abundant mixings and get water;
C, oil phase mix with water: the temperature of step b water is risen to 60 ℃; Pour the oil phase of step a into, start stirring, be dispersed into the pearl body of 0.40-2.00mm to oil phase; Temperature with reaction system rises to 65-70 ℃ again, and the granularity of adjustment polymer dispersion becomes 0.20-1.20mm;
The curing of d, polymer dispersion: the temperature of step c polymer dispersion system is risen to 72-75 ℃; Make the polymer dispersion polymerization, behind the solidified forming, be incubated 1-2 hour; Temperature with polymerization reaction system rises to 80 ℃, 85 ℃, 90 ℃, 95 ℃ successively then, and is incubated 2-3 hour respectively;
The formation of e, resin bead body: the temperature of steps d polymerization reaction system is reduced to 30-50 ℃, leach the resin bead body;
The processing of f, resin: earlier with the resin bead body of running water washing step e 3-5 time; Use steam distillation device boiling 2-3h then; To remove unreacted pore-foaming agent; Wash with industrial alcohol again,, obtain product with 2 1N HCl, 3 1N NaOH alternate treatment at last to remove unconverted monomer and oligomer.
Embodiment 7
In the 2000ml there-necked flask, add distilled water 700ml successively, suspension dispersive agent polyvinyl alcohol 10g, oxygen scavenger methylene blue 2g; Start stirring temperature of reaction system is risen to 50 ℃, dissolve as water subsequent use fully until the suspension dispersive agent polyvinyl alcohol; In a beaker, taking by weighing dimethylaminoethyl acrylate methyl ammonia ethyl ester 50g, methyl acrylate 10g, divinylbenzene 40g, 200# gasoline 100g, azodiisobutyronitrile 2g and stirring by prescription makes it miscible subsequent use as oil phase; After the there-necked flask aqueous phase adds 100g industry NaCl and it is dissolved fully, temperature is risen to 60 ℃, the oil phase in the beaker is poured in the there-necked flask; Start stirring and make oil phase be scattered in aqueous phase, and make oil phase be dispersed into the pearl body of 0.40-2.00mm; Temperature of reaction system is risen to 65-70 ℃, continue the granularity 0.20-1.20mm of adjustment polymer dispersion; The polymerization system temperature is risen to 70-75 ℃ make the polymer dispersion polymerization, behind the solidified forming, be incubated 1-2 hour; The temperature of polymerization reaction system is risen to 80 ℃, 85 ℃, 90 ℃, 95 ℃ successively, and be incubated 2-3 hour respectively; The polymerization reaction system temperature is reduced to 30-50 ℃, leach the resin bead body; Earlier with the resin bead body of running water washing step e 3-5 time; Use steam distillation device boiling 2-3h then,, wash with industrial alcohol again to remove unreacted pore-foaming agent; To remove unconverted monomer and oligomer, obtain product with 2 1N HCl, 3 1N NaOH alternate treatment at last.
Embodiment 8
In the 2000ml there-necked flask, add distilled water 800ml successively, suspension dispersive agent polyvinyl alcohol 10g, oxygen scavenger methylene blue 2g; Start stirring temperature of reaction system is risen to 50 ℃, dissolve as water subsequent use fully until the suspension dispersive agent polyvinyl alcohol; In a beaker, taking by weighing dimethylaminoethyl acrylate methyl ammonia ethyl ester 50g, methacrylate glycol ester 40g, acrylonitrile 20g, xylenes 120g, dibenzoyl peroxide 2g and stirring by prescription makes it miscible subsequent use as oil phase; In there-necked flask, add 100g industry Na
2SO
4And after it is dissolved fully, temperature is risen to 60 ℃, the oil phase in the beaker is poured in the there-necked flask; Start stirring and make oil phase be scattered in aqueous phase, and make oil phase be dispersed into the pearl body of 0.40-2.00mm; Temperature of reaction system is risen to 65-70 ℃, and the granularity that continues the adjustment polymer dispersion reaches 0.20-1.20mm; The polymerization system temperature is risen to 70-75 ℃ make the polymer dispersion polymerization, behind the solidified forming, be incubated 1-2 hour; The temperature of polymerization reaction system is risen to 80 ℃, 85 ℃, 90 ℃, 95 ℃ successively, and be incubated 2-3 hour respectively; The polymerization reaction system temperature is reduced to 30-50 ℃, leach the resin bead body; Earlier with the resin bead body of running water washing step e 3-5 time; Use steam distillation device boiling 2-3h then,, wash with industrial alcohol again to remove unreacted pore-foaming agent; To remove unconverted monomer and oligomer, obtain product with 2 1N HCl, 3 1N NaOH alternate treatment at last.
Embodiment 9
In 250ml tool plug triangular flask, adding 100ml content is the Cr of 1000mg/l
2O
7 2-Solution, the tertiary-amino-containing macroporous anion exchange resin of adding 0.5-1.0g, vibration absorption is 4 hours in 60 ℃ of water-baths, calculates the Cr of resin
2O
7 2-The exchange adsorbance.
Embodiment 10
Filling 15ml tertiary-amino-containing macroporous anion exchange resin in the glass adsorption column of φ 2 * 20mm, Cr
2O
7 2-Concentration is that the simulation of 1000mg/L contains Cr
2O
7 2-The factory effluent from top to down flows through adsorption column, and control simulation factory effluent flow velocity is 1-2BV per hour.Room temperature condition is 5-36 ℃, Cr in the timing sampling analysis stream fluid
2O
7 2-Concentration until reaching the original liquid concentration adsorption equilibrium, promptly stops absorption.Flow out the Cr of liquid with determined by ultraviolet spectrophotometry
2O
7 2-Concentration.Calculate the Cr of resin
2O
7 2-The exchange adsorbance.