A kind of heavy metal wastewater thereby nonionic adsorption resin and preparation method thereof
Technical field
The invention belongs to environmental protection technical field, more particularly to a kind of heavy metal wastewater thereby nonionic adsorption resin and its preparation
Method.
Background technology
In recent years, with the quickening of global industry process, environmental pollution getting worse, turn into and hinder the one of human development
Big barrier, the heavy metal ion pollution in its reclaimed water is one kind more serious in numerous environmental problems, and its harm to the human body is very
Greatly, into can make one carcinogenic, teratogenesis after human body, cause chromosome mutation.
Administering the method for effluent containing heavy metal ions at present includes ion-exchange, electrochemical process, membrane separation process, chemical method
And bioanalysis.These methods are effective to removing heavy metal ion, but equipment is complicated, cause secondary pollution, and operating cost is high,
Waste is difficult.Have been reported that using sorbing material this method is easy and effective to adsorb heavy metal ion in the prior art, processing effect
Fruit is preferable.But the sorbing material on current market is more or less present, and adsorption capacity is relatively low, reproducibility is bad, expensive
Defect.
Therefore, need that a kind of heavy metal ionic adsorption effect is good, cost is low, adsorption capacity is big, easy De contamination badly in the industry
Sorbing material.
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of heavy metal wastewater thereby nonionic adsorption resin and preparation method thereof,
The preparation method is simple and easy, and not high to equipment requirement, raw material is easy to get, and cost is cheap, the heavy metal adsorption resin being prepared
Mechanical mechanics property is excellent, and heavy metal ionic adsorption effect is good, cost is low, adsorption capacity is big, easy De contamination.
To achieve the above object, the present invention provides following technical scheme, a kind of heavy metal wastewater thereby nonionic adsorption resin
Preparation method, comprise the following steps:
1) preparation of polymerization type monomer:By double (oxiranylmethyl radical) -5- (2- the acrylic) -1,3,5- triazines of 1,3- -
2,4,6 (1H, 3H, 5H)-triketones, ethylenediamine tetra-acetic acid mix in a solvent, and be stirred at room temperature reaction 8-10 hours, after
It is evaporated under reduced pressure at 40-50 DEG C and removes solvent;
2) preparation of resin:Polymerization type monomer, four [4- (4- carboxyl phenyls) phenyl] that step 1) is prepared will be passed through
Ethene is dissolved in high boiling solvent, adds initiator, polymerisation 3-5 hours, then settle out in water at 40-50 DEG C, obtain
To resin;
Wherein, double (oxiranylmethyl radical) -5- (2- acrylic) -1,3,5-triazines -2,4 of 1,3- described in step 1), 6
(1H, 3H, 5H)-triketone, ethylenediamine tetra-acetic acid, the mass ratio of solvent are (1.2-2):1:(3-5);
One or more of the solvent in isopropanol, ethanol, dichloromethane;
Polymerization type monomer described in step 2), four [4- (4- carboxyl phenyls) phenyl] ethene, high boiling solvent, initiator
Mass ratio is (3-5):(1-2):(10-15):(0.03-0.05);
One kind in dimethyl sulfoxide, N,N-dimethylformamide, 1-METHYLPYRROLIDONE of the high boiling solvent or
It is several;
One or more of the initiator in azodiisobutyronitrile, ABVN;
A kind of heavy metal wastewater thereby nonionic adsorption resin, using the preparation method system of the efficient heavy nonionic adsorption resin
It is standby to obtain.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
(1) preparation method of efficient heavy nonionic adsorption resin provided by the invention is simple and easy, to equipment requirement not
Height, raw material are easy to get, cheap.
(2) efficient heavy nonionic adsorption resin provided by the invention, by chemical modification, allow on strand and be rich in carboxylic
Base, hydroxyl, amino groups, substantially increase the adsorption capacity of heavy metal ion, while De contamination ability is also relatively strong, can be with
Recycling is often.
(3) efficient heavy nonionic adsorption resin provided by the invention, four [4- (4- carboxyl benzene are used on molecular backbone
Base) phenyl] ethene as one of polymerized monomer, contains larger aromatic ring structure so that film while efficient absorption is kept,
Also there is good mechanical mechanics property and chemical stability.
(4) efficient heavy nonionic adsorption resin provided by the invention, contain conjugated structure in strand, keeping efficient
While adsorptivity, also acted on visible light catalytic, so as to effectively handle other organic pollutions in sewage.
Embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment to this hair
Bright product is described in further detail.
Embodiment 1
A kind of preparation method of heavy metal wastewater thereby nonionic adsorption resin, comprises the following steps:
1) preparation of polymerization type monomer:By double (oxiranylmethyl radical) -5- (2- the acrylic) -1,3,5- triazines of 1,3- -
2,4,6 (1H, 3H, 5H)-triketone 120g, ethylenediamine tetra-acetic acid 100g are mixed in isopropanol 300g, and are stirred at room temperature anti-
Answer 8 hours, after at 40 DEG C be evaporated under reduced pressure remove solvent;
2) preparation of resin:Polymerization type monomer 90g, four [4- (4- carboxyl phenyls) benzene that step 1) is prepared will be passed through
Base] ethene 30g is dissolved in dimethyl sulfoxide 300g, add azodiisobutyronitrile 0.9g, polymerisation 3 hours at 40 DEG C, then
Settled out in water, obtain resin;
A kind of heavy metal wastewater thereby nonionic adsorption resin, using the preparation method system of the efficient heavy nonionic adsorption resin
It is standby to obtain.
Embodiment 2
A kind of preparation method of heavy metal wastewater thereby nonionic adsorption resin, comprises the following steps:
1) preparation of polymerization type monomer:By double (oxiranylmethyl radical) -5- (2- the acrylic) -1,3,5- triazines of 1,3- -
2,4,6 (1H, 3H, 5H)-triketone 140g, ethylenediamine tetra-acetic acid 100g are mixed in ethanol 350g, and reaction 9 are stirred at room temperature
Hour, after at 45 DEG C be evaporated under reduced pressure remove solvent;
2) preparation of resin:Polymerization type monomer 110g, four [4- (4- carboxyl phenyls) that step 1) is prepared will be passed through
Phenyl] ethene 40g is dissolved in, in DMF 350g, add ABVN 1.2g, the polymerisation at 45 DEG C
4 hours, then settled out in water, obtain resin;
A kind of heavy metal wastewater thereby nonionic adsorption resin, using the preparation method system of the efficient heavy nonionic adsorption resin
It is standby to obtain.
Embodiment 3
A kind of preparation method of heavy metal wastewater thereby nonionic adsorption resin, comprises the following steps:
1) preparation of polymerization type monomer:By double (oxiranylmethyl radical) -5- (2- the acrylic) -1,3,5- triazines of 1,3- -
2,4,6 (1H, 3H, 5H)-triketone 180g, ethylenediamine tetra-acetic acid 100g are mixed in 400g dichloromethane, and are stirred at room temperature
Reaction 9.5 hours, after at 47 DEG C be evaporated under reduced pressure remove solvent;
2) preparation of resin:Polymerization type monomer 130g, four [4- (4- carboxyl phenyls) that step 1) is prepared will be passed through
Phenyl] ethene 50g is dissolved in 1-METHYLPYRROLIDONE 400g, add initiator 1.3g, polymerisation 4.5 hours at 48 DEG C,
Then settled out in water, obtain resin;
The initiator is selected from azodiisobutyronitrile, ABVN in mass ratio 2:1 mixture being mixed to form;
A kind of heavy metal wastewater thereby nonionic adsorption resin, using the preparation method system of the efficient heavy nonionic adsorption resin
It is standby to obtain.
Embodiment 4
A kind of preparation method of heavy metal wastewater thereby nonionic adsorption resin, comprises the following steps:
1) preparation of polymerization type monomer:By double (oxiranylmethyl radical) -5- (2- the acrylic) -1,3,5- triazines of 1,3- -
2,4,6 (1H, 3H, 5H)-triketone 200g, ethylenediamine tetra-acetic acid 100g are mixed in isopropanol 500g, and are stirred at room temperature anti-
Answer 10 hours, after at 50 DEG C be evaporated under reduced pressure remove solvent;
2) preparation of resin:Polymerization type monomer 150g, four [4- (4- carboxyl phenyls) that step 1) is prepared will be passed through
Phenyl] ethene 60g is dissolved in high boiling solvent 450g, add initiator 1.5g, polymerisation 5 hours, Ran Hou at 50 DEG C
Settled out in water, obtain resin;
The high boiling solvent is selected from N,N-dimethylformamide, 1-METHYLPYRROLIDONE in mass ratio 3:7 are mixed to form
Mixture;
The initiator is selected from azodiisobutyronitrile, ABVN in mass ratio 5:7 mixtures being mixed to form;
A kind of heavy metal wastewater thereby nonionic adsorption resin, using the preparation method system of the efficient heavy nonionic adsorption resin
It is standby to obtain.
Comparative example 1
Commercially available activated carbon granule;
Heavy metal prepared by the embodiment of the present invention:The embodiment of the present invention and comparative example determine with the following method heavy metal from
The adsorption capacity of son:Take the sorbing material of certain mass to be placed in conical flask with cover, be separately added into the heavy metal of certain volume from
In sub- solution, 25 DEG C of isothermal vibration regular hours in isothermal vibration device, pass through the change of concentration of heavy metal ion in feed liquid
Calculate adsorption capacity;Concentration of heavy metal ion is determined using UV2450 types ultraviolet-uisible spectrophotometer, according to adsorption capacity formula
(1) calculate:
The adsorption capacity of Qeq- heavy metal ion, mg/g;CO- feed liquid initial concentration, mg/mL;
Ct- feed liquid is in time t concentration, mg/mL;VfThe volume of-feed liquid, mL;The weight of W- sorbing materials, g.
The present embodiment determines desorption rate with the following method:Sorbing material after adsorption equilibrium is washed with distilled water to filter
Untill metal ion is not present in liquid, then the sulfuric acid solution with the 2% of certain volume mixes, and constant temperature shakes in constant temperature oscillator
Swing the regular hour, determine the concentration of heavy metal ion in solution, desorption rate is calculated by formula (2):
In formula, η is desorption rate, and C is the concentration (mgL of metal ion in eluent-1), V is the volume (L) of eluent, Q
It is the adsorption capacity (mgg of membrane adsorbent before eluting-1), m is the quality (g) of sorbing material.
The present embodiment is to select Pb2+、Cu2+、Cd3+To determine its adsorption capacity and desorption rate, test result is shown in Table 1.
The embodiment of the present invention of table 1 and comparative example absorption and De contamination the performance test results
As seen from Table 1, compared with conventional commercial activated carbon granule, the efficient heavy polymeric adsorbent that is prepared in the present embodiment
Heavy metal ion has efficient absorption and De contamination performance.
The foregoing is only a preferred embodiment of the present invention, not makees any formal limitation to the present invention;It is all
The those of ordinary skill of the industry can swimmingly implement the present invention described in by specification;But all it is familiar with this professional skill
Art personnel without departing from the scope of the present invention, made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, it is the equivalent embodiment of the present invention;Meanwhile all substantial technologicals pair according to the present invention
Variation, modification and evolution of any equivalent variations that above example is made etc., still fall within the guarantor of technical scheme
Within the scope of shield.