CN105566517B - A kind of preparation method and applications of nitrogen heterocyclic functionalization ion exchange material - Google Patents
A kind of preparation method and applications of nitrogen heterocyclic functionalization ion exchange material Download PDFInfo
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- CN105566517B CN105566517B CN201510996364.4A CN201510996364A CN105566517B CN 105566517 B CN105566517 B CN 105566517B CN 201510996364 A CN201510996364 A CN 201510996364A CN 105566517 B CN105566517 B CN 105566517B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B19/02—Elemental selenium or tellurium
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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Abstract
The invention discloses a kind of preparation method and applications of nitrogen heterocyclic functionalization ion exchange material, the preparation method of ion exchange material is to be immersed in the solution of nitrogen heterocyclic ring function monomer and carry out substitution reaction the acrylonitrile-styrol copolymer of chloromethylation and/or chloromethylated styrene divinylbenzene co-polymer, reaction product after drying to get；This method flow is simple, at low cost, reaction condition is mild, the ion exchange material of preparation can be applied to the selenium in selective recovery selenium-containing wastewater, have the characteristics that the rate of recovery is high, environmental pollution is few, and nitrogen heterocyclic functionalization ion exchange material can be regenerated and be reused, use cost is low.
Description
Technical field
The present invention relates to a kind of nitrogen heterocyclic functionalization ion exchange material and its recycling Selenium in Wastewater application,
More particularly to a kind of method recycling selenium from waste acid belongs to metallurgical and field of environment engineering.
Background technology
Selenium is dilute expensive nonmetallic, is widely used in the various fields such as metallurgy, electronics, solar energy, because of its limits throughput, selenium valence
Lattice go up year by year.Content of the selenium in the earth's crust is relatively low, is general very difficult to form industrial rich ore, general association in the concentrate such as copper-lead,
Therefore selenium is a significant by-products during Copper making.In smelting process, since the high temperature desulfurizing of copper concentrate roasts, lead
It causes in a part of selenium vaporization at high temperature to flue gas during smelting in concentrate, then enters eventually into waste acid after washing.Waste acid ingredient is multiple
Miscellaneous, acidity is high, contains a large amount of poisonous and harmful substance, it is necessary to purify, no it will cause serious environmental pollutions.
Currently, the method for domestic processing acid water mainly has lime neutralisation, neutralization-molysite coprecipitation and vulcanization
Method.Lime neutralisation is that lime is directly added into waste acid, and neutralization-molysite method is that iron is added on the basis of adjusting waste acid pH
Salt, vulcanization are that vulcanizing agent such as vulcanized sodium, hydrogen sulfide etc. is added directly into waste acid.These three processing methods will produce largely
Precipitation, in purification process, selenium in waste acid is co-precipitated in slag.Se content is low in slag, can not recycle, and causes selenium money
The waste in source.Therefore, it is a problem selenium resource how effectively to be recycled from waste acid.
Invention content
It is temporarily difficult to recycle the selenium resource in the selenium-containing wastewaters such as waste acid for the prior art, leads to selenium serious waste of resources
Defect, it is simple, at low cost that of the invention first purpose is intended to provide a kind of flow, prepares contain to waste acid etc. in a mild condition
The method that selenium Selenium in Wastewater has the nitrogen heterocyclic functionalization ion exchange material of selective absorption function.
Another object of the present invention is to be to provide a kind of nitrogen heterocyclic functionalization ion exchange material to exist
The application in terms of Selenium in Wastewater is recycled, which is chimed in by ion-exchange absorption containing selenium
Selective recovery selenium in waste water, organic efficiency is high and material can be regenerated and be reused, and production cost is low, makes suitable for promoting
With nitrogen heterocyclic functionalization ion exchange material is especially suitable for the selective recovery selenium from the waste acid of complicated component.
In order to achieve the above technical purposes, the present invention provides a kind of nitrogen heterocyclic functionalization ion exchange materials
Preparation method, this method are that the propylene-styrene copolymer of chloromethylation and/or chloromethylated styrene-divinylbenzene is total
Polymer, which is immersed in the solution of nitrogen heterocyclic ring function monomer, carries out substitution reaction, reaction product after drying to get；Described
Azacyclo- function monomer is pyrroles and azole derivatives, imidazoles and imdazole derivatives, pyridine and pyridine derivate, quinoline and quinoline
At least one of derivative.
Technical scheme of the present invention uses the propylene-styrene copolymer and/or chloromethylated styrene-two of chloromethylation
Ethenylbenzene copolymer is basis material, by nucleophilic substitution be grafted pyrroles and azole derivatives, imidazoles and imdazole derivatives,
The heterocyclic nitrogen compounds function monomers such as pyridine and pyridine derivate, quinoline and quinoline, obtain azacyclo- functionalization from
Sub- exchange material.These resins contain the groups such as special pyrroles, imidazoles, pyridine, quinoline, and the ion exchange with quaternary ammonium salt is special
Property.The preparation process flow of nitrogen heterocyclic functionalization ion exchange material is short, reaction condition is mild, overcomes existing extraction
Drench the defects of resin synthesis process is complicated, of high cost.
Preferred scheme, the mass percent concentration of azacyclo- function monomer is in the solution of nitrogen heterocyclic ring function monomer
2%~10%.
Preferred scheme, substitution reaction temperature are 40~70 DEG C, and the substitution reaction time is 24~48h.
Preferred scheme, drying are to dry reaction product to constant weight under 50~70 DEG C of temperature condition.
The preparation method of the nitrogen heterocyclic functionalization ion exchange material of the present invention specifically includes following steps：
(1) polymer such as polypropylene-styrene or styrene-divinylbenzene are subjected to Blanc chloromethylations；It is described
Blanc chloromethylations be to use chloromethyl ether for chloromethyl source, H2SO4, HCl and ZnCl2、SnCl4、FeCl3、CaCl2、
AlCl3、CuCl2At least one of Lewis acid be catalyst, the molar ratio of lewis acid and raw material is 1~3:1, VHCl：
VH2SO4It is 1~3:1, H2SO4Mass fraction be 40%~80%, reaction temperature be 40~70 DEG C, the reaction time be 12~
48h；
(2) and then by reaction product it is immersed in the nitrogen heterocyclic ring function monomer that mass percent concentration is 2%~10%
In solution at a temperature of 40~70 DEG C the reaction time be 24~48h, reaction product after drying to get；The nitrogen heterocyclic ring
Function monomer function monomer is pyrroles and azole derivatives, imidazoles and imdazole derivatives, pyridine and pyridine derivate, quinoline and quinoline
At least one of quinoline derivant.
The present invention also provides the applications of the nitrogen heterocyclic functionalization ion exchange material, by the azepine
Cycle compound functionalization ion exchange material is applied to the selenium in selective recovery selenium-containing wastewater.
Technical scheme of the present invention finds that there is nitrogen heterocyclic functionalization ion exchange material selectivity to exchange for the first time
The characteristic of Selenium in Wastewater is adsorbed, the selenium in waste water can be recycled with high efficiency, there is prodigious application value.
Preferred scheme, Se content is 50~100mg/L in selenium-containing wastewater, and arsenic content is 1000~10000mg/L, and zinc contains
Amount is 10~500mg/L, and lead content is 5~50mg/L, and fluorine content is 500~3000mg/L, and chlorinity is 1000~4000mg/
L, sulfuric acid content are 30~100g/L.
Preferred scheme carries out the plasma selenium in selenium-containing wastewater by nitrogen heterocyclic functionalization ion exchange material
Exchange adsorption, the nitrogen heterocyclic functionalization ion exchange material for loading selenium are desorbed using stripping liquid, obtain Se accumulation liquid.It is logical
Exchange adsorption and desorption are crossed, realize Selenium in Wastewater efficiently separates recycling.
More preferably scheme, stripping liquid be the hypo solution of a concentration of 0.5~2mol/L, sodium sulfite solution,
At least one of sulfurous acid solution, solution of sodium bisulfite, ortho phosphorous acid sodium solution.
More preferably scheme, desorption process carry out under 30~60 DEG C of temperature conditions.
More preferably scheme, after loading the nitrogen heterocyclic functionalization ion exchange material of selenium using stripping liquid desorption,
Further use NaOH and/or NaCl solution and/or ammonia spirit regeneration.Nitrogen heterocyclic functionalization ion exchange after regeneration
Material may be reused, and reuse effect is good, recycle 15 times or more, adsorption effect decaying unobvious.
Preferred scheme, Se accumulation liquid are restored by sulphur dioxide flue gas and obtain elemental selenium product.
The nitrogen heterocyclic functionalization ion exchange material of the present invention can prepare powdering, spherical, fibrous or film
Shape.
More preferably scheme, selenium-containing wastewater are waste acid.Waste acid complicated component, including a large amount of heavy metal ion and your gold
Belong to, it, can be with by nitrogen heterocyclic functionalization ion exchange material and strippant appropriate while also including nonmetal arsenic etc.
Realize the Selective Separation of selenium and these impurity.
Present invention method detailed process of selective recovery selenium from selenium-containing wastewater is as follows：Pond is homogenized selenium-containing wastewater after the adjustment
After first pass through accurate filter removing suspended matter, then with the flow velocity of 2~10BV/h be passed through adsorption tanks carry out selective absorption selenium,
Nitrogen heterocyclic functionalization ion exchange material is filled in adsorption tanks, waste acid enters next treatment process after adsorbing selenium, inhales
Adsorption tanks are desorbed using stripping liquid after the completion of attached, and solution sucks rear nitrogen heterocyclic functionalization ion exchange material material and adopts
It after regenerated liquid activating and regenerating, is recycled, stripping liquid recycles elemental selenium using sulfur dioxide reduction method.
The accurate filter is organic porous material, and main material is at least one in PP, PE, PO, PVDF, PTFE
Kind, pore size filter is 0.5~1 μm, and filtered version is PP cottons filter, dagger-axe membrane filter, one kind in bag filter or several
Kind.
Material compared with the prior art, the advantageous effect that technical scheme of the present invention is brought：
1, nitrogen heterocyclic functionalization ion exchange material preparation method flow of the invention is simple, reaction condition temperature
With, it is at low cost, meet industrialized production；Overcome the defects of existing sorbing material preparation method flow is complicated, of high cost.
2, nitrogen heterocyclic functionalization ion exchange material prepared by the present invention has ion exchanging function, Ke Yixuan
Selenium in selecting property exchange adsorption selenium-containing wastewater is particularly adapted to the Selective Separation recycling of waste acid selenium.
3, the nitrogen heterocyclic functionalization ion exchange material stability that prepared by the present invention is good, can regenerate, revival
Fruit is good, may be reused, and recycles for 15 times or more, and adsorption effect is decayed unobvious, and use cost is low.
4, the method that the present invention recycles Selenium in Wastewater by nitrogen heterocyclic functionalization ion exchange material protects environment
It protects, non-secondary pollution.
Description of the drawings
【Fig. 1】For the process flow chart of the present invention；
【Fig. 2】The α amino pyridine functional ion exchange material IR Characterization prepared for embodiment 1；
【Fig. 3】The N methylimidazole functionalization ion exchange material IR Characterizations prepared for embodiment 2.
Specific implementation mode
It is intended to further illustrate the present invention with reference to embodiments, be not intended to limit the present invention claims.
Embodiment 1
(1) prepared by sorbing material
A. polypropylene-styrene fiber is subjected to chloromethylation, using Chloromethyl methyl ether as chloromethyl source, Lewis acid, sulphur
Acid, hydrochloric acid are catalyst, and the molar ratio of Lewis acid and raw material is 1.1:1, sulfuric acid mass fraction is 80%, V hydrochloric acid：V sulfuric acid is
2:1, reaction temperature is 50 DEG C, reaction time 12h；B. addition α amino pyridine mass fraction is 8% after detaching a reaction products
Solution in react, controlling reaction temperature be 60 DEG C, the reaction time be for 24 hours；C. the last temperature by reaction product at 50~70 DEG C
It is dried under the conditions of degree to constant weight to get to nitrogen heterocyclic functionalization ion exchange material.
(2) sorbing material application
The acid water of certain smelting enterprise is entered to selection absorption dress after water quality is homogenized and filters particle and colloidal impurity
It sets, the aperture of filtering material is 10 μm when filtering；Filtering material is organic porous material PP, and filtered version is bag filter.
It is 5BV/h by coutroi velocity when selective absorption tank, after adsorption saturation, is solved using the sodium sulfite solution of 2mol/L
Analysis, desorbed solution use sulfur dioxide (content 99%) to be restored, and are separated by solid-liquid separation after reduction and obtain impure selenium, the rate of recovery of selenium is
99.5%, the position of selenium is 90%.
Spent acid stoste main component (unit g/L) before and after 1 adsorption reaction of table
| Main component | Se | As | F | Cl | H2SO4 | Cd | Pb |
| Before processing | 0.05 | 6.500 | 2.25 | 3.75 | 66.52 | 0.034 | 0.041 |
| After processing | 0.0003 | 6.48 | 2.24 | 3.74 | 66.48 | 0.034 | 0.041。. |
Embodiment 2
(1) prepared by sorbing material
A. styrene-divinylbenzene bead is subjected to chloromethylation, using Chloromethyl methyl ether as chloromethyl source, Lewis acid,
Sulfuric acid, hydrochloric acid are catalyst, and the molar ratio of Lewis acid and raw material is 1.1:1, sulfuric acid mass fraction is 80%, V hydrochloric acid：V sulfuric acid
It is 2:1, reaction temperature is 50 DEG C, reaction time 12h；B. addition N methylimidazole mass fractions are after detaching a reaction products
It is reacted in 8% solution, controlling reaction temperature is 60 DEG C, and the reaction time is for 24 hours；C. finally by reaction product at 50~70 DEG C
It is dried under temperature condition to constant weight to get to nitrogen heterocyclic functionalization ion exchange material.
(2) sorbing material application
The acid water of certain smelting enterprise is entered to selection absorption dress after water quality is homogenized and filters particle and colloidal impurity
It sets, the aperture of filtering material is 10 μm when filtering；Filtering material is organic porous material PP, and filtered version is bag filter.
It is 8BV/h by coutroi velocity when selective absorption tank, after adsorption saturation, is solved using the sodium sulfite solution of 1.5mol/L
Analysis, desorbed solution use sulfur dioxide (content 99%) to be restored, and are separated by solid-liquid separation after reduction and obtain impure selenium, the rate of recovery of selenium is
99.0%, the grade of selenium is 92%.
Spent acid stoste main component (unit g/L) before and after 2 adsorption reaction of table
Embodiment 3
(1) prepared by sorbing material
A. styrene-divinylbenzene film is subjected to chloromethylation, using Chloromethyl methyl ether as chloromethyl source, Lewis acid,
Sulfuric acid, hydrochloric acid are catalyst, and the molar ratio of Lewis acid and raw material is 1.1:1, sulfuric acid mass fraction is 80%, V hydrochloric acid：V sulfuric acid
It is 2:1, reaction temperature is 50 DEG C, reaction time 12h；B. addition α amino pyridine mass fraction is after detaching a reaction products
It is reacted in 10% solution, controlling reaction temperature is 60 DEG C, and the reaction time is for 24 hours；C. finally by reaction product at 50~70 DEG C
Temperature condition under dry to constant weight to get to nitrogen heterocyclic functionalization ion exchange material.
(2) sorbing material application
The acid water of certain smelting enterprise is entered to selection absorption dress after water quality is homogenized and filters particle and colloidal impurity
It sets, the aperture of filtering material is 10 μm when filtering；Filtering material is organic porous material PP, and filtered version is bag filter.
It is 10BV/h by coutroi velocity when selective absorption tank, after adsorption saturation, is solved using the sodium sulfite solution of 1mol/L
Analysis, desorbed solution use sulfur dioxide (content 99%) to be restored, and are separated by solid-liquid separation after reduction and obtain impure selenium, the rate of recovery of selenium is
99.3%, the grade of selenium is 93%.
Spent acid stoste main component (unit g/L) before and after 3 adsorption reaction of table
| Main component | Se | As | F | Cl | H2SO4 | Cd | Pb |
| Before processing | 0.10 | 1.9 | 1.5 | 1.56 | 65.43 | 0.084 | 0.038 |
| After processing | 0.0007 | 1.89 | 1.48 | 1.54 | 65.40 | 0.084 | 0.038。. |
Claims (8)
1. a kind of application of nitrogen heterocyclic functionalization ion exchange material, it is characterised in that：Contain applied to selective recovery
Selenium in selenium waste water；
In the selenium-containing wastewater, Se content be 50~100mg/L, arsenic content be 1000~10000mg/L, Zn content be 10~
500mg/L, lead content are 5~50mg/L, and fluorine content is 500~3000mg/L, and chlorinity is 1000~4000mg/L, and sulfuric acid contains
Amount is 30~100g/L；
The nitrogen heterocyclic functionalization ion exchange material is prepared via a method which to obtain：By the third of chloromethylation
Alkene-styrol copolymer and/or chloromethylated styrene-divinylbenzene co-polymer are immersed in the molten of nitrogen heterocyclic ring function monomer
Carry out substitution reaction in liquid, reaction product after drying to get；The azacyclo- function monomer is pyrroles and pyrrole derivatives
At least one of object, imidazoles and imdazole derivatives, pyridine and pyridine derivate, quinoline and quinoline.
2. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 1, it is characterised in that：It is described
Azacyclo- function monomer solution in azacyclo- function monomer mass percent concentration be 2%~10%.
3. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 1, it is characterised in that：Substitution
Reaction temperature is 40~70 DEG C, and the substitution reaction time is 24~48h.
4. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 1, it is characterised in that：Pass through
Nitrogen heterocyclic functionalization ion exchange material swaps absorption to the plasma selenium in selenium-containing wastewater, loads the azacyclo- of selenium
Compound functionalization ion exchange material is desorbed using stripping liquid, obtains Se accumulation liquid.
5. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 4, it is characterised in that：It is described
Stripping liquid be a concentration of 0.5~2mol/L hypo solution, sodium sulfite solution, sulfurous acid solution, bisulfite
At least one of sodium solution, ortho phosphorous acid sodium solution.
6. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 4, it is characterised in that：Desorption
Process carries out under 30~60 DEG C of temperature conditions.
7. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 1, it is characterised in that：Load
After the nitrogen heterocyclic functionalization ion exchange material of selenium is using stripping liquid desorption, NaOH and/or NaCl solution are further used
And/or ammonia spirit regeneration.
8. the application of nitrogen heterocyclic functionalization ion exchange material according to claim 1, it is characterised in that：Selenium is rich
Liquid collecting is restored by sulphur dioxide flue gas and obtains elemental selenium product.
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| CN1858088A (en) * | 2006-04-25 | 2006-11-08 | 南京大学 | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method |
| DE102008012223A1 (en) * | 2008-03-03 | 2009-09-10 | Lanxess Deutschland Gmbh | picolylamine resins |
| CN101735371B (en) * | 2009-12-10 | 2012-05-23 | 中国科学院长春应用化学研究所 | Hydroxyl type anion resin containing imidazole structure, method for preparing same and application thereof in preparation of biodiesel |
| CN102189008B (en) * | 2011-04-11 | 2013-05-08 | 常州大学 | Novel strongly and weakly alkaline anion exchange resin and preparation method thereof |
| CN102295723B (en) * | 2011-05-24 | 2013-03-27 | 南京大学 | 6-aminopyridine-3-carboxylic acid chelating resin and its preparation method |
| CN104231141B (en) * | 2014-08-29 | 2017-03-29 | 西安蓝晓科技新材料股份有限公司 | A kind of amino nitrogen heterocyclic ring resin and preparation method thereof |
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