CN107057004A - A kind of high density high adsorption is except nitrate nitrogen resin and preparation method thereof - Google Patents
A kind of high density high adsorption is except nitrate nitrogen resin and preparation method thereof Download PDFInfo
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- CN107057004A CN107057004A CN201610910673.XA CN201610910673A CN107057004A CN 107057004 A CN107057004 A CN 107057004A CN 201610910673 A CN201610910673 A CN 201610910673A CN 107057004 A CN107057004 A CN 107057004A
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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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
Abstract
The invention discloses a kind of high density high adsorption except nitrate nitrogen resin and preparation method thereof, belong to ion exchange resin field.The resin is by resin matrix and is wrapped in composite inorganic composition granule therein and constitutes.Styrene monomer and crosslinking agent, initiator, pore-foaming agent are mixed into oil phase, and after uniformly being mixed with the composite inorganic composition granule after pretreatment well, polymer beads are obtained with the aqueous suspension polymerization that is mixed with dispersant, final finished resin is obtained by chloromethylation, amination step.Rate of small round spheres is 70~98% after the resin mill being made, wet true density is 1.2~1.4g/mL, the composite inorganic particle of the parcel modifying agent equivalent to the 5~20% of reactant quality is added, resin density can be made to improve 20%~40%, so as to improve the settling property and antifouling property of resin.The resin to the high adsorption capacity of nitrate and to nitrate-selective it is high the advantages of, can be widely applied to drinking water treatment, city domestic sewage advanced treating field, have a good application prospect and Practical significance.
Description
Technical field
Nitrate nitrogen resin and its synthetic method are removed the invention discloses a kind of high density high adsorption, is in particular one
Plant the polystyrene alkali anion that internal package has composite inorganic composition granule and has higher removal effect to nitrate nitrogen simultaneously
Exchanger resin and preparation method thereof.
Background technology
Nitrate nitrogen is widely present in natural water body.In recent years, with the continuous quickening of modernization, work, agricultural
Development also deepens continuously so that the nitrogenous effluent amount for being discharged into water body constantly increases, and beyond the self-purification capacity of nature, draws
The source water nitrate-N pollution problem in global range is sent out.The exceeded feelings of nitrate nitrogen are shown in the underground water in Europe
Condition.China's underground water pollution condition survey result shows that underground water " three nitrogen " pollution is more protruded in China, many
The nitrate in groundwater in area exceedes national standard, and azotate pollution is in the trend spread to deep phreatic water.Cross
High nitrate nitrogen intake can directly result in the illnesss such as stomachache, diarrhoea, hypertension, or even can trigger cancer, seriously endanger human body and be good for
Health.Therefore, nitrate nitrogen has important practical significance in reduction water.
For the processing of nitrate nitrogen in waste water, traditional processing method has physical partition method, chemical reduction method, biological anti-nitre
Change denitrogenation etc., above-mentioned technology has the advantage of itself and deficiency.In recent years, various new technologies are studied is applied to remove
Nitrate nitrogen, wherein, the use of the ion-exchange of resin is a kind of simple, efficient physical removal methods, has been widely used for
Water treatment field.
By composite inorganic composition granule parcel into microballoon resin skeleton, obtained resin not only has good settleability
Can, while there is preferable absorption property to nitrate nitrogen ion.At present, traditional anion exchange resin such as D201, D301
Deng when carrying out water body purification, sulfate ion and chlorion that can be common in Preferential adsorption water body make resin to nitrate
Clearance is reduced；Patent CN103524657A disclose it is a kind of go water removal in nitrate macroporous strong basic anion exchange resin
Preparation method, this resin improves the removal effect for nitrate, but is due to the larger (0.5- of particle diameter to a certain extent
1.5mm), resin density is small, and the rate of settling is low, is only applicable to traditional fixed-bed process；It refer in patent AU744706
Magnetic resin, with preferable settling property and superior dynamic performance, stillMagnetic resin mechanical strength is low, holds
It is broken, and do not have Preferential adsorption to nitrate ion, it is less efficient in the exceeded water body of processing nitrate.
The content of the invention
1st, problems to be solved by the invention
The problem of there is the slow rate of settling and low regeneration service efficiency for existing ion exchange resin, the present invention provides one
High density high adsorption is planted except nitrate nitrogen resin and preparation method thereof, the ion exchange resin prepared by this method will have
Preferable settling property and higher nitrate nitrogen clearance；Improve the absorption regeneration ability to nitrate nitrogen.
2nd, technical scheme
In order to solve the above problems, nitrate nitrogen resin is removed the invention provides a kind of high density high adsorption.With tradition from
Sub-exchange resin is compared, and the density of the novel ion exchanger resin improves 20%~40%；And use process in water process regeneration
In, the resin improves 5%~20% to the adsorption efficiency of nitrate nitrogen.Its concrete scheme is as follows：
A kind of high density high adsorption removes nitrate nitrogen resin, and wet true density is 1.2~1.4g/mL, and rate of small round spheres is 70 after mill
~98%, it has high selection adsorptivity to anion, and its selectivity order to anion isIn sulphur
The selectivity factor under system to nitrate coexists with nitrate for hydrochlorateFor 50~100, coexisted in sodium chloride with sodium nitrate
To the selectivity factor of nitrate under systemFor 5~20.
Above-mentioned resin full exchange capacity be 2.0~4.0mmol/g, strong alkali anion exchange capacity be 2.5~
3.9mmol/g,
Specifically carry out as follows：
1) pre-process：
First several a certain amount of inorganic matters are added in water and methanol solution, at 10~20 DEG C, stirring 0.5~
1.0h；A certain amount of modifying agent is added, 30~40 DEG C are warming up to, 1.0~2.0h is stirred；Continuously add another several a certain amount of nothings
Machine thing, is cooled to 20~30 DEG C, stirs 0.5~1.0h；A certain amount of modifying agent is added, 40~50 DEG C are warming up to, stirring 1.0~
2.0h；Adding a certain amount of ammoniacal liquor, then be warming up to 50~60 DEG C, continue to stir 2.0~3.0h, mixing speed is 300~
400rpm；Finally, clean several all over rear standby with methanol；Described composite inorganic particle, water, methanol solution mass ratio are 1~2:
3:1, described composite inorganic particle and modifying agent mass ratio is 20~120:1；Described composite inorganic particle and ammoniacal liquor quality
Than for 5~10:1；The modifying agent is methacryloxypropyl silane, γ-aminopropyl the triethyl silicane, (β-first of vinyl three
Epoxide ethyoxyl) silane, the one or more in VTES.
2) suspension polymerization：
The preparation of aqueous phase：In aqueous phase add account for aqueous phase mass ratio be 7~30% sodium chloride, account for aqueous phase quality 0.3~
6.0% dispersant, accounts for the methylene blue solution of aqueous phase quality 0.2~2.0%；Wherein dispersant be gelatin, sodium dihydrogen phosphate,
Tertiary sodium phosphate, sodium lignin sulfonate；
The preparation of oil phase：Oil phase is made up of monomer, crosslinking agent, pore-foaming agent, initiator；Described monomer and the matter of crosslinking agent
Amount is than being 1:0.16~0.23；The mass ratio of monomer and initiator is 1:0.015~0.2；Described monomer and the matter of pore-foaming agent
Amount is than being 1:0.3~2.4；Described monomer is styrene, and crosslinking agent is divinylbenzene, and pore-foaming agent is isobutanol, and initiator is
Benzoyl peroxide；
It polymerize synthesis technique：First the pretreated composite inorganic thing of step (1) is added in oil phase, at 30~50 DEG C
When, stir 0.5~1.0h；Then the aqueous phase of step (10) is added in the oil phase containing composite inorganic thing, at 40~50 DEG C
When, stir 0.5~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein stir
Speed is mixed for 300~500rpm；
3) chloromethylation：
The resin obtained in step (3) is mixed with chlorination reagent, the mass ratio of resin and chlorination reagent is 1:4~6, often
Temperature is swelled 2~4h；Add a certain amount of catalyst, the mass ratio of resin and catalyst is 1:0.8~1, it is warming up to 40~45
DEG C insulation 40~50h；Described chlorination reagent is chloromethyl ether, and catalyst is the one or two of zinc chloride or iron chloride.Reaction
After end, cleaned successively with organic solvent, pure water.
4) aminating reaction：
The resin obtained in step (3) is mixed with amination reagent, the mass ratio of resin and amination reagent is 1:4~6, rise
Temperature reacts 8~12h to 70~80 DEG C；Described amination reagent is triethylamine.Reaction terminates after cooling, is cleaned with pure water 2~3 times
After obtain a kind of high density high adsorption except nitrate nitrogen resin.
Further, the inorganic matter in step (1) is transition metal oxide+rare earth oxide, transition metal oxide
Selected from titanium dioxide, zirconium oxide, zinc oxide, magnesia one or more, rare earth oxide be selected from lanthana, cerium oxide, oxygen
Change the one or more of yttrium, the transition metal oxide：Rare earth oxide mass ratio is 4~9:1.
Rate of small round spheres is 70~98% after the ion exchange resin mill of the addition composite inorganic thing prepared according to the method described above, wet
Real density is 1.2~1.4g/mL, and modified ion exchange resin is with traditional ion exchange resin (i.e. according to claim 2
In (2), (3), (4) prepare the resin without inorganic particle) compare, its resin density improve 20%~40%.
The ion exchange resin and traditional amberlite lipid phase of the addition composite inorganic thing prepared according to the method described above
Than its removal regeneration efficiency to the nitrate nitrogen in water improves 5%~20%.
3rd, beneficial effect
The invention provides a kind of high density high adsorption except nitrate nitrogen resin and preparation method thereof, with prior art phase
Than it has following positive effect：
(1) by during resin-made is standby, adding composite inorganic thing, the close of ion exchange resin can be significantly improved
Degree, improves the settling property of resin, and the fixed-bed process broken traditions, it is adaptable to resin regeneration technique is cost-effective, operation letter
It is single；
(2) present invention can also improve resin adsorption regeneration service efficiency, can not only improve resin for nitric acid in water
The adsorption effect of salt nitrogen, while improve the service life of resin, can avoid because of frequent numerous and diverse operation for bringing of replacing resin and into
This pressure.
(3) composite inorganic thing of the present invention, raw material sources extensively, without heavy metallic oxides such as Cd, Cr, Ni, have
Beneficial to environmental protection and human health.
Brief description of the drawings
Fig. 1 is that, except nitrate nitrogen resin electromicroscopic photograph, wherein figure (a) is unmodified, figure (b) composite inorganic thing is modified.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
(1) pre-process：
2g titanium dioxide, 2g zirconium oxides both inorganic matters are added in 15g water and 5g methanol solutions, at 10 DEG C,
Stir 0.5~1.0h；0.15g methacryloxypropyl silanes are subsequently added, 30 DEG C are warming up to, 1.0~2.0h is stirred；Continue to add
Enter 1g lanthanas, be cooled to 20 DEG C, stir 0.5~1.0h；0.1g γ-aminopropyl triethyl silicane is continuously added, 40 are warming up to
DEG C, stir 1.0~2.0h；1g ammoniacal liquor is added, 50 DEG C are continuously heating to, 2.0~3.0h is stirred, mixing speed is
300rpm；Finally, clean several all over rear standby with methanol.
(2) suspension polymerization：
(1) preparation of aqueous phase：0.50g gelatin is mixed with 250g water, 0.5~1.0h is stirred at 50~55 DEG C of temperature；
75~80 DEG C are warming up to, 0.2g sodium dihydrogen phosphates and 0.05g tertiary sodium phosphates is added, continues to stir 0.5~1.0h；It is eventually adding
17.5g sodium chloride and 0.5g methylene blues, are cooled to 0.5~1.0h of stirring at 70 DEG C；After the completion of cool down it is standby；
(2) preparation of oil phase：Styrene 100g, divinylbenzene 16g, isobutanol 30g, benzoyl peroxide 1.5g are mixed
It is uniform standby；
(3) synthesis technique：First the composite inorganic thing pre-processed in (one) is added in oil phase, at 30 DEG C, stirring
0.5~1.0h；Then aqueous phase standby in (1) is added in the oil phase containing composite inorganic thing, at 40 DEG C, stirring 0.5
~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein mixing speed is
300rpm；
Reaction terminate after with the filtering of the standard screen in 30~60 mesh apertures, and cleaned with clear water after 2~3 times, place into 60~
Soaked in 70 DEG C of hot water, be put into 50 DEG C of baking ovens and dry after a period of time, then after being cleaned up with clear water, you can obtain white shape
Resin.
(3) chloromethylation：
100g white bead-like resin is mixed with 400mL chloromethane etherifying reagent, normal temperature is swelled 2~4h；Add 80g chlorine
Change zinc as catalyst, be warming up to 40~45 DEG C of insulation 40h.After reaction terminates, cleaned successively with organic solvent, pure water.
(4) aminating reaction：
Resin after 100g chloromethylations is mixed with 400mL triethylamine reagents, 70~80 DEG C of 8~12h of reaction are warming up to.
Reaction terminates after cooling, is cleaned with pure water and a kind of high density high adsorption is obtained after 2~3 times removes nitrate nitrogen resin.
Comparative example, the resin without inorganic particle prepared by the step more than in (two), (three) and (four) is biography
System styrenic anion exchanger resin, abbreviation conventional resins A.
Nitrate nitrogen resin is removed to the high density high adsorption being made and carries out performance test：Wet true density is 1.22g/mL, entirely
Exchange capacity 3.18mmol/g, (wherein solid-to-liquid ratio is 1 to nitrate nitrogen clearance up to 90.93%:200) after, regenerating 30 times, absorption
Ability only reduces by 1.58%.By the obtained ion exchange resin containing additive and traditional resin for not containing additive
Dynamic Adsorption experiment is carried out, as a result as shown in table 1：
The physical and chemical index and water treatment effect (50mg/L nitrate nitrogens waste water) of 1 two kinds of different resins of table
Embodiment 2
(1) pre-process：
3g titanium dioxide, 2g zirconium oxides, 2g zinc oxide these three inorganic matters are added in 20g water and 7g methanol solutions,
At 15 DEG C, 0.5~1.0h is stirred；0.15g methacryloxypropyl silanes are subsequently added, 35 DEG C are warming up to, stirring 1.0~
2.0h；2g lanthanas, 1g cerium oxide are continuously added, 25 DEG C are cooled to, 0.5~1.0h is stirred；Continuously add 0.1g vinyl three
('beta '-methoxy ethyoxyl) silane, is warming up to 45 DEG C, stirs 1.0~2.0h；1.5g ammoniacal liquor is added, 55 are continuously heating to
DEG C, 2.0~3.0h is stirred, mixing speed is 350rpm；Finally, clean several all over rear standby with methanol.
(2) suspension polymerization：
(1) preparation of aqueous phase：1.0g gelatin is mixed with 250g water, 0.5~1.0h is stirred at 50~55 DEG C of temperature；Rise
Temperature adds 3.0g sodium dihydrogen phosphates and 0.75g tertiary sodium phosphates to 75~80 DEG C, continues to stir 0.5~1.0h；Continuously add
0.25g sodium lignin sulfonates, stir 0.5~1.0h at 85~90 DEG C；It is eventually adding 30.0g sodium chloride and 2.5g methylene
Indigo plant, is cooled to 0.5~1.0h of stirring at 75 DEG C；After the completion of cool down it is standby；
(2) preparation of oil phase：Styrene 100g, divinylbenzene 18g, isobutanol 80g, benzoyl peroxide 7.5g are mixed
It is uniform standby；
(3) synthesis technique：First the composite inorganic thing pre-processed in (one) is added in oil phase, at 35 DEG C, stirring
0.5~1.0h；Then aqueous phase standby in (1) is added in the oil phase containing composite inorganic thing, at 45 DEG C, stirring 0.5
~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein mixing speed is
350rpm；
Reaction terminate after with the filtering of the standard screen in 30~60 mesh apertures, and cleaned with clear water after 2~3 times, place into 60~
Soaked in 70 DEG C of hot water, be put into 50 DEG C of baking ovens and dry after a period of time, then after being cleaned up with clear water, you can obtain white shape
Resin.
(3) chloromethylation：
100g white bead-like resin is mixed with 500mL chloromethane etherifying reagent, normal temperature is swelled 2~4h；Add 90g chlorine
Change zinc as catalyst, be warming up to 40~45 DEG C of insulation 45h.After reaction terminates, cleaned successively with organic solvent, pure water.
(4) aminating reaction：
Resin after 100g chloromethylations is mixed with 500mL triethylamine reagents, 70~80 DEG C of 8~12h of reaction are warming up to.
Reaction terminates after cooling, is cleaned with pure water and a kind of high density high adsorption is obtained after 2~3 times removes nitrate nitrogen resin.
Comparative example, the resin without inorganic particle prepared by the step more than in (two), (three) and (four) is biography
System styrenic anion exchanger resin, abbreviation conventional resins B.
Nitrate nitrogen resin is removed to the high density high adsorption being made and carries out performance test：Wet true density is 1.32g/mL, entirely
Exchange capacity 3.42mmol/g, (wherein solid-to-liquid ratio is 1 to nitrate nitrogen clearance up to 93.48%:200) after, regenerating 30 times, absorption
Ability only reduces by 1.86%.By the obtained ion exchange resin containing additive and traditional resin for not containing additive
Dynamic Adsorption experiment is carried out, as a result as shown in table 1：
The physical and chemical index and water treatment effect (50mg/L nitrate nitrogens waste water) of 2 two kinds of different resins of table
Embodiment 3
(1) pre-process：
5g titanium dioxide, 4g zirconium oxides, 3g magnesia these three inorganic matters are added in 22g water and 8g methanol solutions,
At 20 DEG C, 0.5~1.0h is stirred；0.15g vinyl three ('beta '-methoxy ethyoxyl) silane is subsequently added, 40 DEG C are warming up to,
Stir 1.0~2.0h；2g lanthanas, 1g yittrium oxide both inorganic matters are continuously added, 30 DEG C are cooled to, 0.5~1.0h is stirred；
0.15g VTESs are continuously added, 50 DEG C are warming up to, 1.0~2.0h is stirred；1.5g ammoniacal liquor is added, after
It is continuous to be warming up to 60 DEG C, 2.0~3.0h is stirred, mixing speed is 400rpm；Finally, clean several all over rear standby with methanol.
(2) suspension polymerization：
(1) preparation of aqueous phase：2.25g gelatin is mixed with 250g water, 0.5~1.0h is stirred at 50~55 DEG C of temperature；
75~80 DEG C are warming up to, 8.5g sodium dihydrogen phosphates and 2.25g tertiary sodium phosphates is added, continues to stir 0.5~1.0h；；Continuously add
1.5g sodium lignin sulfonates, stir 0.5~1.0h at 85~90 DEG C；50.0g sodium chloride and 3.0g methylene blues are eventually adding,
It is cooled to 0.5~1.0h of stirring at 75 DEG C；After the completion of cool down it is standby；
(2) preparation of oil phase：Styrene 100g, divinylbenzene 20g, isobutanol 150g, benzoyl peroxide 15g are mixed
It is uniform standby；
(3) synthesis technique：First the composite inorganic thing pre-processed in (one) is added in oil phase, at 40 DEG C, stirring
0.5~1.0h；Then aqueous phase standby in (1) is added in the oil phase containing composite inorganic thing, at 50 DEG C, stirring 0.5
~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein mixing speed is
400rpm；
Reaction terminate after with the filtering of the standard screen in 30~60 mesh apertures, and cleaned with clear water after 2~3 times, place into 60~
Soaked in 70 DEG C of hot water, be put into 50 DEG C of baking ovens and dry after a period of time, then after being cleaned up with clear water, you can obtain white shape
Resin.
(3) chloromethylation：
100g white bead-like resin is mixed with 550mL chloromethane etherifying reagent, normal temperature is swelled 2~4h；Add 100g
Zinc chloride is warming up to 40~45 DEG C of insulation 48h as catalyst.After reaction terminates, cleaned successively with organic solvent, pure water.
(4) aminating reaction：
Resin after 100g chloromethylations is mixed with 550mL triethylamine reagents, 70~80 DEG C of reactions 8~12 are warming up to.
Reaction terminates after cooling, is cleaned with pure water and a kind of high density high adsorption is obtained after 2~3 times removes nitrate nitrogen resin.
Comparative example, the resin without inorganic particle prepared by the step more than in (two), (three) and (four) is biography
System styrenic anion exchanger resin, abbreviation conventional resins C.
Nitrate nitrogen resin is removed to the high density high adsorption being made and carries out performance test：Wet true density is 1.37g/mL, entirely
Exchange capacity 3.57mmol/g, (wherein solid-to-liquid ratio is 1 to nitrate nitrogen clearance up to 95.36%:200) after, regenerating 30 times, absorption
Ability only reduces by 1.25%.By the obtained ion exchange resin containing additive and traditional resin for not containing additive
Dynamic Adsorption experiment is carried out, as a result as shown in table 1：
The physical and chemical index and water treatment effect (50mg/L nitrate nitrogens waste water) of 3 two kinds of different resins of table
Embodiment 4
(1) pre-process：
6g titanium dioxide, 6g zirconium oxides, 3g zinc oxide these three inorganic matters are added in 30g water and 10g methanol solutions,
At 20 DEG C, 0.5~1.0h is stirred；0.08g methacryloxypropyl silanes are subsequently added, 35 DEG C are warming up to, stirring 1.0~
2.0h；3g lanthanas, 2g yittrium oxide both inorganic matters are continuously added, 20 DEG C are cooled to, 0.5~1.0h is stirred；Continuously add
0.09g VTESs, are warming up to 45 DEG C, stir 1.0~2.0h；1.5g ammoniacal liquor is added, is continuously heating to
60 DEG C, 2.0~3.0h is stirred, mixing speed is 400rpm；Finally, clean several all over rear standby with methanol.
(2) suspension polymerization：
(1) preparation of aqueous phase：2.50g gelatin is mixed with 250g water, 0.5~1.0h is stirred at 50~55 DEG C of temperature；
75~80 DEG C are warming up to, 9.0g sodium dihydrogen phosphates and 2.50g tertiary sodium phosphates is added, continues to stir 0.5~1.0h；Continuously add
1.0g sodium lignin sulfonates, stir 0.5~1.0h at 85~90 DEG C；75g sodium chloride and 5g methylene blues are eventually adding, is cooled
0.5~1.0h is stirred to 80 DEG C；After the completion of cool down it is standby；
(2) preparation of oil phase：Styrene 100g, divinylbenzene 23g, isobutanol 240g, benzoyl peroxide 20g are mixed
It is uniform standby；
(3) synthesis technique：First the composite inorganic thing pre-processed in (one) is added in oil phase, at 50 DEG C, stirring
0.5~1.0h；Then aqueous phase standby in (1) is added in the oil phase containing composite inorganic thing, at 50 DEG C, stirring 0.5
~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein mixing speed is
500rpm；
Reaction terminate after with the filtering of the standard screen in 30~60 mesh apertures, and cleaned with clear water after 2~3 times, place into 60~
Soaked in 70 DEG C of hot water, be put into 50 DEG C of baking ovens and dry after a period of time, then after being cleaned up with clear water, you can obtain white shape
Resin.
(3) chloromethylation：
100g white bead-like resin is mixed with 600mL chloromethane etherifying reagent, normal temperature is swelled 2~4h；Add 800g
Zinc chloride, 20g iron chloride are warming up to 40~45 DEG C of insulation 50h as catalyst.Reaction terminate after, with organic solvent, pure water according to
Secondary cleaning.
(4) aminating reaction：
Resin after 100g chloromethylations is mixed with 600mL triethylamine reagents, 70~80 DEG C of reactions 8~12 are warming up to.
Reaction terminates after cooling, is cleaned with pure water and a kind of high density high adsorption is obtained after 2~3 times removes nitrate nitrogen resin.
Comparative example, the resin without inorganic particle prepared by the step more than in (two), (three) and (four) is biography
System styrenic anion exchanger resin, abbreviation conventional resins D.
Nitrate nitrogen resin is removed to the high density high adsorption being made and carries out performance test：Wet true density is 1.43g/mL, entirely
Exchange capacity 3.69mmol/g, (wherein solid-to-liquid ratio is 1 to nitrate nitrogen clearance up to 99.83%:200) after, regenerating 30 times, absorption
Ability only reduces by 1.32%.By the obtained ion exchange resin containing additive and traditional resin for not containing additive
Dynamic Adsorption experiment is carried out, as a result as shown in table 1：
The physical and chemical index and water treatment effect (50mg/L nitrate nitrogens waste water) of 4 two kinds of different resins of table
Claims (7)
1. a kind of high density high adsorption removes nitrate nitrogen resin, it is characterised in that：Wet true density is circle after 1.2~1.4g/mL, mill
Ball rate is 70~98%, and it has high selection adsorptivity to anion, and its selectivity order to anion isIn the case where system coexists in sulfate and nitrate to the selectivity factor of nitrateFor 50~100,
In the case where system coexists in sodium chloride and sodium nitrate to the selectivity factor of nitrateFor 5~20.
2. a kind of high density high adsorption described in claim 1 removes nitrate nitrogen resin, it is characterised in that full exchange capacity is 2.0
~4.0mmol/g.
3. a kind of high density high adsorption described in claim 1 or 2 removes nitrate nitrogen resin, it is characterised in that strong alkali anion is handed over
Capacity is changed for 2.5~3.9mmol/g.
4. a kind of high density high adsorption described in claim 1 removes the preparation method of nitrate nitrogen resin, its step is：
(1) pre-process：
First transition metal oxide is added in water and methanol solution, at 10~20 DEG C, 0.5~1.0h is stirred；Addition changes
Property agent, be warming up to 30~40 DEG C, stir 1.0~2.0h；Rare earth oxide is continuously added, 20~30 DEG C are cooled to, stirring 0.5~
1.0h；Modifying agent is added, 40~50 DEG C are warming up to, 1.0~2.0h is stirred；A certain amount of ammoniacal liquor is added, then is warming up to 50~60
DEG C, continue to stir 2.0~3.0h, mixing speed is 300~400rpm；Finally, it is standby after being cleaned with methanol；Described compound nothing
Machine particle, water, methanol solution mass ratio are 1~2:3:1, described composite inorganic particle and modifying agent mass ratio is 20~120:
1；Described composite inorganic particle is 5~10 with ammoniacal liquor mass ratio:1；Transition metal oxide be selected from titanium dioxide, zirconium oxide,
The one or more of zinc oxide, magnesia, rare earth oxide is selected from lanthana, cerium oxide, the one or more of yittrium oxide；
(2) suspension polymerization：
The preparation of aqueous phase：The sodium chloride for accounting for that aqueous phase mass ratio is 7~30% is added in aqueous phase, aqueous phase quality 0.3~6.0% is accounted for
Dispersant, account for the methylene blue solution of aqueous phase quality 0.2~2.0%；
The preparation of oil phase：Oil phase is made up of monomer, crosslinking agent, pore-foaming agent, initiator；Described monomer and the mass ratio of crosslinking agent
For 1:0.16~0.23；The mass ratio of monomer and initiator is 1:0.015~0.2；Described monomer and the mass ratio of pore-foaming agent
For 1:0.3~2.4；Described monomer is styrene, and crosslinking agent is divinylbenzene, and pore-foaming agent is isobutanol, and initiator is peroxide
Change benzoyl；
It polymerize synthesis technique：First the pretreated composite inorganic thing of step (1) is added in oil phase, at 30~50 DEG C, stirred
Mix 0.5~1.0h；Then the aqueous phase of step (10) is added in the oil phase containing composite inorganic thing, at 40~50 DEG C, stirred
Mix 0.5~1.0h；80 DEG C are warming up to again, are incubated 4~5h；When being finally warming up to 85~90 DEG C, 4~5h is incubated；Wherein stir speed
Spend for 300~500rpm；
(3) chloromethylation：
The resin obtained in step (3) is mixed with chlorination reagent, the mass ratio of resin and chlorination reagent is 1:4~6, normal temperature is molten
Swollen 2~4h；Add a certain amount of catalyst, the mass ratio of resin and catalyst is 1:0.8~1, it is warming up to 40~45 DEG C of guarantors
40~50h of temperature；Described chlorination reagent is chloromethyl ether, and catalyst is the one or two of zinc chloride or iron chloride.Reaction terminates
Afterwards, cleaned successively with organic solvent, pure water.
(4) aminating reaction：
The resin obtained in step (3) is mixed with amination reagent, the mass ratio of resin and amination reagent is 1:4~6, it is warming up to
70~80 DEG C of 8~12h of reaction；Described amination reagent is triethylamine.Reaction terminates after cooling, obtains highly dense after being cleaned with pure water
Spend high adsorption and remove nitrate nitrogen resin.
5. a kind of high density high adsorption described in claim 4 removes the preparation method of nitrate nitrogen resin, it is characterised in that step
(1) transition metal oxide described in：Rare earth oxide mass ratio is 4~9:1.
6. a kind of high density high adsorption according to claim 4 or 5 removes the preparation method of nitrate nitrogen resin, its feature
Be, in the step (1) modifying agent be methacryloxypropyl silane, γ-aminopropyl triethyl silicane, vinyl three (β-
Methoxy ethoxy) silane, the one or more in VTES.
7. a kind of high density high adsorption according to claim 4 or 5 removes the preparation method of nitrate nitrogen resin, its feature
It is, the dispersant in step (2) is one kind in gelatin, sodium dihydrogen phosphate, tertiary sodium phosphate, sodium lignin sulfonate or appoints several
Kind.
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Cited By (4)
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| CN107445249A (en) * | 2017-09-04 | 2017-12-08 | 南京大学盐城环保技术与工程研究院 | A kind of two-stage resin strengthens mutually the method for removing useless Organic substance in water and nitrate nitrogen |
| CN113769793A (en) * | 2021-09-27 | 2021-12-10 | 安徽皖东树脂科技有限公司 | Method for regulating and controlling particle size of macroporous anion exchange resin microspheres |
| CN113831032A (en) * | 2021-05-03 | 2021-12-24 | 浙江红狮环保股份有限公司 | Cement clinker generation method using gold tailing slag as raw material |
| WO2022135494A1 (en) * | 2020-12-24 | 2022-06-30 | 西安蓝晓科技新材料股份有限公司 | Resin for removing phosphorus from water body, and preparation method therefor and application thereof |
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| WO2022135494A1 (en) * | 2020-12-24 | 2022-06-30 | 西安蓝晓科技新材料股份有限公司 | Resin for removing phosphorus from water body, and preparation method therefor and application thereof |
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| CN113769793A (en) * | 2021-09-27 | 2021-12-10 | 安徽皖东树脂科技有限公司 | Method for regulating and controlling particle size of macroporous anion exchange resin microspheres |
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