CN105482041A - Cation exchange resin as well as preparation method and application thereof - Google Patents

Cation exchange resin as well as preparation method and application thereof Download PDF

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Publication number
CN105482041A
CN105482041A CN201511008946.3A CN201511008946A CN105482041A CN 105482041 A CN105482041 A CN 105482041A CN 201511008946 A CN201511008946 A CN 201511008946A CN 105482041 A CN105482041 A CN 105482041A
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CN
China
Prior art keywords
preparation
zeo
karb
base material
exchange resin
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CN201511008946.3A
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Chinese (zh)
Inventor
赵龙
杜纪富
董珍
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Zhejiang Xiangshan Risui Chemical Technology Co Ltd
Hubei University of Science and Technology
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Zhejiang Xiangshan Risui Chemical Technology Co Ltd
Hubei University of Science and Technology
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Priority to CN201511008946.3A priority Critical patent/CN105482041A/en
Publication of CN105482041A publication Critical patent/CN105482041A/en
Pending legal-status Critical Current

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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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to the technical fields of nuclear technology application and environmental protection and particularly relates to cation exchange resin as well as a preparation method and application thereof. The cation exchange resin is prepared by the step of grafting water-soluble monomers to a high polymer substrate by virtue of a pre-irradiation grafting technique and a one-step method, and carrying out H formation. The synthetic method has the beneficial effects that the grafting rate is high, an initiator does not need to be added, no residue remains in products, and the process is simple and easy to control. The cation exchange resin is capable of effectively adsorbing ammonium ions in water and can be utilized for replacing business resin to be applied to industrial adsorption columns.

Description

A kind of Zeo-karb, preparation method and application thereof
Technical field
The invention belongs to Application of Nuclear Technology and environmental protection technical field, relate to a kind of Zeo-karb, preparation method and application thereof.
Background technology
Ion exchange resin is the functional polymer compound of a class with functional group, is widely used in the aspects such as water treatment, foodstuffs industry, chemical enterprise.Traditional ion exchange resin is polymer build network structure polymer, most resin-made for time need two step processes, first synthesize three-dimensional netted skeleton, then by reaction skeleton on introduce functional group.Polystyrene-divinylbenzene sulfonic acid cation exchange resin is resin the widest in ion exchange resin application, about the sulfonation by strong oxidizers such as the vitriol oil, chlorsulfonic acid, sulphur trioxide and oleums, crosslinked vinylbenzene phenyl ring introduces sulfonic group make, preparation process is complicated, activity time is long, and consume a large amount of sulfuric acid, operating process is dangerous simultaneously, and do not wash clean clearly, the discharge of sulfuric acid causes the pollution to environment.
Publication number is that the Chinese patent application of CN104437676A improves skeleton structure, with the cross-linking copolymer of acrylic acid or the like glycidyl ester and Vinylstyrene for skeleton, introducing sulfonic group by epoxide group ring-opening reaction is functional group, do not re-use the vitriol oil, effectively avoid spent acid and discharge the environmental problem brought, production safety problem.But the functional group that method disclosed in this patent imports is distributed in the whole system of resin, and resin, to the absorption of specific ion, resin surface mainly occurs, therefore, there is the low and shortcoming that adsorption/desorption speed is slow of functional group utilization ratio in commercialization Zeo-karb.
The exchange capacity of current Zeo-karb obtains effective raising, but pore size distribution is uneven, and aperture ratio is excessive, and during exchange, water intermediate ion needs to penetrate into resin inside, so exchange velocity is low, the resin regeneration time is long simultaneously.
The method that direct grafting sulfonic groups rolls into a ball substrate surface effectively can overcome the absorption of current commercial resin slowly, regenerates slow defect, also can avoid preparing the problem of environmental pollution caused in resin process.Application number is the preparation method disclosing a kind of cationic exchange membrane in the Chinese patent of 200410067791.6 and 200410017965.8, it selects two kinds of monomer copolymerization grafting to prepare the cationic exchange membrane of sulfonic group and acrylate functional group by irradiation grafting technology, and it adopts the method for copolymerization together with other monomers just can be grafted on base material.After simultaneous reactions, containing more multipolymer in solution, compare waste, also introduce copper sulfate simultaneously, the inorganicss such as sodium-acetate.
Summary of the invention
In order to overcome the deficiency of above-mentioned Zeo-karb production technology, the object of the present invention is to provide a kind of Zeo-karb, preparation method and application thereof.Present method adopts polymer microsphere to be base material, and independent graft phenylethene sodium sulfonate is simple to operate; Be simultaneously medium with water, select water-solubility function monomer, monomer solution can Reusability, more saves cost, is applicable to large-scale production; The functional group of the Zeo-karb obtained is distributed in polymer base material surface, can realize the quick adsorption to object ion and desorb, is more better than alternative commercial resin.
Goal of the invention of the present invention is achieved through the following technical solutions:
The invention provides a kind of preparation method of Zeo-karb, concrete steps are as follows:
1) polymer base material is loaded letting nitrogen in and deoxidizing in plastics bag, under adopting dry ice cooling conditions, carry out pre-irradiation, produce living radical;
2) by step 1) in the postradiation polymer base material Sodium styrene sulfonate that joins rapidly prior deoxygenation or sodium vinylsulphonate solution, at 40 DEG C of-60 DEG C of temperature, react under agitation condition;
3) by step 2) the sorbing material solvent wash that obtains after reaction, obtain graftomer;
4) by step 3) graftomer that obtains is placed in acid solution H type, dries in vacuum drying oven.
Above-mentioned steps 1) in, described polymer base material is ethylene-vinyl alcohol copolymer or granule of polyvinyl alcohol, and mean diameter is 180 μm ~ 250 μm.
Above-mentioned steps 1) in, adopt in pre-irradiation 60co gamma-radiation, electron beam or X-ray, absorption dose is 50-400kGy.
Above-mentioned steps 3) in, the percentage of grafting acquiring graftomer is 50%-80%.
Above-mentioned steps 4) in, acid solution is hydrochloric acid soln, concentration 1mol/L.
Above-mentioned steps 4) in, in vacuum drying oven, place 12 ~ 24h at 30 ~ 80 DEG C of temperature.
The present invention also provides above-mentioned preparation method the Zeo-karb obtained.
The present invention also provides the application in the ammonium ion separating technology of above-mentioned Zeo-karb in fractionation by adsorption water.
Compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention adopts ionizing rays crosslinking technology to have can to select arbitrarily the kind of base material and monomer, substrate shapes is not limited, the not advantage such as residual catalyst in graft product, particularly electron beam causes pre-irradiation grafting method, the radiative process of base material and monomer-grafted reaction process can be separated, be not easy in reaction process to produce homopolymer, reaction efficiency high controllability is strong, is adapted at material surface high-density and imports specific functional group.Preparation method is simple, condition easily controls, consume energy low, safety and environmental protection, is more applicable to industrial production.
2) the present invention selects water-soluble phenylethene sodium sulfonate monomer, and single stage method is directly grafted on polymer base material, eliminates complicated sulfonation process, and preparation method's environmental protection more.
3) the present invention selects common being easy to get, and microspheroidal macromolecular material with low cost, as base material, can replace existing commercial resin to use in adsorption column/tower more easily
4) cation adsorbing material from traditional is different, present invention achieves and import ion functional group on polymer base material surface, make resin material particle diameter can reach 300-400 micron, meet the demand that in industry, adsorption column filling uses, there is very large industrial applications prospect.
5) the H type Zeo-karb that prepared by the present invention has the feature of quick adsorption desorb, can realize repeatedly Reusability, have good economic benefit.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1 prepares Zeo-karb
1) with ethylene-vinyl alcohol copolymer (EVOH) (mean diameter 180-250 microns) for polymer base material, 10 grams of above-mentioned materialss are put into the PE bag containing nitrogen, use rumbatron to carry out electron beam irradiation, make it produce to can be used for the living radical of graft reaction.Illuminate condition: irradiation voltage 2MeV, irradiation dose is 200kGy, dose rate 50kGy/pass.
2) postradiation above-mentioned particulate, drops at once and carries out graft polymerization reaction by (Sodium styrene sulfonate/water=30/70w/w) in styrene sulfonic acid sodium solution.Styrene sulfonic acid sodium solution is blown into the nitrogen of 30 minutes before use continuously to discharge the oxygen in water.Graft polymerization reaction carries out at 50 DEG C, (percentage of grafting of base material reaches about 80%) termination reaction after about 2 hours, after adopting solvent wash.
3) above-mentioned graft product, is placed in 1mol/LHCl in clean dry and reacts 24 hours, take out, after ethanol and water washing, dry, obtain ammonium ion attachment resin at vacuum drying oven 50 DEG C of temperature.
Embodiment 2
Consistent with the synthetic method of embodiment 1, replace Sodium styrene sulfonate as reaction monomers with sodium vinyl sulfonate.
The characterization of adsorption of embodiment 3 two kinds of polymeric adsorbents compares
In Example 1, the cation-adsorption resin 0.5g of preparation joins the NH of 100mL 4 +in solution, initial soln concentration is 10mg/L.Above-mentioned adsorption test is at room temperature stirred, and after absorption certain hour, reclaims its supernatant liquor, detects ammonium concentration in solution.Conveniently compare, existing PK228 is evaluated its absorption property according to same experiment condition simultaneously.
The Zeo-karb of embodiment 1 and the kinetics of adsorption data of PK228 resin to ammonium ion as shown in table 1.
Zeo-karb prepared by table 1 the present invention and PK228 resin carry out the ammonium concentration (mg/L) after Static Adsorption to solution
Can find out with the Performance comparision of PK228, the rate of adsorption of Zeo-karb prepared by the present invention is faster, and 5min just can reach balance, and PK228 needs 10min to reach balance.
The characterization of adsorption of embodiment 4 two kinds of polymeric adsorbents compares
By the PK228 of the Zeo-karb for preparing in embodiment 1 and purchase respectively at moisture state retrofilling in 7.5mL adsorption column, adsorption column is of a size of Φ 16 × 38mm, evaluate its dynamic adsorption with what modulate in advance containing ammonium ion solution, ammonium ion starting point concentration is 200mg/L.
Carried out adsorption assessment experiment according to above-mentioned condition, control solution is different in flow rate, and in exit sampling analysis omission timber concentration, concentration data is as shown in table 2.
The ammonium concentration (mg/L) that the adsorption column of Zeo-karb prepared by table 2 the present invention and PK228 resin fill exports under different in flow rate
Above-mentioned data presentation, Zeo-karb prepared by the present invention, when flow velocity is up to 5.3L/h, still can be good at adsorbing ammonium ion, ensure that outlet spills without ammonium ion, and PK228 is when flow velocity is 1.35L/h, just start to spill, the Zeo-karb that performance is prepared far below the present invention.
Although preferred embodiment discloses as above by the present invention; so itself and be not used to limit content of the present invention; anyly be familiar with this those skilled in the art; not departing from main spirits of the present invention and context; when doing various change and retouching, the protection domain therefore invented should be as the criterion with the basic right claimed range applied for a patent.

Claims (8)

1. a preparation method for Zeo-karb, is characterized in that, concrete steps are as follows:
1) polymer base material is loaded letting nitrogen in and deoxidizing in plastics bag, under adopting dry ice cooling conditions, carry out pre-irradiation, produce living radical;
2) by step 1) in the postradiation polymer base material Sodium styrene sulfonate that joins rapidly prior deoxygenation or sodium vinylsulphonate solution, at 40 DEG C of-60 DEG C of temperature, react under agitation condition;
3) by step 2) the sorbing material solvent wash that obtains after reaction, obtain graftomer;
4) by step 3) graftomer that obtains is placed in acid solution H type, dries in vacuum drying oven.
2. preparation method according to claim 1, is characterized in that: step 1) in, polymer base material is ethylene-vinyl alcohol copolymer or granule of polyvinyl alcohol, and mean diameter is 180 μm ~ 250 μm.
3. preparation method according to claim 1, is characterized in that: step 1) in, adopt in pre-irradiation 60co gamma-radiation, electron beam or X-ray, absorption dose is 50-400kGy.
4. preparation method according to claim 1, is characterized in that: step 3) in, solvent to be selected from deionized water or ethanol one or both.
5. preparation method according to claim 1, is characterized in that: step 4) in, acid solution is hydrochloric acid soln, concentration 1mol/L.
6. preparation method according to claim 1, is characterized in that: step 4) in, in vacuum drying oven, place 12 ~ 24h at 30 ~ 80 DEG C of temperature.
7., according to the Zeo-karb that the preparation method one of claim 1-6 Suo Shu obtains, the percentage of grafting of its graftomer is 50-80%.
8. the application in the ammonium ion separating technology of Zeo-karb according to claim 7 in fractionation by adsorption water.
CN201511008946.3A 2015-12-29 2015-12-29 Cation exchange resin as well as preparation method and application thereof Pending CN105482041A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106732831A (en) * 2016-12-22 2017-05-31 宁海东方鸿业新材料有限公司 A kind of solvay-type macroporous ion exchange resin and preparation method thereof
CN109994763A (en) * 2019-01-09 2019-07-09 华中科技大学 A kind of preparation method of all-vanadium flow battery diaphragm

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535378A (en) * 2006-09-29 2009-09-16 图莱乐株式会社 Coated particles, process for production thereof, cation adsorbents, and water treatment system
CN102784625A (en) * 2012-07-26 2012-11-21 湖北科技学院 Radiation synthetic method for high-speed selective adsorption material
JP2014133225A (en) * 2013-01-11 2014-07-24 Kankyo Joka Kenkyusho:Kk Method for removing urea within pure water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535378A (en) * 2006-09-29 2009-09-16 图莱乐株式会社 Coated particles, process for production thereof, cation adsorbents, and water treatment system
CN102784625A (en) * 2012-07-26 2012-11-21 湖北科技学院 Radiation synthetic method for high-speed selective adsorption material
JP2014133225A (en) * 2013-01-11 2014-07-24 Kankyo Joka Kenkyusho:Kk Method for removing urea within pure water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杜晋等: "新型阳离子交换树脂D301-g-PSSS的制备及其对金属离子的吸附性能", 《工程塑料应用》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106732831A (en) * 2016-12-22 2017-05-31 宁海东方鸿业新材料有限公司 A kind of solvay-type macroporous ion exchange resin and preparation method thereof
CN106732831B (en) * 2016-12-22 2020-08-04 宁海东方鸿业新材料有限公司 Preparation method of complex type macroporous ion exchange resin
CN109994763A (en) * 2019-01-09 2019-07-09 华中科技大学 A kind of preparation method of all-vanadium flow battery diaphragm
CN109994763B (en) * 2019-01-09 2021-11-02 华中科技大学 Preparation method of all-vanadium redox flow battery diaphragm

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Application publication date: 20160413