CN103497281A - Weak acid modified magnetic resin with high specific surface area and preparation method thereof, as well as high efficient purification method for slightly polluted water body - Google Patents
Weak acid modified magnetic resin with high specific surface area and preparation method thereof, as well as high efficient purification method for slightly polluted water body Download PDFInfo
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- CN103497281A CN103497281A CN201310330339.3A CN201310330339A CN103497281A CN 103497281 A CN103497281 A CN 103497281A CN 201310330339 A CN201310330339 A CN 201310330339A CN 103497281 A CN103497281 A CN 103497281A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011347 resin Substances 0.000 title claims abstract description 133
- 229920005989 resin Polymers 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000746 purification Methods 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000006249 magnetic particle Substances 0.000 claims abstract description 17
- 108010010803 Gelatin Proteins 0.000 claims abstract description 15
- 239000008273 gelatin Substances 0.000 claims abstract description 15
- 229920000159 gelatin Polymers 0.000 claims abstract description 15
- 235000019322 gelatine Nutrition 0.000 claims abstract description 15
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 19
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 19
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 19
- 230000008929 regeneration Effects 0.000 claims description 19
- 238000011069 regeneration method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000009719 regenerative response Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000000088 plastic resin Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a weak acid modified magnetic resin with a high specific surface area, a preparation method, a high efficient purification method thereof for slightly polluted water body, and belongs to the field of purification method for slightly polluted water body. The preparation method comprises following steps: (a) preparing a water phase; (b) preparing an oil phase; (c) adding Fe3O4 magnetic particles in the oil phase, then adding the oil phase into the water phase, stirring to carry out reactions, washing the reaction product, filtering, drying in vacuum so as to obtain the resin; (d) mixing the resin with methyl acrylate, adding an initiator, evenly mixing, then adding the mixture into the water phase, wherein the water phase comprises gelatin and sodium chloride, stirring to carry out reactions, maintaining the temperature, washing the reaction product, filtering, drying in vacuum so as to obtain magnetic resin with a high specific surface area containing ester groups; (e) impregnating the resin in a sodium hydroxide water solution to carry out reactions, centrifugally separating after cooling, washing the reaction product, filtering, and drying in vacuum so as to obtain the weak acid modified magnetic resin with a high specific surface area. The method and the resin provided in the invention can eliminate the toxic organic materials and heavy metals in the slightly polluted water body at the same time.
Description
Technical field
The invention belongs to micropollutant water purifying method field, more particularly, relate to a kind of weak acid and modify high-specific surface area magnetic resin and preparation method thereof, and the method that this resin is used for removing micropollutant water organism and heavy metal.
Background technology
China's water resources is most deficient, and the occupancy volume per person is only 1/4th of world's per capita share, is a member in 13 listed poor-water states of United Nations.In recent years, increasing rapidly of domestic economy total amount makes water resources day aobvious rare.Being tending towards of the fast development of urbanization, regional economy concentrates and environmental pollution day by day serious, strengthened especially the localised load of water resources.The regeneration of sewage is the indispensable important measures that solve the shortage of water resources problem.The quantity of wastewater effluent of China ranks first in the world, and wherein the quantity discharged of municipal effluent accounts for more than 60%.The water yield of municipal effluent is stable, and the change of water quality amplitude is little, and its foreign matter content low (being less than 0.l%), can after second-stage treatment, add the appropriate depth treatment measures, just can meet the water quality requirement of different reuse water purposes.
Along with the usage quantity of reuse water and the demand of use range increase day by day, the water quality safety of reuse water is had higher requirement.When especially reuse water is used in agricultural, forestry, herding, fishery, groundwater recharge and tap water and the approach such as augments, there is larger ecological risk.Due to the second-stage treatment of municipal effluent can not the micro-Organic Pollutants of fine removal, the high toxic material such as heavy metal, if can not effectively harmful toxic matter be removed in the advanced treatment process of following adopted, they will inevitably enter into environment along with the use of reuse water, and then bring harm to the ecosystem.
New type water treatment technology based on magnetic resin has been successfully applied to (patent publication No.: CN101781437A) in the advanced treatment of city domestic sewage and reuse.The resin of this utilization is magnetic acrylic acid series anionite-exchange resin, and it mainly relies on ion exchange the electronegativity organic pollutant in water body is removed.Yet, this technology for existing a large amount of micro-Organic Pollutants in reuse water as the low-poles such as endocrine disrupter or nonpolar organic matter removal effect poor, simultaneously, in reuse water, another highly toxic material heavy metal is all to exist with the positive electricity form, is difficult to have an effect with this resin.For this reason, although this technology can reduce colourity and the total organic content of municipal effluent bio-chemical effluent greatly, to effect that wherein highly toxic material produces a little less than, need the new technology of exploitation make up this defect.
Summary of the invention
The problem that 1, will solve
The poor problem of removal effect to the low-poles such as a large amount of endocrine disrupters in reuse water, nonpolar micro-Organic Pollutants and heavy metal time for current resin technology, the invention provides a kind of weak acid and modify the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof, method of the present invention and resin can efficiently be removed in micropollutant water and poison organism and heavy metal simultaneously.
2, technical scheme
In order to address the above problem, the technical solution adopted in the present invention is as follows:
A kind of weak acid is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) be equipped with water: add in water and account for the gelatin that the water quality is 1%～3% and account for the sodium-chlor that the water quality is 10%～25%;
(b) be equipped with oil phase: oil phase consists of reactant monomer divinylbenzene and pore-creating agent toluene, the mass ratio 1:0.5 of divinylbenzene and toluene～2, in oil phase, add the benzoyl peroxide that accounts for divinylbenzene and toluene total mass 1%～3% to make initiator, stir it is fully dissolved;
(c) to the Fe that adds the oleic acid parcel that particle diameter is 0.1～1 μ m in the oil phase of step (b)
3o
4magnetic-particle, magnetic-particle accounts for oil phase total mass 10%～25%, then, will containing the oil phase of magnetic-particle, join in water, the mass ratio of oil phase and water is 1:5～10, add fashionable the stirring, stirring velocity is 100～400rpm, and temperature is controlled at 60～80 ℃, react and be incubated 5～12 hours after 3～9 hours under 85～95 ℃, cooling be filtered dry with deionized water and washing with acetone afterwards, vacuum-drying, obtain magnetic high-specific surface area resin;
(d) resin prepared by previous step mixes with methyl acrylate, methyl acrylate is 1:2～10 with the resin quality ratio, add the initiator benzoyl peroxide that accounts for resin quality 2%～4%, after mixing, join in water, wherein, in this water, gelatin accounts for water quality 1%～4%, sodium-chlor accounts for water quality 5%～20%, join in the process of water and stirred, stirring velocity is 100～400rpm, temperature is controlled at 50～70 ℃, react and be incubated 5～12 hours after 3～9 hours under 85～95 ℃, cooling be filtered dry with deionized water and washing with acetone afterwards, vacuum-drying, the magnetic high-specific surface area resin that must contain ester group,
(e) resin impregnation prepared by previous step reacts in aqueous sodium hydroxide solution, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying, obtain weak acid and modify the high-specific surface area magnetic resin.
Preferably, in described step (b), the purity of described divinylbenzene is for being the 80%(mass percent).
Preferably, in described step (e), the consumption of described aqueous sodium hydroxide solution is resin quality 1～8 times, the mass concentration of aqueous sodium hydroxide solution is 5%, resin impregnation temperature of reaction in aqueous sodium hydroxide solution is 60～70 ℃, and the reaction times is 5～10 hours.
A kind of weak acid prepared is modified the high-specific surface area magnetic resin.
A kind of weak acid is modified the method for high-specific surface area magnetic resin high-efficient purification micropollutant water, the steps include:
(1) add above-mentioned magnetic resin in reactor, resin accounts for 0.1%～0.5% of reactor volume; The biochemical tail water reactor of flowing through, simultaneously from the fresh resin tank to the mixed solution that pumps into magnetic resin and clear water in reactor, the mixed solution flow accounts for 0.1%～0.5% of biochemical tail water flow;
(2) resin after processing carries out magnetic with the biochemical tail water mixed solution or natural subsidence is separated;
(3) resin settled down in step (2) is partly refluxed to reactor, part is sent into regenerating tank;
(4) in regenerating tank, add regenerator to be regenerated to resin, used regenerator purified reuse or disposal;
(5) by step (4), through the resin of regeneration, sending into the resin storage tank, be delivered to reactor while needing and carry out reuse.
Preferably, in described step (1), the hydraulic detention time of biochemical tail water in reactor is 5～200min, and liquid-solid abundant mixing comprises that mechanical stirring, strength stir or hydraulic mixing.
Preferably, in described step (3), the regenerator in regenerating tank is compound desorbing agent, and in this compound desorbing agent, Inorganic salt is 5～30%, and the hydrochloric acid mass concentration is 0.01～0.025%, and the regenerative response time is 10～30min.
3, beneficial effect
Than prior art, the invention has the advantages that:
(1) the invention provides a kind of weak acid and modify high-specific surface area magnetic resin and preparation method thereof, resin prepared by the method had both had higher specific surface area, had abundant carboxylic group simultaneously.Compare existing magnetic acrylic acid series ion exchange resin, this resin not only can be removed the ionic state pollutent, can also have removal effect preferably to molecular state pollutent in water body simultaneously.Than existing cross-linking adsorbent resin with ultrahigh magnetic property, this resin can be by having higher adsorptive power by ion exchange to the Heavy Metals in Waters ion.Can, in a set of equipment, efficiently remove dissimilar organism and inorganics impurity in sewage simultaneously;
(2) method of the high-efficient purification micropollutant water based on this resin provided by the invention, compare with the conventional depth treatment process, simple to operate, and investment running cost is low, and treatment effect is good.Sewage after processing can meet purposes such as being back to industry, city, view, in the reuse field of reuse water, has good application prospect.
The accompanying drawing explanation
Fig. 1 is the resin FT-IR collection of illustrative plates that in the embodiment of the present invention 1, in preparation process, different step obtains.
Embodiment
Below in conjunction with specific embodiment, the present invention further is described.
Embodiment 1
A kind of weak acid of the present embodiment is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) 500g gelatin and 5kg sodium-chlor are dissolved in the 50L deionized water and are made into water;
(b) oil phase consists of 2.5kg divinylbenzene and 2.5kg toluene, in oil phase, adds the 150g benzoyl peroxide to make initiator, stirs it is fully dissolved;
(c) add the Fe of the oleic acid parcel that the 1.25kg particle diameter is 0.1 μ m to oil phase
3o
4magnetic-particle, will contain benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in water and is stirred, and stirring velocity is 200rpm, and under 70 ℃, reaction was incubated 12 hours after 6 hours under 85 ℃, and cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(d) the 2kg resin of getting wherein mixes with the 1kg methyl acrylate, joining 10L after adding the 40g benzoyl peroxide to mix contains in 100g gelatin and 1kg sodium-chlor water, in adition process, stirred, stirring velocity is 100rpm, temperature is controlled at reaction under 60 ℃ and is incubated 5 hours after 6 hours under 95 ℃, cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(e) get the resin 2kg made, impregnated in the 16L mass concentration and be in 5% aqueous sodium hydroxide solution 60 ℃ of reactions 10 hours, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying, obtain weak acid and modify the high-specific surface area magnetic resin.
The resin prepared in above-mentioned steps is tested, and its result as shown in Figure 1.Fig. 1 is the resin FT-IR collection of illustrative plates that in preparation process of the present invention, different step obtains (infared spectrum and Fig. 1 of the resin of following examples 2～5 preparations is basic identical, and charateristic avsorption band is the same).In figure, (d), (e) represent respectively in preparation process the resin obtained while proceeding to step (d), (e).As can be seen from Figure 1, the resin that prepared by step (d) is at 1740cm
-1place has the charateristic avsorption band of " C=O ", shows divinylbenzene and methyl acrylate grafting success; After step (e) reaction, compare 3440cm in Fig. 1 (e) with Fig. 1 (d)
-1" OH " charateristic avsorption band appears in place, shows that step (e) is hydrolyzed successfully.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.15m
3the flow of/h evenly flows into 0.5m
3in the steel mechanically stirred reactor, the magnetic resin that adds in advance the 0.5L aforesaid method to prepare in reactor, enter the mixed solution of resin and clear water with the flow pump of 0.75L/h from the fresh resin tank, carry out absorption reaction in reactor simultaneously.After resin has reacted in reactor with water, carry out magnetic or natural subsidence and separate, the water outlet of settling tank top can be back to process water, and the mixed solution 80% that the resin content of bottom settlings is higher pumps into the reactor reuse, remains 20% and sends into regeneration tank.After utilizing mass concentration to be 5% sodium chloride aqueous solution and 0.025% hydrochloric acid soln regeneration 10min in regeneration tank, send into the recycle of fresh resin tank, the regenerator after use is through the purification reuse.Water-quality guideline is as following table (mg/L of unit) before and after plastic resin treatment:
| ? | COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before processing | 45 | 15 | 7.6 | 0.45 | 0.32 | 2.8 |
| After processing | 20 | 10 | 4.9 | 0.18 | 0.14 | 1.1 |
。
Embodiment 2
A kind of weak acid of the present embodiment is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) 600g gelatin and 7.5kg sodium-chlor are dissolved in the 30L deionized water and are made into water;
(b) oil phase consists of 2.5kg divinylbenzene and 1.25kg toluene, in oil phase, adds the 75g benzoyl peroxide to make initiator, stirs it is fully dissolved;
(c) add the Fe of the oleic acid parcel that the 750g particle diameter is 0.5 μ m to oil phase
3o
4magnetic-particle, will contain benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in water and is stirred, and stirring velocity is 100rpm, and under 60 ℃, reaction was incubated 8 hours after 9 hours under 90 ℃, and cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(d) the 2kg resin of getting wherein mixes with the 400g methyl acrylate, joining 10L after adding the 60g benzoyl peroxide to mix contains in 200g gelatin and 500g sodium-chlor water, in adition process, stirred, stirring velocity is 400rpm, temperature is controlled at reaction under 50 ℃ and is incubated 10 hours after 9 hours under 85 ℃, cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(e) get the resin 2kg made, impregnated in the 10L mass concentration and be in 5% aqueous sodium hydroxide solution 65 ℃ of reactions 8 hours, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying, obtain weak acid and modify the high-specific surface area magnetic resin.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.6m
3the flow of/h evenly flows into 0.5m
3in the steel mechanically stirred reactor, the magnetic resin that adds in advance the 1L aforesaid method to prepare in reactor, enter the mixed solution of resin and clear water with the flow pump of 1L/h from the fresh resin tank, carry out absorption reaction in reactor simultaneously.After resin has reacted in reactor with water, carry out magnetic or natural subsidence and separate, the water outlet of settling tank top can be back to town water, and the mixed solution 70% that the resin content of bottom settlings is higher pumps into the reactor reuse, remains 30% and sends into regeneration tank.After utilizing mass concentration to be 15% sodium chloride aqueous solution and 0.02% hydrochloric acid soln regeneration 20min in regeneration tank, send into the recycle of fresh resin tank, the regenerator after use is through the purification reuse.Water-quality guideline is as following table (mg/L of unit) before and after plastic resin treatment:
| ? | COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before processing | 48 | 16 | 7.8 | 0.51 | 0.25 | 2.5 |
| After processing | 25 | 9 | 5.0 | 0.23 | 0.08 | 1.2 |
。
Embodiment 3
A kind of weak acid of the present embodiment is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) 1.125kg gelatin and 7.5kg sodium-chlor are dissolved in the 37.5L deionized water and are made into water;
(b) oil phase consists of 2.5kg divinylbenzene and 5kg toluene, in oil phase, adds the 75g benzoyl peroxide to make initiator, stirs it is fully dissolved;
(c) add the Fe of the oleic acid parcel that the 750g particle diameter is 1 μ m to oil phase
3o
4magnetic-particle, will contain benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in water and is stirred, and stirring velocity is 400rpm, and under 80 ℃, reaction was incubated 5 hours after 3 hours under 95 ℃, and cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(d) the 2kg resin of getting wherein mixes with the 200g methyl acrylate, joining 10L after adding the 80g benzoyl peroxide to mix contains in 400g gelatin and 2kg sodium-chlor water, in adition process, stirred, stirring velocity is 300rpm, temperature is controlled at reaction under 70 ℃ and is incubated 12 hours after 3 hours under 90 ℃, cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(e) get the resin 2kg made, impregnated in the 2L mass concentration and be in 5% aqueous sodium hydroxide solution 70 ℃ of reactions 5 hours, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying, obtain weak acid modification high-specific surface area magnetic resin.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 6m
3the flow of/h evenly flows into 0.5m
3in the steel mechanically stirred reactor, the magnetic resin that adds in advance the 2.5L aforesaid method to prepare in reactor, enter the mixed solution of resin and clear water with the flow pump of 6L/h from the fresh resin tank, carry out absorption reaction in reactor simultaneously.After resin has reacted in reactor with water, carry out magnetic or natural subsidence and separate, the water outlet of settling tank top can be back to landscape water, and the mixed solution 65% that the resin content of bottom settlings is higher pumps into the reactor reuse, remains 35% and sends into regeneration tank.After utilizing mass concentration to be 30% sodium chloride aqueous solution and 0.01% hydrochloric acid soln regeneration 30min in regeneration tank, send into the recycle of fresh resin tank, the regenerator after use is through the purification reuse.Water-quality guideline is as following table (mg/L of unit) before and after plastic resin treatment:
| ? | COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before processing | 40 | 12 | 8.0 | 0.48 | 0.20 | 2.0 |
| After processing | 23 | 8 | 4.5 | 0.27 | 0.12 | 0.8 |
。
Embodiment 4
A kind of weak acid of the present embodiment is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) 500g gelatin and 5kg sodium-chlor are dissolved in the 50L deionized water and are made into water;
(b) oil phase consists of 2.5kg divinylbenzene and 2.5kg toluene, in oil phase, adds the 150g benzoyl peroxide to make initiator, stirs it is fully dissolved;
(c) add the Fe of the oleic acid parcel that the 1.25kg particle diameter is 0.1 μ m to oil phase
3o
4magnetic-particle, will contain benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in water and is stirred, and stirring velocity is 200rpm, and under 70 ℃, reaction was incubated 12 hours after 6 hours under 85 ℃, and cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(d) the 2kg resin of getting wherein mixes with the 1kg methyl acrylate, joining 10L after adding the 40g benzoyl peroxide to mix contains in 100g gelatin and 1kg sodium-chlor water, in adition process, stirred, stirring velocity is 100rpm, temperature is controlled at reaction under 60 ℃ and is incubated 5 hours after 6 hours under 95 ℃, cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(e) get the resin 2kg made, impregnated in 16L 5% aqueous sodium hydroxide solution 60 ℃ of reactions 10 hours, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying obtains efficiently removing the magnetic resin of organism and heavy metal in micropollutant water simultaneously.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.3m
3the flow of/h evenly flows into 0.5m
3in the steel mechanically stirred reactor, the magnetic resin that adds in advance the 0.8L aforesaid method to prepare in reactor, enter the mixed solution of resin and clear water with the flow pump of 0.75L/h from the fresh resin tank, carry out absorption reaction in reactor simultaneously.After resin has reacted in reactor with water, carry out magnetic or natural subsidence and separate, the water outlet of settling tank top can be back to process water, and the mixed solution 80% that the resin content of bottom settlings is higher pumps into the reactor reuse, remains 20% and sends into regeneration tank.Utilize 10% sodium chloride aqueous solution and 0.02% hydrochloric acid soln regeneration 10min in regeneration tank after, after regeneration 20min, send into the recycle of fresh resin tank, the regenerator after use is through the purification reuse.Water-quality guideline is as following table (mg/L of unit) before and after plastic resin treatment:
| ? | COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before processing | 46 | 14 | 7.5 | 0.55 | 0.30 | 3.0 |
| After processing | 22 | 9 | 5.2 | 0.20 | 0.15 | 1.5 |
。
Embodiment 5
A kind of weak acid of the present embodiment is modified the preparation method of high-specific surface area magnetic resin, the steps include:
(a) 600g gelatin and 7.5kg sodium-chlor are dissolved in the 30L deionized water and are made into water;
(b) oil phase consists of 2.5kg divinylbenzene and 1.25kg toluene, in oil phase, adds the 75g benzoyl peroxide to make initiator, stirs it is fully dissolved;
(c) add the Fe of the oleic acid parcel that the 750g particle diameter is 0.5 μ m to oil phase
3o
4magnetic-particle, will contain benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in water and is stirred, and stirring velocity is 100rpm, and under 60 ℃, reaction was incubated 8 hours after 9 hours under 90 ℃, and cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(d) the 2kg resin of getting wherein mixes with the 400g methyl acrylate, joining 10L after adding the 60g benzoyl peroxide to mix contains in 200g gelatin and 500g sodium-chlor water, in adition process, stirred, stirring velocity is 400rpm, temperature is controlled at reaction under 50 ℃ and is incubated 10 hours after 9 hours under 85 ℃, cooling rear deionized water and washing with acetone are filtered dry, vacuum-drying;
(e) get the resin 2kg made, impregnated in 10L 5% aqueous sodium hydroxide solution 65 ℃ of reactions 8 hours, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying obtains efficiently removing the magnetic resin of organism and heavy metal in micropollutant water simultaneously.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 1.5m
3the flow of/h evenly flows into 0.5m
3in the steel mechanically stirred reactor, the magnetic resin that adds in advance the 1.5L aforesaid method to prepare in reactor, enter the mixed solution of resin and clear water with the flow pump of 2L/h from the fresh resin tank, carry out absorption reaction in reactor simultaneously.After resin has reacted in reactor with water, carry out magnetic or natural subsidence and separate, the water outlet of settling tank top can be back to town water, and the mixed solution 70% that the resin content of bottom settlings is higher pumps into the reactor reuse, remains 30% and sends into regeneration tank.Utilize 25% sodium chloride aqueous solution and 0.015% hydrochloric acid soln regeneration 15min in regeneration tank after, send into the recycle of fresh resin tank, the regenerator after use is through the purification reuse.
Water-quality guideline is as following table (mg/L of unit) before and after plastic resin treatment:
| ? | COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before processing | 45 | 14 | 8.0 | 0.42 | 0.22 | 2.4 |
| After processing | 21 | 10 | 4.5 | 0.18 | 0.08 | 1.3 |
。
Claims (7)
1. the preparation method that weak acid is modified the high-specific surface area magnetic resin, the steps include:
(a) be equipped with water: add in water and account for the gelatin that the water quality is 1%～3% and account for the sodium-chlor that the water quality is 10%～25%;
(b) be equipped with oil phase: oil phase consists of reactant monomer divinylbenzene and pore-creating agent toluene, the mass ratio 1:0.5 of divinylbenzene and toluene～2, in oil phase, add the benzoyl peroxide that accounts for divinylbenzene and toluene total mass 1%～3% to make initiator, stir it is fully dissolved;
(c) to the Fe that adds the oleic acid parcel that particle diameter is 0.1～1 μ m in the oil phase of step (b)
3o
4magnetic-particle, magnetic-particle accounts for oil phase total mass 10%～25%, then, will containing the oil phase of magnetic-particle, join in water, the mass ratio of oil phase and water is 1:5～10, add fashionable the stirring, stirring velocity is 100～400rpm, and temperature is controlled at 60～80 ℃, react and be incubated 5～12 hours after 3～9 hours under 85～95 ℃, cooling be filtered dry with deionized water and washing with acetone afterwards, vacuum-drying, obtain magnetic high-specific surface area resin;
(d) resin prepared by previous step mixes with methyl acrylate, methyl acrylate is 1:2～10 with the resin quality ratio, add the initiator benzoyl peroxide that accounts for resin quality 2%～4%, after mixing, join in water, wherein, in this water, gelatin accounts for water quality 1%～4%, sodium-chlor accounts for water quality 5%～20%, join in the process of water and stirred, stirring velocity is 100～400rpm, temperature is controlled at 50～70 ℃, react and be incubated 5～12 hours after 3～9 hours under 85～95 ℃, cooling be filtered dry with deionized water and washing with acetone afterwards, vacuum-drying, the magnetic high-specific surface area resin that must contain ester group,
(e) resin impregnation prepared by previous step reacts in aqueous sodium hydroxide solution, cooling after by the resin centrifugation, with deionized water and washing with acetone, be filtered dry, vacuum-drying, obtain weak acid and modify the high-specific surface area magnetic resin.
2. the preparation method that a kind of weak acid according to claim 1 is modified the high-specific surface area magnetic resin, it is characterized in that: in described step (b), the purity of described divinylbenzene is 80%.
3. the preparation method that a kind of weak acid according to claim 1 and 2 is modified the high-specific surface area magnetic resin, it is characterized in that: in described step (e), the consumption of described aqueous sodium hydroxide solution is 1～8 times of resin quality, the mass concentration of aqueous sodium hydroxide solution is 5%, resin impregnation temperature of reaction in aqueous sodium hydroxide solution is 60～70 ℃, and the reaction times is 5～10 hours.
4. the weak acid that a claim 3 prepares is modified the high-specific surface area magnetic resin.
5. the method that weak acid is modified high-specific surface area magnetic resin high-efficient purification micropollutant water, the steps include:
(1) add the magnetic resin in claim 4 in reactor, resin accounts for 0.1%～0.5% of reactor volume; The biochemical tail water reactor of flowing through, simultaneously from the fresh resin tank to the mixed solution that pumps into magnetic resin and clear water in reactor, the mixed solution flow accounts for 0.1%～0.5% of biochemical tail water flow;
(2) resin after processing carries out magnetic with the biochemical tail water mixed solution or natural subsidence is separated;
(3) resin settled down in step (2) is partly refluxed to reactor, part is sent into regenerating tank;
(4) in regenerating tank, add regenerator to be regenerated to resin, used regenerator purified reuse or disposal;
(5) by step (4), through the resin of regeneration, sending into the resin storage tank, be delivered to reactor while needing and carry out reuse.
6. a kind of weak acid according to claim 5 is modified the method for high-specific surface area magnetic resin high-efficient purification micropollutant water, it is characterized in that: in described step (1), the hydraulic detention time of biochemical tail water in reactor is 5～200min, and liquid-solid abundant mixing comprises that mechanical stirring, strength stir or hydraulic mixing.
7. modify the method for high-specific surface area magnetic resin high-efficient purification micropollutant water according to a kind of weak acid described in claim 6, it is characterized in that: in described step (3), regenerator in regenerating tank is compound desorbing agent, in this compound desorbing agent, Inorganic salt is 5～30%, the hydrochloric acid mass concentration is 0.01～0.025%, and the regenerative response time is 10～30min.
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