CN103497281B - A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof - Google Patents
A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof Download PDFInfo
- Publication number
- CN103497281B CN103497281B CN201310330339.3A CN201310330339A CN103497281B CN 103497281 B CN103497281 B CN 103497281B CN 201310330339 A CN201310330339 A CN 201310330339A CN 103497281 B CN103497281 B CN 103497281B
- Authority
- CN
- China
- Prior art keywords
- resin
- magnetic
- surface area
- specific surface
- aqueous phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of method that weak acid modifies high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof, belong to micropollutant water purifying method field.This preparation method's step is: (a) is equipped with aqueous phase; B () is equipped with oil phase; C () adds Fe in oil phase
3o
4magnetic-particle, then oil phase is joined in aqueous phase, stir, reaction, washing is filtered dry, vacuum-drying, obtains resin; D resin mixes with methyl acrylate by (), add initiator, joins in aqueous phase after mixing, and aqueous phase comprises gelatin and sodium-chlor, stirs, reaction, insulation, and washing is filtered dry, vacuum-drying, must contain the magnetic high-specific surface area resin of ester group; E resin impregnation reacts by () in aqueous sodium hydroxide solution, centrifugation after cooling, and washing is filtered dry, vacuum-drying, obtains weak acid and modifies high-specific surface area magnetic resin.Method of the present invention and resin can be removed in micropollutant water simultaneously poison organism and heavy metal.
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 be used for this resin to remove the method for organism and heavy metal in micropollutant water.
Background technology
China's water resources is most deficient, and occupancy volume per person is only 1/4th of world's per capita share, is a member in 13 poor-water states listed by United Nations.In recent years, increasing rapidly of domestic economy total amount makes water resources day show rare.The fast development of urbanization, regional economy be tending towards concentrate and environmental pollution day by day serious, increase the localised load of water resources especially.The regeneration of sewage is the indispensable important measures solving 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 stablized, and change of water quality amplitude is little, and its foreign matter content low (being less than 0.l%), add appropriate depth treatment measures after caning be passed through second-stage treatment, 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.Especially, when reuse water is used in the approach such as agricultural, forestry, herding, fishery, groundwater recharge and tap water supplement, there is larger ecological risk.Because the second-stage treatment of municipal effluent can not remove the high toxic materials such as micro-Organic Pollutants, heavy metal very well, if can not effectively harmful toxic matter be removed in the advanced treatment process of follow-up employing, they will inevitably enter into environment along with the use of reuse water, and then bring harm to the ecosystem.
In the advanced treatment being successfully applied to city domestic sewage based on the new type water treatment technology of magnetic resin and reuse (patent publication No.: CN101781437A).The resin that this technology uses is magnetic acrylic acid series anionite-exchange resin, and it mainly relies on ion exchange and removes the electronegativity organic pollutant in water body.But, this technology for a large amount of micro-Organic Pollutants existing in reuse water as the low-poles such as endocrine disrupter or nonpolar organic matter removal effect poor, meanwhile, in reuse water, another highly toxic material heavy metal is all exist with 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, more weak to the effect of wherein highly toxic material generation, need to develop new technology to make up this defect.
Summary of the invention
The problem that 1, will solve
For current resin technology to the poor problem of removal effect while low-pole, nonpolar micro-Organic Pollutants and the heavy metals such as a large amount of endocrine disrupters in reuse water, the invention provides a kind of method that weak acid modifies high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof, method of the present invention and resin efficiently can be removed in micropollutant water simultaneously poison organism and heavy metal.
2, technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
Weak acid modifies a preparation method for high-specific surface area magnetic resin, the steps include:
(a) be equipped with aqueous phase: add in aqueous phase account for aqueous phase quality be 1% ~ 3% gelatin and account for the sodium-chlor that aqueous phase quality is 10% ~ 25%;
B () is equipped with oil phase: oil phase is made up of reactant monomer divinylbenzene and pore-creating agent toluene, mass ratio 1:0.5 ~ 2 of divinylbenzene and toluene, in oil phase, add the benzoyl peroxide accounting for divinylbenzene and toluene total mass 1% ~ 3% make initiator, stir and make it fully dissolve;
C () adds the Fe that particle diameter is the oleic acid parcel of 0.1 ~ 1 μm in the oil phase of step (b)
3o
4magnetic-particle, magnetic-particle accounts for oil phase total mass 10% ~ 25%, then, joins in aqueous phase by the oil phase containing magnetic-particle, the mass ratio of oil phase and aqueous phase is 1:5 ~ 10, add fashionable stirring, stirring velocity is 100 ~ 400rpm, and temperature controls at 60 ~ 80 DEG C, react after 3 ~ 9 hours and be incubated 5 ~ 12 hours at 85 ~ 95 DEG C, cool rear deionized water and washing with acetone is filtered dry, vacuum-drying, obtain magnetic high-specific surface area resin;
D resin that previous step is prepared by () mixes with methyl acrylate, methyl acrylate and resin quality are than being 1:2 ~ 10, add the initiator benzoyl peroxide accounting for resin quality 2% ~ 4%, join after mixing in aqueous phase, wherein, in this aqueous phase, gelatin accounts for aqueous phase quality 1% ~ 4%, sodium-chlor accounts for aqueous phase quality 5% ~ 20%, join in the process of aqueous phase and stir, stirring velocity is 100 ~ 400rpm, temperature controls at 50 ~ 70 DEG C, react after 3 ~ 9 hours and be incubated 5 ~ 12 hours at 85 ~ 95 DEG C, cool rear deionized water and washing with acetone is filtered dry, vacuum-drying, the magnetic high-specific surface area resin of ester group must be contained,
E resin impregnation that previous step is prepared by () reacts in aqueous sodium hydroxide solution, by resin centrifugation after cooling, is filtered dry, vacuum-drying with deionized water and washing with acetone, obtains weak acid and modifies high-specific surface area magnetic resin.
Preferably, in described step (b), the purity of described divinylbenzene is for being 80%(mass percent).
Preferably, in described step (e), the consumption of described aqueous sodium hydroxide solution is 1 ~ 8 times of resin quality, and the mass concentration of aqueous sodium hydroxide solution is 5%, resin impregnation temperature of reaction in aqueous sodium hydroxide solution is 60 ~ 70 DEG C, and the reaction times is 5 ~ 10 hours.
A kind of weak acid prepared modifies high-specific surface area magnetic resin.
Weak acid modifies a method for high-specific surface area magnetic resin high-efficient purification micropollutant water, the steps include:
(1) add above-mentioned magnetic resin in the reactor, resin accounts for 0.1% ~ 0.5% of reactor volume; Biochemical tail water flows through reactor, and from fresh resin tank, pump into the mixed solution of magnetic resin and clear water in reactor, mixed solution flow accounts for 0.1% ~ 0.5% of biochemical tail water flow simultaneously;
(2) resin after process carries out magnetic with biochemical tail water mixed solution or natural subsidence is separated;
(3) resin portion settled down in step (2) is back to reactor, part sends into regenerating tank;
(4) in regenerating tank, add regenerator to regenerate resin, used regenerator carries out purification reuse or disposal;
(5) send into resin reservoir by step (4) through the resin of regeneration, be delivered to reactor when needing and carry out reuse.
Preferably, in described step (1), biochemical tail water hydraulic detention time is in the reactor 5 ~ 200min, and liquid-solid abundant mixing comprises mechanical stirring, pneumatic agitation 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 hydrochloric acid mass concentration is 0.01 ~ 0.025%, and the regenerative response time is 10 ~ 30min.
3, beneficial effect
Compared to 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 can not only remove ionic state pollutent, can also have good removal effect to water body Middle molecule state pollutent simultaneously.Compared to existing cross-linking adsorbent resin with ultrahigh magnetic property, this resin can by having higher adsorptive power by ion exchange to Heavy Metals in Waters ion.Can in a set of equipment, dissimilar organism and inorganic contaminants in efficient removal sewage simultaneously;
(2) method of the high-efficient purification micropollutant water based on this resin provided by the invention, compared with conventional depth treatment process, simple to operate, and investment running cost is low, and treatment effect is good.Sewage after process can meet purposes such as being back to industry, city, view, has good application prospect in the reuse field of reuse water.
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 is described further.
Embodiment 1
A kind of weak acid of the present embodiment modifies the preparation method of high-specific surface area magnetic resin, the steps include:
A 500g gelatin and 5kg sodium-chlor are dissolved in 50L deionized water and are made into aqueous phase by ();
B () oil phase is made up of 2.5kg divinylbenzene and 2.5kg toluene, add 150g benzoyl peroxide and make initiator in oil phase, stirs and makes it fully dissolve;
C () adds to oil phase the Fe that 1.25kg particle diameter is the oleic acid parcel of 0.1 μm
3o
4magnetic-particle, will containing benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in aqueous phase and stirs, and stirring velocity is 200rpm, and react at 70 DEG C after 6 hours and be incubated 12 hours at 85 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
D 2kg resin that () gets wherein mixes with 1kg methyl acrylate, add and join 10L after 40g benzoyl peroxide mixes and contain in 100g gelatin and 1kg sodium-chlor aqueous phase, stir in adition process, stirring velocity is 100rpm, temperature controls to react at 60 DEG C after 6 hours and be incubated 5 hours at 95 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
E () gets obtained resin 2kg, impregnated in 16L mass concentration be in 5% aqueous sodium hydroxide solution 60 DEG C reaction 10 hours, by resin centrifugation after cooling, be filtered dry with deionized water and washing with acetone, vacuum-drying, obtains weak acid and modifies high-specific surface area magnetic resin.
Test the resin prepared in above-mentioned steps, its result as shown in Figure 1.Fig. 1 is the resin FT-IR collection of illustrative plates (infared spectrum of resin prepared by following examples 2 ~ 5 is substantially identical with Fig. 1, and charateristic avsorption band is the same) that in preparation process of the present invention, different step obtains.In figure, (d), (e) represent in preparation process the resin obtained when proceeding to step (d), (e) respectively.As can be seen from Figure 1, the resin prepared of 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, compared with Fig. 1 (d), 3440cm in Fig. 1 (e)
-1there is "-OH " charateristic avsorption band in place, shows that step (e) is hydrolyzed successfully.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.15m
3the uniform flow of/h flows into 0.5m
3in steel mechanically stirred reactor, in reactor, add magnetic resin prepared by 0.5L aforesaid method in advance, pump into the mixed solution of resin and clear water simultaneously from fresh resin tank with the flow of 0.75L/h, carry out absorption reaction in the reactor.After resin and water have reacted in reactor, carry out magnetic or natural subsidence separation, 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 reactor reuse, and residue 20% sends into regeneration tank.In regeneration tank, utilize mass concentration to be after 5% sodium chloride aqueous solution and 0.025% hydrochloric acid soln regenerate 10min, send into the recycle of fresh resin tank, the regenerator after using is through purification reuse.Before and after plastic resin treatment, water-quality guideline is as following table (unit mg/L):
| COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness | |
| Before process | 45 | 15 | 7.6 | 0.45 | 0.32 | 2.8 |
| After process | 20 | 10 | 4.9 | 0.18 | 0.14 | 1.1 |
Embodiment 2
A kind of weak acid of the present embodiment modifies the preparation method of high-specific surface area magnetic resin, the steps include:
A 600g gelatin and 7.5kg sodium-chlor are dissolved in 30L deionized water and are made into aqueous phase by ();
B () oil phase is made up of 2.5kg divinylbenzene and 1.25kg toluene, add 75g benzoyl peroxide and make initiator in oil phase, stirs and makes it fully dissolve;
C () adds to oil phase the Fe that 750g particle diameter is the oleic acid parcel of 0.5 μm
3o
4magnetic-particle, will containing benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in aqueous phase and stirs, and stirring velocity is 100rpm, and react at 60 DEG C after 9 hours and be incubated 8 hours at 90 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
D 2kg resin that () gets wherein mixes with 400g methyl acrylate, add and join 10L after 60g benzoyl peroxide mixes and contain in 200g gelatin and 500g sodium-chlor aqueous phase, stir in adition process, stirring velocity is 400rpm, temperature controls to react at 50 DEG C after 9 hours and be incubated 10 hours at 85 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
E () gets obtained resin 2kg, impregnated in 10L mass concentration be in 5% aqueous sodium hydroxide solution 65 DEG C reaction 8 hours, by resin centrifugation after cooling, be filtered dry with deionized water and washing with acetone, vacuum-drying, obtains weak acid and modifies high-specific surface area magnetic resin.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.6m
3the uniform flow of/h flows into 0.5m
3in steel mechanically stirred reactor, in reactor, add magnetic resin prepared by 1L aforesaid method in advance, pump into the mixed solution of resin and clear water simultaneously from fresh resin tank with the flow of 1L/h, carry out absorption reaction in the reactor.After resin and water have reacted in reactor, carry out magnetic or natural subsidence separation, 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 reactor reuse, and residue 30% sends into regeneration tank.In regeneration tank, utilize mass concentration to be after 15% sodium chloride aqueous solution and 0.02% hydrochloric acid soln regenerate 20min, send into the recycle of fresh resin tank, the regenerator after using is through purification reuse.Before and after plastic resin treatment, water-quality guideline is as following table (unit mg/L):
| COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness | |
| Before process | 48 | 16 | 7.8 | 0.51 | 0.25 | 2.5 |
| After process | 25 | 9 | 5.0 | 0.23 | 0.08 | 1.2 |
Embodiment 3
A kind of weak acid of the present embodiment modifies 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 37.5L deionized water and are made into aqueous phase by ();
B () oil phase is made up of 2.5kg divinylbenzene and 5kg toluene, add 75g benzoyl peroxide and make initiator in oil phase, stirs and makes it fully dissolve;
C () adds to oil phase the Fe that 750g particle diameter is the oleic acid parcel of 1 μm
3o
4magnetic-particle, will containing benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in aqueous phase and stirs, and stirring velocity is 400rpm, and react at 80 DEG C after 3 hours and be incubated 5 hours at 95 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
D 2kg resin that () gets wherein mixes with 200g methyl acrylate, add and join 10L after 80g benzoyl peroxide mixes and contain in 400g gelatin and 2kg sodium-chlor aqueous phase, stir in adition process, stirring velocity is 300rpm, temperature controls to react at 70 DEG C after 3 hours and be incubated 12 hours at 90 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
E () gets obtained resin 2kg, impregnated in 2L mass concentration be in 5% aqueous sodium hydroxide solution 70 DEG C reaction 5 hours, by resin centrifugation after cooling, be filtered dry with deionized water and washing with acetone, vacuum-drying, obtains weak acid and modifies high-specific surface area magnetic resin.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 6m
3the uniform flow of/h flows into 0.5m
3in steel mechanically stirred reactor, in reactor, add magnetic resin prepared by 2.5L aforesaid method in advance, pump into the mixed solution of resin and clear water simultaneously from fresh resin tank with the flow of 6L/h, carry out absorption reaction in the reactor.After resin and water have reacted in reactor, carry out magnetic or natural subsidence separation, 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 reactor reuse, and residue 35% sends into regeneration tank.In regeneration tank, utilize mass concentration to be after 30% sodium chloride aqueous solution and 0.01% hydrochloric acid soln regenerate 30min, send into the recycle of fresh resin tank, the regenerator after using is through purification reuse.Before and after plastic resin treatment, water-quality guideline is as following table (unit mg/L):
| COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness | |
| Before process | 40 | 12 | 8.0 | 0.48 | 0.20 | 2.0 |
| After process | 23 | 8 | 4.5 | 0.27 | 0.12 | 0.8 |
Embodiment 4
A kind of weak acid of the present embodiment modifies the preparation method of high-specific surface area magnetic resin, the steps include:
A 500g gelatin and 5kg sodium-chlor are dissolved in 50L deionized water and are made into aqueous phase by ();
B () oil phase is made up of 2.5kg divinylbenzene and 2.5kg toluene, add 150g benzoyl peroxide and make initiator in oil phase, stirs and makes it fully dissolve;
C () adds to oil phase the Fe that 1.25kg particle diameter is the oleic acid parcel of 0.1 μm
3o
4magnetic-particle, will containing benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in aqueous phase and stirs, and stirring velocity is 200rpm, and react at 70 DEG C after 6 hours and be incubated 12 hours at 85 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
D 2kg resin that () gets wherein mixes with 1kg methyl acrylate, add and join 10L after 40g benzoyl peroxide mixes and contain in 100g gelatin and 1kg sodium-chlor aqueous phase, stir in adition process, stirring velocity is 100rpm, temperature controls to react at 60 DEG C after 6 hours and be incubated 5 hours at 95 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
E () gets obtained resin 2kg, to impregnated in 16L5% aqueous sodium hydroxide solution 60 DEG C of reactions 10 hours, by resin centrifugation after cooling, be filtered dry with deionized water and washing with acetone, vacuum-drying, obtains the magnetic resin simultaneously efficiently can removing organism and heavy metal in micropollutant water.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 0.3m
3the uniform flow of/h flows into 0.5m
3in steel mechanically stirred reactor, in reactor, add magnetic resin prepared by 0.8L aforesaid method in advance, pump into the mixed solution of resin and clear water simultaneously from fresh resin tank with the flow of 0.75L/h, carry out absorption reaction in the reactor.After resin and water have reacted in reactor, carry out magnetic or natural subsidence separation, 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 reactor reuse, and residue 20% 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 using is through purification reuse.Before and after plastic resin treatment, water-quality guideline is as following table (unit mg/L):
| COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness | |
| Before process | 46 | 14 | 7.5 | 0.55 | 0.30 | 3.0 |
| After process | 22 | 9 | 5.2 | 0.20 | 0.15 | 1.5 |
Embodiment 5
A kind of weak acid of the present embodiment modifies the preparation method of high-specific surface area magnetic resin, the steps include:
A 600g gelatin and 7.5kg sodium-chlor are dissolved in 30L deionized water and are made into aqueous phase by ();
B () oil phase is made up of 2.5kg divinylbenzene and 1.25kg toluene, add 75g benzoyl peroxide and make initiator in oil phase, stirs and makes it fully dissolve;
C () adds to oil phase the Fe that 750g particle diameter is the oleic acid parcel of 0.5 μm
3o
4magnetic-particle, will containing benzoyl peroxide and Fe
3o
4the oil phase of magnetic-particle joins in aqueous phase and stirs, and stirring velocity is 100rpm, and react at 60 DEG C after 9 hours and be incubated 8 hours at 90 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
D 2kg resin that () gets wherein mixes with 400g methyl acrylate, add and join 10L after 60g benzoyl peroxide mixes and contain in 200g gelatin and 500g sodium-chlor aqueous phase, stir in adition process, stirring velocity is 400rpm, temperature controls to react at 50 DEG C after 9 hours and be incubated 10 hours at 85 DEG C, after cooling, deionized water and washing with acetone are filtered dry, vacuum-drying;
E () gets obtained resin 2kg, to impregnated in 10L5% aqueous sodium hydroxide solution 65 DEG C of reactions 8 hours, by resin centrifugation after cooling, be filtered dry with deionized water and washing with acetone, vacuum-drying, obtains the magnetic resin simultaneously efficiently can removing organism and heavy metal in micropollutant water.
Certain city domestic sewage treatment plant secondary biochemical tail water is with 1.5m
3the uniform flow of/h flows into 0.5m
3in steel mechanically stirred reactor, in reactor, add magnetic resin prepared by 1.5L aforesaid method in advance, pump into the mixed solution of resin and clear water simultaneously from fresh resin tank with the flow of 2L/h, carry out absorption reaction in the reactor.After resin and water have reacted in reactor, carry out magnetic or natural subsidence separation, 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 reactor reuse, and residue 30% 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 using is through purification reuse.
Before and after plastic resin treatment, water-quality guideline is as following table (unit mg/L):
| COD | BOD 5 | Ammonia nitrogen | Fe 3+ | Mn 2+ | Hardness |
| Before process | 45 | 14 | 8.0 | 0.42 | 0.22 | 2.4 |
| After process | 21 | 10 | 4.5 | 0.18 | 0.08 | 1.3 |
Claims (7)
1. weak acid modifies a preparation method for high-specific surface area magnetic resin, the steps include:
(a) be equipped with aqueous phase: add in aqueous phase account for aqueous phase quality be 1% ~ 3% gelatin and account for the sodium-chlor that aqueous phase quality is 10% ~ 25%;
B () is equipped with oil phase: oil phase is made up of reactant monomer divinylbenzene and pore-creating agent toluene, mass ratio 1:0.5 ~ 2 of divinylbenzene and toluene, in oil phase, add the benzoyl peroxide accounting for divinylbenzene and toluene total mass 1% ~ 3% make initiator, stir and make it fully dissolve;
C () adds the Fe that particle diameter is the oleic acid parcel of 0.1 ~ 1 μm in the oil phase of step (b)
3o
4magnetic-particle, magnetic-particle accounts for oil phase total mass 10% ~ 25%, then, joins in aqueous phase by the oil phase containing magnetic-particle, the mass ratio of oil phase and aqueous phase is 1:5 ~ 10, add fashionable stirring, stirring velocity is 100 ~ 400rpm, and temperature controls at 60 ~ 80 DEG C, react after 3 ~ 9 hours and be incubated 5 ~ 12 hours at 85 ~ 95 DEG C, cool rear deionized water and washing with acetone is filtered dry, vacuum-drying, obtain magnetic high-specific surface area resin;
D resin that previous step is prepared by () mixes with methyl acrylate, methyl acrylate and resin quality are than being 1:2 ~ 10, add the initiator benzoyl peroxide accounting for resin quality 2% ~ 4%, join after mixing in aqueous phase, wherein, in this aqueous phase, gelatin accounts for aqueous phase quality 1% ~ 4%, sodium-chlor accounts for aqueous phase quality 5% ~ 20%, join in the process of aqueous phase and stir, stirring velocity is 100 ~ 400rpm, temperature controls at 50 ~ 70 DEG C, react after 3 ~ 9 hours and be incubated 5 ~ 12 hours at 85 ~ 95 DEG C, cool rear deionized water and washing with acetone is filtered dry, vacuum-drying, the magnetic high-specific surface area resin of ester group must be contained,
E resin impregnation that previous step is prepared by () reacts in aqueous sodium hydroxide solution, by resin centrifugation after cooling, is filtered dry, vacuum-drying with deionized water and washing with acetone, obtains weak acid and modifies high-specific surface area magnetic resin.
2. a kind of weak acid according to claim 1 modifies the preparation method of high-specific surface area magnetic resin, and it is characterized in that: in described step (b), the purity of described divinylbenzene is 80%.
3. a kind of weak acid according to claim 1 and 2 modifies the preparation method of 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 DEG C, and the reaction times is 5 ~ 10 hours.
4. the weak acid that a claim 3 prepares modifies high-specific surface area magnetic resin.
5. weak acid modifies a method for high-specific surface area magnetic resin purifying slightly polluted water body, the steps include:
(1) add the magnetic resin in claim 4 in the reactor, resin accounts for 0.1% ~ 0.5% of reactor volume; Biochemical tail water flows through reactor, and from fresh resin tank, pump into the mixed solution of magnetic resin and clear water in reactor, mixed solution flow accounts for 0.1% ~ 0.5% of biochemical tail water flow simultaneously;
(2) resin after step (1) process carries out magnetic with biochemical tail water mixed solution or natural subsidence is separated;
(3) resin portion settled down in step (2) is back to reactor, part sends into regenerating tank;
(4) in regenerating tank, add regenerator to regenerate resin, used regenerator carries out purification reuse or disposal;
(5) send into fresh resin tank by step (4) through the resin of regeneration, be delivered to reactor when needing and carry out reuse.
6. a kind of weak acid according to claim 5 modifies the method for high-specific surface area magnetic resin purifying slightly polluted water body, it is characterized in that: in described step (1), biochemical tail water hydraulic detention time is in the reactor 5 ~ 200min, and liquid-solid abundant mixing comprises mechanical stirring, pneumatic agitation or hydraulic mixing.
7. the method for high-specific surface area magnetic resin purifying slightly polluted water body is modified according to a kind of weak acid described in claim 6, it is characterized in that: in described step (4), regenerator in regenerating tank is compound desorbing agent, in this compound desorbing agent, Inorganic salt is 5 ~ 30%, hydrochloric acid mass concentration is 0.01 ~ 0.025%, and the regenerative response time is 10 ~ 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310330339.3A CN103497281B (en) | 2013-07-31 | 2013-07-31 | A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310330339.3A CN103497281B (en) | 2013-07-31 | 2013-07-31 | A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103497281A CN103497281A (en) | 2014-01-08 |
| CN103497281B true CN103497281B (en) | 2016-04-06 |
Family
ID=49862552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310330339.3A Active CN103497281B (en) | 2013-07-31 | 2013-07-31 | A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497281B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904769B (en) * | 2017-04-28 | 2022-04-12 | 南京环保产业创新中心有限公司 | Method for integrated adsorption and desorption liquid application for removing total nitrogen pollutants in wastewater |
| CN106892543A (en) * | 2017-04-28 | 2017-06-27 | 南京环保产业创新中心有限公司 | The method that depth removes Coal Gas Washing Cycling Water nitrate nitrogen |
| CN107999037B (en) * | 2017-12-18 | 2020-07-31 | 南京大学 | Magnetic polymer adsorption material, preparation method and application |
| CN109485130B (en) * | 2018-12-27 | 2023-04-11 | 中冶京诚工程技术有限公司 | Magnetic carrier particle manufacturing equipment and magnetic carrier particle manufacturing method |
| CN113083256A (en) * | 2021-04-13 | 2021-07-09 | 北京赛科康仑环保科技有限公司 | Adsorbing material for deep oil removal of neutral phosphorus-containing extraction system and preparation and application methods thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701054B (en) * | 2009-12-01 | 2011-06-29 | 福州大学 | Surface decorating method of porous polymer microspheres |
| CN101905931A (en) * | 2010-02-11 | 2010-12-08 | 南京大学 | Advanced treating method of biochemical tail water based on magnetic resin |
| CN101948554A (en) * | 2010-10-09 | 2011-01-19 | 南京大学 | Weak acid cation exchange microballoon resin of magnetic acrylic acid series and synthesis method thereof |
| CN102049243B (en) * | 2011-01-12 | 2012-11-07 | 南京大学 | Cross-linking adsorbent resin with ultrahigh magnetic property and preparation method thereof |
| CN102381742B (en) * | 2011-09-30 | 2013-05-08 | 南京大学 | Processing method for deeply purifying urban sewage |
| CN102516679B (en) * | 2011-12-19 | 2014-08-13 | 南京大学 | Magnetic microsphere resin with high specific surface area and preparation method and application thereof |
| CN103159891B (en) * | 2013-03-28 | 2015-03-18 | 南京大学 | Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof |
-
2013
- 2013-07-31 CN CN201310330339.3A patent/CN103497281B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103497281A (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103497281B (en) | A kind of weak acid modifies the method for high-specific surface area magnetic resin, its preparation method and high-efficient purification micropollutant water thereof | |
| CN103466768B (en) | Floc reflux coagulation process for treating biochemical printing and dyeing effluent | |
| CN103771671B (en) | Excess sludge treatment method | |
| CN101905931A (en) | Advanced treating method of biochemical tail water based on magnetic resin | |
| CN102145952B (en) | Method for treating fracturing reverse drainage liquid of petroleum exploitation by microwave rapid catalysis | |
| CN104724874A (en) | Sewage pretreatment method | |
| CN104129831A (en) | Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin | |
| CN109626672A (en) | Based on nitrate nitrogen method in electrochemistry and resin combination technique advanced treatment of waste water | |
| CN102295389B (en) | Industrial waste water treating technology | |
| CN111892133B (en) | Biochemical tail water deep nitrogen and phosphorus removal method based on magnetic coagulation-adsorption coupling | |
| CN101423314A (en) | High efficiency denitrification, phosphorus removal and phosphorus resource recovery composite for urban sewage | |
| CN202936235U (en) | Multistage efficient flocculation reaction system | |
| CN107324606B (en) | Sewage treatment system and method for recycling iron-rich excess sludge dephosphorization membrane bioreactor | |
| CN111253004B (en) | Multi-group chelating type magnetic hypha water purifying agent circulating treatment process and treatment system | |
| CN103387301B (en) | Deep purification method for urban sewage | |
| CN103435181B (en) | A kind of efficient process of chemical wastewater biochemical water outlet and reuse method | |
| CN201626864U (en) | Magnetization, oxidization and magnetic separation device | |
| CN101497032A (en) | Method for preparing biological sorbent and method of use thereof | |
| CN108928971A (en) | A kind of processing system and its implementation of chromium-containing dyeing waste water | |
| CN202658021U (en) | Manganese-containing wastewater purifying and recycling device | |
| CN104326611A (en) | Method for processing organic wastewater by electro-fenton | |
| CN204607770U (en) | A kind of DYE PRODUCTION oxidation pond concentrates the treatment unit of waste water | |
| CN207918505U (en) | The sewage and wastewater treatment system of coagulation flco reflux | |
| CN103253727B (en) | A kind of method of high-phosphorus iron ore mine tailing deep purifying Removal of Phosphorus in Wastewater | |
| CN102381742B (en) | Processing method for deeply purifying urban sewage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |