CN102558416A - Metal-doped high molecular material and preparation method thereof and application thereof to ammonia nitrogen removal - Google Patents
Metal-doped high molecular material and preparation method thereof and application thereof to ammonia nitrogen removal Download PDFInfo
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- CN102558416A CN102558416A CN201110446676XA CN201110446676A CN102558416A CN 102558416 A CN102558416 A CN 102558416A CN 201110446676X A CN201110446676X A CN 201110446676XA CN 201110446676 A CN201110446676 A CN 201110446676A CN 102558416 A CN102558416 A CN 102558416A
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Abstract
The invention provides a metal-doped high molecular material, which consists of a matrix polymer, a hydrophilic group and a transition metal ion which is doped on the matrix polymer, wherein the matrix polymer is formed by polymerizing an organic compound containing -C=C- and a compound containing -C=C-......-C=C-; the quantity of C in the organic compound containing -C=C- is 2-10; the quantity of C in the organic compound containing -C=C-......-C=C- is 4-15; the hydrophilic group is one or more of sulfonyl, cyan, tertiary amino, quaternary ammonium group or hydroxyl; and the transition metal ion is an ion of Ti, V, Cr, Fe, Cu, Ni or Zn. A relatively stable complex can be formed by the transition metal ion and ammonia nitrogen in water, so that the aim of removing ammonia nitrogen from water is fulfilled. The metal-doped high polymer material provided by the invention has the advantages of high absorptive selectivity to ammonia nitrogen in sewage, high absorption amount, concentration of effluent ammonia nitrogen in water less than 10 ppm, convenience for regenerating and simple process.
Description
Technical field
The present invention relates to the ammonia nitrogen technology of removing, be specifically related to a kind of metal-doped macromolecular material that removes ammonia nitrogen that is used as, the application in removing ammonia nitrogen of the preparation method of this macromolecular material and this macromolecular material nitrogen-containing wastewater.
Background technology
Nitrogen-containing wastewater is present in many trade effluents, particularly production processes such as iron and steel, chemical fertilizer, inorganic chemical industry, iron alloy, glass manufacturing, meat processing and feed.Ammonia nitrogen is meant in the water with free ammonia (NH
3) and ammonium ion (NH
4 +) nitrogen that exists of form.Ammonia nitrogen is the nutrient substance in the water body, can cause the water eutrophication phenomenon to produce.Ammonia nitrogen in the water can change into nitrite under certain condition, if long-term drinking, the nitrite in the water will form NSC 223080 with protein bound, and this is a kind of strong carcinogen.It is very big that free ammonia in the ammonia nitrogen plays damaging effect to aquatic organism, and increase with the enhancing of alkalescence.Can cause fish kills.
The common method of removing ammonia nitrogen has: chemical precipitation method, membrane filter method, ammonia stripping-vaporizing extract process, break point chlorination, biological denitrificaion method, absorption method etc.Chemical precipitation method, treatment of high concentration ammonia nitrogen effect is better, but water outlet can not reach discharging standards, needs to use MgO and H
3PO
4As precipitation agent, consumption rate is bigger, and cost is high, and the throw out MgNH that generates
4PO
4Do not have economic worth, produce secondary pollution; Membrane filter method needs bigger hydraulic pressure, thereby equipment and capital construction cost are higher; Ammonia stripping-vaporizing extract process flow process is simple, and working cost is low, but it is poor to be lower than 10.5 ammonia nitrogen waste water effect for pH, and generates incrustation scale easily, causes serious operational issue; Break point chlorination is very high at treatment of high concentration ammonia nitrogen cost; The biological denitrificaion method comprises biological nitration and biological denitrification method, floor space is big, the low temperature aging rate is low, be subject to the toxic substance influence and operational management cumbersome.
Absorption method mainly contain ion exchange resin, gac and Activated Zeolite Adsorption, though oil suction is respond well, ion exchange resin and gac do not have selectivity for ammonia nitrogen, so adsorptive capacity is little, chemical efficiency is low; Though zeolite has certain selectivity to ammonia nitrogen, same problem is that adsorptive capacity is little, and is not suitable for high-concentration ammonia nitrogenous wastewater.
Summary of the invention
The problem that the present invention solves is to provide a kind of metal-doped macromolecular material, uses it to adsorb except that ammonia nitrogen, and clearance is high.The present invention also provides by the preparation method of this metal-doped macromolecular material and the application of this macromolecular material in removing ammonia nitrogen.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of metal-doped macromolecular material is by matrix polymer, be positioned at the hydrophilic radical on the matrix polymer and the transition metal ion that is doped on the matrix polymer constitutes;
Said matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized, and the quantity of C is 2～10 in the organic cpds of said containing-C=C-; Said containing-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-;
Said hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl;
Said transition metal ion is the ion of Ti, V, Cr, Fe, Cu, Ni or Zn.
As preferably; The organic cpds of said containing-C=C-be ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid; Methyl acrylate, methylacrylic acid, one or more in the TEB 3K.
As preferably, said containing-C=C-... The organic cpds of-C=C-is a dibutene, limonene, isoprene, two hexenes, dissident's diene, divinylbenzene, kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene.
A kind of preparation method of metal-doped macromolecular material may further comprise the steps:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-C=C-... The organic cpds of-C=C-and the oil phase of initiator mix, and add perforating agent, carry out suspension polymerization, process matrix polymer,
The weight ratio composition that said water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that said oil phase contains is to contain-organic cpds of C=C-: contain-C=C-... The organic cpds of-C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01; The weight ratio of oil phase and water is 1: 4～6, and the weight of said perforating agent accounts for 10%～20% of water and oil phase weight sum;
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a;
C, at room temperature is mixed with solution with the compound of transition metal, with the product of this solution stream through step b, carries out dynamically metal-doped.
As preferably, suspension polymerization is specially each composition is added in the reaction kettle among the said a, in reaction kettle, feeds pressurized air or nitrogen; Make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle, be warming up to 70 ℃～90 ℃, be incubated 2 hours～24 hours; Be warming up to 100 ℃～150 ℃ again; Be incubated 4 hours～36 hours, washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
As preferably; Dispersion agent among the said a is one or both in inorganic dispersant or the organic dispersing agent; Said inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and said organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.
As preferably, the dispersion aids among the said a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
As preferably, the initiator among the said a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd.
As preferably, said initiator is peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
As preferably, the perforating agent among the said a is one or more in paraffin, sal epsom, yellow soda ash, gelatin or the glycerine.
As preferably, amination described in the said b is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction.
As preferably, said aminating agent is a Trimethylamine 99.
As preferably, sulphonating agent is sulphur trioxide, mass concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more among the said b.
As preferably, the matrix polymer to step a among the said b carries out carrying out alkali cleaning again after the amination, and perhaps the matrix polymer to step a carries out carrying out pickling again after the sulfonation.
As preferably, the mass and size percentage concentration of the solution that the compound of transition metal is mixed with among the said c is 10%～60%.
As preferably, the solution that the compound of transition metal is mixed with among the said c carries out dynamically metal-doped with the flow through product of step b of the flow velocity of 5BV/h～30BV/h.
As preferably, the compound of said transition metal is nitrate salt, muriate or the vitriol of said transition metal, and said transition metal is Ti, V, Cr, Fe, Cu, Ni or Zn.
A kind of each described metal-doped macromolecular material of claim 1 to 3 that uses may further comprise the steps containing the method for removing ammonia nitrogen of ammonia-nitrogen sewage:
1., said metal-doped macromolecular material is packed in the container;
2., will contain ammonia-nitrogen sewage pH regulator to 9～12, make then to contain ammonia-nitrogen sewage through having filled the container of said metal-doped macromolecular material;
3., when the ammonia-nitrogen content of effusive sewage from container surpasses when requiring, make dilute stream of sulphuric acid through this container, said metal-doped macromolecular material is regenerated.
As preferably, said 2. in, containing the temperature of ammonia-nitrogen sewage through said container is 10 ℃～80 ℃, institute tells that to contain the ammonia-nitrogen sewage flow velocity be 2BV/h～30BV/h.
As preferably, said 3. in the concentration of volume percent of dilute sulphuric acid be 5%～20%.
The ammonia nitrogen that the present invention provides metal-doped macromolecular material to be used for removing sewage, this is based on the specific absorption property of transition metal to ammonia nitrogen in the water.Ammonia nitrogen is with NH in the water
3Perhaps NH
4 +Form exist, it be electron rich molecule or ion, and transition metal can electrolysis produce the metals ion with empty electronic orbit in solution, when suitable pH, its can with the NH of electron rich in the solution
3Perhaps NH
4 +Have powerful avidity, form metastable type of complex compound, thereby reach the purpose of removing ammonia nitrogen in the water through effects such as covalence key chemisorption, electrostatic adhesion and IX absorption.Use metal-doped macromolecular material of the present invention strong to the adsorption selectivity of ammonia nitrogen in the sewage, adsorptive capacity is big, and the concentration of water outlet ammonia nitrogen is lower than 10ppm; Regeneration is convenient, and technology is simple.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
A kind of metal-doped macromolecular material provided by the invention by matrix polymer, be positioned at the hydrophilic radical on the matrix polymer and the transition metal ion that is doped on the matrix polymer constitutes, matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized.Contain-organic cpds of C=C-in the quantity of C be 2～10; Be preferably ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid; Methyl acrylate, methylacrylic acid, one or more in the TEB 3K; Contain-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-, is preferably dibutene, limonene, isoprene, two hexenes, dissident's diene, divinylbenzene, kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene; Hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl; Transition metal ion is the ion of Ti, V, Cr, Fe, Cu, Ni or Zn.
The preparation method of metal-doped macromolecular material provided by the invention comprises:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-organic cpds of C=C-and the oil phase of initiator mix, and adds perforating agent, carries out suspension polymerization, processes matrix polymer,
The weight ratio composition that water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that oil phase contains is to contain-organic cpds of C=C-: contain-C=C-... The organic cpds of-C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01; The weight ratio of oil phase and water is 1: 4～6, and the weight of perforating agent accounts for 10%～20% of water and oil phase weight sum.
Dispersion agent is one or both in inorganic dispersant or the organic dispersing agent; Inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.Dispersion aids is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
Initiator is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd, is preferably peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
Perforating agent is one or more in paraffin, sal epsom, yellow soda ash, gelatin or the glycerine
Suspension polymerization is specially each composition is added in the reaction kettle, in reaction kettle, feeds pressurized air or nitrogen, makes that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle; Be warming up to 70 ℃～90 ℃; Be incubated 2 hours～24 hours, be warming up to 100 ℃～150 ℃ again, be incubated 4 hours～36 hours; Washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a.Amination is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction, and chloromethylation reagent is chloromethyl ether, and aminating agent is a Trimethylamine 99.Sulphonating agent is sulphur trioxide, concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more, is preferably mass concentration and is 100%～106% oleum or in the sulphur trioxide one or both.
Preferably can the matrix polymer that carry out after the amination be carried out alkali cleaning, make it alkalization; If matrix polymer is carried out sulfonation, then preferably can the matrix polymer after the sulfonation be used pickling, make it acidifying, the matrix polymer after handling like this is containing transition metal more easily.
C, at room temperature is mixed with solution with the compound of transition metal, stirs and mixes 2 hours～24 hours, with the product of this solution stream through step b, carries out dynamically metal-doped.
The mass and size percentage concentration of the solution that the compound of transition metal is mixed with is preferably 10%～60%, and solution carries out dynamically metal-doped with the flow velocity of the 5BV/h～30BV/h product that step b makes of flowing through.The compound of transition metal is preferably nitrate salt, muriate or the vitriol of this transition metal, and transition metal is Ti, V, Cr, Fe, Cu, Ni or Zn.Transition metal ion is entrained on the matrix polymer through hydrogen ion on the substituted sulfonic acid base or amido.
Carry out after the alkali cleaning doping metals again if will carry out matrix polymer after the amination, then transition metal ion is with substituted hydroxy; If with the matrix polymer after the sulfonation with pickling after doping metals again, then transition metal ion will replace hydrogen ion.
Use metal-doped macromolecular material provided by the invention to containing the method that ammonia-nitrogen sewage removes ammonia nitrogen, comprising:
The metal-doped macromolecular material that 1., will prepare is packed in the container.
2., will contain ammonia-nitrogen sewage pH regulator to 9～12, make then to contain ammonia-nitrogen sewage through having filled the container of metal-doped macromolecular material.
Containing the temperature of ammonia-nitrogen sewage through container is 10 ℃～80 ℃, and containing the ammonia-nitrogen sewage flow velocity is 2BV/h～30BV/h, and the ammonia-nitrogen content in the water outlet generally can be reduced to below the 10ppm.
3., surpass (generally reaching 15ppm) when requiring when the ammonia-nitrogen content of effusive sewage from container; Out of service; Dilute sulphuric acid is regenerated to metal-doped macromolecular material through container, and the concentration of volume percent of dilute sulphuric acid is 5%～20%, and flow velocity is 2BV/h～20BV/h; Can collect mass percent greater than 20% ammonium sulfate liquid concentrator by the outflow end of container, can recycle.
Macromolecular material provided by the invention is doped with transition metal; Transition metal forms metastable type of complex form with ammonia nitrogen through effects such as covalence key chemisorption, electrostatic adhesion and IX absorption in water, thereby ammonia nitrogen is had specific absorption property.This macromolecular material is fairly regular spheroidal, has similar particle diameter, the about 1.2g/cm of density
3, there is a large amount of spaces inside, has bigger specific surface area, and the splendid ammonia nitrogen effect of removing is arranged, and can avoid the various spinoffs that other impurity brought in the water.When nitrogen-containing wastewater touched this macromolecular material, ammonia nitrogen molecule (ion) can form a type complex compound material with adulterated transition metal ion on the spheroidal material, thereby is adsorbed.The size of particles of this macromolecular material excellent mechanical intensity and homogeneous has guaranteed to remove ammonia nitrogen equipment can steady running, can not cause hydraulic pressure to increase or flow gets clogged.
Use metal-doped macromolecular material provided by the invention strong to the flexibility of former water except that the method for ammonia nitrogen in the sewage; Can be used for containing ammonia nitrogen 50ppm～300ppm, pH is 9～12 sewage, and the water outlet after the processing contains the ammonia nitrogen amount less than 10ppm; Remove the ammonia nitrogen rate greater than 90%, the ammonia nitrogen recovery is greater than 95%.
Embodiment 1:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 45 ℃; Under whipped state, add 10g magnesiumcarbonate, 20g gelatin and 0.15g methylene blue respectively; Stir the back and add the oil phase that mixes by 3kg vinyl toluene, 1kg kautschin, 20g Lucidol, add paraffin 2.6kg again.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 100 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 2.35kg that granularity is 0.5-0.8mm.
(2) amination: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add the 10kg chloromethyl ether, temperature is controlled at 60 ℃, stirs 6h; In still, add 10 liters of entry again, Trimethylamine 99 5kg stirs 1h, adds yellow soda ash again; Be warming up to 80 ℃, insulation 20h, cooling; Add washing to neutral, drying gets resin 4.13kg.
(3) metal-doped: as the resin after the amination to be packed in the glass column of 20L preparation 100L20%CuSO
4Solution is with this CuSO
4Solution carries out metal-doped with the flow velocity of the 5BV/h glass column of flowing through.After finishing, clean, dry with deionized water, get resin 5.42kg.
Get 200 milliliters of this resins and directly pack steel into, contain ammonia nitrogen amount 50ppm in the water of inflow except that in the ammonia nitrogen equipment, pH=10, water outlet contains ammonia nitrogen amount 9.4ppm.Flow velocity 3BV/h moved after 21 hours, and ammonia-nitrogen content surpasses 15ppm in the water outlet.
Embodiment 2:
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water; Be heated to 40 ℃; Under whipped state, add 10g lime carbonate, 20g Z 150PH and 0.15g calcium mahogany sulfonate respectively; Stir the back and add the oil phase that mixes by 3kg propylene, 1kg isoprene, 20g Diisopropyl azodicarboxylate, add glycerine 3.6kg again.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.04MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 100 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 2.67kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add the 10kg sulphur trioxide, be warming up to 110 ℃; Insulation 16h, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out, continues to drip pure water, so is operated in the still sulfuric acid concentration less than 5%; A large amount of pure water are washed till neutrality, and drying gets resin 4.24kg.
(3) metal-doped: the resin after the sulfonation is packed in the glass column of 20L, preparation 200L30%FeCl3 solution with the flow velocity of the 10BV/h glass column of flowing through, carries out metal-doped this FeCl3 solution.After finishing, clean, dry with deionized water, get resin 5.35kg.
Get 200 milliliters of this resins and directly pack steel into, contain ammonia nitrogen amount 106ppm in the water of inflow except that in the ammonia nitrogen equipment, pH=9.8, water outlet contains ammonia nitrogen amount 9.6ppm.Flow velocity 10BV/h moved after 15 hours, and ammonia-nitrogen content surpasses 15ppm in the water outlet.
Embodiment 3:
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water; Be heated to 40 ℃; Under whipped state, add 12g magnesiumcarbonate, 25g Xylo-Mucine and 0.18g calcium dodecylbenzene sulphonate respectively; Stir the back and add the oil phase that mixes by 3.6kg isopentene, 1.2kg Diethylene Glycol divinyl ether, 25g Sodium Persulfate, add yellow soda ash 4.8kg again.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.05MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 90 ℃, is incubated 9 hours, is warming up to 120 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 3.12kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, and adding 10kg mass concentration is 105% oleum, is warming up to 110 ℃; Insulation 16h, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out, continues to drip pure water, so is operated in the still sulfuric acid concentration less than 5%; A large amount of pure water are washed till neutrality, and drying gets resin 4.28kg.
(3) metal-doped: as the resin after the sulfonation to be packed in the glass column of 20L preparation 300L50%Zn (NO
3)
2Solution is with this Zn (NO
3)
2Solution carries out metal-doped with the flow velocity of the 15BV/h glass column of flowing through.After finishing, clean, dry with deionized water, get resin 5.57kg.
Get 200 milliliters of this resins and directly pack steel into, contain ammonia nitrogen amount 120ppm in the water of inflow except that in the ammonia nitrogen equipment, pH=10.2, water outlet contains ammonia nitrogen amount 9.8ppm.Flow velocity 20BV/h moved after 13 hours, and ammonia-nitrogen content surpasses 15ppm in the water outlet.
Embodiment 4:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 45 ℃; Under whipped state, add 10g magnesiumcarbonate, 20g gelatin and 0.15g methylene blue respectively; Stir the back and add the oil phase that mixes by 3kg vinyl toluene, 1kg kautschin, 20g Lucidol, add sal epsom 3.1kg again.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 100 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 2.51kg that granularity is 0.5-0.8mm.
(2) amination: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add 10kg methyl alcohol, temperature is controlled at 60 ℃, and stirring 4h adds 10 liters of entry again in still, and ammoniacal liquor 8kg stirs 1h, adds washing to neutral, and drying gets resin 4.16kg.
(3) metal-doped: as the resin after the sulfonation to be packed in the glass column of 20L preparation 200L40%TiCl
4Solution is with this TiCl
4Solution carries out metal-doped with the flow velocity of the 8BV/h glass column of flowing through.After finishing, clean, dry with deionized water, get resin 5.42kg.
Get 200 milliliters of this resins and directly pack steel into, contain ammonia nitrogen amount 200ppm in the water of inflow except that in the ammonia nitrogen equipment, pH=10.5, water outlet contains ammonia nitrogen amount 9.3ppm.Flow velocity 12BV/h moved after 12 hours, and ammonia-nitrogen content surpasses 15ppm in the water outlet.
Embodiment 5:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 50 ℃; Under whipped state, add 8g barium stearate, 22g ZX-I and 0.15g methylene blue respectively; Stir the back and add the oil phase that mixes by 4.5kg methylacrylic acid, 1.5kg alloocimene, 25g Lucidol, add gelatin 2.8kg again.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 120 ℃ again, insulation 22h, and filtration, washing, drying, screening obtain the Archon 3.32kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, and adding 10kg mass concentration is 105% oleum, is warming up to 120 ℃; Insulation 18h, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out, continues to drip pure water, so is operated in the still sulfuric acid concentration less than 5%; A large amount of pure water are washed till neutrality, and drying gets resin 4.21kg.
(3) metal-doped: as the resin after the sulfonation to be packed in the glass column of 20L preparation 500L55%VCl
2Solution is with this VCl
2Solution carries out metal-doped with the flow velocity of the 15BV/h glass column of flowing through.After finishing, clean, dry with deionized water, get resin 5.68kg.
Get 200 milliliters of this resins and directly pack steel into, contain ammonia nitrogen amount 260ppm in the water of inflow, pH=11, water outlet oleaginousness 9.6ppm except that in the ammonia nitrogen equipment.Flow velocity 25BV/h moved after 13 hours, and ammonia-nitrogen content surpasses 15ppm in the water outlet.
Can see through embodiment, use macromolecular material size of particles provided by the invention and can control that it is effective to remove ammonia nitrogen, can obtain the ammonium sulfate of high density in the regenerated liquid, can recycle.
More than metal-doped macromolecular material provided by the present invention and preparation method thereof and the application in removing ammonia nitrogen are being carried out detailed introduction.Used concrete example among this paper principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (20)
1. a metal-doped macromolecular material is characterized in that, by matrix polymer, be positioned at the hydrophilic radical on the matrix polymer and the transition metal ion that is doped on the matrix polymer constitutes;
Said matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized, and the quantity of C is 2～10 in the organic cpds of said containing-C=C-; Said containing-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-;
Said hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl;
Said transition metal ion is the ion of Ti, V, Cr, Fe, Cu, Ni or Zn.
2. macromolecular material according to claim 1; It is characterized in that; The organic cpds of said containing-C=C-be ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid; Methyl acrylate, methylacrylic acid, one or more in the TEB 3K.
3. macromolecular material according to claim 1 is characterized in that, said containing-C=C-... The organic cpds of-C=C-is a dibutene, limonene; Isoprene, two hexenes, dissident's diene, divinylbenzene; Kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene.
4. the preparation method of a metal-doped macromolecular material is characterized in that, may further comprise the steps:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-C=C-... The organic cpds of-C=C-and the oil phase of initiator mix, and add perforating agent, carry out suspension polymerization, process matrix polymer,
The weight ratio composition that said water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that said oil phase contains is to contain-organic cpds of C=C-: contain-C=C-... The organic cpds of-C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01; The weight ratio of oil phase and water is 1: 4～6, and the weight of said perforating agent accounts for 10%～20% of water and oil phase weight sum;
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a;
C, at room temperature is mixed with solution with the compound of transition metal, with the product of this solution stream through step b, carries out dynamically metal-doped.
5. preparation method according to claim 4 is characterized in that, suspension polymerization is specially each composition is added in the reaction kettle among the said a; In reaction kettle, feed pressurized air or nitrogen, make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle, be warming up to 70 ℃～90 ℃; Be incubated 2 hours～24 hours, be warming up to 100 ℃～150 ℃ again, be incubated 4 hours～36 hours; Washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
6. according to claim 4 or 5 described preparing methods; It is characterized in that; Dispersion agent among the said a is one or both in inorganic dispersant or the organic dispersing agent; Said inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and said organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.
7. according to claim 4 or 5 described preparing methods; It is characterized in that the dispersion aids among the said a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
8. according to claim 4 or 5 described preparing methods, it is characterized in that the initiator among the said a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd.
9. preparation method according to claim 8 is characterized in that, said initiator is peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
10. according to claim 4 or 5 described preparing methods, it is characterized in that the perforating agent among the said a is one or more in paraffin, sal epsom, yellow soda ash, gelatin or the glycerine.
11. preparation method according to claim 4 is characterized in that, amination described in the said b is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction.
12., it is characterized in that said aminating agent is a Trimethylamine 99 according to claim 4 or 11 described preparing methods.
13. preparation method according to claim 4 is characterized in that, sulphonating agent is sulphur trioxide, mass concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more among the said b.
14. preparation method according to claim 4 is characterized in that, the matrix polymer to step a among the said b carries out carrying out alkali cleaning again after the amination, and perhaps the matrix polymer to step a carries out carrying out pickling again after the sulfonation.
15. preparation method according to claim 4 is characterized in that, the mass and size percentage concentration of the solution that the compound of transition metal is mixed with among the said c is 10%～60%.
16. preparation method according to claim 4 is characterized in that, the solution that the compound of transition metal is mixed with among the said c carries out dynamically metal-doped with the flow through product of step b of the flow velocity of 5BV/h～30BV/h.
17., it is characterized in that the compound of said transition metal is nitrate salt, muriate or the vitriol of said transition metal according to claim 4,15 or 16 described preparing methods, said transition metal is Ti, V, Cr, Fe, u, Ni or Zn.
18. one kind is used each described metal-doped macromolecular material of claim 1 to 3 to containing the method for removing ammonia nitrogen of ammonia-nitrogen sewage, it is characterized in that, may further comprise the steps:
1., said metal-doped macromolecular material is packed in the container;
2., will contain ammonia-nitrogen sewage pH regulator to 9～12, make then to contain ammonia-nitrogen sewage through having filled the container of said metal-doped macromolecular material;
3., when the ammonia-nitrogen content of effusive sewage from container surpasses when requiring, make dilute stream of sulphuric acid through this container, said metal-doped macromolecular material is regenerated.
19. the method for removing ammonia nitrogen according to claim 18 is characterized in that, said 2. in, containing the temperature of ammonia-nitrogen sewage through said container is 10 ℃～80 ℃, institute tells that to contain the ammonia-nitrogen sewage flow velocity be 2BV/h～30BV/h.
20. the method for ammonia nitrogen according to claim 18 is characterized in that, the said 3. concentration of volume percent of middle dilute sulphuric acid is 5%～20%.
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| WO2015014091A1 (en) * | 2013-08-01 | 2015-02-05 | Yu Jie | New structure product, preparation method and use of styrenic resin |
| CN107349912A (en) * | 2017-08-10 | 2017-11-17 | 武汉科技大学 | A kind of carbon composite gelatin sponge and preparation method thereof |
| CN109012627A (en) * | 2018-08-03 | 2018-12-18 | 中国科学院上海应用物理研究所 | A kind of adsorbent material that improves is to the method and a metal ion species support type adsorbent material of uranyl ion adsorption efficiency |
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Cited By (4)
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| WO2015014091A1 (en) * | 2013-08-01 | 2015-02-05 | Yu Jie | New structure product, preparation method and use of styrenic resin |
| CN107349912A (en) * | 2017-08-10 | 2017-11-17 | 武汉科技大学 | A kind of carbon composite gelatin sponge and preparation method thereof |
| CN109012627A (en) * | 2018-08-03 | 2018-12-18 | 中国科学院上海应用物理研究所 | A kind of adsorbent material that improves is to the method and a metal ion species support type adsorbent material of uranyl ion adsorption efficiency |
| CN109012627B (en) * | 2018-08-03 | 2021-09-03 | 中国科学院上海应用物理研究所 | Method for improving adsorption efficiency of adsorption material on uranyl ions and metal ion loaded adsorption material |
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