WO2022135494A1 - 一种用于从水体中除磷的树脂、制备方法及其应用 - Google Patents

一种用于从水体中除磷的树脂、制备方法及其应用 Download PDF

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WO2022135494A1
WO2022135494A1 PCT/CN2021/140580 CN2021140580W WO2022135494A1 WO 2022135494 A1 WO2022135494 A1 WO 2022135494A1 CN 2021140580 W CN2021140580 W CN 2021140580W WO 2022135494 A1 WO2022135494 A1 WO 2022135494A1
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Prior art keywords
resin
water
water body
removing phosphorus
body according
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PCT/CN2021/140580
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English (en)
French (fr)
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刘恒
高文晋
李岁党
刘琼
寇晓康
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西安蓝晓科技新材料股份有限公司
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Priority to US18/044,321 priority Critical patent/US20230331591A1/en
Priority to EP21909489.3A priority patent/EP4190754A4/en
Priority to CA3187096A priority patent/CA3187096A1/en
Publication of WO2022135494A1 publication Critical patent/WO2022135494A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0207—Compounds of Sc, Y or Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28088—Pore-size distribution
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/07—Processes using organic exchangers in the weakly acidic form
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J47/14—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/06—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J49/60—Cleaning or rinsing ion-exchange beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/18—PO4-P
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

Definitions

  • the invention belongs to the field of functional macromolecules and the field of wastewater treatment, in particular, the application relates to a resin for removing phosphorus from water bodies.
  • Phosphorus-containing wastewater is one of the most seriously polluted typical industrial wastewaters.
  • the wastewater contains a large amount of phosphate, mainly from various industrial raw materials, agricultural raw materials, and detergents.
  • Phosphorus-containing wastewater will cause eutrophication of water bodies, and then lead to red tide phenomenon, which will make the water body abnormal, change its color, deteriorate the water quality, stink, and deteriorate the water body conditions, which is a danger signal of water body ecological damage.
  • red tide phenomenon which will make the water body abnormal, change its color, deteriorate the water quality, stink, and deteriorate the water body conditions, which is a danger signal of water body ecological damage.
  • the deterioration of water quality in rivers, lakes, oceans and other waters has become more and more serious.
  • the mass concentration of total phosphorus in the water body exceeds 20 mg/L, it can be considered that the water body is in eutrophication. Therefore, the effective treatment of phosphorus-containing wastewater is of great practical significance. Effective treatment
  • the typical treatment methods of phosphorus-containing wastewater are: coagulation sedimentation method, crystallization method, ion exchange adsorption method, electrodialysis, reverse osmosis and other processes.
  • phosphorus in wastewater is mainly removed by methods such as aluminum salts, lime, etc., which can form insoluble phosphate precipitates with phosphate radicals.
  • the method has low efficiency and large pollution, and the ion exchange adsorption method can solve this problem well.
  • the existing phosphorus removal ion exchange resin has the problems of low selectivity, slow adsorption and low adsorption capacity. .
  • This patent is mainly aimed at optimizing and innovating the ion exchange adsorption method.
  • the lanthanum oxygen bond is used to selectively adsorb phosphate, so as to improve the adsorption speed and adsorption capacity of the resin, and at the same time, it has a high degree of selectivity for phosphate.
  • my country's emission standards are becoming increasingly stringent, so phosphorus removal resin has broad application prospects.
  • lanthanum oxide has high selective adsorption to phosphorus through the coordination with phosphate, and the raw material of lanthanum is cheap.
  • lanthanum oxide powder is inconvenient to use in practical applications, and it is necessary to find a suitable carrier to facilitate the application.
  • Typical carriers are silica gel, molecular sieve, activated carbon, etc., and macroporous ion exchange resin is also a good carrier.
  • the present invention provides an ion exchange resin for removing phosphorus from a water body, which is easy to decompose with lye, and is convenient to use, low in cost, and does not produce two secondary pollution.
  • the present invention provides a lanthanum-loaded phosphorus removal resin.
  • the resin is characterized in that the resin particle size is 0.5-0.8 mm ; The apparent density is 0.68-0.74g/cm 3 ; the wet true density is 1.12-1.18g/cm 3 ; the water content of the resin is 43-57% (w/w); Selectively adsorb phosphate in water. It is easy to ion exchange with the phosphate in the system.
  • the preparation method of the phosphorus removal resin is as follows:
  • Step (1) prepare the monofunctional monomer, cross-linking agent, porogen, and initiator into oil phase, dispersant and water into water phase, prepare resin by suspension polymerization, and after polymerization is completed, the causative agent in resin is prepared.
  • the pore agent is removed to obtain resin-based balls;
  • Step (2) subjecting the resin-based balls to chlorination reaction and amination reaction, and adding alkali to the resin after the amination reaction to carry out hydrolysis reaction to obtain amine balls;
  • Step (3) the amine ball is reacted with organic weak acid to obtain weak acid cation resin
  • Step (4) loading the lanthanum compound on the surface of the weak acid cation resin to obtain a phosphorus removal resin.
  • the monofunctional monomer used in the step (1) can be one or more of styrene series, acrylic series and acrylonitrile series.
  • the crosslinking agent used in the step (1) can be one or more of divinylbenzene, diisocyanate, and N,N-methylenebisacrylamide.
  • the proportion of the cross-linking agent in the monomer ie the degree of cross-linking is 2-30% (W/W); more preferably 4-15% (W/W); more preferably 5-10% (W/W) .
  • the porogen in the step (1) can be one or more of toluene, isooctane, gasoline, aviation gasoline, n-heptane, cyclohexane, liquid paraffin, and white oil.
  • the initiator can be lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, One or more of potassium persulfate, sodium persulfate, ammonium persulfate azobisisobutyronitrile and azobisisoheptanenitrile.
  • the dispersing agent can be one or more of polyvinyl alcohol, gelatin, fatty acids, aliphatic amides, paraffins, and celluloses.
  • the ratio of the water phase to the oil is 10:1-1:1 (V/V).
  • the suspension polymerization temperature is 40-100°C
  • a gradient heating method is adopted, the first stage is 40-60°C, the second stage is 60-80°C, and the third stage is 80-100°C.
  • the reagent used in the chlorination reaction in the step (2) is chloromethyl ether.
  • the catalyst used in the chlorination reaction can be one or more of zinc chloride, aluminum chloride, ferric chloride, boron trifluoride, niobium pentachloride and trifluoromethanesulfonate.
  • the solvent used in the chlorination reaction can be one or more of methanol, ethanol, acetone, toluene, isopropanol, diethyl ether, and methylal.
  • the chlorination reaction temperature is 25-50°C, and the chlorination reaction time is 1-15h.
  • the temperature of the amination reaction is 50-120° C.
  • the reagents used in the amination reaction are phthalimide, ethylenediamine, hexamethyleneimine, dimethylamine, trimethylamine, hexane.
  • diamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine are one or more of diamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
  • the catalyst used during the hydrolysis reaction in the step (2) can be one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite, sulfuric acid, nitric acid, and hydrochloric acid, and the hydrolysis reaction temperature is 85 °C. -130°C.
  • the weak organic acid used for reacting with the amine ball can be one or more of chloroacetic acid, chloropropionic acid, dichloroacetic acid, phosphorous acid+formaldehyde, pyrophosphoric acid+formaldehyde, and the amine ball and the The temperature of the organic weak acid reaction is 40-90°C.
  • the catalyst for the reaction between the amine ball and the organic weak acid can be one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and sodium bisulfite.
  • the lanthanum compound used can be one or more of hydrates of lanthanum chloride, lanthanum nitrate, lanthanum sulfate, lanthanum phosphate and the above lanthanum compounds. kind.
  • the temperature at which the weak acid cation resin reacts with the lanthanum compound is 35-90°C.
  • the solvent used when the cation resin reacts with the lanthanum compound can be water, methanol, ethanol, formic acid, ethylene glycol, propylene glycol, glycerol, acetic acid, propionic acid, isopropanol, and water and the above reagents in any proportion. solvent.
  • the catalyst for the reaction between the weak acid cation resin and the lanthanum compound can be one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bisulfite and ammonia water.
  • the reaction time of the weak acid cation resin and the lanthanum compound is 1-30h .
  • the macroporous ion exchange resin prepared by the invention can selectively adsorb phosphate, hydrogen phosphate and dihydrogen phosphate in the water body, and can be regenerated, and hardly adsorb other anions. In practical application, it is more economical and efficient than traditional disposable phosphorus adsorbents, and produces less secondary pollution.
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After the polymerization was completed, boiled at 95 °C for 1.5 h to remove toluene and washed to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 19.4 m 2 /g, a median pore diameter of 8.6 nm, and a wet apparent density of 0.718 g/cm 3 ; wet true density is 1.15 g/cm 3 ; resin moisture content is 47.9% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve to form water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C.
  • the toluene was removed by boiling at 95°C for 1.5 h, and the resin-based balls were obtained by washing.
  • phosphorus removal resin Take 50g weak acid cation resin, add 15g lanthanum chloride hexahydrate, add 300ml 25% (w/w) ethanol solution, stir at room temperature for 2h, slowly add 200ml 1mol/L sodium hydroxide solution dropwise, until the pH of the system reaches 13,60 °C Stir for 6h to obtain a phosphorus removal resin; the prepared phosphorus removal resin has a particle size of 0.5-0.8mm, a porous structure, a specific surface area of 17.9m 2 /g, and a median pore diameter of 8.2nm; the wet apparent density is 0.721g/cm 3 ; wet true density is 1.19 g/cm 3 ; resin moisture content is 46.3% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g hydroxymethyl cellulose in the water and stir and dissolve to become water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After boiling at 95°C for 1.5 h, removing toluene and washing to obtain resin-based balls.
  • phosphorus removal resin Take 50g weak acid cation resin, add 15g lanthanum chloride hexahydrate, add 300ml 25% (w/w) ethanol solution, stir at room temperature for 2h, slowly add 200ml 1mol/L sodium hydroxide solution dropwise, until the pH of the system reaches 13,60 °C Stirring for 6h to obtain a phosphorus removal resin; the prepared phosphorus removal resin has a particle size of 0.5-0.8mm, a porous structure, a specific surface area of 17.9m 2 /g, and a median pore diameter of 7.2nm; wet apparent density is 0.731g/cm 3 ; wet true density is 1.21g/cm 3 ; resin moisture content is 48.5%.
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After boiling at 95°C for 1.5 h, removing toluene and washing to obtain resin-based balls.
  • phosphorus removal resin Take 50g weak acid cation resin, add 15g lanthanum chloride hexahydrate, add 300ml 25% (w/w) ethanol solution, stir at room temperature for 2h, slowly add 200ml 1mol/L sodium hydroxide solution dropwise, until the pH of the system reaches 13,60 °C Stirring for 6h to obtain a phosphorus removal resin; the prepared phosphorus removal resin has a particle size of 0.5-0.8mm, a porous structure, a specific surface area of 17.9m 2 /g, and a median pore diameter of 6.9nm; wet apparent density is 0.722g/cm 3 ; wet true density is 1.14 g/cm 3 ; resin moisture content is 48.3% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After boiling at 95°C for 1.5 h, removing toluene and washing to obtain resin-based balls.
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After boiling at 95°C for 1.5 h, removing toluene and washing to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 15.6 m 2 /g, a median pore diameter of 10.5 nm, and a wet apparent density of 0.724 g/cm 3 ; wet true density is 1.23 g/cm 3 ; resin water content is 47.2% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After boiling at 95°C for 1.5 h, removing toluene and washing to obtain resin-based balls.
  • phosphorus removal resin Take 50g weak acid cation resin, add 15g lanthanum chloride hexahydrate, add 300ml 25% (w/w) ethanol solution, stir at room temperature for 2h, slowly add 200ml 1mol/L sodium hydroxide solution dropwise, until the pH of the system reaches 13,60 °C Stir for 6h to obtain a phosphorus removal resin; the prepared phosphorus removal resin has a particle size of 0.5-0.8mm, a porous structure, a specific surface area of 19.1m 2 /g, and a median pore diameter of 8.2nm; the wet apparent density is 0.724g/cm 3 ; wet true density is 1.17 g/cm 3 ; resin moisture content is 46.8% (w/w).
  • 20g 55% (w/w) divinylbenzene, 80g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve to become water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 40°C, 2 hours at 60°C, and 2 hours at 75°C. After the polymerization was completed, boiled at 95 °C for 1.5 h to remove toluene and washed to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 17.5 m 2 /g, a median pore diameter of 9.2 nm, and a wet apparent density of 0.723 g/cm 3 ; wet true density is 1.13 g/cm 3 ; resin moisture content is 48.2% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 70°C, and 2 hours at 85°C. After the polymerization was completed, boiled at 95 °C for 1.5 h to remove toluene and washed to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, has a porous structure, a specific surface area of 18.4 m 2 /g, a median pore diameter of 7.5 nm; a wet apparent density of 0.724 g/cm 3 ; The density was 1.11 g/cm 3 ; the resin moisture content was 47.2% (w/w).
  • 30g 55% (w/w) divinylbenzene, 70g styrene, 70g toluene, 1g BPO are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g polyvinyl alcohol and 1g gelatin in the water and stir and dissolve into water box.
  • the oil phase was added to the kettle, and under stirring, the temperature was kept at 50°C for 2 hours, at 70°C for 2 hours, and at 85°C for 2 hours. After the polymerization was completed, boiled at 95 °C for 1.5 h to remove toluene and washed to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 19.4 m 2 /g, a median pore diameter of 8.6 nm, and a wet apparent density of 0.718 g/cm 3 ; wet true density is 1.15g/cm 3 ; resin moisture content is 47.9%.
  • 30g 55% (w/w) divinylbenzene, 70g acrylonitrile, 70g isooctane, 1g cumene hydroperoxide are prepared as oil phase, add 500ml water in 1L reactor, add 0.5g carboxymethyl in the water Base cellulose and stir to dissolve into water phase.
  • the oil phase was added to the kettle, and the mixture was stirred for 2 hours at 50°C, 2 hours at 65°C, and 2 hours at 80°C. After the polymerization was completed, boiled at 95°C for 1.5 h to remove isooctane and washed to obtain resin-based balls.
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 17.8 m 2 /g, a median pore diameter of 8.2 nm, and a wet apparent density of 0.727 g/cm 3 ; wet true density is 1.18 g/cm 3 ; resin moisture content is 46.5% (w/w).
  • the prepared phosphorus removal resin has a particle size of 0.5-0.8 mm, a porous structure, a specific surface area of 16.3 m 2 /g, a median pore diameter of 7.7 nm; a wet apparent density of 0.734 g/cm 3 ; The density was 1.11 g/cm 3 ; the resin moisture content was 44.7% (w/w).

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Abstract

一种用于从水体中除磷树脂及其制备方法和应用，该树脂粒径为0.5-0.8mm；具有多孔结构，比表面积为8-25m 2/g，孔径分布为3-15nm；湿视密度为0.68-0.74g/cm 3；湿真密度为1.12-1.18g/cm 3；树脂含水量以重量百分数计为43-57％。树脂上负载有镧氧键的官能团使其能够选择性吸附水体中的磷酸根。该树脂采用弱酸阳树脂负载镧的方式，利用镧氧键对磷酸根的高选择性，能够选择性去除水体中磷，并且易解析，合成成本低，可以重复利用。能够有效去除富营养化的水和废水中的磷，水体中磷酸根含量可控制在20ppm之内，降低了水体除磷的成本，相较于传统的一次性磷吸附剂具有很大优势。

Description

一种用于从水体中除磷的树脂、制备方法及其应用 技术领域
本发明属于功能高分子领域和废水处理领域，具体地，本申请涉及一种用于从水体中除磷的树脂。
背景技术
含磷废水是污染极为严重的典型工业废水之一，其废水中含有大量磷酸盐，主要来自于各种工业原料、农业原料、洗涤剂，一旦处理不当而排入河道将严重污染自然环境。含磷废水会引发水体的富营养化，随即引发赤潮现象，使水体异常，颜色改变，水质变坏，发臭，恶化了水体条件，是水体生态破坏的一种危险信号。近年来，河流、湖泊、海洋等水域的水质恶化现象越来越严重。一般来讲，水体中总磷质量浓度超过20mg/L，即可认为水体处于富营养化。因此，对含磷废水进行有效处理的现实意义巨大。运用针对性的工艺对含磷废水进行有效处理，使其能达到排放标准，是当下环保重视的课题。
含磷废水的典型处理方法有：混凝沉淀法、结晶法、离子交换吸附法、电渗析、反渗透等工艺。目前主要利用铝盐、石灰等能与磷酸根生成难溶磷酸盐沉淀物的方法去除废水中的磷。但是在较低浓度的含磷废水中，该方法效率低、污染大，而离子交换吸附法可以很好地解决这个问题。但现有的除磷离子交换树脂存在选择性较低，吸附较慢，吸附量较低的问题。。本专利主要针对离子交换吸附法进行优化创新，采用镧氧键选择性吸附磷酸根，以此提高树脂的吸附速度和吸附量，同时对磷酸根具有高度选择性。随着我国工业的快速发展，我国的排放标准也日益严苛，因此除磷树脂有广阔的应用前景。
发明内容
通过研究发现，氧化镧通过与磷酸根的配位作用，对磷具有高度选择吸附性，且镧原料价格低廉。但是氧化镧粉体在实际应用中使用不便，需要找到合适的载体以便于实施应用。典型的载体有硅胶、分子筛、活性炭等，同时大孔离子交换树脂也是良好的载体。
针对现有技术的不足，本发明提供了一种用于从水体中除磷的离子交换树脂，并且用碱液易解析，相比现有的除磷技术，使用方便，成本低，不产生二次污染。
本发明提出了一种负载镧的除磷树脂，该树脂的特征是：树脂粒径为0.5-0.8mm；具 有多孔结构，比表面积为8-25m 2/g，孔径分布为3-15nm；湿视密度为0.68-0.74g/cm 3；湿真密度为1.12-1.18g/cm 3；树脂含水量为43-57％(w/w)；树脂上负载有镧氧键合的官能团使其能够选择性吸附水体中的磷酸根。易与体系中的磷酸根发生离子交换。所述除磷树脂制备方法如下：
步骤(1)：将单官能团单体、交联剂、致孔剂、引发剂配制成油相，分散剂和水配制成水相，采用悬浮聚合法制备树脂，聚合完成后将树脂中的致孔剂除去，得到树脂基球；
步骤(2)：将树脂基球进行氯化反应、胺化反应，将胺化反应后的树脂加碱进行水解反应得到胺球；
步骤(3)：胺球与有机弱酸进行反应，得到弱酸阳树脂；
步骤(4)：将镧化合物负载到弱酸阳树脂表面，得到除磷树脂。
更进一步地，所述步骤(1)用的单官能团单体可以是苯乙烯系、丙烯酸系列、丙烯腈系中的一种或几种。
所述步骤(1)用的交联剂可以是二乙烯基苯、二异氰酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种。交联剂占单体的比例(即交联度)为2-30％(W/W)；较优选为4-15％(W/W)；更优选为5-10％(W/W)。
所述步骤(1)中致孔剂可以是甲苯、异辛烷、汽油、航空汽油、正庚烷、环己烷、液体石蜡、白油中的一种或几种。
所述步骤(1)中引发剂可以是过氧化月桂酰、过氧化苯甲酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠、过硫酸铵偶氮二异丁腈、偶氮二异庚腈中的一种或几种。
所述步骤(1)中分散剂可以是聚乙烯醇、明胶、脂肪酸类、脂肪族酰胺类、石蜡类、纤维素类中的一种或几种。
所述步骤(1)中，水相和油相比为10:1-1:1(V/V)。
所述步骤(1)中，悬浮聚合温度为40-100℃，采用梯度升温的办法，第一阶段为40-60℃，第二阶段为60-80℃，第三阶段为80-100℃。
所述步骤(2)中氯化反应时使用的试剂为氯甲醚。氯化反应时使用的催化剂可以是氯化锌、氯化铝、氯化铁、三氟化硼、五氯化铌和三氟甲磺酸盐中的一种或几种。氯化反应时使用的溶剂可以是甲醇、乙醇、丙酮、甲苯、异丙醇、乙醚、甲缩醛中的一种或几种。 氯化反应温度为25-50℃，氯化反应时间为1-15h。
所述步骤(2)中胺化反应温度为50-120℃，胺化反应使用试剂为邻苯二甲酰亚胺、乙二胺、六次甲基亚胺、二甲胺、三甲胺、己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或几种。
所述步骤(2)中水解反应时使用的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、硫酸、硝酸、盐酸中的一种或几种，水解反应温度为85-130℃。
所述步骤(3)中，用于与胺球反应的有机弱酸可以是氯乙酸、氯丙酸、二氯乙酸、亚磷酸+甲醛、焦磷酸+甲醛中的一种或几种，胺球与有机弱酸反应的温度为40-90℃。胺球与有机弱酸反应的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠中的一种或几种。
所述步骤(4)中，在弱酸阳树脂基体上负载镧化合物时，使用的镧化合物可以是氯化镧、硝酸镧、硫酸镧、磷酸镧及以上镧化合物的水合物中的一种或几种。弱酸阳树脂与镧化合物反应的温度为35-90℃。阳树脂与镧化合物反应时使用的溶剂可以是水、甲醇、乙醇、甲酸、乙二醇、丙二醇、丙三醇、乙酸、丙酸、异丙醇、以及水与以上试剂任意比例互溶配成的溶剂。弱酸阳树脂与镧化合物反应的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、氨水中的一种或几种，弱酸阳树脂与镧化合物反应的时间为1-30h。
本发明制备的大孔离子交换树脂，能选择性地吸附水体中的磷酸根、磷酸氢根、磷酸二氢根，并且可再生，几乎不吸附其他阴离子。实际应用中比传统一次性磷吸附剂更经济高效，产生的二次污染更小。
具体实施方式
为了说明本发明的效果，列举实施例对本发明作进一步详细说明，但本发明并不仅限于这些实施例。
实施例1
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。聚合完成后，95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为19.4m 2/g，孔径中值为8.6nm；湿视密度为0.718g/cm 3；湿真密度为1.15g/cm 3；树脂含水量为47.9％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为7ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为85％。
实施例2
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解形成水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯，洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入10g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃下搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为18.7m 2/g， 孔径中值为7.6nm；湿视密度为0.723g/cm 3；湿真密度为1.14g/cm 3；树脂含水量为45.8％(w/w)。
取5ml除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，吸附50ml后，吸附贫液中磷含量为14ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为82％。
实施例3
将20g 55％(w/w)的二乙烯苯、80g苯乙烯、50g甲苯、1.2g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下60℃保温2h，80℃保温2h，95℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.9m 2/g，孔径中值为8.2nm；湿视密度为0.721g/cm 3；湿真密度为1.19g/cm 3；树脂含水量为46.3％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为21ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为84％。
实施例4
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g羟甲基纤维素并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，丙酮100g，加入1g氯化铁作催化剂，在38℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.9m 2/g，孔径中值为7.2nm；湿视密度为0.731g/cm 3；湿真密度为1.21g/cm 3；树脂含水量为48.5％。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为17ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为81％。
实施例5
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，90℃下胺化8h，然后加入8％(w/w)氢氧化钾15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入15g氯乙酸，缓慢加入40g 20％(w/w)氢氧化钠溶液，60℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.9m 2/g，孔径中值为6.9nm；湿视密度为0.722g/cm 3；湿真密度为1.14g/cm 3；树脂含水量为48.3％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为16ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为83％。
实施例6
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g硝酸镧，加入300ml 25％(w/w)异丙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.7m 2/g，孔径中值为7.5nm；湿视密度为0.716g/cm 3；湿真密度为1.19g/cm 3；树脂含水量为44.8％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为16ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液， 解析5BV，水洗2BV，解析率为83％。
实施例7
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钾溶液，直到体系pH达到11，50℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为15.6m 2/g，孔径中值为10.5nm；湿视密度为0.724g/cm 3；湿真密度为1.23g/cm 3；树脂含水量为47.2％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为31ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为82％。
实施例8
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃ 下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h,得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为19.1m 2/g，孔径中值为8.2nm；湿视密度为0.724g/cm 3；湿真密度为1.17g/cm 3；树脂含水量为46.8％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至6左右。以5BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为31ppm，停止吸附，水洗2BV，配制6％(w/w)的氢氧化钾+5％(w/w)的碳酸钠溶液，解析5BV，水洗2BV，解析率为81％。
实施例9
将20g 55％(w/w)的二乙烯苯、80g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下40℃保温2h，60℃保温2h，75℃保温2h。聚合完成后，95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.5m 2/g，孔径中值为9.2nm；湿视密度为0.723g/cm 3；湿真密度为1.13g/cm 3；树脂含水量为48.2％ (w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为17ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为81％。
实施例10
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。聚合完成后，95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入25g磷酸镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为18.4m 2/g，孔径中值为7.5nm；湿视密度为0.724g/cm 3；湿真密度为1.11g/cm 3；树脂含水量为47.2％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右。以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为13ppm，停止吸附，水洗2BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硫酸钠溶液，解析5BV，水洗2BV，解析率为85％。
实施例11
将30g 55％(w/w)的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相。将油相 加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h。聚合完成后，95℃下水煮1.5h除去甲苯洗涤得到树脂基球。
称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％(w/w)氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为19.4m 2/g，孔径中值为8.6nm；湿视密度为0.718g/cm 3；湿真密度为1.15g/cm 3；树脂含水量为47.9％。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为32ppm，停止吸附，水洗4BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硝酸钠溶液，解析10BV，水洗4BV，解析率为82％。
实施例12
将30g 55％(w/w)的二乙烯苯、70g丙烯腈、70g异辛烷、1g异丙苯过氧化氢配制为油相，在1L反应釜中加入500ml水，水中加入0.5g羧甲基纤维素并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，65℃保温2h，80℃保温2h。聚合完成后，95℃下水煮1.5h除去异辛烷洗涤得到树脂基球。
向50g树脂中加入六次甲基亚胺15g，80℃下胺化10h；取50g胺球加入18g氯丙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g六水氯化镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为17.8m 2/g，孔径中值为8.2nm；湿视密度为0.727g/cm 3；湿真密度为1.18g/cm 3；树脂含水量为46.5％ (w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为31ppm，停止吸附，水洗4BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硝酸钠溶液，解析10BV，水洗4BV，解析率为79％。
实施例13
将12g的N,N-亚甲基双丙烯酰胺、70g丙烯腈、70g航空汽油、1g过氧化二异丙苯配制为油相，在1L反应釜中加入500ml水，水中加入0.5g羟乙基纤维素并搅拌溶解成为水相。将油相加入釜中，搅拌下50℃保温2h，75℃保温2h，90℃保温2h。聚合完成后，95℃下水煮1.5h除去航空汽油洗涤得到树脂基球。
向50g树脂中加入三乙烯四胺15g，95℃下胺化10h；取50g胺球加入18g二氯乙酸，缓慢加入50g 20％(w/w)氢氧化钠溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
取50g弱酸阳树脂加入15g硝酸镧，加入300ml 25％(w/w)乙醇溶液，室温下搅拌2h，缓慢滴加200ml 1mol/L氢氧化钠溶液，直到体系pH达到13，60℃搅拌6h，得到除磷树脂；制备的除磷树脂粒径为0.5-0.8mm，具有多孔结构，比表面积为16.3m 2/g，孔径中值为7.7nm；湿视密度为0.734g/cm 3；湿真密度为1.11g/cm 3；树脂含水量为44.7％(w/w)。
取5ml上述除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L硫酸溶液将正磷酸钠溶液pH调至8左右。以6BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为38ppm，停止吸附，水洗4BV，配制8％(w/w)的氢氧化钠+5％(w/w)的硝酸钠溶液，解析10BV，水洗4BV，解析率为81％。

Claims (38)

  1. 一种用于从水体中除磷的树脂，其特征在于，树脂粒径为0.5-0.8mm；具有多孔结构，比表面积为8-25m 2/g，孔径分布为3-15nm；湿视密度为0.68-0.74g/cm 3；湿真密度为1.12-1.18g/cm 3；树脂含水量以重量百分数计为43-57％；树脂上负载有镧氧键的官能团使其能够选择性吸附水体中的磷酸根。
  2. 根据权利要求1所述的用于从水体中除磷的树脂，其特征在于，比表面积为12-20m 2/g，孔径中值为5-10nm；湿视密度为0.70-0.74g/cm 3；湿真密度为1.13-1.17g/cm 3；树脂含水量以重量百分数计为46-55％。
  3. 根据权利要求1所述的用于从水体中除磷的树脂，其特征在于，比表面积为19.4m 2/g，孔径中值为8.6nm；湿视密度为0.718g/cm 3；湿真密度为1.15g/cm 3；树脂含水量以重量百分数计为47.9％。
  4. 根据权利要求1所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，包括如下步骤：
    步骤(1)：将单官能团单体、交联剂、致孔剂、引发剂配制成油相，分散剂和水配制成水相，采用悬浮聚合法制备树脂，聚合完成后将树脂中的致孔剂除去，得到树脂基球；
    步骤(2)：将树脂基球进行氯化反应、胺化反应，将胺化反应后的树脂加碱进行水解反应得到胺球；
    步骤(3)：胺球与有机弱酸进行反应，得到弱酸阳树脂；
    步骤(4)：将镧化合物负载到弱酸阳树脂表面，得到除磷树脂。
  5. 根据权利要求4所述的用于从水体中除磷的树脂的制备方法，其特征在于，步骤(1)中用的单官能团单体可以是苯乙烯系、丙烯酸系列、丙烯腈系中的一种或几种。
  6. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)用的交联剂可以是二乙烯基苯、二异氰酸酯、N,N-亚甲基双丙烯酰胺中的一种或几种。
  7. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)中致孔剂可以是甲苯、异辛烷、汽油、航空汽油、正庚烷、环己烷、液体石蜡、白油中的一种或几种。
  8. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)中引发剂可以是过氧化月桂酰、过氧化苯甲酰、异丙苯过氧化氢、叔丁基过氧 化氢、过氧化二叔丁基、过氧化二异丙苯、过硫酸钾、过硫酸钠、过硫酸铵偶氮二异丁腈、偶氮二异庚腈中的一种或几种。
  9. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)中分散剂可以是聚乙烯醇、明胶、脂肪酸类、脂肪族酰胺类、石蜡类、纤维素类中的一种或几种。
  10. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)中，水相和油相比为10:1-1:1V/V。
  11. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(1)中，悬浮聚合温度为40-100℃，采用梯度升温的办法，第一阶段为40-60℃，第二阶段为60-80℃，第三阶段为80-100℃。
  12. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中氯化反应时使用的试剂为氯甲醚。
  13. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中氯化反应时使用的催化剂可以是氯化锌、氯化铝、氯化铁、三氟化硼、五氯化铌和三氟甲磺酸盐中的一种或几种。
  14. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中氯化反应时使用的溶剂可以是甲醇、乙醇、丙酮、甲苯、异丙醇、乙醚、甲缩醛中的一种或几种。
  15. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)氯化反应温度为25-50℃，氯化反应时间为1-15h。
  16. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中胺化反应温度为50-120℃。
  17. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中胺化反应使用试剂为邻苯二甲酰亚胺、乙二胺、六次甲基亚胺、二甲胺、三甲胺、己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或几种。
  18. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中水解反应时使用的催化剂可以是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、硫酸、硝酸、盐酸中的一种或几种。
  19. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(2)中水解反应温度为85-130℃。
  20. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(3)中，用于与胺球反应的有机弱酸可以是氯乙酸、氯丙酸、二氯乙酸、亚磷酸+甲醛、焦磷酸+甲醛中的一种或几种。
  21. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(3)中，胺球与有机弱酸反应的温度为40-90℃。
  22. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，所述步骤(3)中，胺球与有机弱酸反应的催化剂是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠中的一种或几种。
  23. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，其特征在于，步骤(1)中交联剂占单体的比例即交联度为2-30％W/W。
  24. 根据权利要求23所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，交联剂占单体的比例为4-15％W/W。
  25. 根据权利要求24所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，交联剂占单体的比例为5-10％W/W。
  26. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，步骤(4)中使用的镧化合物可以是氯化镧、硝酸镧、硫酸镧、磷酸镧及以上镧化合物的水合物中的一种或多种的混合物。
  27. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，步骤(4)中弱酸阳树脂与镧化合物反应的温度为15-90℃。
  28. 根据权利要求27所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，弱酸阳树脂与镧化合物反应的温度为35-90℃。
  29. 根据权利要求28所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，弱酸阳树脂与镧化合物反应的温度为50-70℃。
  30. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，步骤(4)中弱酸阳树脂与镧化合物反应的溶剂是水、甲醇、乙醇、甲酸、乙二醇、丙二醇、丙三醇、乙酸、丙酸、异丙醇中的一种或几种的混合物，以及水与以上试剂任意比例互溶 配成的溶剂。
  31. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，步骤(4)中弱酸阳树脂与镧化合物反应的催化剂是氢氧化钠、氢氧化钾、氢氧化钙、亚硫酸氢钠、氨水中的一种或几种。
  32. 根据权利要求4所述的一种用于从水体中除磷的树脂的制备方法，其特征在于，步骤(4)中弱酸阳树脂与镧化合物反应的时间为1-30h。
  33. 根据权利要求4所述的一种用于从水体除磷的树脂，其特征在于，制备步骤过程如下：
    将30g 55％w/w的二乙烯苯、70g苯乙烯、70g甲苯、1g BPO配制为油相，在1L反应釜中加入500ml水，水中加入0.5g聚乙烯醇和1g明胶并搅拌溶解成为水相，将油相加入釜中，搅拌下50℃保温2h，70℃保温2h，85℃保温2h，聚合完成后，95℃下水煮1.5h除去甲苯洗涤得到树脂基球；
    称量50g树脂基球，加入氯甲醚12g，甲缩醛100g，加入1g氯化锌作催化剂，在42℃下搅拌并保温12小时，然后水洗即得到氯化后的树脂；向氯化后的树脂中加入邻苯二甲酰亚胺15g，80℃下胺化10h，然后加入10％氢氧化钠15g，160℃下水解2h，水洗后得到胺球；取50g胺球加入18g氯乙酸，缓慢加入50g 20％氢氧化钠w/w溶液，50℃下反应10h，水洗至中性即得到弱酸阳树脂。
  34. 根据权利要求1-3中任一所述的一种用于从水体除磷的树脂以及权利要求4-33中任一所述的制备方法制备得到的从水体中除磷的树脂的应用方法，其特征在于，从水体中除磷的应用方法按照以下步骤进行：取一定量的树脂装柱，将含磷酸根的溶液以一定的流速过柱，当出口溶液中磷酸根浓度大于阈值时，停止吸附，使用解析剂解析，然后水洗树脂即可进行下一周期的吸附，水体中磷的残留率在20ppm以下。
  35. 根据权利要求35所述的一种从水体除磷的树脂的应用方法，其特征在于，从水体除磷的应用方法按照以下步骤进行：取一定量的树脂装柱，将含磷酸根的溶液以1-10BV/h的流速过柱，吸附5-15BV后，当出口溶液中磷酸根浓度大于20ppm时停止吸附，水洗，使用解析剂解析，解析1-15BV后，使用2BV的去离子水清洗树脂即可再次使用。
  36. 根据权利要求35所述的一种从水体除磷的树脂的应用方法，其特征在于，解析剂可以是1-15％w/w的氢氧化钠溶液，1-15％w/w的硫酸钠溶液，1-15％w/w的碳酸钠溶液或1-15％w/w的硝酸铵溶液中的一种或几种的混合物。
  37. 根据权利要求35所述的一种从水体除磷的树脂的应用方法，其特征在于，包括如下步骤：取5ml除磷树脂装柱，配制400ppm的正磷酸钠溶液，并用0.5mol/L盐酸溶液将正磷酸钠溶液pH调至4左右；以3BV/h的速度过柱，过柱吸附50ml后，吸附贫液中磷含量为7ppm，停止吸附，水洗2BV，配制8％的氢氧化钠+5％的硫酸钠溶液，解析5BV，水洗2BV。
  38. 根据权利要求35所述的一种从水体除磷的树脂的应用方法，其特征在于，其特征在于，水体中磷酸根含量可控制在20ppm之内。
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