Organic-pollution-resistant ion exchange resin and preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-10919786-B2
Application number	US-201414914547-A
Country	US
Kind code	B2
Filing date	Aug 27, 2014
Priority date	Aug 30, 2013
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

Implementations herein relate to a method for preparing organic-pollution-resistant ion exchange resins and application thereof. The method includes adding modified inorganic particles to prepare novel ion exchange resins containing inorganic particles modified by a parcel modifier. A weight ratio between the monomer of the ion exchange resins and the modified inorganic particles is about 0.1% to 30%. The method may increase moisture content of the resins 3 to 30% such as to improve the structures of the resins, and therefore increase the regeneration efficiency 0.4 to 70%, as compared to conventions resins. The method improves resistance of resins to organic pollution, increases regeneration efficiency, and extends service life of the resins. In the process of water treatment, the ion exchange resin of the implementations may be regenerated with long-term stability. In addition to securing the water treatment efficiency, the method may avoid frequent replacement operations and lower the costs.

First claim

What is claimed is:

1. A method for preparing organic-pollution-resistant ion exchange resins, the method comprising:
(1) mixing a monomer, a crosslinking agent, and an initiator to obtain an oil phase, wherein a weight ratio between the monomer and the crosslinking agent is about 1:0.02 to 0.45, a weight ratio between the monomer and the initiator is about 1:0.003 to 0.15, and the monomer includes at least one of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, acrylonitrile, glycidyl methacrylate, styrene, p-chlorostyrene, divinylbenzene, nitrostyrene, dichloro styrene, methyl styrene polychloroprene, methyl cellulose, carboxymethyl cellulose, sodium alginate, chitosan or derivatives thereof;
(2) adding 0.2 to 3% by weight of a dispersant to a water phase, wherein a weight ratio between the water phase and the oil phase is about 1:0.4 to 1, and the dispersant includes at least one of polyvinyl alcohol, gelatin, starch, methyl cellulose and derivatives thereof, calcium carbonate, calcium phosphate, talc, diatomaceous earth, bentonite, salt, or silicate;
(3) adding inorganic particles to a methanol solution to obtain a mixture, stirring the mixture at 20° C. to 90° C. with 30 to 250 rpm for 0.5 h to 4 h, adding a modifier to the mixture and stirring the mixture for 0.5 h to 10 h, and drying the mixture to obtain modified inorganic particles, wherein a weight ratio between the inorganic particles and the methanol solution is about 1:3 to 10, and a weight ratio between the modifier and the inorganic particles is about 1:0.05 to 5; wherein the inorganic particles are selected from at least one kaolin, titanium dioxide, clay, talc, montmorillonite, calcium carbonate, iron, TiO 2 , WO 3 , Fe 3 O 4 , SiO 2 , ZrO 2 , CuO, Al 2 O 3 , or ZnO, and sizes of the inorganic particles are about 5 nm to 5000 nm;
(4) adding the modified inorganic particles to the water phase, or the oil phase, wherein a weight ratio between the modified inorganic particles and the monomer is about 0.1% to 30%; wherein as compared to ion exchange resins without the modified inorganic particles, moisture content of the ion exchange resins containing the modified inorganic particles increases 3% to 30%, and after regenerated about 50 times, regeneration efficiency of the ion exchange resins containing the modified inorganic particles increases 1% to 50% with respect to removal of humic acid in biochemical tailwater; and
(5) adding the oil phase to the stirred water phase for polymerization, by keeping stirring at a speed of 100 to 1500 rpm, keeping the temperature at 50 to 80° C., with a polymerization duration of 2 to 8 hours; afterwards, raising the temperature to 75 to 95° C. and keeping the temperature for about 1 to 15 hours; afterwards, cooling the products, separating resins from the polymerization reaction suspension, and drying the resins after extraction or washing; wherein the order of the steps (1), (2), and (3) are flexible, and the step 4 is performed after the steps (1), (2), and (3), and prior to step 5.

2. The method of claim 1 , wherein the modifier includes at least one of γ-chloropropyl trichlorosilane, γ-chloropropyl trimethoxy silane, γ-chloropropyl triethoxysilane, γ-chloropropyl methyl dimethoxy silane, γ-aminopropyl triethoxysilane, γ-(methacryloxypropyl) trimethoxysilane, γ-glycidyl propyl trimethoxy silane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, γ-ureido propyl triethoxy silane, γ-(3,2-epoxypropoxy) methyl trimethoxysilane, γ-(ethylenediamine) aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxy silane, vinyltriethoxysilane, vinyltrimethoxysilane, bis-[3-(triethoxysilyl) silylpropyl] tetrasulfide, diethylenetriaminepentaacetic aminopropyl trimethoxysilane, γ-ethylene amino triethoxysilane, A-(ethylenediamine-yl) methyl triethoxysilane, methyl triethoxysilane aniline, aniline methyl trimethoxysilane, bis (3-triethoxysilylpropyl silyl propyl) tetrasulfide carbon, cyclohexyl methyl dimethoxysilane, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl dioleate acyloxy group (acyloxy dioctyl phosphate) titanate, mono alkoxylated unsaturated fatty acid titanate, bis (dioctyl pyrophosphate group) ethylene titanate triethanolamine esters and chelates, pyrophosphate type monoalkoxy titanate type, a phosphoric acid compound class monoalkoxy titanates, alkanolamine titanate, di (octyl phenol ethoxylates) phosphate ester, tetraisopropyl bis (octyl acid phosphate group) titanate, polyester hyperdispersant, fatty alcohol ethoxylates, or cetyl trimethyl ammonium chloride.

3. An organic-pollution-resistant ion exchange resins comprising the ion exchange resins prepared in claim 1 .

4. A method for using the organic-pollution-resistant ion exchange resins containing the modified inorganic particles prepared using the method of claim 1 , comprising:
treating biochemical tailwater of municipal wastewater using the resins of claim 1 , wherein, as compared to ion exchange resins without the modified inorganic particles:
regeneration efficiency of the resins with respect to removal of tannic acid in the biochemical tailwater increases 0.6% to 39%;
regeneration efficiency of the resins removing UV 254 of the biochemical tailwater increases 1% to 40%; and
regeneration efficiency of the resins with respect to removal of SUVA of the biochemical tailwater increases 0.8% to 46%.

5. A method for using organic-pollution-resistant ion exchange resins containing the modified inorganic particles prepared in claim 1 , the method comprising:
treating biochemical tailwater of dyeing wastewater using the resins, wherein, as compared to ion exchange resins without the modified inorganic particles:
regeneration efficiency of the resins with respect to removal of UV 254 in the biochemical tailwater increases 1% to 40%;
regeneration efficiency of the resins with respect to removal of TOC in the biochemical tailwater increases 0.5% to 35%; and
regeneration efficiency of the resins with respect to removal of COD Cr in the biochemical tailwater increases 1% to 28%.

6. A method for using organic-pollution-resistant ion exchange resins containing the modified inorganic particles prepared in claim 1 , the method comprising:
treating surface water, drinking water and food source wastewater using the resins, wherein, as compared to ion exchange resins without the modified inorganic particles:
regeneration efficiency of the resins with respect to removal of DOC of the surface water increases 0.5% to 45%;
regeneration efficiency of the resins with respect to removal of UV 254 in the surface water increases 1% to 40%;
regeneration efficiency of the resins with respect to removal of COD Cr in the food wastewater increases 1% to 28%.

7. A method for using organic-pollution-resistant ion exchange resins containing the modified inorganic particles prepared in claim 1 , the method comprising:
treating metallurgical wastewater and coking wastewater using the resins, wherein, as compared to ion exchange resins without the modified inorganic particles:
regeneration efficiency of the resins with respect to removal of COD Cr in CN— in the coking wastewater increases 1% to 55%; and
regeneration efficiency of the resins with respect to removal of AsO 3 in the metallurgical wastewater increases 1% to 55%.

8. A method for using organic-pollution-resistant ion exchange resins containing the modified inorganic particles prepared in claim 1 , the method comprising:
treating electroplating wastewater, wherein, as compared to ion exchange resins without the modified inorganic par

Assignees

• Nanjing University Of Technology

Inventors

• Li Aimin
• Li Haibo
• Shuang Chendong
• Zhou Qing
• Yang Hu
• Zhang Mancheng
• Zhou Yang

Classifications

• C02F2103/16

  from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes · CPC title

• C08F220/44

  Acrylonitrile · CPC title

• C02F2103/30

  from the textile industry · CPC title

• B01J39/17

  containing also inorganic materials, e.g. inert material coated with an ion-exchange resin · CPC title

• B01J39/20

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title