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CN-122011285-A - Salt-resistant chelating resin suitable for high-salt wastewater and preparation method thereof

CN122011285ACN 122011285 ACN122011285 ACN 122011285ACN-122011285-A

Abstract

The invention belongs to the technical field of chelating resins, and relates to a salt-tolerant chelating resin suitable for high-salt wastewater and a preparation method thereof. The salt-resistant chelating resin suitable for the high-salt wastewater is prepared by the reaction of chloromethylation spherical porous polystyrene resin, functional monomers and iminodisuccinic acid, wherein the functional monomers are glycidyl methacrylate and vinyl phosphoric acid. The salt-resistant chelate resin provided by the invention solves the problem that the traditional chelate resin has poor calcium and magnesium ion adsorption effect under the high-salt condition.

Inventors

  • CHANG KAI
  • LIN GUANGYUE
  • LIN XIONGSHUI

Assignees

  • 同舟纵横（厦门）流体技术有限公司

Dates

Publication Date
20260512
Application Date
20260228

Claims (10)

  1. 1. A salt-tolerant chelating resin suitable for high-salt wastewater is characterized by being prepared by reacting chloromethylated spherical porous polystyrene resin, functional monomers and iminodisuccinic acid, wherein the functional monomers are glycidyl methacrylate and vinyl phosphoric acid.
  2. 2. The salt-tolerant chelate resin suitable for high-salt wastewater, which is characterized in that the preparation method of the chloromethylated spherical porous polystyrene resin comprises the steps of mixing a dispersing agent, deionized water and sodium chloride to obtain a water phase, mixing p-chloromethylstyrene, styrene, divinylbenzene, styrylphosphoric acid, an initiator and a pore-forming agent to obtain an oil phase, adding the water phase into the oil phase for polymerization reaction, and removing the pore-forming agent after the polymerization reaction is finished to obtain the chloromethylated spherical porous polystyrene resin.
  3. 3. The salt-tolerant chelating resin suitable for high-salt wastewater according to claim 2, wherein the dispersant is at least one selected from the group consisting of polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose, and the initiator is at least one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile and dilauroyl peroxide.
  4. 4. A salt tolerant chelating resin suitable for high salt wastewater according to claim 3, wherein said porogen is selected from at least one of gasoline, isobutanol and toluene.
  5. 5. The salt-tolerant chelate resin suitable for high-salt wastewater according to claim 4, wherein the oil phase comprises 20-30 parts by mass of p-chloromethyl styrene, 10-15 parts by mass of styrene, 15-25 parts by mass of divinylbenzene, 5-10 parts by mass of styryl phosphoric acid, 0.5-1 part by mass of an initiator and 40-70 parts by mass of a pore-forming agent.
  6. 6. The salt-tolerant chelate resin suitable for high-salt wastewater of claim 5, wherein the water phase comprises, by mass, 1-2 parts of a dispersing agent, 4-6 parts of sodium chloride and 100 parts of deionized water.
  7. 7. The salt tolerant chelating resin for high salt wastewater according to claim 6, wherein the volume ratio of the oil phase to the water phase is 4-7:1.
  8. 8. The method for preparing the salt-tolerant chelate resin suitable for high-salt wastewater as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: Mixing chloromethyl spherical porous polystyrene resin, a functional monomer, cuprous bromide, 2-bipyridine and N, N-dimethylformamide, wherein the functional monomer is glycidyl methacrylate and vinyl phosphoric acid, reacting under the protection of nitrogen, filtering, washing and drying after the reaction is finished to obtain an intermediate product; mixing the intermediate product with N-methyl-2-pyrrolidone, soaking and swelling, adding tetrasodium iminodisuccinate and sodium carbonate, reacting, filtering, washing and drying after the reaction is finished, and obtaining the salt-resistant chelating resin suitable for high-salt wastewater.
  9. 9. The preparation method of the salt-tolerant chelate resin suitable for high-salt wastewater, which is characterized in that the mass ratio of chloromethyl spherical porous polystyrene resin, vinyl phosphoric acid, glycidyl methacrylate, cuprous bromide, 2-bipyridine and N, N-dimethylformamide is 40-60:70-90:10-15:1-3:3-8:100-120.
  10. 10. The method for preparing a salt-tolerant chelating resin suitable for high-salt wastewater according to claim 8, wherein the mass ratio of the intermediate product, N-methyl-2-pyrrolidone, tetrasodium iminodisuccinate and sodium carbonate is 1:5-10:2-3:4-5.

Description

Salt-resistant chelating resin suitable for high-salt wastewater and preparation method thereof Technical Field The invention belongs to the technical field of chelating resins, and particularly relates to a salt-tolerant chelating resin suitable for high-salt wastewater and a preparation method thereof. Background The high-salt wastewater generally refers to the wastewater with the total salt content of 1% or more, namely the wastewater contains more than 10000 mg of salt substances per liter, contains a large amount of soluble inorganic salt ions such as higher calcium, magnesium, sodium, chlorine, sulfate radical and the like, and is mainly derived from the fields of sea water desalination, chemical plants, petroleum, natural gas and the like. The direct discharge of high-salt wastewater can cause serious environmental pollution, such as soil hardening, plant growth incapability and the like, and the treatment and recycling of the high-salt wastewater are necessary trends of environmental protection and sustainable development. At present, the treatment process flow of the high-salt wastewater mainly comprises the following steps of sequentially carrying out biochemical treatment on the wastewater to remove organic matters to obtain wastewater with high salt content, membrane concentration, salt separation, removal of calcium and magnesium ions by chelating resin, and bipolar membrane treatment to enable Na 2SO4 to generate NaOH and HCl. Under the high-salt environment, sodium ions can compete with calcium and magnesium ions to adsorb, so that the active sites of the chelating resin are occupied in a non-selective way, the effective exchange capacity is reduced, and on the other hand, sodium ions can inhibit the adsorption rate of calcium and magnesium ions, so that the adsorption effect of calcium and magnesium ions is seriously influenced, and salt separation treatment is needed before the chelating resin is used for carrying out an adsorption process, so that the salt-resistant chelating resin can be directly used for high-salt wastewater, and the method has important significance in simplifying the treatment process flow of the high-salt wastewater. The prior art has recently reported that salt tolerant chelating resins, chinese patent publication No. CN1143876C discloses improved chelating resins capable of removing cations (e.g. calcium, magnesium, barium and strontium) from brine and macroporous aminoalkylphosphonic or iminodiacetic acid chelating resins with improved stability and capacity in terms of removing metals (e.g. nickel, copper and zinc) from waste streams, however this solution is applicable to low concentrations of calcium magnesium ions. Disclosure of Invention Based on the above, it is necessary to provide a salt-tolerant chelating resin suitable for high-salt wastewater and a preparation method thereof, so as to solve the problem that the conventional chelating resin has poor calcium and magnesium ion adsorption effect under the high-salt condition. The above object of the present invention is achieved by the following technical solutions: The invention provides a salt-tolerant chelating resin suitable for high-salt wastewater, which is prepared by reacting chloromethylated spherical porous polystyrene resin, functional monomers and iminodisuccinic acid, wherein the functional monomers are glycidyl methacrylate and vinyl phosphoric acid. In the salt-tolerant chelating resin provided by the invention, the structural formula of the vinyl phosphoric acid is as follows: 。 In some preferred embodiments, the preparation method of the chloromethylated spherical porous polystyrene resin comprises the steps of mixing a dispersing agent, deionized water and sodium chloride to obtain an aqueous phase, mixing p-chloromethylstyrene, styrene, divinylbenzene, styryl phosphoric acid, an initiator and a pore-forming agent to obtain an oil phase, adding the aqueous phase into the oil phase for polymerization, and removing the pore-forming agent after the polymerization is finished to obtain the chloromethylated spherical porous polystyrene resin. In some preferred embodiments, the dispersant is selected from at least one of polyvinyl alcohol, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose. In some preferred embodiments, the initiator is selected from at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile and dilauroyl peroxide. In some preferred embodiments, the porogen is selected from at least one of gasoline, isobutanol and toluene. In the salt-tolerant chelating resin provided by the invention, the structural formula of the styryl phosphoric acid is as follows: 。 in some preferred embodiments, the oil phase comprises 20-30 parts by mass of p-chloromethyl styrene, 10-15 parts by mass of styrene, 15-25 parts by mass of divinylbenzene, 5-10 parts by mass of styryl phosphoric acid, 0.5-1 part by mass of initiator and 40-70 parts by mass