Aluminum-doped, iminodiacetic acid group-containing chelate resins

Patent metadata

Field	Value
Publication number	US-10017401-B2
Application number	US-201515116553-A
Country	US
Kind code	B2
Filing date	Feb 4, 2015
Priority date	Feb 7, 2014
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

The present invention relates to aluminum-doped chelate resins containing iminodiacetic acid groups, to a production process for aluminum-doped chelate resins containing iminodiacetic acid groups, and to a device comprising at least one layer of at least one aluminum-doped chelate resin containing iminodiacetic acid groups, and to the uses of this device and of the chelate resins for removal of fluoride from water.

First claim

What is claimed is:

1. An aluminum-doped chelate resin for absorption of anions, the resin comprising a polymer comprising a plurality of phenyl groups functionalized at a first substitution level of 0.6 to 1.5 with functional groups represented by the structural formula (I)
—CH 2 —NR 2 ,  (I)

where each R is independently —H or —CH 2 COO − ; the nitrogen is functionalized with acetate groups at a functionalization level of 1.4 to 1.65; and the acetate ions are conjugated with AIX, where X is any monovalent anion.

2. The resin according to claim 1 , wherein the first substitution level is 0.6 to 1.2.

3. The resin according to claim 1 , wherein the first substitution level is 0.7 to 0.9.

4. The resin according to claim 1 , wherein:
the polymer comprises repeat units derived from at least one monovinylaromatic compound and at least one polyvinylaromatic compound; and
X is nitrate, nitrite, hydrogensulfate, hydrogencarbonate or a halide.

5. The resin according to claim 1 , wherein:
the monovinylaromatic compounds include styrene, vinyltoluene, ethylstyrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, alkyl acrylates or alkyl methacrylates;
the polyvinylaromatic compounds include divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, 1,7-octadiene, 1,5-hexadiene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate; and
X is halide.

6. The resin according to claim 3 , wherein
the monovinylaromatic compound is styrene;
the polyvinylaromatic compound divinylbenzene; and
X is chlorine.

7. A process for producing the chelate resin as claimed in claim 1 , the process comprising:
converting monomer droplets composed of at least one monovinylaromatic compound, at least one polyvinylaromatic compound, at least one porogen, and at least one initiator to a crosslinked bead polymer;
phthalimidomethylating aromatic groups of the crosslinked bead polymer at the first substitution level of 0.6 to 1.5 with phthalimide derivatives to produce phthalimidomethylated bead polymer;
converting the phthalimidomethylated bead polymer to aminomethylated bead polymer to produce aminomethylated bead polymer;
reacting the aminomethyl groups of the aminomethylated bead polymer with chloroacetic acid or salts thereof to produce chelate resins having iminoacetate groups at the functionalization level of 1.4 to 1.65; and
contacting the chelate resin containing aminoacetate groups with an aluminum salt solution of a trivalent aluminum ion to produce the chelate resin.

8. The process according to claim 7 , wherein:
the phthalimidomethylation reaction comprises a molar ratio of phthalimide derivative to bead polymer of 0.7 mol to 1.7 mol; and
the reaction with chloroacetic acid comprises a molar ratio of chloroacetic acid or salts thereof to aminomethylated bead polymer of 1.8:1 to 2.5:1 for functionalization of amino groups at the functionalization level of 1.4 to 1.65.

9. The process according to claim 8 , wherein the phthalimidomethylation is conducted at a temperature of 60° C. to 80° C.

10. The process according to claim 9 , wherein the phthalimidomethylation comprises a condensation of the phthalimide derivative with the bead polymer using a catalyst in a molar ratio of 0.1:1 to 0.45:1 in relation to the amount of bead polymer used.

11. The process as claimed in claim 10 , wherein the contacting of the chelate resin containing iminoacetate groups with an aluminum salt solution comprises contacting the resin with 2 to 6 mol of aluminum based on one liter of chelate resin containing iminoacetate groups.

12. The process according to claim 7 , wherein:
the phthalimidomethylation reaction comprises a molar ratio of phthalimide derivative to bead polymer of 0.7 mol to 1.35 mol; and
the reaction with chloroacetic acid comprises a molar ratio of chloroacetic acid or salts thereof to aminomethylated bead polymer of 1.8:1 to 2.5:1 for functionalization of the amino groups at the functionalization level of 1.4 to 1.65.

13. A device for removing fluoride from water, the device comprising at least one layer of at least one aluminum-doped chelate resin containing iminoacetate groups as claimed in claim 1 .

14. A method for removing fluoride from water, the method comprising contacting water containing fluoride with the aluminum-doped chelate resin of claim 1 to absorb fluoride ions from the water.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Neumann Stefan
• Klipper Reinhold
• Makropoulos Pavlos
• Barbier Jenny
• Schroeder Maresa

Classifications

• C02F2103/346

  from semiconductor processing, e.g. waste water from polishing of wafers · CPC title

• C02F2103/12

  from the silicate or ceramic industries, e.g. waste waters from cement or glass factories · CPC title

• C02F2101/14

  Fluorine or fluorine-containing compounds · CPC title

• C02F1/683 Primary

  by addition of complex-forming compounds · CPC title

• C02F1/285

  using synthetic organic sorbents · CPC title