# US 5,707,525 A · Process for separating and recovering an anionic dye from an aqueous solution

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- Number: US 5,707,525 A
- Document ID: US5707525A
- Status: Granted
- Kind: A
- Application number: 08/655,251
- Filed: 1996-06-05
- Granted: 1998-01-13
- Earliest claimed: 1995-06-07
- Assignees: Arch Development Corporation; Northern Illinois University
- Inventors: Robin Rogers; E. Philip Horwitz; Andrew H. Bond
- Web page: https://patentgrep.com/patent/US5707525A

## CPC

- B01D 15/08: Selective adsorption, e.g. chromatography
- B01D 15/22: relating to the construction of the column
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/321: {consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds}
- B01J 20/3212: {consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds}
- B01J 20/3219: {involving a particular spacer or linking group, e.g. for attaching an active group}
- B01J 20/3227: {by end-capping, i.e. with or after the introduction of functional or ligand groups}
- B01J 20/3272: {Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds}
- B01J 20/3276: {Copolymers}
- B01J 20/3278: {Polymers being grafted on the carrier}
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

## Claims

### Claim 1

A process for separating and recovering an anionic dye from an aqueous solution that comprises the steps of:
(a) contacting separation particles with an aqueous solution containing (i) an anionic dye and (ii) a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt to form a solid/liquid phase admixture, said anionic dye containing a 5- or 6-membered aromatic ring and at least one substituent group having a pK.sub.a value equal the pH value of said aqueous solution, said separation particles comprising particles having a plurality of covalently bonded --X-- (CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 R groups wherein X is O, S, NH or N--(CH.sub.2 CH.sub.2 O).sub.m --R.sup.3 where m is a number having an average value of zero to about 225, n is a number having an average value of about 15 to about 225, R.sup.3 is hydrogen, C.sub.1 -C.sub.2 alkyl, 2-hydroxyethyl or CH.sub.2 CH.sub.2 R, and R is selected from the group consisting of --OH, C.sub.1 -C.sub.10 hydrocarbyl ether having a molecular weight up to about one-tenth that of the --(CH.sub.2 CH.sub.2 O).sub.n -- portion, carboxylate, sulfonate, phosphonate and --NR.sup.1 R.sup.2 groups where each of R.sup.1 and R.sup.2 is independently hydrogen, C.sub.2 -C.sub.3 hydroxyalkyl, C.sub.1 -C.sub.6 alkyl, or --NR.sup.1 R.sup.2 together form a 5- or 6-membered cyclic amine having zero or one oxygen atoms or zero or one additional nitrogen atoms in the ring, said separation particles having a percent CH.sub.2 O/mm.sup.2 of particle surface area of greater than about 8000 and less than about 1,000,000;
(b) maintaining said contact for a time period sufficient to form anionic dye-bound separation particles and an aqueous solution having a reduced concentration of anionic dye;
(c) contacting said anionic dye-bound separation particles of step (b) with a second aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of dissolved salt to free the anionic dye from the separation particles and form an aqueous solution containing free anionic dye; and
(d) recovering the anionic dye containing aqueous solution of step (c).

### Claim 2 (depends on 1)

The process according to claim 1 wherein n has an average value of about 40 to about 130.

### Claim 3 (depends on 1)

The process according to claim 1 wherein R is a C.sub.1 -C.sub.10 hydrocarbyl ether group.

### Claim 4 (depends on 1)

The process according to claim 1 wherein said percent CH.sub.2 O/mm.sup.2 of particle surface area is about 9,000 to about 20,000.

### Claim 5 (depends on 4)

The process according to claim 4 wherein said poly(ethylene glycol) liquid/liquid biphase-forming dissolved salt has an ammonium or alkali metal cation and an anion selected from the group consisting of carbonate, sulfate, phosphate and chloride.

### Claim 6 (depends on 1)

The process according to claim 1 wherein said particles are reacted cross-linked poly(styrene-vinyl benzyl halide) particles.

### Claim 7 (depends on 1)

The process according to claim 1 including the further step of separating said anionic dye-bound separation particles from the aqueous solution of step (b) prior to step (c), said separation being carried out in the presence of an aqueous solution of a poly(ethylene glycol) liquid/liquid biphase-forming amount of a salt to form a second solid/liquid phase admixture containing anionic dye-bound separation particles.

### Claim 8

A process for separating and recovering anionic dye molecules from an aqueous solution that comprises the steps of:
(a) contacting separation particles with an aqueous solution containing (i) anionic dye molecules and (ii) a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form a solid/liquid phase admixture, said anionic dye molecules containing at least two 5- or 6-membered aromatic rings and at least one substituent group having a pK.sub.a value one unit below the pH value of said aqueous solution, said separation particles comprising reacted cross-linked poly(styrene-vinyl benzyl halide) particles having a plurality of covalently bonded --X--(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 R groups wherein X is O, S, NH or N--(CH.sub.2 CH.sub.2 O).sub.m --R.sup.3 where m is a number having an average value of zero to about 225, n is a number having an average value of about 40 to about 130, R.sup.3 is hydrogen, C.sub.1 -C.sub.2 alkyl, 2-hydroxyethyl or CH.sub.2 CH.sub.2 R, and R is a C.sub.1 -C.sub.10 hydrocarbyl ether having a molecular weight up to about one-tenth that of the --(CH.sub.2 CH.sub.2 O).sub.n -- portion, said separation particles having a percent CH.sub.2 O/mm.sup.2 of particle surface area of greater than about 9000 and to about 20,000;
(b) maintaining said contact for a time period sufficient to form anionic dye molecule-bound separation particles and an aqueous solution having a reduced concentration of anionic dye molecules;
(c) separating said anionic dye molecule-bound separation particles from the aqueous solution of step (b) in the presence of an aqueous solution of a poly(ethylene glycol) liquid/liquid biphase-forming amount of a salt to form a second solid/liquid phase admixture containing anionic dye molecule-bound separation particles;
(d) contacting said anionic dye molecule-bound separation particles of step (c) with second aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of dissolved salt to free the anionic dye molecules from the separation particles and form an aqueous solution containing free anionic dye molecules at a higher concentration than that of said first-named aqueous solution of step (a); and
(e) recovering the anionic dye molecule-containing aqueous solution of step (d).

### Claim 9 (depends on 8)

The process according to claim 8 wherein X is O.

### Claim 10 (depends on 9)

The process according to claim 9 wherein said poly(ethylene glycol) liquid/liquid biphase-forming dissolved salt has an ammonium or alkali metal cation and an anion selected from the group consisting of hydroxide, fluoride, carbonate, silicate, sulfate, phosphate, formate, acetate, succinate, tartrate, citrate, chromate, molybdate, tungstate, orthovanadate, chloride, thiocyanate, thiosulfate, fluorosilicate, orthosilicate, hydroxyethane-1,1-diphosphonate, vinylidene-1,1-diphosphonate and the protonated anionic forms thereof.

### Claim 11 (depends on 10)

The process according to claim 10 wherein said anionic dye molecules contain at least one sulfonate functional group.

### Claim 12

A process for recovering anionic dye molecules from an aqueous solution that comprises the steps of:
(a) contacting separation particles with an aqueous solution containing (i) anionic dye molecules and (ii) a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form a solid/liquid phase admixture, said anionic dye molecules containing at least two 5- or 6-membered aromatic rings and at least one sulfonate substituent group, said separation particles comprising reacted cross-linked poly(styrene-vinyl benzyl halide) particles having a plurality of covalently bonded --O--(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 R groups wherein n is a number having an average value of about 40 to about 130, and R is a C.sub.1 -C.sub.10 hydrocarbyl ether having a molecular weight up to about one-tenth that of the --(CH.sub.2 CH.sub.2 O).sub.n -- portion, said separation particles having a percent CH.sub.2 O/mm.sup.2 of particle surface area of greater than about 9000 and to about 20,000;
(b) maintaining said contact for a time period sufficient to form anionic dye molecule-bound separation particles and an aqueous solution having a reduced concentration of anionic dye molecules;
(c) separating said anionic dye molecule-bound separation particles from the aqueous solution of step (b) in the presence of an aqueous solution of a poly(ethylene glycol) liquid/liquid biphase-forming amount of a salt to form a second solid/liquid phase admixture containing anionic dye molecule-bound separation particles;
(d) contacting said anionic dye molecule-bound separation particles of step (c) with second aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of dissolved salt to free the anionic dye molecules from the separation particles and form an aqueous solution containing free anionic dye molecules at a higher concentration than that of said first-named aqueous solution of step (a); and
(e) recovering the anionic dye molecule-containing aqueous solution of step (d).