Cross-linked polymeric resin and methods for wastewater treatment

Patent metadata

Field	Value
Publication number	US-10370266-B2
Application number	US-201615163360-A
Country	US
Kind code	B2
Filing date	May 24, 2016
Priority date	May 24, 2016
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

Abstract

A cross-linked polymeric resin which contains reacted monomer units of an aniline, a diaminoalkane, and an aldehyde, and which is functionalized with at least one dithiocarbamate moiety. A process for producing the cross-linked polymeric resin whereby an aniline and a diaminoalkane are linked together by Mannich-type polycondensation reactions with an aldehyde. The resulting Mannich-type polycondensation product is converted into the cross-linked polymeric resin through functionalization of one or more amine functional groups with dithiocarbamate moieties. A method for removing heavy metals, such as Hg(II), from an aqueous solution, whereby the cross-linked polymeric resin is contacted with the aqueous solution, and the heavy metal is thus adsorbed onto the cross-linked polymeric resin.

First claim

The invention claimed is:

1. A cross-linked polymeric resin of formula (I)

or a salt, solvate, tautomer or stereoisomer thereof;
wherein, each R 1 is independently H, —CS 2 − Z + , an alkyl, a cycloalkyl, or an aryl with the proviso that at least one R 1 is —CS 2 − Z + ;
each R 2 is independently H, —F, —Cl, —Br, —CN, —OR 3 , an alkyl, a cycloalkyl, or an aryl;
each R 3 is independently —H, an alkyl, a cycloalkyl, or an aryl;
Z is —H or an alkali metal counter ion;
n is a positive whole number in the range of 2-16;
X is a positive whole number; and
A 1 forms a bond to A 2 .

2. The cross-linked polymeric resin of claim 1 , wherein each R 1 is —CS 2 − Z + .

3. The cross-linked polymeric resin of claim 1 , wherein the compound of formula (I) is

or a salt, solvate, tautomer or stereoisomer thereof;
wherein, n is a positive whole number in the range of 4-12;
X is a positive whole number; and
A 1 forms a bond to A 2 .

4. The cross-linked polymeric resin of claim 1 , which is in the form of polyhedral nanometer sized structures having an average width in the range of 10 to 30 nm and an average height in the range of 4-16 {acute over (Å)}.

5. The cross-linked polymeric resin of claim 1 , which has a BET surface area in the range of 2.0 to 15.0 m 2 g −1 .

6. A process for producing the cross-linked polymeric resin of claim 1 , comprising:
reacting an aniline compound with a diaminoalkane compound in the presence of an aldehyde to form the cross-linked polymeric resin wherein R 1 is —H; and
reacting the cross-linked polymeric resin wherein R 1 is —H with carbon disulfide in the presence of an alkali metal hydroxide to form the cross-linked polymeric resin wherein at least one R 1 is CS 2 − Z + .

7. The process of claim 6 , wherein the molar ratio of the aldehyde to the aniline compound is in the range of 4:1 to 8:1.

8. The process of claim 6 , wherein the molar ratio of the diaminoalkane compound to the aniline compound is in the range of 1:1 to 5:1.

9. The process of claim 6 , wherein the aniline compound is aniline, the aldehyde is paraformaldehyde and the diaminoalkane compound is at least one selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane.

10. A method for removing a heavy metal from an aqueous solution, comprising:
contacting the cross-linked polymeric resin of claim 1 with the aqueous solution comprising the heavy metal; and
adsorbing the heavy metal onto the cross-linked polymeric resin to form a heavy metal loaded cross-linked polymeric resin.

11. The method of claim 10 , further comprising:
desorbing the heavy metal from the heavy metal loaded cross-linked polymeric resin by treating with an acid to reform the cross-linked polymeric resin; and
reusing the cross-linked polymeric resin up to 15 times without a loss in adsorption capacity.

12. The method of claim 10 , wherein the heavy metal is at least one ion selected from the group consisting of Hg, Cu, Zn, Mn, Fe, and Ni.

13. The method of claim 10 , wherein the heavy metal is Hg(II).

14. The method of claim 10 , wherein the cross-linked polymeric resin has an adsorption capacity in the range of 15-35 mg of the heavy metal per g of the cross-linked polymeric resin.

15. The method of claim 10 , wherein the aqueous solution has a pH in the range of 2 to 8.

16. The method of claim 10 , wherein the aqueous solution has an initial heavy metal concentration in the range of 0.05 mmol L −1 to 1.0 mmol L −1 .

17. The method of claim 10 , wherein the cross-linked polymeric resin is present at a concentration in the range of 0.02-5.0 g of the cross-linked polymeric resin per L of the aqueous solution during the contacting.

18. The method of claim 10 , wherein the cross-linked polymeric resin is contacted with the aqueous solution for 0.1 to 24 hours.

19. The method of claim 10 , wherein the contacting is performed at a temperature in the range of 20° C. to 60° C.

20. The method of claim 10 , wherein greater than 90% of the total mass of the heavy metal is removed from the aqueous solution.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Akintola Oluwafemi S
• Awadh Tawfik Abdo Saleh
• KHALED Mazen Mohammad
• Al Hamouz Othman Charles Sadeq

Classifications

• C02F2303/16

  Regeneration of sorbents, filters · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• C08G12/06

  Amines · CPC title

• C08G12/40

  Chemically modified polycondensates · CPC title

• C02F1/285 Primary

  using synthetic organic sorbents · CPC title