Carboxymethyl cellulose hydrogel loaded with titanium oxide nanoparticles for wastewater treatment

Patent metadata

Field	Value
Publication number	US-12434987-B1
Application number	US-202519015470-A
Country	US
Kind code	B1
Filing date	Jan 9, 2025
Priority date	Jan 9, 2025
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

A carboxymethyl cellulose hydrogel loaded with TiO 2 nanoparticles for wastewater treatment is provided. The TiO 2 NPs@CMC hydrogel is made by a method including providing raw date fiber, bleaching the raw date fiber, delignifying the bleached raw date fiber, and then performing alkalization and etherification on the bleached raw date fiber to produce date derived CMC; followed by dissolving the CMC in calcium chloride to form a paste-like solution, adding TiO 2 NPs to the paste-like solution, and freeze-drying the paste-like solution to obtain the TiO 2 NPs@CMC hydrogel. The TiO 2 NPs@CMC hydrogel is effective for degrading pathogens contaminating wastewater and preventing biofilm formation in wastewater systems.

First claim

The invention claimed is:

1. A method of making a carboxymethyl cellulose (CMC) hydrogel loaded with TiO 2 nanoparticles (NPs) comprising:
providing raw date fiber;
bleaching the raw date fiber to obtain bleached date fiber;
delignifying the bleached date fiber to obtain delignified date fiber;
alkalizing the delignified date fiber to obtain alkalized date fiber;
esterifying the alkalized date fiber to obtain date derived carboxymethyl cellulose;
dissolving the date derived carboxymethyl cellulose in calcium chloride to form a paste solution of CMC-CaCl 2 ;
adding about 0.6 g of TiO 2 NPs to the paste solution to obtain a mixture;
stirring the mixture for about 4 hours to obtain a TiO 2 NPs-CMC-CaCl 2 paste;
storing the TiO 2 NPs-CMC-CaCl 2 paste for about 24 hours followed by washing and centrifuging to obtain washed TiO 2 NPs-CMC-CaCl 2 paste;
refrigerating the washed TiO 2 NPs-CMC-CaCl 2 paste for about 24 hours; and freeze drying for about 48 hours to obtain a TiO 2 NPs-CMC-CaCl 2 ) hydrogel.

2. The method of claim 1 , comprising:
the bleaching the raw date fiber comprises using about 4% w/v NaClO 2 solution acidified to a pH of about 3.5-4.0 with 10% v/v glacial acetic acid.

3. The method of claim 2 , wherein the bleaching the raw date fiber is performed under constant stirring at about 80° C. for about 1 hour.

4. The method of claim 3 , wherein the bleaching is performed using about 1:50 fiber-to-NaClO 2 solution ratio.

5. The method of claim 1 , comprising washing the bleached date fiber prior to the delignifying step, wherein the washing comprises:
washing the bleached date fiber until the pH of filtrate of the bleached date fiber reaches about 6.5-7;
and drying the bleached date fiber at about 105° C. for about 24 hours.

6. The method of claim 1 , comprising:
the delignifying the bleached date fiber with about 4% w/v NaOH solution at about 25-30° C. for about 30 minutes, using a 1:50 bleached date fiber-to-NaOH solution ratio.

7. The method of claim 6 , comprising washing the delignified date fiber prior to the alkalizing step, wherein the washing comprises:
rinsing the delignified date fiber until pH of a filtrate of the delignified date fiber reaches about 6.5-7; and
drying the rinsed delignified date fiber at about 105° C. for about 24 hours.

8. The method of claim 1 , comprising:
in the dissolving the date derived carboxymethyl cellulose, about 25% w/v date derived carboxymethyl cellulose is dissolved in about 5% w/v calcium chloride solution under constant stirring for about 4 hours to obtain the paste solution of CMC-CaCl 2 ); and
placing the paste solution in a petri dish and storing the paste solution for about 24 hours to allow cross-linking to complete.

9. The method of claim 8 , comprising:
washing the paste solution prior to the step of adding TiO 2 nanoparticles, wherein the washing step includes:
washing the paste solution three times with water; and
centrifuging the paste solution to remove any residual CaCl 2 .

10. The method of claim 1 , comprising:
making the TiO 2 nanoparticles by a process comprising hydrolysis and peptization steps.

11. The method of claim 10 , wherein the hydrolysis step comprises adding titanium isopropoxide (TIPP) to nitric acid (HNO 3 ) in a dropwise fashion under constant stirring to obtain a slurry comprising a white precipitate.

12. The method of claim 11 , wherein the peptization step comprises heating the slurry comprising the white precipitate to 80° C. with mechanical stirring for about 12 hours.

13. The method of claim 12 , comprising:
centrifuging the heated slurry to isolate the white precipitate;
drying the white precipitate to obtain a dried white precipitate; and
calcining the dried white precipitate to obtain the TiO 2 nanoparticles.

14. The method of claim 11 , comprising adding about 100 mL titanium isopropoxide (TIPP) to about 300 mL nitric acid (HNO 3 , 0.1M) dropwise at room temperature under constant stirring to obtain the white precipitate.

15. The method of claim 14 , wherein the peptization step comprises heating a slurry comprising the white precipitate to 80° C. with mechanical stirring for about 12 hours.

16. The method of claim 12 , comprising:
centrifuging the heated slurry to isolate a white precipitate;
drying the white precipitate at about 80° C. to obtain a dried white precipitate; and
calcining the dried white precipitate at about 500° C. for about 2 hours to obtain the TiO 2 nanoparticles.

17. A method of preventing biofilm formation in wastewater systems, comprising:
the method of making the carboxymethyl cellulose hydrogel loaded with TiO 2 nanoparticles of claim 1 ; and
administering the carboxymethyl cellulose hydrogel loaded with TiO 2 nanoparticles to a wastewater system at a concentration between about 5 mg/mL and about 45 mg/mL.

18. A method of disinfecting wastewater, comprising:
the method of making the carboxymethyl cellulose hydrogel loaded with TiO 2 nanoparticles of claim 1 ; and
administering the carboxymethyl cellulose hydrogel loaded with TiO 2 nanoparticles to wastewater at a concentration of about 2 times minimum inhibitory concentration (2×MIC) for a contaminant.

Assignees

• Univ King Faisal

Inventors

• El-Lateef Ahmed Hany Mohamed Abd
• Ali Mai Mostafa Khalaf
• Gouda Mohamed
• Alsaeed Mohammed Abbas
• Al Rasheed Fatima Essa

Classifications

• C08L1/286

  substituted with acid radicals, e.g. carboxymethyl cellulose [CMC] (C08L1/282 takes precedence) · CPC title

• C08B11/12

  substituted with carboxylic radicals {, e.g. carboxymethylcellulose [CMC]} · CPC title

• C02F2305/08

  Nanoparticles or nanotubes · CPC title

• C02F2303/04

  Disinfection · CPC title

• B01J37/12

  Oxidising · CPC title