Ammonia removal in freshwater and saltwater systems

10766,790

16/200212

November 26, 2018

An ammonia adsorption product is described which may be used for fresh caught fish and bait. The product may comprise functionalized tectosilicate compound and a buffer. High concentrations of ammonia produced by fish waste can be lethal, even though oxygen availability is rich enough to keep fish breathing. The product is a user-friendly, sustainable, affordable product which is able to extend the life of the fish by safely removing ammonia by an ion-exchange mechanism. This product can convert toxic ammonia into ammonium and uptake ammonium by releasing sodium ions in the water.

Alcantar, Norma A. (Tampa, FL, US); Zhao, Wen (Temple Terrace, FL, US); Ergas, Sarina Joy (Tampa, FL, US)

University of South Florida (Tampa, FL, US)

1. A method for producing an ammonia removal agent for saltwater environments, comprising: obtaining a tectosilicate compound wherein the tectosilicate compound is chabazite; functionalizing the tectosilicate compound, comprising soaking the tectosilicate compound in a synthetic saltwater solution for 24 hours and replacing cations in the tectosilicate compound with sodium ions wherein the synthetic saltwater solution consists of: an amount of water; 10.780 g/L of sodium; 0.42 g/L of potassium; 1.32 g/L of magnesium; 19.290 g/L of chloride 0.400 g/L of calcium; 0.200 g/L of bicarbonate; 2.66 g/L of sulfate; and 0.241 g/L of alkalinity; washing the functionalized tectosilicate compound in deionized water; and drying the functionalized tectosilicate compound.

2. The method of claim 1 , further comprising washing the tectosilicate compound in deionized water and drying the tectosilicate compound prior to soaking the tectosilicate compound in the synthetic saltwater solution.

3. The method of claim 2 , wherein the tectosilicate compound is washed using a shaker table for 24 hours to remove small particles.

4. The method of claim 1 , wherein functionalizing the tectosilicate compound increases a percentage of sodium in the tectosilicate compound by at least 30 percent.

5. The method of claim 1 , wherein the functionalized tectosilicate compound is dried in an oven at 110° C. for 5 hours.

6. The method of claim 1 , wherein the functionalized tectosilicate compound is regenerated by removing adsorbed ammonium ions and replacing them with sodium ions.

7. A method for controlling an ammonia level in a water environment, comprising: providing a water environment; providing a functionalized tectosilicate compound, the functionalized tectosilicate compound produced by the steps of: obtaining a tectosilicate compound wherein the tectosilicate compound is chabazite; functionalizing the tectosilicate compound, comprising: soaking the tectosilicate compound in a synthetic freshwater solution or a synthetic saltwater solution; and removing ions from the tectosilicate compound that have a lower cationic affinity than ammonium ions when the synthetic freshwater solution is used or replacing cations in the tectosilicate compound with sodium ions when the synthetic saltwater solution is used; wherein the synthetic freshwater solution consists of: an amount of water; 0.075 g/L of sodium; 0.00312 g/L of potassium; 0.024 g/L of magnesium; 0.193 g/L of chloride 0.043 g/L of calcium; 0.0048 g/L of bicarbonate; 0.096 g/L of sulfate; and 0.310 g/L of alkalinity; wherein the synthetic saltwater solution consists of: an amount of water; 10.780 g/L of sodium; 0.42 g/L of potassium; 1.32 g/L of magnesium; 19.290 g/L of chloride 0.400 g/L of calcium; 0.200 g/L of bicarbonate; 2.66 g/L of sulfate; and 0.241 g/L of alkalinity; washing the functionalized tectosilicate compound in deionized water and then drying the compound; and providing a container for the functionalized tectosilicate compound and a solid pH buffer, the container comprising a porous material to allow liquid to flow through the material; providing for the container of functionalized tectosilicate compound to be placed in a water environment comprising a source of ammonia; buffering the water system to a pH of about 7 and shifting an equilibrium between ammonia and ammonium in the water environment towards ammonium; and adsorbing the ammonium using the functionalized tectosilicate.

8. The method of claim 7 , further comprising regenerating the functionalized tectosilicate compound by removing the adsorbed ammonium and replacing with sodium ions.

9. The method of claim 7 , further comprising washing the tectosilicate compound in deionized water and drying the tectosilicate compound prior to soaking the tectosilicate compound in the synthetic freshwater solution or the synthetic saltwater solution.

10. The method of claim 7 , wherein removing ions from the tectosilicate compound soaked in the synthetic freshwater solution comprises removing sodium ions from the tectosilicate compound.

11. The method of claim 10 , wherein functionalizing the tectosilicate compound reduces a percentage of sodium ionically bound to the compound by at least 50 percent.

12. The method of claim 7 , wherein the functionalized tectosilicate compound is dried in an oven at 110° C. for 5 hours.

13. The method of claim 7 , wherein functionalizing the tectosilicate compound by soaking the tectosilicate compound in the synthetic saltwater solution increases a percentage of sodium in the tectosilicate compound by at least 30 percent.

14. A system for removing ammonia from a saltwater environment, comprising: a saltwater environment containing ammonia; a functionalized tectosilicate compound, the functionalized tectosilicate compound produced by the steps of: obtaining a tectosilicate compound wherein the tectosilicate compound is chabazite; functionalizing the tectosilicate compound, comprising soaking the tectosilicate compound in a synthetic saltwater solution and replacing cations in the tectosilicate compound with sodium ions wherein the synthetic saltwater solution consists of: an amount of water; 10.780 g/L of sodium; 0.42 g/L of potassium; 1.32 g/L of magnesium; 19.290 g/L of chloride 0.400 g/L of calcium; 0.200 g/L of bicarbonate; 2.66 g/L of sulfate; and 0.241 g/L of alkalinity; washing the functionalized tectosilicate compound in deionized water and then drying the compound; and a pH buffer, wherein the pH buffer is a phosphate buffer in a solid state wherein an amount of the pH buffer used is such that the pH buffer maintains a pH of 7 in the saltwater environment; and a container holding the functionalized tectosilicate compound and the pH buffer, the container comprising a porous material to allow water to flow through the material; wherein the pH of 7 of the water environment shifts an equilibrium between ammonia and ammonium in the water environment towards ammonium, and the ammonium is adsorbed by the functionalized tectosilicate.

15. The system of claim 14 , wherein the functionalized tectosilicate compound is regenerated after use by removing the adsorbed ammonium and replacing with sodium ions.

16. The system of claim 14 , wherein functionalizing the tectosilicate compound increases a percentage of sodium in the compound by at least 30 percent.

17. The system of claim 14 , wherein the phosphate buffer is Na 2 HPO 4 , NaH 2 PO 4 , or a combination thereof.

5019254 May 1991 Abrevaya
5489323 February 1996 Yoshida
5837638 November 1998 Van Der Stok et al.
8257764 September 2012 Peterson
10138143 November 2018 Alcantar
10166528 January 2019 Alcantar
2018/0194643 July 2018 Litz et al.
0072147 February 1983
2192808 January 1988
2245809 January 1992

Mook, W.T. et al. Removal of total ammonia nitrogen (TAN), nitrate and total organic carbon (TOC) from aquaculture wastewater using electrochemical technology: A review. Desalination 285 (2012) 1-13. cited by applicant
Zhang, A. and P. Perschbacher. Comarison of the Zeolite Sodium Chabazite and Activated Charcoal for Ammonia Control in Sealed Containers. Asian Fisheries Science 16 (2003): 141-145. cited by applicant
Bhatnagar, Amit and Mika Sillanpaa. A review of emerging adsorbents for nitrate removal from water. Chemical Engineering Journal 168 (2011) 493-504. cited by applicant
Bergero, D. et al. Ammonia removal capacity of European natural zeolite tuffs: application to aquaculture waste water. Aquaculture and Fisheries Management 1994, 25, 813-821. cited by applicant
Zhou, Li et al. Total ammonia nitrogen removal from aqueous solutions by the natural zeolite; mordenite: A laboratory test and experimental study. Aquaculture 432 (2014) 252-257. cited by applicant
Emadi, H. et al. In vitro Comparison of Zeolite (Clinoptilolite) and Activated Carbon as Ammonia Absorbants in Fish Culture. Naga, The ICLARM Quarterly, vol. 24, Nos. 1 & 2, Jan.-Jun. 2001. cited by applicant
Lopez-Ruiz, J.L. et al. Zeolites in Marine Nitrogen Transformations. Aquacultural Engineering 13 (1994) 147-152. cited by applicant
Sing, R.K. et al. Water quality management during transportation of fry of Indian major carps, Catla catla (Hamilton), Labeo rohita (Hamilton) and Cirrhinus mrigala (Hamilton). Aquaculture 235 (2004) 297-302. cited by applicant
Aponte-Moreales, Veronica et al. Use of Chabazite to Overcome Ammonia Inhibition During Nitrification of High Strength Wastewater. Proceedings of the Water Environment Federation, 2014. 1431-1442.2014. DOI: 10.2175/193864714815941027. cited by applicant
Ghasemi, Zahra et al. Application of zeolites in aquaculture industry: a review. Reviews in Aquaculture (2018) 10, 75-95. cited by applicant
Colella, C. Ion exchange equilibria in zeolite minerals. Mineral. Deposita 31, 554-562 (1996). cited by applicant
Treacy, M.M.J. and J.M. Gibson. The effects of elastic relaxation on transmission electron microscopy studies of thinned compostiion-modulated materials. Journal of Vacuum Science & Technology B: Microelectronics Processing and Phenomena 4, 1458 (1996). DOI: 10.1116/1583473. cited by applicant
Gendel, Youri and Ori Lahay. A novel approach for ammonia removal from fresh-water recirculated aquaculture systems, comprising ion exchange and electrochemical regeneration. Aquacultural Engineering 52 (2013) 27-38. cited by applicant
Moussavi, Gholamreza et al. The investigation of mechanism, kinetic and isotherm of ammonia and humic acid co-adsorption onto natural zeolite. Chemical Engineering Journal 171 (2011) 1159-1169. cited by applicant
Burgess, R.M. et al. Use of Zeolite for Removing Ammonia and Ammonia-Caused Toxicity in Marine Toxicity Identification Evaluations. Arch. Environ. Contain. Toxicol, 2004. 47, 440-447. cited by applicant
Leyva-Ramos, R. et al. Removal of ammonium from aqueous solution by ion exchange on natural and modified chabazite, Journal of Environmental Management 91 (2010) 2662-2668. cited by applicant
Alshameri, Aref et al. An investigation into the adsorption removal of ammonium by salt activated Chinese (Hulaodu) natural zeolite: Kinetics, isotherms, and thermodynamics. Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554-564. cited by applicant
Karadag, Dogan et al. Removal of ammonium ion from aqueous solution using natural Turkish clinoptilolite. Journal of Hazardous Materials B136 (2006) 604-609. cited by applicant
Al Dwairi, Reyad A. et al. Potential use of faujasite-phillipsite and phillipsite-chabazite tuff in purification of treated effluent from domestic wastewater treatment plants, Environ Earth Sci (2014) 71:5071-5078. DOI: 10.1007/s12665-013-2911-0. cited by applicant
Smith, Daniel P. Chabazite Biofilter for Enhanced Stormwater Nitrogen Removal. Water Environment Research Apr. 2011, vol. 83, No. 4, pp. 373-384. cited by applicant
Non-final office action dated Sep. 19, 2018 for corresponding U.S. Appl. No. 16/023,396. cited by applicant
Verma, S.S. Wonders of Zeolite. Chemical Business, 2012, 26(2), pp. 10-12. cited by applicant
Non-final office action dated May 14, 2018 for corresponding U.S. Appl. No. 14/997,793. cited by applicant
Durborow, R.M. et al. Ammonia in Fish Ponds. Southern Regional Aquaculture Center, 1992, No. 463. cited by applicant
Final office action dated Sep. 19, 2018 for corresponding U.S. Appl. No. 14/997,793. cited by applicant
Gyrus, Johnsely S. and G.B. Reddy. Sorption and desorption of ammonium by zeolite: Batch and column studies. Journal of Environmental Science and Health Part A (2011) 46, 408-414. DOI: 10.1080/02773813.2010.542398. cited by applicant
Miladinovic, N. et al. Ammonia Removal from Saline Wastewater by Ion Exchange. Water, Air, and Soil Pollution: Focus 4: 169-177, 2004. cited by applicant
Orr, M. et al. What Does That Number Really Mean? Aquarium Water Testing Methods, Results and Interpretation, Sea Scope, 2008, vol. 24, pp. 1-2. cited by applicant

edspgr.10766790