Skip to main content
Log in

Nitric acid recycling and copper nitrate recovery from effluent

  • Review Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

The recycling of nitric acid and copper nitrate contained in an industrial effluent was studied. The experiments conducted on such a medium showed that the presence of copper nitrate significantly improves nitric acid-water separation during distillation in an azeotropic medium. At the temperature of the azeotrope, however, this metal salt starts to precipitate, making the medium pasty, thus inhibiting the nitric acid extraction process. The optimisation of parameters such as column efficiency and adding water to the boiler at the azeotrope temperature are recommended in this protocol in order to collect the various components while avoiding the formation of by-products: NOx compounds. Thus, the absence of column, along with the addition of a small volume of water at a temperature of 118 °C, significantly increases the yield, allowing 94 % nitric acid to be recovered at the end of the process, along with the residual copper nitrate. The resulting distillate, however, is sufficiently dilute to not be used as is. Rectification is required to obtain concentrated nitric acid at 15 mol·l−1, along with a weakly acidic distillate from the distillation front. This latter is quenched using potassium hydroxide and is used as a fertiliser solution for horticulture or sheltered market gardening. This process thus allows complete recycling of all the medium’s components, including that of the distillate resulting from the nitric acid rectification operation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Aguinet G, Le Bras A, Manoury J, Martin E ( 1971) Manufacture of nitric acid GB 1 353 359

  • Alguacil FJ, Alonso M, Sastre AM (2002a) Copper separation from nitrate/nitric acid media using Acorga M5640 extractant: Part II. Supported liquid membrane study. Chem Eng J 85:265–272

    Article  CAS  Google Scholar 

  • Alguacil FJ, Cobo A, Alonso M (2002b) Copper separation from nitrate/nitric acid media using Agora M5640 extractant Part I: solvent extraction study. Chem Eng J 85:259–263

    Article  CAS  Google Scholar 

  • Allied Chemical Corporation (1969) Concentrating nitric acid. Patent GB 1 146 338

  • Brenner W (1974) Nitric acid recovery system. Patent US 3 852 412

  • Dharmendira Kumar M, Rajendran M (2000) Salt effect on enthalpy of mixing of methanol + ethyl acetate at 303.15 K. J Chem Eng Data 45:11–14

    Article  Google Scholar 

  • Dow Chemical Company (1963) Separation of nitric acid from its sels. Patent GB 929 356

    Google Scholar 

  • Echegaray D F, Velloso A A, Wagner M L (2000) Method for production of nitric acid. Patent EP 1 013 604 (A1)

  • Furter WF (1977) Salt effect in distillation: a literature review II. Can J Chem Eng 55:229–239

    Article  CAS  Google Scholar 

  • Furter WF, Cook RA (1976) Salt effect in distillation: a literature review. Int J Heat Mass Transfer 10:23–36

    Article  Google Scholar 

  • Henry K, Pratley C (1976) Nitric acid regeneration process. Patent GB 1 442 208

  • Johnston A M, Haynes B S (2012) Apparatus for use in production of nitric acid. Patent WO 2012/071614 A1

  • Kongshaug G, Mejdell G T, Mathisen K (1987) Method and apparatus for reduction of the nitrogen oxide content in effluent gases from absorption column for manufacture of nitric acid. Patent EP 0 256 533 A2

  • Lei Z, Zhou R, Duan Z (2002) Application of scaled particle theory in extractive distillation with salt. Fluid Phase Equilibra 200:187–201

    Article  CAS  Google Scholar 

  • Morozov IV, Znamenkov KO, Korenev YM, Shlyakhtin OA (2003) Thermal decomposition of Cu(NO3)2.3H2O at reduced pressures. Thermochim Acta 403:173–179

    Article  CAS  Google Scholar 

  • Munnik P, Wolters M, Gabrielsson A et al (2011) Copper nitrate redispersion to arrive at highly active silica supported copper catalysts. J Phys Chem C 115(30):14698–14706

    Article  CAS  Google Scholar 

  • Oberste-Berghaus G (1970) Process for the production of nitric acid with a concentration of over 70 percent by weight. Patent US 3 716 625

  • Robert Mathew MC (1972) A process for the manufacture of nitric acid. Patent US 1 402 455

  • Sander B, Rasmussen P, Fredenslund A (1986) Calculation of vapour-liquid equilibria in nitric acid-eau-nitrate salt systems using an extended UNIQUAC equation. Chem Eng Sci 41:1185–1195

    Article  CAS  Google Scholar 

  • Sardul S P (1984) Chemical of the month. J Chem Educ: volume 61 number 2

  • Sloan JG (1976) The extractive distillation process for nitric acid concentration using magnesium nitrate. Adv Chem 155:128–142. doi:10.1021/ba-1976-0155.ch009, Thermodynamic behavior of electrolytes in mixed solvents, Chapter 9

    Article  CAS  Google Scholar 

  • Vaillancourt JA (1976) Use of magnesium nitrate in the extractive distillation of nitric acid. Adv Chem 155:143–149. doi:10.1021/ba-1976-0155.ch010, Thermodynamic behavior of electrolytes in mixed solvents, Chapter 10

    Article  CAS  Google Scholar 

  • Vlaming R, Koening J, Arpentinier P ( 1997) Nitric acid production. Patent EP 0 834 466 (A1)

  • Yamamoto H, Shibata H (2004) Concentration method of nitric acid aqueous solution. Patent JP2004250294(A) ; in Japanese

Download references

Acknowledgments

We would like to thank the Martinique Regional Council, the Martinique Water Agency and the Martinique Jewellers Group who contributed to the funding of this effluent recycling project.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to L. F. Jô.

Additional information

Responsible editor: Philippe Garrigues

Rights and permissions

Reprints and permissions

About this article

Cite this article

Jô, L.F., Marcus, R. & Marcelin, O. Nitric acid recycling and copper nitrate recovery from effluent. Environ Sci Pollut Res 21, 6975–6981 (2014). https://doi.org/10.1007/s11356-014-2724-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-014-2724-z

Keywords

Navigation