(435k) Proton-Based Solid Acid for Ammonia Removal

Large amount of water is a NH₃ absorbent in the plant facilities for emergency. NH₃ and NH₄⁺ coexist in ammonia water. For example, potential of hydrogen (pH) is 11 in 2500 ppm ammonia water and the ratio of NH₃ and NH₄⁺ are 98% and 2%, respectively. The aqueous solution releases NH₃ due to the high equilibrium vapor pressure, resulting in increase of the negative effects on the environment. Therefore, in order to reduce ammonia released to the atmosphere, sulfuric acid is added in the aqueous solution. In this case, ammonium sulfate is formed and dissolves in the water. Therefore complicated process for ammonia removal from the solution is required. So, we focused on proton-based solid acids as ammonia storage materials which are insoluble in water. In ammonia water, the proton of the solid acid reacts with NH₃ to form NH₄⁺, and the storage capacity is proportional to the proton concentration.

In this study, we used zirconium phosphate, zeolite and impregnated activated carbon as proton-based solid acids. We also used activated carbon allophane and sepiolite as references. Ammonia storage properties of these samples were evaluated in the water solution. The ammonia storage capacity of zirconium phosphate was 10.2 wt%, which is the highest value among the studied samples.

The proton concentration in the samples was determined by titration experiments using NH₄HCO₃. The proton concentration corresponds to the ammonia storage capacity. This indicates that NH₃ reacts with H⁺ to form NH₄⁺ in the solid acid.

X-ray diffraction was used to estimate the structure of the zirconium phosphate before and after ammonia absorption. We confirmed that the interlayer spacing spreads from 0.77 nm to 0.96 nm by ammonia absorption. Temperature desorption scans of NH₃ absorbedzirconium phosphate indicates that NH₃ is desorbed below 673 K.

Then, zirconium phosphate was heat-treated at 673 K under vacuum and hydrothermally treated at 443 K. XRD measurement showed that the interlayer spacing was shrunk from 0.96 nm to 0.77 nm by the heat and hydrothermal treatments. Therefore, NH₃ absorbed zirconium phosphate can be converted back to zirconium phosphate.

This work was partially supported by Council for Science, Technology and Innovation (CSTI), Cross-ministerial Strategic Innovation Promotion Program (SIP), “energy carrier” (funding agency : JST).