System: Selective Catalytic Reduction (SCR)

Subject: Urea study PACO SCR

Applicable Pollutants: NOx

Objective: Considerations from a chemistry perspective

From the chemical point of view, there are several aspects to consider:

CHEMICAL CONTROL UNIT CONAPRED (National Commission for the Study and Prevention of Drugs).

Ammonia and all its aqueous solutions are considered as controlled substances. This will cause all
transportation and purchases of Ammonia to be monitored by CONAPRED.

Urea has no restrictions for CONAPRED, so it will not be monitored by them.

SAFETY
Ammonia: It has risk associated with transportation, handling and storage (page 8)

Urea: This is a stable, non-volatile and environmentally benign chemical compound. Under ambient
conditions, pure urea is solid and can be safely transported by truck in bulk or in supersacks (page 10).

Chemical reaction notes

Ammonia:
The SCR process utilizes ammonia (NH3), which adsorbs onto the surface of the SCR catalyst where it
reacts with NOX and oxygen to form nitrogen and water according to the following reactions (page 9)

Urea:
Urea reacts with water (*) and heat to produce ammonia and carbon dioxide in a process called hydrolysis
(page 9)

(*) The 50% urea solution must remain above 64 F (18 C) or the solution with begin to salt out (page 11).
By comparing these two reactions, it can be seen that the reaction products of both are not exactly the
same. In the case of ammonia, we observed that the final products of the catalysis are N2 and water.
In the case of Urea, an additional step must be made before the catalysis called hydrolysis, a process that
produces ammonia and CO2 as reaction products, indicating that this process produces a greenhouse gas.
Having to maintain the 50% urea solution with water at a temperature of 17 degrees Celsius, suggests
that an additional cooling system must be installed to handle and maintain the suggested temperature
(stainless steel tank and solutionizing skid). This suggest that if there is any leakage of this solution after
this tank, we would have an aspect of the salts accumulated in the valves or pipes where possible leakage
would occur and causing points of corrosion of the materials coming into contact with this solution.
Ammonium carbamate solutions are notoriously corrosive to metallic construction materials, even more
resistant forms of stainless steelespecially in the hottest parts of the plant such as the stripper.
The existing units at the PACO Power Plant use anhydrous ammonia as the ammonia reagent. The current
ammonia handling equipment is designed to supply 19.75 kg/hour of anhydrous ammonia at 100% MCR
for each unit. This injection rate is based on a SCR design inlet NOx of 147.1 kg/hour and an approximate
design SCR NOX reduction of 33% (page 9), but it is not clear either the percentage of NOx reduction if
we use Urea, the document prepared by Sargent & Lundy does not indicate this. However, if we consider
that the anhydrous ammonia provides a 100% reagent, it can be deduced that when using a solution of
water + urea to be hydrolyzed will provide less reagent for the catalysis reaction, so it is expected that the
urea in the reduction of NOx is lower.
Some example of others considerations about cost and feasibility between Ammonia and Urea in the SCR
System are in the next web: http://www.ecctech.com/pdfs/costanalywashgrp.pdf

Websites consulted:
https://www3.epa.gov/ttncatc1/dir1/fscr.pdf
https://www3.epa.gov/ttn/catc/dir1/cs4-2ch1.pdf
http://files.pfernandezdiez.es/CentralesTermicas/PDFs/33CT.pdf
https://www.epa.gov/sites/production/files/2016-05/documents/fpte.pdf
http://www.yara.us/nox-reduction/nox-reduction-for-stationary-plants/nox-reduction-reagents/urea-
for-nox-control/
http://www.yara.us/nox-reduction/nox-reduction-for-stationary-plants/nox-reduction-
reagents/anhydrous-ammonia-for-nox-control/