ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

Corrosion under Urea production process

Substantial savings can be obtained in many types of plants through the use of corrosion resistant materials of construction (Fontana 1986). The most severe corrosion in a urea plant can occur in the reactors. However, it can be controlled through the careful selection of construction materials and initiation of proper corrosion control procedures. (Krystow 1971) The objective of every industry is to generate money at the lower cost operation; material selection will help to avoid non schedule shutdowns, longer life equipment and a continuous operation increasing the profits of the company. The production of Urea involves the reaction of ammonia with carbon dioxide at 20 to 25 MPa and 190 C. A corrosive intermediate, ammonium carbamate, is responsible for the need for corrosion-resistant construction:

2NH3 + CO2 NH2COONH4 NH2CONH2 + H2O Where NH3: Ammonia (it is substantially noncorrosive) NH2COONH4: Ammonium Carbamate (extremely corrosive) NH2CONH2: Urea (it is substantially noncorrosive)

eq 1

The idea of this job is to find an explanation of the corrosion process that attack reactors during the production of urea. There are multiple failures reported, some catastrophically that yields to explore more in detail of this process. (Wang 2009) The present study makes an estimation of the kinetics parameters of the production of urea; the objective is to find an explanation why this reaction is so aggressive in terms of corrosion to the materials to the construction material of the reactor (titanium, stainless steel) The production of ammonia into urea can be used to produced fertilizer or just as a carbon collector in the flue gas (Conway 2011).

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

The Corrosion process in any metal needs the following to occur: 1. 2. 3. 4. Anode Cathode Electronic path Ionic path or electrolyte

The corrosion process is an electrochemical process that involves two reactions:

M Mn+ + ne2H+ + 2e- H2

anodic reaction cathodic reaction

The Pourbaix diagrams are an excellent tool to exemplify the behavior of the metals in aqueous solutions (Uhlig 2011), Figure 1 shows the Fe Pourbaix diagram at 298 K (25 C), the disadvantages of this tools is that can only be constructed from pure materials, but ii is a good approximation.

Figure 1 The Fe Pourbaix diagram at 298K (25 C) (Uhlig 2011)

The following figures show the way we should read these diagrams and help us to understand the chemical stability of the metal in a certain environment.

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

Figure 2 Maps of the 3 things that can Happen (Corrosion-Akron n.d.)

Figure 3 Iron zones of stabilities (Corrosion-Akron n.d.)

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

Urea corrosion mechanism

Urea is produced on a scale of some 100,000,000 tons per year worldwide (Wikipedia 2011). However, the corrosion problems, and the corrosion mechanism are not yet understood, but with this work with its limitations have the idea to visualize what is happening inside these reactors.

NH3 + CO2 NH2COOH NH2COOH + NH3 (NH2)2CO + H2O

(1) (2)

There are not enough information of the kinetics of urea formation from ammonia and carbon dioxide reaction, but this give me the freedom to play with this kinetics and estimate how these reactions goes forward inside the reactor. Writing the reaction in a simplify way we can get the following:

A+BC C+AD

r1A= -k1CACB r2A= - k2(CACC- CD/K)

Assuming that these reactions are first order and there are no any change in T and P, we can get the following result. We can see in the graph that the carbamic acid (NH2COOH) has a really slow conversion into urea, giving it the opportunity to interact with the metal surface and starting the corrosion process. The corrosion process could be explained as follows (Han 1998): NH2COOH NH2COO- + H+ Me + xNH2COO- Mez+( NH2COO-)x + ZeMez+( NH2COO-)x Mez+ + xNH2COO(3) (4) (5)

The corrosion process can be illustrated in Figure 5, the metal starts from point 1 in the passive behavior and after the urea production starts, the pH inside the reactor changes to more acidic values making the material more susceptible to the corrosion attack point 2. Carbamic acid reaction to form Urea is really slow, compare to the first reaction that forms the carbamic acid. This explains all the time that carbamic acid has to attack the surface of the material and start the corrosion process. As urea production continues the corrosion grows until a failure is present and brakes the material.

ChE 4200:605 Enrique Maya Visuet

250 Concentration 200 150 100 50 0 0

Grad Reaction Kinetics

Teaching Project

Fall 2001

1000

2000

3000 t

4000

5000

6000

C NH2COOH, k1=1e-4,k2=1e-5

C urea, k1=1e-4,k2=1e-5

Figure 4 Urea formation from carbamic acid

Figure 5 Corrosion process (Corrosion-Akron n.d.)

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

Figure 6 Reactor explosion (Wang 2009)

Figure 7 SCC possible cause (Wang 2009)

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

SCC (Stress Corrosion Cracking)

Localized corrosion process, the conjoint of a tensile stress and a corrodent will in some instances result in the cracking of a metal alloy. Stresses that cause cracking arise from residual cold work, welding, thermal treatment or may be externally applied during service. (Carpenter 1971)

Figure 8 SCC intergranular crack (Wang 2009)

To finish this work I want to point that the corrosion process in these urea reactors are not well understood, but we can prevent the corrosion problems with the proper materials selection, for these case, stainless steel and titanium, but buy these material with and certified provider in order to avoid any mechanical problem in the material, and to have an adequate maintenance program to avoid any catastrophic consequence like the explosion on the reactor.

ChE 4200:605 Enrique Maya Visuet

Grad Reaction Kinetics

Teaching Project

Fall 2001

Polymath program

Calculated values of DEQ variables Variable Initial value Minimal value Maximal value Final value 1 2 3 4 5 6 7 8 9 CA CB CC CD K k1 k2 r1A r1B 500. 200. 0 0 5. 0.0001 1.0E-05 -10. -10. 10. 0 0 0 -10. -10. 10. 0 0 100.4004 3.639E-47 0 0 5. 0.0001 1.0E-05 -10. -10. 3.653E-49 -0.2757209 -0.2757209 0 -10. -10. -0.2629426 0 0 500. 200. 123.0523 199.5996 5. 0.0001 1.0E-05 -3.653E-49 -3.653E-49 10. 0 0 0.2757209 -2.835E-06 -3.653E-49 10. 0.2757209 10000. 100.4004 3.639E-47 0.4004307 199.5996 5. 0.0001 1.0E-05 -3.653E-49 -3.653E-49 3.653E-49 -2.835E-06 -2.835E-06 2.835E-06 -2.835E-06 -3.653E-49 -2.835E-06 2.835E-06 10000.

10 r1C 11 r2A 12 r2C 13 r2D 14 rA 15 rB 16 rC 17 rD 18 t

Differential equations 1 d(CA)/d(t) = rA 2 d(CB)/d(t) = rB 3 d(CC)/d(t) = rC 4 d(CD)/d(t) = rD Explicit equations 1 2 3 4 5 6 k2 = 0.00001 k1 = 0.0001 K=5 r2A = -k2*(CA*CC-(CD/K)) r1A = -k1*CA*CB r1B = r1A

ChE 4200:605 Enrique Maya Visuet

7 8 9 rA = r1A+r2A r2C = r2A rB = r1B

Grad Reaction Kinetics

Teaching Project

Fall 2001

10 r2D = -r2A 11 r1C = -r1A 12 rC = r1C+r2C 13 rD = r2D

References 1. Carpenter. Corrosion Causes and Control. NY: McGraw-Hill, 1971. 2. Conway, William. "Kinetics of the Reversible Reaction of CO2(aq) with Ammonia in Aqueous Solution." The Journal of Physical Chemistry, 2011: 6405-6412. 3. Corrosion-Akron. n.d. 4. Fontana, Mars G. Corrosion Engineering. McGraw-Hill Book Company, 1986. 5. Han, Wenan. "Approach to the Cause of Corrosion in Urea Medium." J. Mater. Sci. Technol., 1998: 92-94. 6. Krystow, P. E. "Materials and Corrosion Problems in Urea Plants." Chemical Engineering Progress 67 (1971): 59-64. 7. Uhlig, Herbert. Corrosion Handbook, 3rd edition. The Electrochemical Society, 2011. 8. Wang, Weiqiang. "The explosion reason analysis of urea reactor of Pingyin." Engineering Failure Analysis, 2009: 972986. 9. Wikipedia. Wikipedia. 11 19, 2011. http://en.wikipedia.org/wiki/Urea#cite_note-Ullmann-14 (accessed 11 19, 2011).