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Grad Reaction Kinetics
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)
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).
→ H2 anodic reaction cathodic reaction The Pourbaix diagrams are an excellent tool to exemplify the behavior of the metals in aqueous solutions (Uhlig 2011). Anode Cathode Electronic path Ionic path or electrolyte The corrosion process is an electrochemical process that involves two reactions: M → Mn+ + ne2H+ + 2e. 2.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. but ii is a good approximation. . 3. Figure 1 shows the Fe Pourbaix diagram at 298 K (25 C). 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. the disadvantages of this tools is that can only be constructed from pure materials. 4.
) Figure 3 Iron zones of stabilities (Corrosion-Akron n.) .d.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.
but this give me the freedom to play with this kinetics and estimate how these reactions goes forward inside the reactor. 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. compare to the first reaction that forms the carbamic acid.000. However. but with this work with its limitations have the idea to visualize what is happening inside these reactors. Writing the reaction in a simplify way we can get the following: A+B→C C+A↔D r1A= -k1CACB r2A= . the corrosion problems.000 tons per year worldwide (Wikipedia 2011).+ H+ Me + xNH2COO. 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.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.↔ 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. As urea production continues the corrosion grows until a failure is present and brakes the material. .k2(CACC. and the corrosion mechanism are not yet understood. The corrosion process could be explained as follows (Han 1998): NH2COOH ↔ NH2COO. the pH inside the reactor changes to more acidic values making the material more susceptible to the corrosion attack point 2. we can get the following result. Carbamic acid reaction to form Urea is really slow.CD/K) Assuming that these reactions are first order and there are no any change in T and P. This explains all the time that carbamic acid has to attack the surface of the material and start the corrosion process.
k2=1e-5 Figure 4 Urea formation from carbamic acid Figure 5 Corrosion process (Corrosion-Akron n.d. k1=1e-4.k2=1e-5 C urea.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.) .
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) .
and to have an adequate maintenance program to avoid any catastrophic consequence like the explosion on the reactor. Stresses that cause cracking arise from residual cold work. for these case. . (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. stainless steel and titanium. the conjoint of a tensile stress and a corrodent will in some instances result in the cracking of a metal alloy. but buy these material with and certified provider in order to avoid any mechanical problem in the material.ChE 4200:605 Enrique Maya Visuet Grad Reaction Kinetics Teaching Project Fall 2001 SCC (Stress Corrosion Cracking) Localized corrosion process. but we can prevent the corrosion problems with the proper materials selection. thermal treatment or may be externally applied during service. welding.
835E-06 -2. 123.5996 5.0001 1.653E-49 -2.639E-47 0 0 5.0E-05 -10. -10. -0. 0 0 0.2757209 -0. 0 0 100.0001 K=5 r2A = -k2*(CA*CC-(CD/K)) r1A = -k1*CA*CB r1B = r1A .4004307 199. 0. 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 = 0.5996 5. 0.835E-06 10000.835E-06 -3. 0 0 5. 10. 3.639E-47 0. 0.0E-05 -3.2757209 10000. -10.4004 3.835E-06 2.653E-49 3.653E-49 -2.2629426 0 0 500.653E-49 10. 0.00001 k1 = 0. 10.835E-06 -2.2757209 -2. 100. -10.2757209 0 -10.0523 199.653E-49 -0.835E-06 -3.653E-49 -3.4004 3. 200.653E-49 10. 0.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. 200.835E-06 2.0001 1.0001 1.0001 1. 0 0 0 -10. -10.653E-49 -3.0E-05 -10.0E-05 -3.
The Electrochemical Society. 3rd edition. Wikipedia. Mars G. E. P. Technol. Fontana. Sci. 4. Herbert. n. 2011. 1971. 2. Corrosion Engineering. 5. 8.wikipedia. NY: McGraw-Hill. "The explosion reason analysis of urea reactor of Pingyin. Wenan. Carpenter.d. 2011. 2011: 6405-6412. "Kinetics of the Reversible Reaction of CO2(aq) with Ammonia in Aqueous Solution. 11 19. Corrosion Causes and Control. 3." The Journal of Physical Chemistry." Engineering Failure Analysis. "Materials and Corrosion Problems in Urea Plants. Wang. "Approach to the Cause of Corrosion in Urea Medium. Krystow. 6. 2011). 1998: 92-94. Uhlig. 1986. William. Corrosion-Akron. ..org/wiki/Urea#cite_note-Ullmann-14 (accessed 11 19. 2009: 972–986." J. 7. Wikipedia. Corrosion Handbook. Conway. Weiqiang. 9. Han.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. McGraw-Hill Book Company. Mater." Chemical Engineering Progress 67 (1971): 59-64. http://en.
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