Lecture 25 (CSI) Chemical Reaction Engineering (CRE) is the field that studies the rates and mechanisms of chemical reactions and the design of the reactors.

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Lecture 25 (CSI) Chemical Reaction Engineering (CRE) is the field that studies the rates and mechanisms of chemical reactions and the design of the reactors in which they take place.

CSI Ammonium Nitrate Explosion Monsanto Explosion Lecture 21 3/29/11 Web Lecture 25 – 3/29/2011 Class Lecture 21 CSI Ammonium Nitrate Explosion Monsanto Explosion T2 Laboratories Explosion

CSI: Case I Ammonium Nitrate Explosion Massive blast at Terra plant kills four

Example 1: Safety in Chemical Reactors

Example 1: Safety in Chemical Reactors Only liquid A in the vat as the product gases N2O and H2O escape immediately after being formed.

Unsteady State Energy balance Adiabatic T If the flow rate is shut off, the temperature will rise (possibly to point of explosion!) t (min

CSI: Case II Monsanto Chemical Company Keeping MBAs Away From Chemical Reactors The process worked for 19 years before “they” showed up! Why did they come? What did they want?

Nitroaniline Synthesis Reaction NO2 NH2 Cl + 2NH3 + NH4Cl ONCB + Ammonia Nitroanaline + Ammonium Chloride HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Nitroaniline Synthesis Reaction Autoclave 175 oC ~550 psi NH3 Separation Filter Press NH3 in H2O ONCB O-Nitroaniline Product Stream “fast” Orange To Crystallizing Tanks HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Nitroaniline Synthesis Reaction Old 3 kmol ONCB 43 kmol Ammonia 100 kmol Water V = 3.25 m3 HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Same Nitroaniline Synthesis Reaction NO2 NH2 Cl + 2NH3 + NH4Cl ONCB + Ammonia Nitroanaline + Ammonium Chloride Batch Reactor, 24 hour reaction time Management said: TRIPLE PRODUCTION HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

MBA Style Nitroaniline Synthesis Reactor New 9 kmol ONCB 33 kmol Ammonia 100 kmol Water V = 5 m3 Department of Chemical Engineering, University of Michigan, Ann Arbor HSF, 5/7/2019

Batch Reactor Energy Balance HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

The rate of “heat removed” is For high coolant flow rates, , the maximum rate of heat removal is The rate of “heat generated” is

Recall For isothermal operation at Qr = Qg, T = 448 K Vary to keep “heat removed” equal to “heat generation”

Isothermal operation for 45 min Everything is OK HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Adiabatic Operation for 10 minutes HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Temperature-time trajectory 9:55 t = 0 10:40 10:50 midnight 12:18 Isothermal Operation Cooling Restored Qr = 0 200 175 400 Temperature oC fuse HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

Disk Rupture No explosion The pressure relief disk should have ruptured when the temperature reached 265°C (ca. 700 psi) but it did not. If the disk had ruptured, the maximum mass flow rate out of the reactor would have been 830 kg/min (2-in orifice to 1 atm). No explosion HSF, 5/7/2019 Department of Chemical Engineering, University of Michigan, Ann Arbor

x3!!! All the following Three things must have occurred for the explosion to happen. 1. Tripled Production 2. Heat Exchange Failure 3.Relief Valve Failure

CSI: Case III Manufacture of the fuel additive methylcyclopentadiene manganese tricarbonyl (MCMT)

Production of methylcyclopentadienyl manganese tricarbonyl (MCMT) Production of methylcyclopentadienyl manganese tricarbonyl (MCMT). Step 1a. Reaction between methylcyclopentadiene (MCP) and sodium in a solvent of diethylene glycol dimethyl ether (diglyme, C6H14O3) to produce sodium methylcyclopentadiene and hydrogen gas: Step 1b. At the end of Step 1a, MnCl2 is added to the reactor. It reacts with sodium methylcyclopentadiene to produce manganese dimethylcyclopentadiene and sodium chloride: Step 1c. At the end of Step 1b, CO is added. The reaction between manganese dimethylcyclopentadiene and carbon monoxide produces the final product, methylcyclopentadienyl manganese tricarbonyl (MCMT), a fuel additive.

Only consider Step 1 Desired Reaction Undesired Reaction of Dygline Simplified Model Let A = methycylcopentadiene, B = sodium, S = Solvent (diglyme), and D = H2. These reactions are (1) A + B  C + 1/2 D (gas) (2) S  3 D (gas) + miscellaneous liquid and solid products

(2) Rates Laws: Net Rates: (3) Stoichiometry – Liquid Phase

(4) Energy Balance:

End of Lecture 21

End of Lecture 24