An Example Involving a Continuous Nitration

This example involves a continuous adiabatic nitration process for the manufacture of mono-nitrobenzene (MNB) [215] by the reaction of benzene with nitric acid in a CSTR system. The process is designed to be inherently safe. No external cooling is used, but the reaction mass is heated by the reaction itself to a temperature level controlled by the amount of sulfuric add-water mixture circulating through the system. This acid actually acts as both a heat sink and as a nitration enhancer. If the sulfuric add pumps fail, the nitric add and benzene pumps are automatically shut off. 

In the hazard evaluation of the process, it was found that exotherms occurred with MNB-H2SO4 mixtures at temperatures above 150°C. The initiation temperature and extent of the exotherm depend on the acid concentration. During normal operation, the temperatures in die continuous stirred tank reactors and in the continuously operated separator are between 135 and 148°C. However, operating simulation showed that for certain feed rates well out of the normal operating range, the temperature could reach 180°C and a runaway is thus possible. 

DSC experiments performed in closed vessels, with a heating rate of 5°C/min on samples of 10 to 20 mg, showed that the enthalpy of reaction was from 410 to 1175 kj/kg, a significant variation range. The corresponding adiabatic temperature rise related to the enthalpy of reaction results was about 200 to 580°C. This temperature range yields a pressure rise that would cer- 

Worst-case analysis based on the DSC data, namely, the test with the lowest onset temperature, resulted in a graph showing the relationship between initial temperature and time-to-maximum rate under adiabatic conditions. For an initial temperature of 170°C, it would take 2 hours to reach the maximum rate. Venting simulation tests were undertaken on a larger scale to detect safe venting requirements for the separator and for the MNB hold tank. Several vent sizes were tested. It was found that a 10-cm rupture disc with a burst pressure 1 bar above the operating pressure was adequate. 

A thermal scan showed that the exotherm of the principal reaction can be significant if the system is neither controlled nor vented. From isothermal studies (i.e., experiments at constant temperature), time-to-maximum rate was determined which was comparable to that obtained from the DCS data. The larger scale data showed, not surprisingly, more rapid reactions at elevated temperatures. Thus, it was decided to use the DSC data at lower temperatures, and the larger scale test data at higher temperatures for hazard evaluation. 

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