Is Rust a Problem? Screening of (Oxygenated) Hydrocarbon Reactivity Nick Gonzales, Marc Levin, and Hector Zamora Shell Global Solutions (US) Inc. Mary Kay O’Connor Process Safety Center Annual Symposium Fall 2007 Copyright  2005 by Shell Global Solutions (US) Inc. This document is made available subject to the condition that the recipient will neither use nor disclose the contents except as agreed in writing with the copyright owner.

Outline Background Experimental Description Experimental Results for Species with Rust Summary

Rust – normally iron(III) oxide - is commonly found in petrochemical processing equipment Fines/deposits can provide significant surface area Potential exists for rust to react with or catalyze reaction of process species Screening of reactivity with such contaminants can be easily overlooked Background

APTAC TM Automatic Pressure Tracking Adiabatic Calorimeter APTAC is a trademark of TIAX, LLC Sample Stirring Magnet Ceramic Insulation Pressure Vessel Pressure & Temperature Controlled Chamber Reaction Vessel Heaters Nitrogen TC Sample TC Controlled Vent Gas/Liquid Injection P Transducer

Experimental Details APTAC Air purged - Vacuum/N2 addition - N2 pressure/venting Nitrogen pad gas (except for ethylene tests) Iron(III) oxide (“rust”) - Loaded into basket (C 2 H 4 ;EO) - Poured into cell Titanium cell Teflon TM -coated stir bar sample TC

Systems Studied  Ethylene (1-170  m  -Fe 2 O 3 powder)  Ethylene Oxide (1-170  m  -Fe 2 O 3 powder)  Cumene Hydroperoxide (< 5  m  -Fe 2 O 3 )  Di-tert-Butyl Peroxide (< 5  m  -Fe 2 O 3 )  Ethylene Glycol (< 5  m  -Fe 2 O 3 )  Diethylene Glycol (< 5  m  -Fe 2 O 3 )  Hydrogen Peroxide (< 5  m  -Fe 2 O 3 ) (Diethyl Hydroxyl Amine – not yet tested) In some systems, reaction with other iron oxides (e.g., FeO) was also examined

Ethylene + Iron (III) Oxide, Iron(II) Oxide Temperature constant pressure

Ethylene + Iron (III) Oxide, Iron(II) Oxide Self-Heat constant pressure

Ethylene + Iron (III) Oxide, Iron(II) Oxide Comments: L. Britton (UCC): referred to exotherm onset temperature as low as 100°C (data not presented in ethylene paper). This was “occasionally” observed. At this point, it is not clear why lowering of the onset temperature did not occur in our tests.

Ethylene Oxide + Iron Oxides Temperature Histories

Ethylene Oxide + Iron Oxides Pressure Histories

Ethylene Oxide + Iron Oxides Self-Heat Rates

Ethylene Oxide + Iron Oxides Pressurization Rates

30%w CHP/cumene + Iron(III) Oxide Temperature Histories

30%w CHP/cumene + Iron(III) Oxide Pressure Histories

30%w CHP/cumene + Iron(III) Oxide Self-Heat Rates

30%w CHP/cumene + Iron(III) Oxide Pressurization Rates

30%w CHP/cumene + Iron(III) Oxide Time to Maximum Rate

20%w DTBP/Toluene + Iron(III) Oxide Temperature Histories

20%w DTBP/Toluene + Iron(III) Oxide Pressure Histories

20%w DTBP/Toluene + Iron(III) Oxide Self-Heat Rate

20%w DTBP/Toluene + Iron(III) Oxide Pressurization Rate

Ethylene Glycol + Iron(III) Oxide Temperature Histories

Ethylene Glycol + Iron(III) Oxide Pressure Histories

Ethylene Glycol + Iron(III) Oxide Self-Heat Rates

Ethylene Glycol + Iron(III) Oxide Pressurization Rates

Diethylene Glycol + Iron(III) Oxide Temperature Histories

Diethylene Glycol + Iron(III) Oxide Pressure Histories

Diethylene Glycol + Iron(III) Oxide Self-Heat Rates

Diethylene Glycol + Iron(III) Oxide Pressurization Rates

Hydrogen Peroxide + Iron(III) Oxide Temperature Histories

Hydrogen Peroxide + Iron(III) Oxide Pressure Histories

Hydrogen Peroxide + Iron(III) Oxide Self-Heat Rates

Hydrogen Peroxide + Iron(III) Oxide Pressurization Rates

Hydrogen Peroxide + Iron(III) Oxide Time to Maximum Rate

Summary Of the systems examined, iron(III) Oxide (“rust”) significantly affects only EO. Marginal impact seen for CHP Surprisingly, no significant effect on ethylene Large effect observed for H 2 O 2 Overall conclusion: rust enhances reaction for species that are known for instability or reactivity

Summary Future Interest Continued testing Additional species with  -Fe 2 O 3 Species with FeO Species with high surface area Fe