Is Rust a Problem? Screening of (Oxygenated) Hydrocarbon Reactivity

Transcription

1 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.

2 Background Outline Experimental Description Experimental Results for Species with Rust Summary

3 Background 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

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

5 APTAC Air purged Experimental Details - 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 TC Titanium cell Teflon TM -coated stir bar sample

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

7 Ethylene + Iron (III) Oxide, Iron(II) Oxide Temperature constant pressure psia (A00638) 1561 psig (A00639a) 1799 psig (A00645) psig (A00644) Ethylene + Iron (III) 1330 psig (A00701) Ethylene + Iron (III) 1580 psig (A00702) Ethylene + Iron (II) 1630 psig (A00704) Temperature [ C] Heat-Wait-Search Step Exotherm Time [min]

8 Ethylene + Iron (III) Oxide, Iron(II) Oxide Self-Heat constant pressure psia (A00638) 1561 psig (A00639a) 1799 psig (A00645) psig (A00644) Ethylene + Iron (III) 1330 psig (A00701) Ethylene + Iron (III) 1580 psig (A00702) Ethylene + Iron (II) 1630 psig (A00704) dt/dt [ C/min] 10 1 Heat-Wait-Search Step Exotherm C -0/T [K -1 ]

9 Ethylene + Iron (III) Oxide, Iron(II) Oxide Self-Heat constant pressure psig (A00639a) 1799 psig (A00645) psig (A00644) Ethylene + Iron (III) 1330 psig (A00701) Ethylene + Iron (III) 1580 psig (A00702) Ethylene + Iron (II) 1630 psig (A00704) dt/dt [ C/min] Exotherm threshold /T [K -1 ] C

10 Ethylene + Iron (III) Oxide, Iron(II) Oxide Comments: L. Britton (UCC): referred to exotherm onset temperature as low as 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.

11 Temperature [ C] Ethylene Oxide + Iron Oxides Temperature Histories 20 g EO g alpha-fe3o4 (A00507) 20 g EO g alpha-fe3o4 (A00510) 20 g EO g alpha-fe2o3 (A00370) 20 g EO g hydrated alpha-fe2o3 (A00367) 20 g EO g gamma-fe2o3 (A00362) 20 g EO g gamma-fe2o3 (A00363) 20 g EO g gamma-fe2o3 (A00373) p Time [min]

12 Ethylene Oxide + Iron Oxides Pressure Histories g EO g alpha-fe3o4 (A00507) 20 g EO g alpha-fe3o4 (A00510) 20 g EO g alpha-fe2o3 (A00370) 20 g EO g hydrated alpha-fe2o3 (A00367) 20 g EO g gamma-fe2o3 (A00362) 20 g EO g gamma-fe2o3 (A00363) 20 g EO g gamma-fe2o3 (A00373) Pressure [psia] Time [min]

13 Ethylene Oxide + Iron Oxides Self-Heat Rates g EO g alpha-fe3o4 (A00507) 20 g EO g alpha-fe3o4 (A00510) 20 g EO g alpha-fe2o3 (A00370) 20 g EO g hydrated alpha-fe2o3 (A00367) 20 g EO g gamma-fe2o3 (A00362) 20 g EO g gamma-fe2o3 (A00363) 20 g EO g gamma-fe2o3 (A00373) dt/dt [ C/min] 10 1 Exotherm 0.1 Exotherm Threshold C -0/T [K -1 ]

14 Ethylene Oxide + Iron Oxides Pressurization Rates g EO g alpha-fe3o4 (A00507) 20 g EO g alpha-fe3o4 (A00510) 20 g EO g alpha-fe2o3 (A00370) 20 g EO g hydrated alpha-fe2o3 (A00367) 20 g EO g gamma-fe2o3 (A00362) 20 g EO g gamma-fe2o3 (A00363) 20 g EO g gamma-fe2o3 (A00373) dp/dt [psi/min] /T [K -1 ] C

15 30%w CHP/cumene + Iron(III) Oxide Temperature Histories %w CHP/Cumene (A00874) 30%w CHP/Cumene %w Rust (A00855) Temperature [ C] Heat-Wait-Search Step Exotherm Time [min]

16 30%w CHP/cumene + Iron(III) Oxide Pressure Histories %w CHP/Cumene (A00874) 30%w CHP/Cumene %w Rust (A00855) Pressure [psia] Time [min]

17 30%w CHP/cumene + Iron(III) Oxide Self-Heat Rates %w CHP/Cumene (A00874) 30%w CHP/Cumene %w Rust (A00855) dt/dt [ C/min] 10 1 Heat-Wait-Search Step 0.1 Exotherm detected C -0/T [K -1 ]

18 30%w CHP/cumene + Iron(III) Oxide Pressurization Rates %w CHP/Cumene (A00874) 30%w CHP/Cumene %w Rust (A00855) dp/dt [psi/min] /T [K -1 ] C

19 30%w CHP/cumene + Iron(III) Oxide Time to Maximum Rate %w CHP/Cumene (A00874) 30%w CHP/Cumene %w Rust (A00855) 400 Temperature [ C] Time to Maximum Rate [min]

20 20%w DTBP/Toluene + Iron(III) Oxide Temperature Histories %w DTBP in Toluene (A00575) 20%w DTBP in Toluene %w Rust (A00871) Temperature [ C] Heat-Wait-Search Step Exotherm Time [min]

21 20%w DTBP/Toluene + Iron(III) Oxide Pressure Histories %w DTBP in Toluene (A00575) 20%w DTBP in Toluene %w Rust (A00871) 700 Pressure [psia] Time [min]

22 20%w DTBP/Toluene + Iron(III) Oxide Self-Heat Rate 0 20%w DTBP in Toluene (A00575) 20%w DTBP in Toluene %w Rust (A00871) Heat-Wait-Search Step dt/dt [ C/min] Exotherm detected C -0/T [K -1 ]

23 20%w DTBP/Toluene + Iron(III) Oxide Pressurization Rate %w DTBP in Toluene (A00575) 20%w DTBP in Toluene %w Rust (A00871) dp/dt [psi/min] /T [K -1 ] C

24 Ethylene Glycol + Iron(III) Oxide Temperature Histories Ethylene Glycol (A00824) Ethylene Glycol %w Rust (A00870) Heat-Wait-Search Step Exotherm Temperature [ C] Time [min]

25 Ethylene Glycol + Iron(III) Oxide Pressure Histories Pressure [psia] Ethylene Glycol (A00824) Ethylene Glycol %w Rust (A00870) Time [min]

26 Ethylene Glycol + Iron(III) Oxide Self-Heat Rates Ethylene Glycol (A00824) Ethylene Glycol %w Rust (A00870) 10 dt/dt [ C/min] C -0/T [K -1 ]

27 Ethylene Glycol + Iron(III) Oxide Pressurization Rates 0 Ethylene Glycol (A00824) Ethylene Glycol %w Rust (A00870) 10 dp/dt [psi/min] /T [K -1 ] C

28 Diethylene Glycol + Iron(III) Oxide Temperature Histories DEG (A00869) DEG %w Rust (A00868) Exotherm Temperature [ C] Heat-Wait-Search Step Time [min]

29 Diethylene Glycol + Iron(III) Oxide Pressure Histories Pressure [psia] DEG (A00869) DEG %w Rust (A00868) Time [min]

30 Diethylene Glycol + Iron(III) Oxide Self-Heat Rates 0 DEG (A00869) DEG %w Rust (A00868) dt/dt [ C/min] C -0/T [K -1 ]

31 Diethylene Glycol + Iron(III) Oxide Pressurization Rates 0 DEG (A00869) DEG %w Rust (A00868) 10 dp/dt [psi/min] /T [K -1 ] C

32 Hydrogen Peroxide + Iron(III) Oxide Temperature Histories %w H2O2/Water (A00719) 30%w H2O2/Water (A00881) 30%w H2O2/Water %w Rust (A00883) Temperature [ C] Time [min]

33 Hydrogen Peroxide + Iron(III) Oxide Pressure Histories Pressure [psia] %w H2O2/Water (A00719) 30%w H2O2/Water (A00881) 30%w H2O2/Water %w Rust (A00883) Time [min]

34 Hydrogen Peroxide + Iron(III) Oxide Self-Heat Rates 0 30%w H2O2/Water (A00719) 30%w H2O2/Water (A00881) 30%w H2O2/Water %w Rust (A00883) dt/dt [ C/min] C -0/T [K -1 ]

35 Hydrogen Peroxide + Iron(III) Oxide Pressurization Rates %w H2O2/Water (A00719) 30%w H2O2/Water (A00881) 30%w H2O2/Water %w Rust (A00883) dp/dt [psi/min] /T [K -1 ] C

36 Hydrogen Peroxide + Iron(III) Oxide Time to Maximum Rate %w H2O2/Water (A00719) 30%w H2O2/Water (A00881) %w H2O2/Water %w Rust (A00883) Temperature [ C] Time to Maximum Rate [min]

37 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

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