Operating Guidelines

8/3/2019 Operating Guidelines

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SAMSUNG TOTAL PETROCHEMICALS CO., LTD.

SULFUR BLOCK

NO. 2 AROMATICS COMPLEXDAESAN, KOREA

OPERATING GUIDELINES

Prepared byOrtloff Engineers, Ltd.Midland, Texas USA

Project 507000Fall 2011


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Operating Guidelines Samsung Total Petrochemicals Co., Ltd.Fall 2011 Daesan, Korea

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Table of Contents

Issued 30Aug11 Table of Contents Page i

1. INTRODUCTION .......................................................................................................... 1-12. GENERAL SAFETY ..................................................................................................... 2-1

2.1 DEFINITION OF TERMS ....................................................................................... 2-12.2 HYDROGEN SULFIDE (H2S) ................................................................................ 2-3

2.2.1 Description and Properties ............................................................................. 2-32.2.2 First Aid .......................................................................................................... 2-72.2.3 Precautions (remember these facts) .............................................................. 2-82.2.4 Good Work Practices ...................................................................................... 2-9

2.3 SULFUR DIOXIDE (SO2) ..................................................................................... 2-102.3.1 Description and Properties ........................................................................... 2-102.3.2 First Aid ........................................................................................................ 2-132.3.3 Precautions ................................................................................................... 2-14

2.4 SULFUR .............................................................................................................. 2-152.4.1 Description and Properties ........................................................................... 2-152.4.2 Precautions ................................................................................................... 2-202.4.3 Fire Fighting .................................................................................................. 2-21

2.5 AMMONIA (NH3) .................................................................................................. 2-222.5.1 Description and Properties ........................................................................... 2-222.5.2 First Aid ........................................................................................................ 2-262.5.3 Precautions ................................................................................................... 2-26

2.6 METHYLDIETHANOLAMINE (MDEA, CH3-N-(CH2-CH2-OH)2) ........................... 2-282.6.1 Description and Properties ........................................................................... 2-282.6.2 First Aid ........................................................................................................ 2-292.6.3 Precautions ................................................................................................... 2-30

2.7 SODIUM HYDROXIDE (CAUSTIC SODA, NAOH) ............................................. 2-312.7.1 Description and Properties ........................................................................... 2-312.7.2 First Aid ........................................................................................................ 2-352.7.3 Precautions ................................................................................................... 2-36

2.8 SULFUR PLANT SAFETY ................................................................................... 2-372.8.1 Hydrogen Sulfide .......................................................................................... 2-372.8.2 Sulfur Dioxide ............................................................................................... 2-372.8.3 Sulfur Storage Tank ...................................................................................... 2-38

2.9 HOT WORK ......................................................................................................... 2-392.10 VESSEL ENTRY.................................................................................................. 2-392.11 PIPES AND LINES .............................................................................................. 2-41

2.11.1 General ......................................................................................................... 2-412.11.2 Before Breaking Lines .................................................................................. 2-42


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2.11.3 When Breaking Lines ................................................................................... 2-422.12 ELECTRICAL EQUIPMENT ................................................................................ 2-42

2.12.1

Electrical Repairs .......................................................................................... 2-43

2.12.2 Grounding ..................................................................................................... 2-432.12.3 Conduit, Cables, and Wires .......................................................................... 2-432.12.4 Fuses ............................................................................................................ 2-432.12.5 Switching ...................................................................................................... 2-432.12.6 Hand Tools and Portable Equipment ............................................................ 2-442.12.7 Miscellaneous ............................................................................................... 2-44

2.13 BOILERS AND OTHER DIRECT-FIRED EQUIPMENT ...................................... 2-452.13.1 General ......................................................................................................... 2-452.13.2 Boilers ........................................................................................................... 2-452.13.3 Direct-Fired Equipment ................................................................................. 2-46

2.14 LABORATORY SAFETY ..................................................................................... 2-472.14.1 Good Housekeeping ..................................................................................... 2-472.14.2 Equipment .................................................................................................... 2-472.14.3 Chemical Sorting and Identification .............................................................. 2-472.14.4 Chemical Handling ....................................................................................... 2-48

2.15 MATERIAL SAFETY DATA SHEETS (MSDS) .................................................... 2-493. GENERAL .................................................................................................................... 3-1

3.1 ORGANIZATION ................................................................................................... 3-13.2 GENERAL PRECOMMISSIONING PROCEDURES ............................................. 3-2

3.2.1 Mechanical ..................................................................................................... 3-23.2.2 Electrical ......................................................................................................... 3-33.2.3 Instrumentation ............................................................................................... 3-5

3.3 DESIGN BASIS ..................................................................................................... 3-73.3.1 Plant Capacity ................................................................................................ 3-73.3.2 Sulfur Block Feed Streams ............................................................................. 3-73.3.3 Effluent Stream Conditions ........................................................................... 3-123.3.4 Other Design Requirements ......................................................................... 3-133.3.5 Utility Information .......................................................................................... 3-143.3.6 Plant Site Conditions .................................................................................... 3-16

4. POWER DISTRIBUTION .............................................................................................. 4-14.1 PURPOSE OF SYSTEM ....................................................................................... 4-14.2 SAFETY ................................................................................................................. 4-1

4.2.1 General ........................................................................................................... 4-14.2.2 Hazardous (Classified) Areas ......................................................................... 4-1


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4.3 EQUIPMENT DESCRIPTION ................................................................................ 4-24.3.1 Motors and Motor Controls ............................................................................. 4-2

5. PLANT CONTROL SYSTEMS ..................................................................................... 5-15.1 DISTRIBUTED CONTROL SYSTEM .................................................................... 5-15.2 PROGRAMMABLE LOGIC CONTROL SYSTEM ................................................. 5-25.3 EMERGENCY SHUTDOWN SYSTEMS ............................................................... 5-35.4 LOCAL CONTROL PANELS ................................................................................. 5-3

6. UTILITY SYSTEMS ...................................................................................................... 6-16.1 PURPOSE OF SYSTEM ....................................................................................... 6-16.2 SYSTEM DESCRIPTION ...................................................................................... 6-1

6.2.1 Nitrogen Supply .............................................................................................. 6-16.2.2 C4 LPG and Treated Fuel Gas Supply .......................................................... 6-26.2.3 Hydrogen Supply ............................................................................................ 6-26.2.4 Plant Air .......................................................................................................... 6-36.2.5 Instrument Air ................................................................................................. 6-36.2.6 Sour Water Disposal ....................................................................................... 6-36.2.7 Steam, Condensate, Boiler Feed Water, and Blowdown ............................... 6-4

6.3 PRECOMMISSIONING, STARTUP, AND SHUTDOWN PROCEDURES............. 6-87. AMINE TREATING & AMINE REGENERATION ......................................................... 7-1

7.1 PURPOSE OF SYSTEM ....................................................................................... 7-17.2

SAFETY ................................................................................................................. 7-1

7.3 PROCESS DESCRIPTION .................................................................................... 7-2

7.3.1 General ........................................................................................................... 7-27.3.2 Water Washing ............................................................................................... 7-27.3.3 Sour Gas Contacting ...................................................................................... 7-37.3.4 Solvent Regeneration ..................................................................................... 7-3

7.4 EQUIPMENT DESCRIPTION ................................................................................ 7-67.4.1 Wash Water Column, A2-DA1510 .................................................................. 7-67.4.2 Amine Absorber, A2-DA1511 ......................................................................... 7-67.4.3 Flash Gas Contactor, A2-DA1512 .................................................................. 7-67.4.4 Stripper, A2-DA1513 ...................................................................................... 7-67.4.5 Wash Water Column Packing, A2-DB1510 .................................................... 7-77.4.6 Amine Absorber Trays, A2-DB1511 ............................................................... 7-77.4.7 Stripper Trays, A2-DB1513 ............................................................................ 7-77.4.8 Amine Absorber Overhead Cooler, A2-EA1510 ............................................. 7-87.4.9 Lean/Rich Exchanger, A2-EA1511A/B ........................................................... 7-87.4.10 Stripper Reboiler, A2-EA1512A/B .................................................................. 7-8


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7.4.11 Stripper Reflux Condenser, A2-EC1511 ......................................................... 7-87.4.12 Lean Amine Cooler, A2-EC1510 .................................................................... 7-87.4.13

Wash Water Feed Knock-Out Drum, A2-FA1510 ........................................... 7-8

7.4.14 Amine Absorber Feed Knock-Out Drum, A2-FA1511 ..................................... 7-97.4.15 Amine Absorber Overhead Knock-Out Drum, A2-FA1512 ............................. 7-97.4.16 Rich Amine Flash Drum, A2-FA1513 ............................................................. 7-97.4.17 Stripper Reflux Accumulator, A2-FA1514 ..................................................... 7-107.4.18 Stripper Reboiler Condensate Pot, A2-FA1515A/B ...................................... 7-107.4.19 ATU Skim Oil Sump, A2-FA1516 ................................................................. 7-107.4.20 ATU Skim Oil Pump Sump, A2-FA1517A/B ................................................. 7-107.4.21 ATU Amine Drips Tank, A2-FA1580 ............................................................. 7-117.4.22 MDEA Storage Tank, A2-FB1580 ................................................................ 7-117.4.23 Wash Water Filter, A2-FD1510A/B ............................................................... 7-117.4.24 Rich Amine Filter, A2-FD1511A/B ................................................................ 7-117.4.25 Lean Amine Filter, A2-FD1512 ..................................................................... 7-117.4.26 Lean Amine Carbon Filter, A2-FD1513 ........................................................ 7-127.4.27 Lean Amine After-Filter, A2-FD1514 ............................................................ 7-127.4.28 ATU Amine Drips Filter, A2-FD1580 ............................................................ 7-127.4.29 Wash Water Pump, A2-GA1510A/B ............................................................. 7-137.4.30 Lean Amine Pump, A2-GA1511A/B ............................................................. 7-137.4.31 ATU Skim Oil Pump, A2-GA1512A/B ........................................................... 7-137.4.32 Rich Amine Pump, A2-GA1513A/B .............................................................. 7-137.4.33 Lean Amine Booster Pump, A2-GA1514A/B ................................................ 7-137.4.34 Stripper Reflux Pump, A2-GA1515A/B ......................................................... 7-137.4.35 MDEA Transfer Pump, A2-GA1580 .............................................................. 7-14

7.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 7-157.5.1 Treated Fuel Gas H2S Analyzer ................................................................... 7-157.5.2 ATU Emergency Shutdown Systems ........................................................... 7-15

7.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 7-197.6.1 Amine Absorber Operation ........................................................................... 7-197.6.2 Stripper Operation ........................................................................................ 7-227.6.3

Amine Water Balance ................................................................................... 7-24

7.6.4 Amine Loss ................................................................................................... 7-277.6.5 Operation at Low Flow Rates ....................................................................... 7-29

7.7 PRECOMMISSIONING PROCEDURES ............................................................. 7-307.7.1 Preliminary Check-out .................................................................................. 7-307.7.2 Shutdown System Check-out ....................................................................... 7-317.7.3 Leak Testing the Process Piping and Equipment ......................................... 7-31


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7.7.4 Washing the Wash Water System ................................................................ 7-337.7.5 Washing the Amine System ......................................................................... 7-387.7.6

Purging the Low Pressure Columns ............................................................. 7-50

7.8 STARTUP PROCEDURES .................................................................................. 7-52

7.8.1 Wash Water and Amine Systems ................................................................. 7-527.8.2 Sour Fuel Gas Flow to the Columns ............................................................. 7-53

7.9 SHUTDOWN PROCEDURES ............................................................................. 7-567.9.1 Planned Shutdown - ATU ............................................................................ 7-577.9.2 Planned Shutdown - ATU and ARU ............................................................. 7-607.9.3 Emergency Shutdown .................................................................................. 7-627.9.4 Effects of Shutdowns and Outages in Other Systems .................................. 7-63

7.10 ANALYTICAL PROCEDURES ............................................................................ 7-647.10.1 General Procedures for Analyzing ATU/ARU Solvent, ................................. 7-647.10.2 Determination of Amine Concentration in ATU/ARU Solvent ....................... 7-687.10.3 Determination of Total Acid Gas Loading in ATU/ARU Solvent ................... 7-707.10.4 Determination of H2S and CO2 Loading in ATU/ARU Solvent ...................... 7-727.10.5 Determination of Foaming Tendency of ATU/ARU Solvent .......................... 7-767.10.6 H2S Conc. in Amine Absorber Ovhd by the Tutweiler Method ..................... 7-787.10.7 H2S Conc. in Amine Absorber Ovhd Using Gas Detector Tubes ................. 7-79

8. SOUR WATER STRIPPING ......................................................................................... 8-18.1 PURPOSE OF SYSTEM ....................................................................................... 8-18.2 SAFETY ................................................................................................................. 8-18.3 PROCESS DESCRIPTION .................................................................................... 8-2

8.3.1 General ........................................................................................................... 8-28.3.2 Sour Water Collection ..................................................................................... 8-28.3.3 Sour Water Stripping ...................................................................................... 8-3

8.4 EQUIPMENT DESCRIPTION ................................................................................ 8-58.4.1 Sour Water Stripper, A2-DA1520 ................................................................... 8-58.4.2 Sour Water Stripper Packing and Internals, A2-DB1520 ................................ 8-58.4.3 Stripper Trays, A2-DB1521 ............................................................................ 8-58.4.4 SWS Cross Exchanger, A2-EA1520 .............................................................. 8-58.4.5 Sour Water Stripper Reboiler, A2-EA1521 ..................................................... 8-68.4.6 SWS Quench Water Cooler, A2-EC1520 ....................................................... 8-68.4.7 SWS Bottoms Cooler, A2-EC1521 ................................................................. 8-68.4.8 Sour Water Flash Drum, A2-FA1520 .............................................................. 8-68.4.9 SWS Skim Oil Sump, A2-FA1522 .................................................................. 8-78.4.10 SWS Skim Oil Pump Sump, A2-FA1523A/B .................................................. 8-78.4.11 Sour Water Tank, A2-FB1520 ........................................................................ 8-7


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8.4.12 Sour Water Filter, A2-FD1520A/B .................................................................. 8-78.4.13 Sour Water Transfer Pump, A2-GA1520A/B .................................................. 8-78.4.14

SWS Feed Pump, A2-GA1521A/B ................................................................. 8-8

8.4.15 SWS Quench Water Pump, A2-GA1522A/B .................................................. 8-88.4.16 SWS Bottoms Pump, A2-GA1523A/B ............................................................ 8-88.4.17 SWS Skim Oil Pump, A2-GA1524A/B ............................................................ 8-8

8.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................... 8-98.5.1 SWS Shutdowns and Alarms ......................................................................... 8-9

8.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 8-118.6.1 SWS Stripper Operation ............................................................................... 8-118.6.2 Quench Water Circulation ............................................................................ 8-128.6.3 pH Control .................................................................................................... 8-13

8.7 PRECOMMISSIONING PROCEDURES ............................................................. 8-148.7.1 Preliminary Check-out .................................................................................. 8-148.7.2 Washing the Sour Water System ................................................................. 8-15

8.8 STARTUP PROCEDURES .................................................................................. 8-198.8.1 Initial Startup of the SWS ............................................................................. 8-198.8.2 Normal Startup of the SWS .......................................................................... 8-23

8.9 SHUTDOWN PROCEDURES ............................................................................. 8-298.9.1 Planned Shutdown ....................................................................................... 8-298.9.2 Effects of Shutdowns and Outages in Other Systems .................................. 8-31

9.

SULFUR RECOVERY .................................................................................................. 9-4

9.1 PURPOSE OF SYSTEM ....................................................................................... 9-49.2 SAFETY ................................................................................................................. 9-49.3 PROCESS DESCRIPTION .................................................................................... 9-5

9.3.1 Overview ......................................................................................................... 9-59.3.2 General ........................................................................................................... 9-69.3.3 Feed Gas Processing ..................................................................................... 9-69.3.4 Thermal Processing ........................................................................................ 9-79.3.5 Catalytic Processing ....................................................................................... 9-89.3.6 Air Control System .......................................................................................... 9-99.3.7 Molten Sulfur Handling ................................................................................. 9-109.3.8 Steam Production ......................................................................................... 9-10

9.4 EQUIPMENT DESCRIPTION .............................................................................. 9-119.4.1 Reactor Furnace, A2-BA1530 (A2-BA1540) ................................................. 9-119.4.2 Acid Gas Burner Assembly, A2-BA1531 (A2-BA1541) ................................ 9-129.4.3 Acid Gas Knock-Out Drum, A2-FA1530 (A2-FA1540) ................................. 9-129.4.4 SWS Gas Knock-Out Drum, A2-FA1531 (A2-FA1541) ................................ 9-12


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9.4.5 Reactor, A2-DC1530 (A2-DC1540) .............................................................. 9-139.4.6 Catalyst for Sulfur Plant Reactors, A2-MC1530 (A2-MC1540) ..................... 9-139.4.7

Acid Gas Preheater, A2-EA1530 (A2-EA1540) ............................................ 9-13

9.4.8 Sulfur Condenser, A2-EA1531 (A2-EA1541) ............................................... 9-139.4.9 Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542) ................................ 9-149.4.10 Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543) ................................ 9-149.4.11 Reactor No. 3 Feed Heater, A2-EA1534 (A2-EA1544) ................................ 9-159.4.12 Sulfur Surge Tank, A2-FB1530 (A2-FB1540) ............................................... 9-159.4.13 Acid Gas Knock-Out Drum Pump, A2-GA1530A/B (A2-GA1540A/B) .......... 9-169.4.14 SWS Gas Knock-Out Drum Pump, A2-GA1531A/B (A2-GA1541A/B) ......... 9-179.4.15 Sulfur Storage Tank Vent Ejector, A2-EE1530 (A2-EE1540) ....................... 9-179.4.16 Process Air Blower, A2-GB1530A/B (A2-GB1540A/B) ................................. 9-189.4.17 Air Blower Suction Screen/Silencer, A2-FD1530A/B (A2-FD1540A/B) ........ 9-199.4.18 Process Air Vent Silencer, A2-FG1530A/B (A2-FG1540A/B) ....................... 9-199.4.19 Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D) .................. 9-199.4.20 Refractory for Reactor Furnace and Waste Heat Boiler, A2-MR1530(A2-MR1540) .............................................................................................................. 9-209.4.21 Ceramic Ferrules for Waste Heat Boiler, A2-MR1532 (A2-MR1542) ........... 9-209.4.22 Refractory for Waste Heat Boiler, A2-MR1533 (A2-MR1543) ...................... 9-209.4.23 Refractory for Sulfur Condenser, A2-MR1534 (A2-MR1544) ....................... 9-209.4.24 Refractory for Reactor, A2-MR1535 (A2-MR1545) ...................................... 9-219.4.25 Rainshield for Reactor Furnace, A2-ME1531 (A2-ME1541) ........................ 9-219.4.26 Ceramic Ferrule for Reactor Furnace, A2-MR1531 (A2-MR1541) ............... 9-219.4.27 Waste Heat Boiler, A2-BF1530 (A2-BF1540) ............................................... 9-22

9.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 9-249.5.1 SRU Air:Acid Gas Ratio Control Loop .......................................................... 9-249.5.2 Acid Gas Burner Management System ........................................................ 9-309.5.3 Process Air Blower Controls ......................................................................... 9-349.5.4 Reactor Furnace Temperature Control ......................................................... 9-399.5.5 Knock-Out Drum Pump Control .................................................................... 9-419.5.6 "Ride-Through" System Considerations ....................................................... 9-419.5.7

Boiler Low-Low Level S/D Transmitter Testing ............................................ 9-44

9.5.8 SRU Emergency Shutdown Systems ........................................................... 9-46

9.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 9-569.6.1 Equipment Damage ...................................................................................... 9-569.6.2 Cold Catalyst Bed Startup ............................................................................ 9-589.6.3 Sulfur Solidification ....................................................................................... 9-609.6.4 Ammonia Salt Formation .............................................................................. 9-61


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9.6.5 Catalyst Fouling ............................................................................................ 9-629.6.6 Operation of SRUs in Parallel ....................................................................... 9-629.6.7

Process air Blower Operation ....................................................................... 9-65

9.6.8 Reactor Furnace Temperature ..................................................................... 9-709.6.9 Ammonia Destruction Considerations .......................................................... 9-739.6.10 Sulfur Recovery Efficiency ............................................................................ 9-769.6.11 Operation at Low Flow Rates ....................................................................... 9-789.6.12 Pressure Drop Surveys ................................................................................ 9-829.6.13 Boiler Water Treatment ................................................................................ 9-84

9.7 PRECOMMISSIONING PROCEDURES ............................................................. 9-869.7.1 Preliminary Check-out .................................................................................. 9-869.7.2 Shutdown System Check-out ....................................................................... 9-879.7.3 Leak Testing the Process Piping and Equipment ......................................... 9-889.7.4 Purging the Inlet Knock-Out Drums .............................................................. 9-939.7.5 Commissioning Fuel Gas and Instrument Air to the Process ....................... 9-959.7.6 Commissioning Nitrogen to the Process ...................................................... 9-999.7.7 Commissioning the Sulfur Surge Tank Heating and Ventilation ................. 9-1029.7.8 Pre-filling the Sulfur Drain Seal Assemblies ............................................... 9-104

9.8 STARTUP PROCEDURES ................................................................................ 9-1059.8.1 Initial Firing / Refractory Cure-out ............................................................... 9-1059.8.2 Amine Acid Gas Flow ................................................................................. 9-1179.8.3 SWS Gas Flow ........................................................................................... 9-1249.8.4 Routing SRU Tailgas to the TGCU ............................................................. 9-1279.8.5 Normal Startup - Cold System .................................................................... 9-1299.8.6 Normal Startup - Hot System ...................................................................... 9-1469.8.7 Firing Supplemental Fuel Gas .................................................................... 9-158

9.9 SHUTDOWN PROCEDURES ........................................................................... 9-1649.9.1 Planned Shutdown - No Reactor Entry ....................................................... 9-1659.9.2 Planned Shutdown for Reactor Entry ......................................................... 9-1709.9.3 Shutting Down When Boiler Tubes Are Leaking ........................................ 9-1809.9.4 Emergency Shutdown ................................................................................ 9-1819.9.5

Effects of Shutdowns and Outages in Other Systems ................................ 9-183

9.10 ANALYTICAL PROCEDURES .......................................................................... 9-187

9.10.1 Procedure for Sampling and Titrating with a Tutweiler Apparatus ............. 9-1879.10.2 H2S Concentration in Acid Gas by the Tutweiler Method ........................... 9-1899.10.3 H2S and SO2 Concentration in Tailgas by the Tutweiler Method ................ 9-1929.10.4 Tailgas Analysis Table ................................................................................ 9-1969.10.5 Tailgas Analysis Operating Chart ............................................................... 9-197


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9.10.6 Essential Apparatus for Tutweiler Analysis ................................................ 9-1999.10.7 Materials for Tutweiler Analysis .................................................................. 9-2009.10.8

H2S and SO2 Conc. in Tailgas Using Gas Detector Tubes ......................... 9-200

9.11 ADJUSTING STACKMATCH IGNITOR/PILOTS ............................................. 9-205

10. SULFUR DEGASSING, STORAGE & LOADING .................................................. 10-310.1 PURPOSE OF SYSTEM ..................................................................................... 10-310.2 SAFETY ............................................................................................................... 10-410.3 PROCESS DESCRIPTION .................................................................................. 10-510.4 EQUIPMENT DESCRIPTION .............................................................................. 10-7

10.4.1 Sulfur Degassing Reactor, A2-DC1550 ........................................................ 10-710.4.2 Sulfur Storage Tank, A2-FB1550 ................................................................. 10-710.4.3 Sulfur Feed Pump, A2-GA1532A/B (A2-GA1542A/B) .................................. 10-810.4.4 Sulfur Loading Pump, A2-GA1550A/B ......................................................... 10-810.4.5 Degassing Air Blower, A2-GB1550A/B ......................................................... 10-910.4.6 Bed Support and Limiter for Sulfur Degassing Reactor, A2-DC1551 ........... 10-910.4.7 Degassed Sulfur Drain Seal Assembly, A2-ME1550 .................................... 10-9

10.5 INSTRUMENTATION AND CONTROL SYSTEMS ........................................... 10-1110.5.1 Sulfur Feed Rate Control ............................................................................ 10-1110.5.2 Degassing Air Flow ..................................................................................... 10-1210.5.3 Sulfur Degassing Unit Startup Interlock ...................................................... 10-1310.5.4 Snuffing Steam ........................................................................................... 10-1310.5.5 Sulfur Loading ............................................................................................ 10-1410.5.6 Sulfur Loading Pump Local Stop Switches ................................................. 10-1710.5.7 Sulfur Degassing Shutdown System .......................................................... 10-1810.5.8 Sulfur Loading ESD System ....................................................................... 10-21

10.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 10-2310.6.1 Equipment Damage .................................................................................... 10-2310.6.2 Degassing Air Blower Operation ................................................................ 10-2610.6.3 Sulfur Solidification ..................................................................................... 10-2910.6.4 Sulfur Pumping ........................................................................................... 10-29

10.7 PRECOMMISSIONING PROCEDURES ........................................................... 10-3110.7.1 Preliminary Check-out ................................................................................ 10-3110.7.2 Commissioning the Heating and Ventilation Systems ................................ 10-3210.7.3 Purging the Sulfur Degassing Reactor ....................................................... 10-37

10.8 STARTUP PROCEDURES ................................................................................ 10-4010.8.1 Initial Startup of the Sulfur Degassing Unit ................................................. 10-4010.8.2 Normal Startup of the Sulfur Degassing System ........................................ 10-4610.8.3 Initial Sulfur Loading Operation .................................................................. 10-51


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10.8.4 Normal Sulfur Loading Operation ............................................................... 10-5310.9 SHUTDOWN PROCEDURES ........................................................................... 10-54

10.9.1

Planned Shutdown - No Reactor Entry ....................................................... 10-54

10.9.2 Planned Shutdown for Reactor Entry ......................................................... 10-5510.9.3 Shutdown for Tank Entry ............................................................................ 10-57

11. TAILGAS CLEANUP .............................................................................................. 11-111.1 PURPOSE OF SYSTEM ..................................................................................... 11-111.2 SAFETY ............................................................................................................... 11-211.3 PROCESS DESCRIPTION .................................................................................. 11-3

11.3.1 General ......................................................................................................... 11-311.3.2 Tailgas Hydrogenation/Hydrolysis ................................................................ 11-311.3.3 Process Gas Cooling .................................................................................... 11-411.3.4 Gas Contacting ............................................................................................. 11-511.3.5 Solvent Regeneration Section ...................................................................... 11-611.3.6 Steam Production/Consumption ................................................................... 11-7

11.4 EQUIPMENT DESCRIPTION .............................................................................. 11-811.4.1 TGCU Quench Column, A2-DA1560 ............................................................ 11-811.4.2 TGCU Quench Column Packing, A2-DB1560 .............................................. 11-811.4.3 TGCU Contactor, A2-DA1561 ...................................................................... 11-811.4.4 TGCU Contactor Packing & Internals, A2-DB1561 ...................................... 11-811.4.5 TGCU Stripper, A2-DA1562 ......................................................................... 11-911.4.6 TGCU Stripper Trays, A2-DB1562 ............................................................... 11-911.4.7 TGCU Reactor, A2-DC1560 ....................................................................... 11-1011.4.8 TGCU Stripper Reflux Accumulator, A2-FA1560 ....................................... 11-1011.4.9 Catalyst for TGCU Reactor, A2-MC1560 ................................................... 11-1011.4.10 TGCU Stripper Reboiler Condensate Pot, A2-FA1562 ........................... 11-1011.4.11 TGCU Reactor Feed Heater, A2-EA1560 ............................................... 11-1111.4.12 TGCU Waste Heat Reclaimer, A2-EA1561 ............................................ 11-1111.4.13 TGCU Quench Water Trim Cooler, A2-EA1562A/B ................................ 11-1111.4.14 TGCU Lean/Rich Exchanger, A2-EA1564 .............................................. 11-1111.4.15 TGCU Stripper Reboiler, A2-EA1565 ..................................................... 11-1211.4.16 TGCU Lean Amine Trim Cooler, A2-EA1563 ......................................... 11-1211.4.17 TGCU Quench Water Cooler, A2-EC1560 ............................................. 11-1211.4.18 TGCU Stripper Reflux Condenser, A2-EC1562 ...................................... 11-1211.4.19 TGCU Lean Amine Cooler, A2-EC1561 ................................................. 11-1211.4.20 TGCU Quench Water Pump, A2-GA1560A/B ......................................... 11-1311.4.21 TGCU Rich Amine Pump, A2-GA1561A/B ............................................. 11-1411.4.22 TGCU Stripper Reflux Pump, A2-GA1563A/B ........................................ 11-14


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11.4.23 TGCU Lean Amine Pump, A2-GA1562A/B ............................................. 11-1411.4.24 TGCU Start-Up Blower, A2-GB1560 ....................................................... 11-1411.4.25

Refractory for TGCU Reactor, A2-MR1560 ............................................ 11-15

11.4.26 TGCU Reactor Feed Mixer, A2-ME1560 ................................................ 11-1611.4.27 TGCU Quench Water Filter, A2-FD1560A/B .......................................... 11-1611.4.28 TGCU Rich Amine Filter, A2-FD1562A/B ............................................... 11-1611.4.29 TGCU Lean Amine Filter, A2-FD1563 .................................................... 11-1711.4.30 TGCU Amine Carbon Filter, A2-FD1564 ................................................ 11-1711.4.31 TGCU Amine After-Filter, A2-FD1565 .................................................... 11-1711.4.32 pH Meter Sample Filter, A2-FD1561A/B ................................................. 11-17

11.5 INSTRUMENTATION AND CONTROL SYSTEMS ........................................... 11-1811.5.1 TGCU Reactor Feed Control Loops ........................................................... 11-1811.5.2 Hydrogen and Hydrogen Sulfide Analyzer, A2-AE15858/A2-AE15859 ...... 11-2311.5.3 Boiler Low-Low Level S/D Transmitter Testing .......................................... 11-2411.5.4 Tailgas Switching Valve Controls ............................................................... 11-2611.5.5 TGCU Shutdown System ........................................................................... 11-33

11.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 11-3911.6.1 Equipment Damage .................................................................................... 11-3911.6.2 Catalyst Fouling .......................................................................................... 11-4011.6.3 TGCU Reactor Operation ........................................................................... 11-4111.6.4 TGCU Catalyst ........................................................................................... 11-4311.6.5 TGCU Start-Up Blower Operation .............................................................. 11-4411.6.6 TGCU Quench Column Operation .............................................................. 11-4511.6.7 TGCU Contactor Operation ........................................................................ 11-4811.6.8 TGCU Stripper Operation ........................................................................... 11-5211.6.9 TGCU Amine Water Balance ...................................................................... 11-5511.6.10 TGCU Amine Loss .................................................................................. 11-5911.6.11 Operation at Low Flow Rates .................................................................. 11-6011.6.12 Pressure Drop Surveys ........................................................................... 11-6111.6.13 Boiler Water Treatment ........................................................................... 11-63

11.7 PRECOMMISSIONING PROCEDURES ........................................................... 11-6411.7.1

Preliminary Check-out ................................................................................ 11-64

11.7.2 Shutdown System Check-out ..................................................................... 11-6511.7.3 Commissioning Nitrogen and Utility Air to the Process .............................. 11-6611.7.4 Commissioning Hydrogen to the Process .................................................. 11-7211.7.5 Leak Testing the Process Piping and Equipment ....................................... 11-7511.7.6 Washing the Quench Water System .......................................................... 11-7911.7.7 Washing the Amine System ....................................................................... 11-85


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11.7.8 Purging the Low Pressure TGCU Columns ................................................ 11-9711.8 STARTUP PROCEDURES .............................................................................. 11-102

11.8.1

Initial Startup of the TGCU ....................................................................... 11-102

11.8.2 Pre-Sulfiding the TGCU Catalyst .............................................................. 11-10711.8.3 Routing SRU Tailgas to the TGCU ........................................................... 11-11511.8.4 Quench Water and Amine Systems ......................................................... 11-12211.8.5 Process Gas Flow to the TGCU Columns ................................................ 11-12411.8.6 Normal Startup of the TGCU .................................................................... 11-128

11.9 SHUTDOWN PROCEDURES ......................................................................... 11-14411.9.1 Planned Shutdown - No Reactor Entry ..................................................... 11-14511.9.2 Planned Shutdown for Reactor Entry ....................................................... 11-15111.9.3 Shutting Down When Boiler Tubes Are Leaking ...................................... 11-15811.9.4 Special Precaution During Shutdowns ..................................................... 11-15911.9.5 Emergency Shutdown .............................................................................. 11-16311.9.6 Effects of Shutdowns and Outages in Other Systems .............................. 11-164

11.10 ANALYTICAL PROCEDURES ..................................................................... 11-16711.10.1 General Procedures for Analyzing TGCU Solvent, ............................... 11-16711.10.2 Determination of Amine Concentration in TGCU Solvent ..................... 11-17111.10.3 Determination of Total Acid Gas Loading in TGCU Solvent ................. 11-17311.10.4 Determination of H2S and CO2 Loading in TGCU Solvent .................... 11-17511.10.5 Determination of Foaming Tendency of TGCU Solvent ........................ 11-17911.10.6 H2S Conc. in TGCU Contactor Ovhd by the Tutweiler Method ............. 11-18111.10.7 H2S Conc. in TGCU Contactor Ovhd Using Gas Detector Tubes ......... 11-18211.10.8 Monitoring the Performance Level of TGCU Catalyst ........................... 11-185

12. TAILGAS THERMAL OXIDIZER ............................................................................ 12-212.1 PURPOSE OF SYSTEM ..................................................................................... 12-212.2 SAFETY ............................................................................................................... 12-212.3 PROCESS DESCRIPTION .................................................................................. 12-312.4 EQUIPMENT DESCRIPTION .............................................................................. 12-4

12.4.1 Thermal Oxidizer, A2-BA1570 ...................................................................... 12-412.4.2 Thermal Oxidizer Burner, A2-BA1571 .......................................................... 12-412.4.3 Steam Knock-out Drum, A2-FA1570 ............................................................ 12-412.4.4 Thermal Oxidizer Air Blower, A2-GB1570A/B .............................................. 12-412.4.5 Thermal Oxidizer Vent Stack, A2-ME1570 ................................................... 12-512.4.6 Refractory for Thermal Oxidizer, A2-MR1570 .............................................. 12-512.4.7 Thermal Oxidizer Waste Heat Boiler, A2-BF1570 ........................................ 12-5

12.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 12-712.5.1 Thermal Oxidizer Burner Management System ........................................... 12-7


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12.5.2 Thermal Oxidizer Temperature Control ...................................................... 12-1012.5.3 Thermal Oxidizer Excess Oxygen Control .................................................. 12-1012.5.4

Boiler Low-Low Level S/D Transmitter Testing .......................................... 12-11

12.5.5 Thermal Oxidizer Shutdown System .......................................................... 12-13

12.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 12-1812.6.1 Equipment Damage .................................................................................... 12-1812.6.2 Effect of Upstream Operations on the Thermal Oxidizer ............................ 12-2112.6.3 "Swapping" Air Blowers During Operation .................................................. 12-2312.6.4 Boiler Water Treatment .............................................................................. 12-24

12.7 PRECOMMISSIONING PROCEDURES ........................................................... 12-2612.7.1 Preliminary Check-out ................................................................................ 12-2612.7.2 Shutdown System Check-out ..................................................................... 12-2712.7.3 Commissioning Fuel Gas, Pilot Gas, and I/A to the Process ..................... 12-28

12.8 STARTUP PROCEDURES ................................................................................ 12-3312.8.1 Initial Firing / Refractory Cure-out ............................................................... 12-3312.8.2 Normal Startup ........................................................................................... 12-48

12.9 SHUTDOWN PROCEDURES ........................................................................... 12-5812.9.1 Planned Shutdown - No Entry .................................................................... 12-5912.9.2 Planned Shutdown for Entry ....................................................................... 12-6112.9.3 Shutting Down When Boiler Tubes Are Leaking ........................................ 12-6512.9.4 Emergency Shutdown ................................................................................ 12-6612.9.5 Effects of Shutdowns and Outages in Other Systems ................................ 12-69


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Issued 30 August 2011 Introduction Page 1-1

1. INTRODUCTION

THE INFORMATION IN THESE GUIDELINES IS CONFIDENTIAL. SOME OFTHE PROCESSES, DESIGNS, EQUIPMENT, AND/OR PROCEDURES

DESCRIBED HEREIN ARE PROPRIETARY AND/OR LICENSED BY

BP AMOCO CORPORATION, SHELL GLOBAL SOLUTIONS (US) INC., UOP

LLC. AND/OR ORTLOFF ENGINEERS, LTD. DISCLOSURE, REPRODUCTION,

OR USE OF THESE GUIDELINES FOR ANY REASON OTHER THAN

OPERATION OF THIS FACILITY IS IN VIOLATION OF WRITTEN SECRECY

AGREEMENTS.

These Operating Guidelines have been prepared by Ortloff Engineers, Ltd. as a guide

for the initial operation of the new Sulfur Block at Samsung Total Petrochemicals Co.,

Ltd.s Daesan No. 2 Aromatics Complex. The new Sulfur Block consists of an Amine

Treating Unit (ATU), an Amine Regeneration Unit (ARU), a Sour Water Stripper

(SWS), two parallel Sulfur Recovery Units (SRUs), and a common Sulfur Degassing

Unit (SDU), Tailgas Cleanup Unit (TGCU) and Tailgas Thermal Oxidation Unit (TTO).

These units are to process sour gas and sour water streams to remove the contained

sulfur and produce treated fuel gas for consumption in the complex, treated water

safe for reuse or disposal, and commercial grade molten sulfur for sales. These

guidelines contain information concerning the design, startup, operation, and

shutdown of the new facility to assist plant personnel in developing familiarity withand understanding of the process, equipment, and overall plant operation, and to

supplement equipment manufacturers' operating instructions.

We have tried to present all of the information from an operations viewpoint by

breaking the facility into separate systems for the ease of understanding and startup.

The information for the systems is organized as follows, although some systems will

not require every category:

1. Purpose of System

2. Safety

3. Process Description

4. Instrumentation and Control Systems

5. Operating Principles and Techniques

6. Precommissioning Procedures


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Issued 30 August 2011 Introduction Page 1-2

7. Startup Procedures

8. Shutdown Procedures

9. Setpoints (Controllers, Alarms, Shutdowns, PCVs, PSVs)

10. Analytical Procedures

The instructions in these guidelines are based on past experience with similar plants

and equipment. They are to be used as guidelines for developing detailed operating

procedures customized for your plant and its actual operating conditions. These

instructions are not intended in any way to supersede or supplant operating

procedures and safety practices established by Samsung Total Petrochemicals Co.,

Ltd., nor are they intended to be used independently of equipment manufacturers

operating instructions. In preparing these instructions, it has been assumed that all

startup and operating personnel have been trained in and are knowledgeable of theoperating instructions provided by the manufacturers of the equipment included in this

facility.

It is expected that Samsung Total Petrochemicals Co., Ltd. will revise and improve

upon the operating instructions in this manual as operating experience is gained, and

as required to incorporate any changes resulting from Samsung Total Petrochemicals

Co., Ltd.'s Process Safety Management program. Update and maintenance of this

manual is Samsung Total Petrochemicals Co., Ltd.'s responsibility and is not within

Ortloff's scope of responsibility.

Operating values and numbers quoted in this manual are design values. They are

presented to enable the operator to have a "ball park" idea of plant operating values.

Actual plant operating conditions may deviate from the design figures, yet yield

satisfactory operations and products. We recommend that operating parameters

such as temperatures, pressures, and flow rates be recorded on a routine basis.

Good data, properly gathered and maintained, form a valuable base for plant studies

and performance evaluations.


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Issued 30 August 2011 General Safety Page 2-i

Table of Contents

2. GENERAL SAFETY ..................................................................................................... 2-12.1 DEFINITION OF TERMS ....................................................................................... 2-12.2 HYDROGEN SULFIDE (H2S) ................................................................................ 2-3

2.2.1 Description and Properties ............................................................................. 2-32.2.1.1 General .................................................................................................... 2-32.2.1.2 Toxicity Information ................................................................................. 2-32.2.1.3 Permissible Exposure Limits ................................................................... 2-32.2.1.4 Odor ........................................................................................................ 2-32.2.1.5 Physical Data .......................................................................................... 2-32.2.1.6 Reactivity Data ........................................................................................ 2-42.2.1.7 Corrosivity Data ....................................................................................... 2-52.2.1.8 Water Solubility ....................................................................................... 2-52.2.1.9 Other Characteristics ............................................................................... 2-52.2.1.10 Fire and Explosion Hazard ...................................................................... 2-62.2.1.11 Life Hazard .............................................................................................. 2-6

2.2.2 First Aid .......................................................................................................... 2-72.2.3 Precautions (remember these facts) .............................................................. 2-82.2.4 Good Work Practices ...................................................................................... 2-9

2.3 SULFUR DIOXIDE (SO2) ..................................................................................... 2-102.3.1 Description and Properties ........................................................................... 2-10

2.3.1.1

General .................................................................................................. 2-10

2.3.1.2 Toxicity Information ............................................................................... 2-102.3.1.3 Permissible Exposure Limits ................................................................. 2-102.3.1.4 Odor ...................................................................................................... 2-112.3.1.5 Physical Data ........................................................................................ 2-112.3.1.6 Reactivity Data ...................................................................................... 2-112.3.1.7 Corrosivity Data ..................................................................................... 2-122.3.1.8 Water Solubility ..................................................................................... 2-122.3.1.9 Fire and Explosion Hazard .................................................................... 2-122.3.1.10 Life Hazard ............................................................................................ 2-12

2.3.2 First Aid ........................................................................................................ 2-132.3.3 Precautions ................................................................................................... 2-14

2.4 SULFUR .............................................................................................................. 2-152.4.1 Description and Properties ........................................................................... 2-15

2.4.1.1 General .................................................................................................. 2-152.4.1.2 Toxicity Information ............................................................................... 2-152.4.1.3 Permissible Exposure Limits ................................................................. 2-15


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2.4.1.4 Odor ...................................................................................................... 2-152.4.1.5 Physical Data ........................................................................................ 2-152.4.1.6 Reactivity Data ...................................................................................... 2-162.4.1.7 Corrosivity Data ..................................................................................... 2-192.4.1.8 Other Characteristics ............................................................................. 2-192.4.1.9 Fire and Explosion Hazard .................................................................... 2-192.4.1.10 Life Hazard ............................................................................................ 2-20

2.4.2 Precautions ................................................................................................... 2-202.4.3 Fire Fighting .................................................................................................. 2-21

2.5 AMMONIA (NH3) .................................................................................................. 2-222.5.1 Description and Properties ........................................................................... 2-22

2.5.1.1 General .................................................................................................. 2-222.5.1.2 Toxicity Information ............................................................................... 2-222.5.1.3 Permissible Exposure Limits ................................................................. 2-222.5.1.4 Odor ...................................................................................................... 2-222.5.1.5 Physical Data ........................................................................................ 2-232.5.1.6 Reactivity Data ...................................................................................... 2-232.5.1.7 Corrosivity Data ..................................................................................... 2-252.5.1.8 Water Solubility ..................................................................................... 2-252.5.1.9 Fire and Explosion Hazard .................................................................... 2-252.5.1.10 Life Hazard ............................................................................................ 2-25


2.6 METHYLDIETHANOLAMINE (MDEA, CH3-N-(CH2-CH2-OH)2) ........................... 2-282.6.1 Description and Properties ........................................................................... 2-28

2.6.1.1 General .................................................................................................. 2-282.6.1.2 Toxicity Information ............................................................................... 2-282.6.1.3 Permissible Exposure Limits ................................................................. 2-282.6.1.4 Odor ...................................................................................................... 2-282.6.1.5 Physical Data ........................................................................................ 2-282.6.1.6 Reactivity Data ...................................................................................... 2-282.6.1.7 Corrosivity Data ..................................................................................... 2-292.6.1.8 Water Solubility ..................................................................................... 2-292.6.1.9 Fire and Explosion Hazard .................................................................... 2-292.6.1.10 Life Hazard ............................................................................................ 2-29


2.7 SODIUM HYDROXIDE (CAUSTIC SODA, NAOH) ............................................. 2-312.7.1 Description and Properties ........................................................................... 2-31

2.7.1.1 General .................................................................................................. 2-31


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2.7.1.2 Toxicity Information ............................................................................... 2-312.7.1.3 Permissible Exposure Limits ................................................................. 2-312.7.1.4 Odor ...................................................................................................... 2-312.7.1.5 Physical Data ........................................................................................ 2-322.7.1.6 Reactivity Data ...................................................................................... 2-322.7.1.7 Corrosivity Data ..................................................................................... 2-342.7.1.8 Water Solubility ..................................................................................... 2-342.7.1.9 Fire and Explosion Hazard .................................................................... 2-342.7.1.10 Life Hazard ............................................................................................ 2-35


2.8 SULFUR PLANT SAFETY ................................................................................... 2-372.8.1 Hydrogen Sulfide .......................................................................................... 2-372.8.2 Sulfur Dioxide ............................................................................................... 2-372.8.3 Sulfur Storage Tank ...................................................................................... 2-38

2.8.3.1 Poisonous Gases .................................................................................. 2-382.8.3.2 Explosion and Fire ................................................................................. 2-38

2.9 HOT WORK ......................................................................................................... 2-392.10 VESSEL ENTRY .................................................................................................. 2-392.11 PIPES AND LINES .............................................................................................. 2-41

2.11.1 General ......................................................................................................... 2-412.11.2 Before Breaking Lines .................................................................................. 2-422.11.3 When Breaking Lines ................................................................................... 2-42

2.12 ELECTRICAL EQUIPMENT ................................................................................ 2-422.12.1 Electrical Repairs .......................................................................................... 2-432.12.2 Grounding ..................................................................................................... 2-432.12.3 Conduit, Cables, and Wires .......................................................................... 2-432.12.4 Fuses ............................................................................................................ 2-432.12.5 Switching ...................................................................................................... 2-432.12.6 Hand Tools and Portable Equipment ............................................................ 2-442.12.7 Miscellaneous ............................................................................................... 2-44

2.13 BOILERS AND OTHER DIRECT-FIRED EQUIPMENT ...................................... 2-452.13.1 General ......................................................................................................... 2-452.13.2 Boilers ........................................................................................................... 2-45

2.13.2.1 Repair and Maintenance ....................................................................... 2-452.13.2.2 Operations ............................................................................................. 2-46

2.13.3 Direct-Fired Equipment ................................................................................. 2-462.14 LABORATORY SAFETY ..................................................................................... 2-47

2.14.1 Good Housekeeping ..................................................................................... 2-472.14.2 Equipment .................................................................................................... 2-47


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2.14.3 Chemical Sorting and Identification .............................................................. 2-472.14.4 Chemical Handling ....................................................................................... 2-48

2.15 MATERIAL SAFETY DATA SHEETS (MSDS) .................................................... 2-49A. Hydrogen Sulfide

B. Sulfur Dioxide

C. Sulfur

D. Ammonia

E. Methyldiethanolamine

F. Sodium Hydroxide

G. UOP/ESM S-2001 Sulfur Conversion Catalyst

H. Criterion 234 Tailgas Treating Catalyst


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2. GENERAL SAFETYGeneral

The safety information published herein is for guidance only and is not intended to

supersede or replace your company's safety procedures program where a conflict of

terminology or procedure may exist.

Safety Considerations

An employee's knowledge of the hazardous chemicals and compounds with which he

will be working is one of the most basic prerequisites for his own safety, the safety of

others, and the protection of equipment. All employees should review the following

information occasionally to refresh their memories. New employees should study this

information until it is thoroughly understood.

2.1 Definition of Terms

A. Auto-Ignition Temperature

The minimum temperature to which a substance (the substance may be

solid, liquid, or gaseous) must be heated to ignite independent of other

ignition sources.

B. Flammability Limits (explosive limits)

When flammable vapors are mixed in air, there is a minimumconcentration below which the propagation of flame does not occur upon

contact with a source of ignition. There is also a maximum concentration

above which propagation of flame does not occur. These boundary line

concentrations of vapor in air are called flammable or explosive limits.

Many people are familiar with lower and upper flammability limits in

connection with engine carburetors which, when adjusted improperly, will

prevent the engines from running if the fuel mixture is either too "lean" or

too "rich".

C. Flash Point

Flash point is the lowest temperature of a liquid at which sufficient vapors

are evolved to form an ignitable mixture with air.


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D. Specific Gravity (solids and liquids)

Specific gravity of solids and liquids is the ratio of the weight of any solid

or liquid to the weight of an equal volume of water. Therefore, if the

specific gravity of a substance is a number less than one, it is lighter thanwater, and if the number is greater than one, it is heavier than water.

E. Specific Gravity (gases)

Specific gravity of gases is the ratio of weight of any gas to the weight of

an equal volume of air. Therefore, if the specific gravity of a gas is a

number less than one, it is lighter than air, and if the number is greater

than one, it is heavier than air.

F. Specific Volume

Specific volume of a substance is the volume of a unit mass of the

substance, i.e., the reciprocal of its density. The units used in this manual

are cubic feet per pound, unless otherwise noted.

G. Toxicity

Toxicity is the ability of a chemical or compound to produce injury once it

reaches a susceptible site in or on the body.


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2.2 Hydrogen Sulfide (H2S)

2.2.1 Description and Properties

2.2.1.1 General

Hydrogen sulfide is a colorless, very flammable, highly toxic gas.

2.2.1.2 Toxicity Information

LCLo: 600 PPM / 30 minutes (death of humans after

inhalation)

LCLo: 800 PPM / 5 minutes (death of humans after

inhalation)

LCLo (Lethal Concentration Low) is the lowest concentration of a

substance in air which has been reported to have caused death in

humans or animals. In other words, exposure to 600 PPM of H2S for

30 minutes or to 800 PPM of H2S for 5 minutes can cause death.

2.2.1.3 Permissible Exposure Limits

TLV: 10 PPM in air

TLV (Threshold Limit Value) is the highest level of exposure to a

toxic chemical at which no deleterious effect is noted. The American

Conference of Government Industrial Hygienists (ACGIH) has set

such levels for human exposure in industry. OSHA now uses this

10 PPM limit as the maximum allowable concentration for continuous

exposure during an eight hour working day.

2.2.1.4 Odor

In low concentrations, H2S smells like rotten eggs. Higher

concentrations quickly damage the ability to smell and cannot be

detected by the characteristic rotten egg odor.

2.2.1.5 Physical Data

a. Melting Point: -122F (-86C)

b. Boiling Point: -77F (-61C)

c. Lower Explosive Limit: 4.3% H2S (by volume) vapor in air

d. Upper Explosive Limit: 46% H2S (by volume) vapor in air

e. Auto-Ignition Temperature: 500F (260C)

f. Vapor Specific Gravity: 1.2 (heavier than air)


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2.2.1.6 Reactivity Data

Hydrogen sulfide is dangerously reactive with the following

substances:

Formula NameC2H4O acetaldehyde

BaO + Hg2O + air barium oxide + mercury oxide in air

BaO + NiO + air barium oxide + nickel monoxide in air

BaO2 barium peroxide

BrF5 bromine pentafluoride

C6H4BrN2Cl p-bromobenzene diazonium chloride

ClO chlorine monoxide

ClF3 chlorine trifluoride

CrO3 chromium trioxide (chromic anhydride, chromicacid)

Cu copper

Fe2O3nH2O di-iron trioxide hydrate

F2 fluorine

hydrated iron oxide

PbO2 lead dioxide (lead peroxide)

metal oxides

metals

HNO3 nitric acid

NCl3 nitrogen trichloride

NF3 nitrogen trifluoride

NI3 nitrogen triiodide

oxidizing materials

OF2 oxygen difluoride

ClO3F perchloryl fluoride

C6H5N2Cl phenyl diazonium chloride

rust

Ag2C2N2O2 silver fulminate

NaOH + CaO soda lime (a mixture of sodium hydroxide andcalcium oxide)

Na sodium

NaOH + CaO + air sodium hydroxide + calcium oxide (lime) in air

Na2O2 sodium peroxide


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2.2.1.7 Corrosivity Data

a. H2S readily attacks copper and most copper alloys (brass,

bronze, etc.), so such materials should not be exposed to the

process gases in an SRU, or to the atmosphere around an

SRU.

b. H2S can cause sulfide stress cracking (SSC) in a variety of

materials as discussed in NACE Standard Material

Requirements MR-01-75, "Sulfide Stress Cracking Resistant

Metallic Materials for Oilfield Equipment". Most sulfur plant

equipment operates at sufficiently low pressure to be outside

the conditions at which SSC would be expected and so is not

constructed in accordance with NACE MR-01-75. The

upstream equipment (including the Knock-Out drums and/or

pumps in the SRU, in some cases) is generally constructed of

carbon steel and stress relieved, or is constructed of austenitic

stainless steel, in accordance with NACE MR-01-75.

c. At elevated temperature (generally, above 650F/343C), H2S

will cause rapid corrosion of carbon steel even under low

pressure conditions like those in a sulfur plant. Such steel

surfaces are usually protected by refractory linings, water

cooling, and/or coating the steel surface with a protective

coating (such as Alonizing).

d. H2S is considered to be non-corrosive to aluminum, glass, and

Teflon.

2.2.1.8 Water Solubility

Hydrogen sulfide is soluble in water. At 60F (15C), approximately

3 parts (by volume) H2S will dissolve in one part water.

2.2.1.9 Other Characteristics

Hydrogen sulfide is soluble in liquid sulfur and many hydrocarbons.

Many porous materials, such as muds and residues, tend to absorbhydrogen sulfide. Increased temperature or mechanical disturbance

tends to release the absorbed gas.


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2.2.1.10 Fire and Explosion Hazard

H2S is a dangerous fire hazard when exposed to an ignition source.

2.2.1.11 Life HazardHydrogen sulfide is extremely toxic even in very low concentrations.

The maximum allowable concentration for continuous exposure

during an eight hour working day (per current OSHA regulations) is

10 parts per million by volume, or 0.001%.

Hydrogen sulfide poisoning is not cumulative like mercury, lead, and

some other materials. Repeated exposure to small doses will not

have the same effect as exposure to one long dose.

Hydrogen sulfide is highly irritating to the eyes and mucous

membranes. When inhaled, hydrogen sulfide is both an irritant and

an asphyxiant. Low concentrations of 20-150 PPM cause irritation of

the eyes; slightly higher concentrations may cause irritation of the

upper respiratory tract, and, if exposure is prolonged, pulmonary

edema may result. (Edema is a condition in which irritated tissues

swell, collect fluid, and slowly excrete a watery fluid, in this case into

the lungs or voice box.) The irritation action has been explained on

the basis that H2S combines with the alkali present in moist surface

tissues to form sodium sulfide, a caustic compound. (This compound

is used by the leather industry to help remove hair from animal

hides.)

With higher concentrations, the action of H2S on the nervous system

becomes more prominent. A 30 minute exposure to 500 PPM results

in headache, dizziness, excitement, staggering gait, diarrhea, and

dysuria, followed sometimes by bronchitis or bronchopneumonia.

The action on the nervous system is, with small amounts, one of

depression; in larger amounts, it stimulates; and, with very high

amounts, the respiratory center is paralyzed. Exposure to

800-1000 PPM may be fatal in 30 minutes, and higher

concentrations are instantly fatal. Fatal hydrogen sulfide poisoning

may occur even more rapidly than that following exposure to a

similar concentration of hydrogen cyanide. H2S does not combine

with the hemoglobin of the blood; its asphyxiant action is due to

paralysis of the respiratory center (which is usually the cause of

death).


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With repeated exposures to low concentrations, conjunctivitis,

photophobia, corneal bullae, tearing, pain, and blurred vision are the

most common findings. Higher concentrations may cause rhinitis,

bronchitis, and occasionally pulmonary edema. Exposure to very

high concentrations results in immediate death. Chronic poisoning

results in headache, inflammation of the conjunctivae and eyelids,

digestive disturbances, loss of weight, and general debility. H2S is a

common air contaminant. It is an insidious poison since sense of

smell may be fatigued and fail to give warning of high concentrations.

The following table from the U.S. Bureau of Mines represents the

degree of inhalation hazard with varying concentrations of hydrogen

sulfide:

HYDROGEN SULFIDE INHALATION HAZARDS

PERIOD OF EXPOSURE EXPOSURE

PPM PERCENT

Maximum allowable concentration for

prolonged exposure

10 0.001

Slight symptoms after exposure of several

hours

70-150 0.007-0.015

Maximum concentration that can be inhaled

for one hour without serious consequences

170-300 0.017-0.03

Dangerous after exposure of thirty minutes

to one hour

400-500 0.04-0.05

Fatal in exposures of thirty minutes or less 600 & above 0.06 & above

Concentrations exceeding 0.1% are considered rapidly fatal.

2.2.2 First Aid

Anyone overcome by H2S should be removed immediately to fresh air,

preferably a warm, well ventilated room. If breathing has stopped, begin

artificial respiration immediately. The arm lift-back pressure method of

artificial respiration is recommended. Since H2S paralyzes the respiratory

system, time is very important. Administer oxygen (or carbogen,

97% oxygen and 3% carbon dioxide) if available and if someone trained

with oxygen inhalation apparatus is present. Attempts to give oxygen by

someone unfamiliar with the use of the apparatus may result in the loss of

valuable time or may be harmful to the patient.


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For severe irritation of the eyes, hold the lids open and pour clean water

over the eyeball and lids (or use an eye irrigation fountain). Wash

thoroughly in this fashion for 15 minutes. A physician, preferably an eye

specialist, should be summoned immediately.

2.2.3 Precautions (remember these facts)

1. Odor is not a reliable test for the presence of hydrogen sulfide.

2. Since hydrogen sulfide is heavier than air, it settles when released

into the atmosphere and becomes more concentrated near the

ground and in low places.

3. Water at room temperature will dissolve approximately three times its

volume of hydrogen sulfide. Heating or agitation of the water will

cause the hydrogen sulfide to be released.

4. Hydrogen sulfide dissolves in liquid sulfur and is a hazard in storage

tanks and pits.

5. H2S is a serious fire and explosion hazard.

6. Low concentrations of hydrogen sulfide hinder the ability of an

individual to think clearly and function properly.

7. H2S concentrations higher than 0.06% can be fatal within 30 minutes

and concentrations higher than 0.1% are rapidly fatal.

8. In the Sulfur Block, H2S will always be present in the following

locations:

a. In most of the process gas streams.

b. In the rich and lean amine streams in the Amine Treating Unit.

c. In the rich and lean amine streams in the Amine Regeneration

Unit.

d. In the Sour Water Stripper liquid streams.

e. In the Acid Gas Knock-Out Drum and the SWS Knock-Out

Drum liquids, TGCU quench water, TGCU solvent, and the

TGCU Stripper reflux.

f. In the amine acid gas, the TGCU recycle gas, and the SWS gas

(the feed gases for the Sulfur Recovery Unit).

Operating Guidelines

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