Sei sulla pagina 1di 794

SAMSUNG TOTAL PETROCHEMICALS CO., LTD.

SULFUR BLOCK

NO. 2 AROMATICS COMPLEX

DAESAN, KOREA

OPERATING GUIDELINES

NO. 2 AROMATICS COMPLEX DAESAN, KOREA OPERATING GUIDELINES Prepared by Ortloff Engineers, Ltd. Midland, Texas USA

Prepared by Ortloff Engineers, Ltd. Midland, Texas USA Project 507000 Fall 2011

DAESAN, KOREA OPERATING GUIDELINES Prepared by Ortloff Engineers, Ltd. Midland, Texas USA Project 507000 Fall 2011

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

1. INTRODUCTION

 

1-1

2. GENERAL SAFETY

2-1

2.1 DEFINITION OF TERMS

2-1

2.2 HYDROGEN SULFIDE (H 2 S)

2-3

2.2.1 Description and Properties

2-3

2.2.2 First Aid

 

2-7

2.2.3 Precautions (remember these facts)

2-8

2.2.4 Good Work Practices

2-9

2.3

SULFUR DIOXIDE (SO 2 )

2-10

2.3.1 Description and Properties

2-10

2.3.2 First Aid

 

2-13

2.3.3 Precautions

2-14

2.4

SULFUR

2-15

2.4.1 Description and Properties

2-15

2.4.2 Precautions

 

2-20

2.4.3 Fire Fighting

2-21

2.5

AMMONIA (NH 3 )

2-22

2.5.1 Description and Properties

2-22

2.5.2 First Aid

 

2-26

2.5.3 Precautions

2-26

2.6

METHYLDIETHANOLAMINE (MDEA, CH 3 -N-(CH 2 -CH 2 -OH) 2 )

2-28

2.6.1 Description and Properties

2-28

2.6.2 First Aid

 

2-29

2.6.3 Precautions

2-30

2.7

SODIUM HYDROXIDE (CAUSTIC SODA, NAOH)

2-31

2.7.1 Description and Properties

2-31

2.7.2 First Aid

 

2-35

2.7.3 Precautions

2-36

2.8

SULFUR PLANT SAFETY

2-37

2.8.1 Hydrogen Sulfide

2-37

2.8.2 Sulfur

Dioxide

2-37

2.8.3 Sulfur Storage Tank

2-38

2.9 HOT WORK

 

2-39

2.10 VESSEL ENTRY

2-39

2.11 PIPES AND LINES

2-41

2.11.1 General

 

2-41

2.11.2 Before Breaking Lines

2-42

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

 

2.11.3

When Breaking Lines

2-42

2.12

ELECTRICAL EQUIPMENT

2-42

2.12.1 Electrical Repairs

2-43

2.12.2 Grounding

2-43

2.12.3 Conduit, Cables, and Wires

2-43

2.12.4 Fuses

2-43

2.12.5 Switching

2-43

2.12.6 Hand Tools and Portable Equipment

2-44

2.12.7 Miscellaneous

2-44

2.13

BOILERS AND OTHER DIRECT-FIRED EQUIPMENT

2-45

2.13.1 General

2-45

2.13.2 Boilers

2-45

2.13.3 Direct-Fired Equipment

2-46

2.14

LABORATORY SAFETY

2-47

2.14.1 Good Housekeeping

2-47

2.14.2 Equipment

2-47

2.14.3 Chemical Sorting and Identification

2-47

2.14.4 Chemical

Handling

2-48

2.15

MATERIAL SAFETY DATA SHEETS (MSDS)

2-49

3. GENERAL

3-1

3.1 ORGANIZATION

3-1

3.2 GENERAL PRECOMMISSIONING PROCEDURES

3-2

3.2.1 Mechanical

3-2

3.2.2 Electrical

3-3

3.2.3 Instrumentation

3-5

3.3

DESIGN BASIS

3-7

3.3.1 Plant Capacity

3-7

3.3.2 Sulfur Block Feed Streams

3-7

3.3.3 Effluent Stream Conditions

3-12

3.3.4 Other Design Requirements

3-13

3.3.5 Utility Information

3-14

3.3.6 Plant Site Conditions

3-16

4. POWER DISTRIBUTION

4-1

4.1 PURPOSE OF SYSTEM

4-1

4.2 SAFETY

4-1

4.2.1 General

4-1

4.2.2 Hazardous (Classified) Areas

4-1

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

4.3

EQUIPMENT DESCRIPTION

4-2

4.3.1

Motors and Motor Controls

4-2

5. PLANT CONTROL SYSTEMS

5-1

5.1 DISTRIBUTED CONTROL SYSTEM

5-1

5.2 PROGRAMMABLE LOGIC CONTROL SYSTEM

5-2

5.3 EMERGENCY SHUTDOWN SYSTEMS

5-3

5.4 LOCAL CONTROL PANELS

5-3

6. UTILITY SYSTEMS

6-1

6.1 PURPOSE OF SYSTEM

6-1

6.2 SYSTEM DESCRIPTION

6-1

6.2.1 Nitrogen Supply

6-1

6.2.2 C4 LPG and Treated Fuel Gas Supply

6-2

6.2.3 Hydrogen Supply

6-2

6.2.4 Plant Air

6-3

6.2.5 Instrument Air

6-3

6.2.6 Sour Water Disposal

6-3

6.2.7 Steam, Condensate, Boiler Feed Water, and Blowdown

6-4

6.3

PRECOMMISSIONING, STARTUP, AND SHUTDOWN PROCEDURES

6-8

7. AMINE TREATING & AMINE REGENERATION

7-1

7.1 PURPOSE OF

SYSTEM

7-1

7.2 SAFETY

7-1

7.3 PROCESS DESCRIPTION

7-2

7.3.1 General

7-2

7.3.2 Water Washing

7-2

7.3.3 Sour Gas Contacting

7-3

7.3.4 Solvent Regeneration

7-3

7.4

EQUIPMENT DESCRIPTION

7-6

7.4.1 Wash Water Column, A2-DA1510

7-6

7.4.2 Amine Absorber, A2-DA1511

7-6

7.4.3 Flash Gas Contactor, A2-DA1512

7-6

7.4.4 Stripper, A2-DA1513

7-6

7.4.5 Wash Water Column Packing, A2-DB1510

7-7

7.4.6 Amine Absorber Trays, A2-DB1511

7-7

7.4.7 Stripper Trays, A2-DB1513

7-7

7.4.8 Amine Absorber Overhead Cooler, A2-EA1510

7-8

7.4.9 Lean/Rich Exchanger, A2-EA1511A/B

7-8

7.4.10 Stripper Reboiler, A2-EA1512A/B

7-8

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

7.4.11 Stripper Reflux Condenser, A2-EC1511

7-8

7.4.12 Lean Amine Cooler, A2-EC1510

7-8

7.4.13 Wash Water Feed Knock-Out Drum, A2-FA1510

7-8

7.4.14 Amine Absorber Feed Knock-Out Drum, A2-FA1511

7-9

7.4.15 Amine Absorber Overhead Knock-Out Drum, A2-FA1512

7-9

7.4.16 Rich Amine Flash Drum, A2-FA1513

7-9

7.4.17 Stripper Reflux Accumulator, A2-FA1514

7-10

7.4.18 Stripper Reboiler Condensate Pot, A2-FA1515A/B

7-10

7.4.19 ATU Skim Oil Sump, A2-FA1516

7-10

7.4.20 ATU Skim Oil Pump Sump, A2-FA1517A/B

7-10

7.4.21 ATU Amine Drips Tank, A2-FA1580

7-11

7.4.22 MDEA Storage Tank, A2-FB1580

7-11

7.4.23 Wash Water Filter, A2-FD1510A/B

7-11

7.4.24 Rich Amine Filter, A2-FD1511A/B

7-11

7.4.25 Lean Amine Filter, A2-FD1512

7-11

7.4.26 Lean Amine Carbon Filter, A2-FD1513

7-12

7.4.27 Lean Amine After-Filter, A2-FD1514

7-12

7.4.28 ATU Amine Drips Filter, A2-FD1580

7-12

7.4.29 Wash Water Pump, A2-GA1510A/B

7-13

7.4.30 Lean Amine Pump, A2-GA1511A/B

7-13

7.4.31 ATU Skim Oil Pump, A2-GA1512A/B

7-13

7.4.32 Rich Amine Pump, A2-GA1513A/B

7-13

7.4.33 Lean Amine Booster Pump, A2-GA1514A/B

7-13

7.4.34 Stripper Reflux Pump, A2-GA1515A/B

7-13

7.4.35 MDEA Transfer Pump, A2-GA1580

7-14

7.5

INSTRUMENTATION AND CONTROL SYSTEMS

7-15

7.5.1 Treated Fuel Gas H 2 S Analyzer

7-15

7.5.2 ATU Emergency Shutdown Systems

7-15

7.6

PROCESS PRINCIPLES AND OPERATING TECHNIQUES

7-19

7.6.1 Amine Absorber Operation

7-19

7.6.2 Stripper Operation

7-22

7.6.3 Amine Water Balance

7-24

7.6.4 Amine

Loss

7-27

7.6.5 Operation at Low Flow Rates

7-29

7.7

PRECOMMISSIONING PROCEDURES

7-30

7.7.1 Preliminary Check-out

7-30

7.7.2 Shutdown System Check-out

7-31

7.7.3 Leak Testing the Process Piping and Equipment

7-31

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

 

7.7.4 Washing the Wash Water System

7-33

7.7.5 Washing the Amine System

7-38

7.7.6 Purging the Low Pressure Columns

7-50

7.8

STARTUP PROCEDURES

7-52

7.8.1 Wash Water and Amine Systems

7-52

7.8.2 Sour Fuel Gas Flow to the Columns

7-53

7.9

SHUTDOWN PROCEDURES

7-56

7.9.1 Planned Shutdown - ATU

7-57

7.9.2 Planned Shutdown - ATU and ARU

7-60

7.9.3 Emergency Shutdown

7-62

7.9.4 Effects of Shutdowns and Outages in Other Systems

7-63

7.10

ANALYTICAL

PROCEDURES

7-64

7.10.1 General Procedures for Analyzing ATU/ARU Solvent ,

7-64

7.10.2 Determination of Amine Concentration in ATU/ARU Solvent

7-68

7.10.3 Determination of Total Acid Gas Loading in ATU/ARU Solvent

7-70

7.10.4 Determination of H 2 S and CO 2 Loading in ATU/ARU Solvent

7-72

7.10.5 Determination of Foaming Tendency of ATU/ARU Solvent

7-76

7.10.6 H 2 S Conc. in Amine Absorber Ovhd by the Tutweiler Method

7-78

7.10.7 H 2 S Conc. in Amine Absorber Ovhd Using Gas Detector Tubes

7-79

8.

SOUR WATER STRIPPING

8-1

8.1 PURPOSE OF SYSTEM

8-1

8.2 SAFETY

 

8-1

8.3 PROCESS DESCRIPTION

8-2

8.3.1 General

 

8-2

8.3.2 Sour Water Collection

8-2

8.3.3 Sour Water Stripping

8-3

8.4

EQUIPMENT DESCRIPTION

8-5

8.4.1 Sour Water Stripper, A2-DA1520

8-5

8.4.2 Sour Water Stripper Packing and Internals, A2-DB1520

8-5

8.4.3 Stripper Trays, A2-DB1521

8-5

8.4.4 SWS Cross Exchanger, A2-EA1520

8-5

8.4.5 Sour Water Stripper Reboiler, A2-EA1521

8-6

8.4.6 SWS Quench Water Cooler, A2-EC1520

8-6

8.4.7 SWS Bottoms Cooler, A2-EC1521

8-6

8.4.8 Sour Water Flash Drum, A2-FA1520

8-6

8.4.9 SWS Skim Oil Sump, A2-FA1522

8-7

8.4.10 SWS Skim Oil Pump Sump, A2-FA1523A/B

8-7

8.4.11 Sour Water Tank, A2-FB1520

8-7

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

 

8.4.12 Sour Water Filter, A2-FD1520A/B

8-7

8.4.13 Sour Water Transfer Pump, A2-GA1520A/B

8-7

8.4.14 SWS Feed Pump, A2-GA1521A/B

8-8

8.4.15 SWS Quench Water Pump, A2-GA1522A/B

8-8

8.4.16 SWS Bottoms Pump, A2-GA1523A/B

8-8

8.4.17 SWS Skim Oil Pump, A2-GA1524A/B

8-8

8.5

INSTRUMENTATION AND CONTROL SYSTEMS

8-9

8.5.1

SWS Shutdowns and Alarms

8-9

8.6

PROCESS PRINCIPLES AND OPERATING TECHNIQUES

8-11

8.6.1 SWS Stripper Operation

8-11

8.6.2 Quench Water Circulation

8-12

8.6.3 pH Control

8-13

8.7

PRECOMMISSIONING PROCEDURES

8-14

8.7.1 Preliminary Check-out

8-14

8.7.2 Washing the Sour Water System

8-15

8.8

STARTUP PROCEDURES

8-19

8.8.1 Initial Startup of the SWS

8-19

8.8.2 Normal Startup of the SWS

8-23

8.9

SHUTDOWN PROCEDURES

8-29

8.9.1 Planned Shutdown

8-29

8.9.2 Effects of Shutdowns and Outages in Other Systems

8-31

9.

SULFUR RECOVERY

9-4

9.1 PURPOSE OF SYSTEM

9-4

9.2 SAFETY

9-4

9.3 PROCESS DESCRIPTION

9-5

9.3.1 Overview

9-5

9.3.2 General

9-6

9.3.3 Feed Gas Processing

9-6

9.3.4 Thermal Processing

9-7

9.3.5 Catalytic Processing

9-8

9.3.6 Air Control System

9-9

9.3.7 Molten Sulfur Handling

9-10

9.3.8 Steam Production

9-10

9.4

EQUIPMENT DESCRIPTION

9-11

9.4.1 Reactor Furnace, A2-BA1530 (A2-BA1540)

9-11

9.4.2 Acid Gas Burner Assembly, A2-BA1531 (A2-BA1541)

9-12

9.4.3 Acid Gas Knock-Out Drum, A2-FA1530 (A2-FA1540)

9-12

9.4.4 SWS Gas Knock-Out Drum, A2-FA1531 (A2-FA1541)

9-12

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

9.4.5 Reactor, A2-DC1530 (A2-DC1540)

9-13

9.4.6 Catalyst for Sulfur Plant Reactors, A2-MC1530 (A2-MC1540)

9-13

9.4.7 Acid Gas Preheater, A2-EA1530 (A2-EA1540)

9-13

9.4.8 Sulfur Condenser, A2-EA1531 (A2-EA1541)

9-13

9.4.9 Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542)

9-14

9.4.10 Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543)

9-14

9.4.11 Reactor No. 3 Feed Heater, A2-EA1534 (A2-EA1544)

9-15

9.4.12 Sulfur Surge Tank, A2-FB1530 (A2-FB1540)

9-15

9.4.13 Acid Gas Knock-Out Drum Pump, A2-GA1530A/B (A2-GA1540A/B)

9-16

9.4.14 SWS Gas Knock-Out Drum Pump, A2-GA1531A/B (A2-GA1541A/B)

9-17

9.4.15 Sulfur Storage Tank Vent Ejector, A2-EE1530 (A2-EE1540)

9-17

9.4.16 Process Air Blower, A2-GB1530A/B (A2-GB1540A/B)

9-18

9.4.17 Air Blower Suction Screen/Silencer, A2-FD1530A/B (A2-FD1540A/B)

9-19

9.4.18 Process Air Vent Silencer, A2-FG1530A/B (A2-FG1540A/B)

9-19

9.4.19 Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D)

9-19

9.4.20 Refractory for Reactor Furnace and Waste Heat Boiler, A2-MR1530

(A2-MR1540)

9-20

9.4.21 Ceramic Ferrules for Waste Heat Boiler, A2-MR1532 (A2-MR1542)

9-20

9.4.22 Refractory for Waste Heat Boiler, A2-MR1533 (A2-MR1543)

9-20

9.4.23 Refractory for Sulfur Condenser, A2-MR1534 (A2-MR1544)

9-20

9.4.24 Refractory for Reactor, A2-MR1535 (A2-MR1545)

9-21

9.4.25 Rainshield for Reactor Furnace, A2-ME1531 (A2-ME1541)

9-21

9.4.26 Ceramic Ferrule for Reactor Furnace, A2-MR1531 (A2-MR1541)

9-21

9.4.27 Waste Heat Boiler, A2-BF1530 (A2-BF1540)

9-22

9.5

INSTRUMENTATION AND CONTROL SYSTEMS

9-24

9.5.1 SRU Air:Acid Gas Ratio Control Loop

9-24

9.5.2 Acid Gas Burner Management System

9-30

9.5.3 Process Air Blower Controls

9-34

9.5.4 Reactor Furnace Temperature Control

9-39

9.5.5 Knock-Out Drum Pump Control

9-41

9.5.6 "Ride-Through"

System Considerations

9-41

9.5.7 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

9-56

9.6.1 Equipment Damage

9-56

9.6.2 Cold Catalyst Bed Startup

9-58

9.6.3 Sulfur Solidification

9-60

9.6.4 Ammonia Salt Formation

9-61

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

9.6.5 Catalyst Fouling

 

9-62

9.6.6 Operation of SRUs in Parallel

9-62

9.6.7 Process air Blower Operation

9-65

9.6.8 Reactor Furnace Temperature

9-70

9.6.9 Ammonia Destruction Considerations

9-73

9.6.10 Sulfur Recovery Efficiency

9-76

9.6.11 Operation at Low Flow Rates

9-78

9.6.12 Pressure Drop Surveys

9-82

9.6.13 Boiler Water Treatment

9-84

9.7

PRECOMMISSIONING PROCEDURES

9-86

9.7.1 Preliminary Check-out

9-86

9.7.2 Shutdown System Check-out

9-87

9.7.3 Leak Testing the Process Piping and Equipment

9-88

9.7.4 Purging the Inlet Knock-Out Drums

9-93

9.7.5 Commissioning Fuel Gas and Instrument Air to the Process

9-95

9.7.6 Commissioning Nitrogen to the Process

9-99

9.7.7 Commissioning the Sulfur Surge Tank Heating and Ventilation

9-102

9.7.8 Pre-filling the Sulfur Drain Seal Assemblies

9-104

9.8

STARTUP PROCEDURES

9-105

9.8.1 Initial Firing / Refractory Cure-out

9-105

9.8.2 Amine Acid Gas Flow

9-117

9.8.3 SWS Gas Flow

 

9-124

9.8.4 Routing SRU Tailgas to the TGCU

9-127

9.8.5 Normal Startup - Cold System

9-129

9.8.6 Normal Startup - Hot System

9-146

9.8.7 Firing Supplemental Fuel Gas

9-158

9.9

SHUTDOWN PROCEDURES

9-164

9.9.1 Planned Shutdown - No Reactor Entry

9-165

9.9.2 Planned Shutdown for Reactor Entry

9-170

9.9.3 Shutting Down When Boiler Tubes Are Leaking

9-180

9.9.4 Emergency Shutdown

9-181

9.9.5 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

9-187

9.10.2 H 2 S Concentration in Acid Gas by the Tutweiler Method

9-189

9.10.3 H 2 S and SO 2 Concentration in Tailgas by the Tutweiler Method

9-192

9.10.4 Tailgas Analysis Table

9-196

9.10.5 Tailgas Analysis Operating Chart

9-197

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

9.10.6 Essential Apparatus for Tutweiler Analysis

9-199

9.10.7 Materials for Tutweiler Analysis

9-200

9.10.8 H 2 S and SO 2 Conc. in Tailgas Using Gas Detector Tubes

9-200

9.11

ADJUSTING

STACKMATCH ® IGNITOR/PILOTS

9-205

10.

SULFUR DEGASSING, STORAGE & LOADING

10-3

10.1 PURPOSE OF SYSTEM

10-3

10.2 SAFETY

10-4

10.3 PROCESS DESCRIPTION

10-5

10.4 EQUIPMENT DESCRIPTION

10-7

10.4.1 Sulfur Degassing Reactor, A2-DC1550

10-7

10.4.2 Sulfur Storage Tank, A2-FB1550

10-7

10.4.3 Sulfur Feed Pump, A2-GA1532A/B (A2-GA1542A/B)

10-8

10.4.4 Sulfur Loading Pump, A2-GA1550A/B

10-8

10.4.5 Degassing Air Blower, A2-GB1550A/B

10-9

10.4.6 Bed Support and Limiter for Sulfur Degassing Reactor, A2-DC1551

10-9

10.4.7 Degassed Sulfur Drain Seal Assembly, A2-ME1550

10-9

10.5

INSTRUMENTATION AND CONTROL SYSTEMS

10-11

10.5.1 Sulfur Feed Rate Control

10-11

10.5.2 Degassing Air Flow

10-12

10.5.3 Sulfur Degassing Unit Startup Interlock

10-13

10.5.4 Snuffing Steam

10-13

10.5.5 Sulfur

Loading

10-14

10.5.6 Sulfur Loading Pump Local Stop Switches

10-17

10.5.7 Sulfur Degassing Shutdown System

10-18

10.5.8 Sulfur Loading ESD System

10-21

10.6

PROCESS PRINCIPLES AND OPERATING TECHNIQUES

10-23

10.6.1 Equipment

Damage

10-23

10.6.2 Degassing Air Blower Operation

10-26

10.6.3 Sulfur

Solidification

10-29

10.6.4 Sulfur

Pumping

10-29

10.7

PRECOMMISSIONING PROCEDURES

10-31

10.7.1 Preliminary Check-out

10-31

10.7.2 Commissioning the Heating and Ventilation Systems

10-32

10.7.3 Purging the Sulfur Degassing Reactor

10-37

10.8

STARTUP PROCEDURES

10-40

10.8.1 Initial Startup of the Sulfur Degassing Unit

10-40

10.8.2 Normal Startup of the Sulfur Degassing System

10-46

10.8.3 Initial Sulfur Loading Operation

10-51

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

10.8.4

Normal Sulfur Loading Operation

10-53

10.9

SHUTDOWN PROCEDURES

10-54

10.9.1 Planned Shutdown - No Reactor Entry

10-54

10.9.2 Planned Shutdown for Reactor Entry

10-55

10.9.3 Shutdown for Tank Entry

10-57

11.

TAILGAS CLEANUP

11-1

11.1 PURPOSE OF SYSTEM

11-1

11.2 SAFETY

11-2

11.3 PROCESS DESCRIPTION

11-3

11.3.1 General

11-3

11.3.2 Tailgas Hydrogenation/Hydrolysis

11-3

11.3.3 Process Gas Cooling

11-4

11.3.4 Gas Contacting

11-5

11.3.5 Solvent Regeneration Section

11-6

11.3.6 Steam Production/Consumption

11-7

11.4

EQUIPMENT DESCRIPTION

11-8

11.4.1 TGCU Quench Column, A2-DA1560

11-8

11.4.2 TGCU Quench Column Packing, A2-DB1560

11-8

11.4.3 TGCU

Contactor, A2-DA1561

11-8

11.4.4 TGCU Contactor Packing & Internals, A2-DB1561

11-8

11.4.5 TGCU

Stripper, A2-DA1562

11-9

11.4.6 TGCU Stripper Trays, A2-DB1562

11-9

11.4.7 TGCU

Reactor, A2-DC1560

11-10

11.4.8 TGCU Stripper Reflux Accumulator, A2-FA1560

11-10

11.4.9 Catalyst for TGCU Reactor, A2-MC1560

11-10

11.4.10 TGCU Stripper Reboiler Condensate Pot, A2-FA1562

11-10

11.4.11 TGCU Reactor Feed Heater, A2-EA1560

11-11

11.4.12 TGCU Waste Heat Reclaimer, A2-EA1561

11-11

11.4.13 TGCU Quench Water Trim Cooler, A2-EA1562A/B

11-11

11.4.14 TGCU Lean/Rich Exchanger, A2-EA1564

11-11

11.4.15 TGCU Stripper Reboiler, A2-EA1565

11-12

11.4.16 TGCU Lean Amine Trim Cooler, A2-EA1563

11-12

11.4.17 TGCU Quench Water Cooler, A2-EC1560

11-12

11.4.18 TGCU Stripper Reflux Condenser, A2-EC1562

11-12

11.4.19 TGCU Lean Amine Cooler, A2-EC1561

11-12

11.4.20 TGCU Quench Water Pump, A2-GA1560A/B

11-13

11.4.21 TGCU Rich Amine Pump, A2-GA1561A/B

11-14

11.4.22 TGCU Stripper Reflux Pump, A2-GA1563A/B

11-14

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

11.4.23 TGCU Lean Amine Pump, A2-GA1562A/B

11-14

11.4.24 TGCU Start-Up Blower, A2-GB1560

11-14

11.4.25 Refractory for TGCU Reactor, A2-MR1560

11-15

11.4.26 TGCU Reactor Feed Mixer, A2-ME1560

11-16

11.4.27 TGCU Quench Water Filter, A2-FD1560A/B

11-16

11.4.28 TGCU Rich Amine Filter, A2-FD1562A/B

11-16

11.4.29 TGCU Lean Amine Filter, A2-FD1563

11-17

11.4.30 TGCU Amine Carbon Filter, A2-FD1564

11-17

11.4.31 TGCU Amine After-Filter, A2-FD1565

11-17

11.4.32 pH Meter Sample Filter, A2-FD1561A/B

11-17

11.5

INSTRUMENTATION AND CONTROL SYSTEMS

11-18

11.5.1 TGCU Reactor Feed Control Loops

11-18

11.5.2 Hydrogen and Hydrogen Sulfide Analyzer, A2-AE15858/A2-AE15859

11-23

11.5.3 Boiler Low-Low Level S/D Transmitter Testing

11-24

11.5.4 Tailgas Switching Valve Controls

11-26

11.5.5 TGCU

Shutdown System

11-33

11.6

PROCESS PRINCIPLES AND OPERATING TECHNIQUES

11-39

11.6.1 Equipment Damage

11-39

11.6.2 Catalyst Fouling

11-40

11.6.3 Reactor Operation

TGCU

11-41

TGCU

11.6.4 Catalyst

11-43

11.6.5 TGCU Start-Up Blower Operation

11-44

11.6.6 TGCU Quench Column Operation

11-45

11.6.7 Contactor Operation

TGCU

11-48

11.6.8 Stripper Operation

TGCU

11-52

11.6.9 TGCU Amine Water Balance

11-55

11.6.10 TGCU Amine Loss

11-59

11.6.11 Operation at Low Flow Rates

11-60

11.6.12 Pressure Drop Surveys

11-61

11.6.13 Boiler Water Treatment

11-63

11.7

PRECOMMISSIONING PROCEDURES

11-64

11.7.1 Preliminary Check-out

11-64

11.7.2 Shutdown System Check-out

11-65

11.7.3 Commissioning Nitrogen and Utility Air to the Process

11-66

11.7.4 Commissioning Hydrogen to the Process

11-72

11.7.5 Leak Testing the Process Piping and Equipment

11-75

11.7.6 Washing the Quench Water System

11-79

11.7.7 Washing the Amine System

11-85

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

 

11.7.8

Purging the Low Pressure TGCU Columns

11-97

11.8

STARTUP PROCEDURES

11-102

11.8.1 Initial Startup of the TGCU

11-102

11.8.2 Pre-Sulfiding the TGCU Catalyst

11-107

11.8.3 Routing SRU Tailgas to the TGCU

11-115

11.8.4 Quench Water and Amine Systems

11-122

11.8.5 Process Gas Flow to the TGCU Columns

11-124

11.8.6 Normal Startup of the TGCU

11-128

11.9

SHUTDOWN PROCEDURES

11-144

11.9.1 Planned Shutdown - No Reactor Entry

11-145

11.9.2 Planned Shutdown for Reactor Entry

11-151

11.9.3 Shutting Down When Boiler Tubes Are Leaking

11-158

11.9.4 Special Precaution During Shutdowns

11-159

11.9.5 Emergency Shutdown

11-163

11.9.6 Effects of Shutdowns and Outages in Other Systems

11-164

11.10

ANALYTICAL PROCEDURES

11-167

11.10.1 General Procedures for Analyzing TGCU Solvent ,

11-167

11.10.2 Determination of Amine Concentration in TGCU Solvent

11-171

11.10.3 Determination of Total Acid Gas Loading in TGCU Solvent

11-173

11.10.4 Determination of H 2 S and CO 2 Loading in TGCU Solvent

11-175

11.10.5 Determination of Foaming Tendency of TGCU Solvent

11-179

11.10.6 H 2 S Conc. in TGCU Contactor Ovhd by the Tutweiler Method

11-181

11.10.7 H 2 S Conc. in TGCU Contactor Ovhd Using Gas Detector Tubes

11-182

11.10.8 Monitoring the Performance Level of TGCU Catalyst

11-185

12.

TAILGAS THERMAL OXIDIZER

12-2

12.1 PURPOSE OF SYSTEM

12-2

12.2 SAFETY

12-2

12.3 PROCESS DESCRIPTION

12-3

12.4 EQUIPMENT DESCRIPTION

12-4

12.4.1 Thermal Oxidizer, A2-BA1570

12-4

12.4.2 Thermal Oxidizer Burner, A2-BA1571

12-4

12.4.3 Steam Knock-out Drum, A2-FA1570

12-4

12.4.4 Thermal Oxidizer Air Blower, A2-GB1570A/B

12-4

12.4.5 Thermal Oxidizer Vent Stack, A2-ME1570

12-5

12.4.6 Refractory for Thermal Oxidizer, A2-MR1570

12-5

12.4.7 Thermal Oxidizer Waste Heat Boiler, A2-BF1570

12-5

12.5

INSTRUMENTATION AND CONTROL SYSTEMS

12-7

12.5.1

Thermal Oxidizer Burner Management System

12-7

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

12.5.2 Thermal Oxidizer Temperature Control

12-10

12.5.3 Thermal Oxidizer Excess Oxygen Control

12-10

12.5.4 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

12-18

12.6.1 Equipment Damage

12-18

12.6.2 Effect of Upstream Operations on the Thermal Oxidizer

12-21

12.6.3 "Swapping" Air Blowers During Operation

12-23

12.6.4 Boiler Water Treatment

12-24

12.7

PRECOMMISSIONING PROCEDURES

12-26

12.7.1 Preliminary Check-out

12-26

12.7.2 Shutdown System Check-out

12-27

12.7.3 Commissioning Fuel Gas, Pilot Gas, and I/A to the Process

12-28

12.8

STARTUP PROCEDURES

12-33

12.8.1 Initial Firing / Refractory Cure-out

12-33

12.8.2 Normal Startup

12-48

12.9

SHUTDOWN PROCEDURES

12-58

12.9.1 Planned Shutdown - No Entry

12-59

12.9.2 Planned Shutdown for Entry

12-61

12.9.3 Shutting Down When Boiler Tubes Are Leaking

12-65

12.9.4 Emergency Shutdown

12-66

12.9.5 Effects of Shutdowns and Outages in Other Systems

12-69

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

1.

INTRODUCTION

THE INFORMATION IN THESE GUIDELINES IS CONFIDENTIAL. SOME OF THE 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 with and 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

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

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 the operating 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.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

Table of Contents

2.

GENERAL SAFETY

2-1

2.1 DEFINITION OF TERMS

2-1

2.2 HYDROGEN SULFIDE (H 2 S)

2-3

2.2.1

Description and Properties

2-3

2.2.1.1 General

2-3

2.2.1.2 Toxicity Information

2-3

2.2.1.3 Permissible Exposure Limits

2-3

2.2.1.4 Odor

2-3

2.2.1.5 Physical Data

2-3

2.2.1.6 Reactivity Data

2-4

2.2.1.7 Corrosivity Data

2-5

2.2.1.8 Water Solubility

2-5

2.2.1.9 Other Characteristics

2-5

2.2.1.10 Fire and Explosion Hazard

2-6

2.2.1.11 Life Hazard

2-6

2.2.2 First Aid

2-7

2.2.3 Precautions (remember these facts)

2-8

2.2.4 Good Work Practices

2-9

2.3

SULFUR DIOXIDE (SO 2 )

2-10

2.3.1

Description and Properties

2-10

2.3.1.1 General

2-10

2.3.1.2 Toxicity Information

2-10

2.3.1.3 Permissible Exposure Limits

2-10

2.3.1.4 Odor

2-11

2.3.1.5 Physical Data

2-11

2.3.1.6 Reactivity Data

2-11

2.3.1.7 Corrosivity Data

2-12

2.3.1.8 Water Solubility

2-12

2.3.1.9 Fire and Explosion Hazard

2-12

2.3.1.10 Life Hazard

2-12

2.3.2 First Aid

2-13

2.3.3 Precautions

2-14

2.4

SULFUR

2-15

2.4.1

Description and Properties

2-15

2.4.1.1 General

2-15

2.4.1.2 Toxicity Information

2-15

2.4.1.3 Permissible Exposure Limits

2-15

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.4.1.4 Odor

2-15

2.4.1.5 Physical Data

2-15

2.4.1.6 Reactivity Data

2-16

2.4.1.7 Corrosivity Data

2-19

2.4.1.8 Other Characteristics

2-19

2.4.1.9 Fire and Explosion Hazard

2-19

2.4.1.10 Life Hazard

2-20

2.4.2 Precautions

2-20

2.4.3 Fire Fighting

2-21

2.5

AMMONIA (NH 3 )

2-22

2.5.1

Description and Properties

2-22

2.5.1.1 General

2-22

2.5.1.2 Toxicity Information

2-22

2.5.1.3 Permissible Exposure Limits

2-22

2.5.1.4 Odor

2-22

2.5.1.5 Physical Data

2-23

2.5.1.6 Reactivity Data

2-23

2.5.1.7 Corrosivity Data

2-25

2.5.1.8 Water Solubility

2-25

2.5.1.9 Fire and Explosion Hazard

2-25

2.5.1.10 Life

Hazard

2-25

2.5.2 First Aid

2-26

2.5.3 Precautions

2-26

2.6

METHYLDIETHANOLAMINE (MDEA, CH 3 -N-(CH 2 -CH 2 -OH) 2 )

2-28

2.6.1

Description and Properties

2-28

2.6.1.1 General

2-28

2.6.1.2 Toxicity Information

2-28

2.6.1.3 Permissible Exposure Limits

2-28

2.6.1.4 Odor

2-28

2.6.1.5 Physical Data

2-28

2.6.1.6 Reactivity Data

2-28

2.6.1.7 Corrosivity Data

2-29

2.6.1.8 Water Solubility

2-29

2.6.1.9 Fire and Explosion Hazard

2-29

2.6.1.10 Life

Hazard

2-29

2.6.2 First Aid

2-29

2.6.3 Precautions

2-30

2.7

SODIUM HYDROXIDE (CAUSTIC SODA, NAOH)

2-31

2.7.1

Description and Properties

2-31

2.7.1.1

General

2-31

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

 

2.7.1.2 Toxicity Information

2-31

2.7.1.3 Permissible Exposure Limits

2-31

2.7.1.4 Odor

2-31

2.7.1.5 Physical Data

2-32

2.7.1.6 Reactivity Data

2-32

2.7.1.7 Corrosivity Data

2-34

2.7.1.8 Water Solubility

2-34

2.7.1.9 Fire and Explosion Hazard

2-34

2.7.1.10 Life Hazard

2-35

2.7.2 First Aid

2-35

2.7.3 Precautions

2-36

2.8

SULFUR PLANT SAFETY

2-37

2.8.1 Hydrogen Sulfide

2-37

2.8.2 Sulfur

Dioxide

2-37

2.8.3 Sulfur Storage Tank

2-38

 

2.8.3.1 Poisonous Gases

2-38

2.8.3.2 Explosion and Fire

2-38

2.9 HOT WORK

2-39

2.10 VESSEL ENTRY

2-39

2.11 PIPES AND LINES

2-41

2.11.1 General

2-41

2.11.2 Before Breaking Lines

2-42

2.11.3 When Breaking Lines

2-42

2.12

ELECTRICAL EQUIPMENT

2-42

2.12.1 Electrical Repairs

2-43

2.12.2 Grounding

2-43

2.12.3 Conduit, Cables, and Wires

2-43

2.12.4 Fuses

2-43

2.12.5 Switching

2-43

2.12.6 Hand Tools and Portable Equipment

2-44

2.12.7 Miscellaneous

2-44

2.13

BOILERS AND OTHER DIRECT-FIRED EQUIPMENT

2-45

2.13.1 General

2-45

2.13.2 Boilers

2-45

 

2.13.2.1 Repair and Maintenance

2-45

2.13.2.2 Operations

2-46

2.13.3

Direct-Fired Equipment

2-46

2.14

LABORATORY SAFETY

2-47

2.14.1 Good Housekeeping

2-47

2.14.2 Equipment

2-47

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.14.3 Chemical Sorting and Identification

2-47

2.14.4 Chemical

Handling

2-48

2.15

MATERIAL SAFETY DATA SHEETS (MSDS)

2-49

A. 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

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2. GENERAL SAFETY

General

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 minimum concentration 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.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

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 than water, 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.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.2 Hydrogen Sulfide (H 2 S)

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 H 2 S for 30 minutes or to 800 PPM of H 2 S 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, H 2 S 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:

b. Boiling Point:

c. Lower Explosive Limit:

d. Upper Explosive Limit:

e. Auto-Ignition Temperature:

f. Vapor Specific Gravity:

-122°F (-86°C) -77°F (-61°C) 4.3% H 2 S (by volume) vapor in air 46% H 2 S (by volume) vapor in air 500°F (260°C) 1.2 (heavier than air)

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.2.1.6 Reactivity Data

Hydrogen

sulfide

is

dangerously

reactive

with

the

following

substances:

Formula

Name

 

C 2 H 4 O acetaldehyde

BaO + Hg 2 O + air

barium oxide + mercury oxide in air

BaO + NiO + air

barium oxide + nickel monoxide in air

BaO 2 barium peroxide

BrF 5

bromine pentafluoride

C 6 H 4 BrN 2 Cl

p-bromobenzene diazonium chloride

ClO

chlorine monoxide

ClF 3

chlorine trifluoride

CrO 3

chromium trioxide (chromic anhydride, chromic acid)

Cu

copper

Fe 2 O 3 ·nH 2 O

di-iron trioxide hydrate

F 2

fluorine

hydrated iron oxide

PbO 2

lead dioxide (lead peroxide)

metal oxides

metals

HNO 3

nitric acid

NCl 3

nitrogen trichloride

NF 3

nitrogen trifluoride

NI 3

nitrogen triiodide

oxidizing materials

OF 2

oxygen difluoride

ClO 3 F

perchloryl fluoride

C 6 H 5 N 2 Cl

phenyl diazonium chloride

rust

Ag 2 C 2 N 2 O 2

silver fulminate

NaOH + CaO

soda lime (a mixture of sodium hydroxide and calcium oxide)

Na

sodium

NaOH + CaO + air

sodium hydroxide + calcium oxide (lime) in air

Na 2 O 2

sodium peroxide

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.2.1.7 Corrosivity Data

a. H 2 S 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. H 2 S 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 650°F/343°C), H 2 S 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. H 2 S is considered to be non-corrosive to aluminum, glass, and Teflon ® .

2.2.1.8 Water Solubility

Hydrogen sulfide is soluble in water. At 60°F (15°C), approximately 3 parts (by volume) H 2 S 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 absorb hydrogen sulfide. Increased temperature or mechanical disturbance tends to release the absorbed gas.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.2.1.10 Fire and Explosion Hazard

H 2 S is a dangerous fire hazard when exposed to an ignition source.

2.2.1.11 Life Hazard

Hydrogen 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 H 2 S 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 H 2 S 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. H 2 S 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).

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

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. H 2 S 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

10

0.001

prolonged exposure

 

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 H 2 S 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 H 2 S paralyzes the respiratory system, time is very important. Administer oxygen (or carbogen, 97% oxygen and 3% carbon dioxide) if available and if someone trained

Attempts to give oxygen by

with oxygen inhalation apparatus is present.

someone unfamiliar with the use of the apparatus may result in the loss of valuable time or may be harmful to the patient.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

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. H 2 S 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. H 2 S 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, H 2 S 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 Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

g. In all of the Sulfur Recovery, Tailgas Cleanup, Tailgas Thermal Oxidation, and Sulfur Degassing system process gases, with the exception of the incinerated vent gas.

h. In the vapors from the molten sulfur storage tank.

2.2.4 Good Work Practices

Know the above facts and use caution when working around any equipment that may contain H 2 S. If H 2 S will be a hazard in any operation:

1. Make adequate plans to cope with any situation that may develop.

2. Adequate respiratory protective equipment is essential; have it available and use it. Persons who must work in an atmosphere contaminated with H 2 S should use either a self-contained breathing unit or a hose mask with a hand-operated blower.

3. Observe the wind direction. Stay upwind if possible and warn others who may be downwind.

4. Keep ignition sources away from the area.

5. Two men should always be present when opening a flange or performing any other work where the release of H 2 S is possible.

6. When one man is working in an area of potential H 2 S exposure, the other man should concentrate on the wind direction and on the action of the man performing the work. At the first sign of loss of coordination or illogical action, the worker should be removed immediately to fresh air. If a man is being overcome by H 2 S, he will be outwardly sluggish and poorly coordinated (although inwardly he will be peacefully unconcerned) and he will then begin illogical actions as his mind begins to imagine things. Any sign of actions that are out of the ordinary is a last minute warning.

Operating Guidelines Fall 2011

Samsung Total Petrochemicals Co., Ltd. Daesan, Korea

SULFUR BLOCK

2.3 Sulfur Dioxide (SO 2 )

2.3.1 Description and Properties

2.3.1.1 General

Sulfur dioxide is a colorless, nonflammable, highly toxic gas.

2.3.1.2 Toxicity Information

LCLo:

400 PPM / 1 minute

(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 400 PPM of SO 2 for 1 minute can cause death.

TCLo: