0
Chlorine Production
     and Uses




                      1
Objectives
This web seminar will enable the participant to
 • identify the hazards of chlorine (Cl2)
 • describe chlorine ...
References
 Many key safety related publications are
 available for download free of charge from
     The Chlorine Institu...
Chlorine Production
• Most Cl2 is produced at large facilities by
  electrolysis of salt brine:
   2 NaCl + 2 H2O  Cl2↑ +...
Chlorine Production

Hydro
Power




                                                Major
  Adapted from Kirk-Othmer, Enc...
Chlorine Production
• Much chlorine consumed close to
  production sites to make chlorinated
  intermediates, e.g., vinyl ...
Chlorine Consumption

              Chlorinated
                                  Organics, 27%
               Inter., 8%
...
Chlorine Helps Make…

• Vinyl chloride  PVC plastic
• Phosgene  Polycarbonates,
  pharmaceuticals
• Chlorine Dioxide / H...
Chlorine Properties




                      9
Physical / Chemical
• Yellowish-green gas at room temperature
• Boiling Point -29 F
• Gas specific gravity 2.4 (at room
  ...
Physical / Chemical
• Stable
• A powerful oxidizer – supports combustion
  of many materials
• “Dry” chlorine has no free ...
Physical / Chemical
• Reactive with many materials
  ●
      Steel preferred as material of construction for
      dry Cl2...
Release Properties
• Liquid releases boil (auto-refrigerate)
  releasing flash vapor
• Vapor heavier than air – releases t...
Properties of Chlorine –
                                Vapor Pressure
                      550
                      50...
Properties of Chlorine –
                                       Liquid Density
                          100
             ...
Health Effects of Chlorine
• Chlorine is extremely
  irritating and can burn the              0
  skin and eyes
• If inhal...
Health Effects of Chlorine Exposure

Concentration
                                   Health Effects
 (ppm in air)

   1-3...
Exposure Limits for Chlorine
Standard Permissible
 Setting  Exposure                   Description
  Body      ppm
 NIOSH ...
Chlorine Transfer
   Operations




                    19
Chlorine Transfer Operations
• Major users may take delivery directly from
  Cl2 producers via railcar
• Cylinders and con...
Chlorine Transfer Operations




                               21
Chlorine Re-packagers
          xx

                                                x                                     ...
Chlorine Transfer Operations
                                                                    Container being
         ...
Chlorine Transfer Operations
• Liquid Cl2 is displaced from the railcar using
  dry gas (air or nitrogen)
• Liquid Cl2 flo...
Chlorine Transfer Operations
• Cl2 vapor flows to a scrubber, typically filled
  with NaOH solution
• The reaction produce...
Chlorine Transfer Operations
• Scrubbing is normally ~100% efficient
• The scrubbing solution is monitored using
  redunda...
Chlorine Transfer Operations
• The bleach produced may be sold as a
  product
• Some (~0.5 – 1.0%) residual caustic must
 ...
Chlorine Transfer Operations
 When isolation
 valves fail –
 Festus, MO,
 August 2002


• Ci Pamphlet 57
  has details on
...
Water Disinfection
 with Chlorine




                     29
Chlorine in Water
   Treatment
• Excellent sanitizing agent
• Forms hypochlorous acid in
  solution – active biocidal mate...
Chlorine in Water Treatment
• Facilities tend to be lightly staffed
• May be located in populated areas
• Key components:
...
Chlorine in Water Treatment


                                                       To
                                  ...
Chlorine in Water Treatment
                      Ventilation In


Storage Shed                               Loss of Vacu...
Chlorine Incident
    History




                    34
IMIS* Chlorine Incidents

 • ~ 175 total incidents
     – All SICs
     – Since 1984




* Based on review of IMIS data on...
IMIS* Fatal Chlorine Incidents
• 11 total fatal incidents related to chlorine
  release and acute exposure

   – 5 fatal i...
IMIS* Fatal Chlorine Incidents

• 2 fatal incidents related to chemical processing
  facilities (SIC 28)
  – Bleed valve n...
IMIS* Chlorine Incidents Related to
Chemical Manufacturing (SIC 28)
• 37 total incidents (fatalities + others)
   – Chlori...
IMIS* Chlorine Incidents Related to
  Chemical Manufacturing (SIC 28)
• Subcontract employees were working ~ 50 ft from a
...
Cl2 Release DPC Enterprises

•A hose used to transfer Cl2
from a railroad tank car
suddenly burst and released
thousands o...
CSB Issues with DPC Cl2 Release
• Emergency training and drills were inadequate
• Facility Siting of the Cl2 protective ge...
Chlorine Specific PSM
        Issues




                        42
43
Process Safety Information
         1910.119 (d): Piping

• Do materials for piping and components
  comply with Ci recomm...
Process Safety
Information (d)
(Piping) cont.

•Are gaskets
compatible with
liquid and gaseous
chlorine? – Ci 95 Sec 3



...
Process Safety Information (d)
           (piping) cont.
• Is piping adequately
  supported and braced?
  – Ci 6 Sec 10
• ...
Process Safety Information (d)
           (Piping) cont.
• Are there expansion
  pots where liquid Cl2
  can be blocked in...
Process Safety Information (d)
           (Piping) cont.

• Are liquid valves
  designed to prevent
  trapping Cl2 in the
...
Process Safety Information (d)
           (Vaporizers)
• Is the vaporizer heating medium non-organic
  and limited to 250 ...
Process Safety Information (d)
     (Bulk Container Unloading)
• Are there a remotely operated or automatically
  actuated...
Process Safety Information (d)
 (Bulk Container Unloading) cont.
• Does the padding system include backflow
  prevention? ...
Process Safety Information (d)
         (Storage Systems)
• Is the Cl2 tank protected with a pressure relief device?
  – C...
Process Safety Information (d)
       (General Process)
• Are process areas monitored for chlorine?
 – Ci 1 Sec 7
• Are in...
Process Safety Information (d)
          (Scrubbers) cont.
• Is there a means to process chlorine gas
  vented from equipm...
Process Safety Information (d)
         (Scrubbers) cont.

• Is the scrubbing solution monitored to
  confirm continued ca...
Process Safety Information (d)
     (Packaging / Processing)

• Are there chlorine monitors in packaging
  and processing ...
Process Hazard Analysis
             1910.119 (e)
• Is there chlorine monitoring at the railcar
  unloading site?
  – Ci 6...
Operating Procedures
          1910.119 (f)
   (Bulk Container Unloading)
• Do procedures include the following:
  – PPE f...
Operating Procedures (f)
     (Packaging / Processing)
• Do procedures include the following:
  – Appropriate steps for ev...
Training - 1910.119 (f)
     (employees and contractor)
• Have employees been trained on
  (Ci 1 Sec 5):
  – Operation of ...
Training (g) (Employees and
        Contractor) cont.
• Location, purpose and use of emergency
  equipment, fire fighting ...
Pre-startup Safety Review
            1910.119 (i)
• Is new or replacement piping properly
  cleaned and inspected for chl...
Mechanical Integrity
                   1910.119 (j)
• Do procedures require leaks to be repaired
  before allowing operat...
67
Mechanical Integrity (j)
• Is the piping system routinely inspected?
  (Ci 6 Sec 12)
  – Flange bolt condition and tightne...
Mechanical Integrity (j)
• Are underground piping systems protected
  by cathodic protection? – Ci 60 Sec 3
• Are chlorine...
Mechanical Integrity (j)
• Are there scheduled routine external and
  detailed internal inspections of the
  vaporizer? - ...
Honeywell - Baton Rouge
           Incident Timeline

•   Chlorine cooler failed
•   Liquid chlorine entered the coolant s...
Honeywell Baton Rouge
         Incident Timeline cont.
• 3:05 am – Operator notices leak, Cl2 gas
  enters the control for...
74
75
76
Honeywell Citations
• j(4)(i) – failure to inspect, test, or otherwise
  evaluate air supply pipes for the control
  room ...
Honeywell Citations (cont.)
• e(3)(iv) – PHA did not provide description
  of the consequences for deviations
• d(3)(i)(e)...
Honeywell Citations (cont.)
• f(1)(i)(D) – Operating procedures did not
  address emergency shut down
  procedures and con...
Honeywell Citations (cont.)
• l(1) – MOCs were not completed for a
  previous coolant change or when the
  positive pressu...
Closing




          81
Chlorine Hazards 2009
Chlorine Hazards 2009
Chlorine Hazards 2009
Chlorine Hazards 2009
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  • TOXIC TRAIN SAFETY - A First Responders Petition caused The Chlorine Institute to conduct a five-month study comparing the safety of secondary containment to the chlorine “C”-Kit for chlorine tank cars. The study proved secondary containment to be, by far, the safest technology for containing and preventing releases of chlorine gas. To see secondary containment - search “CHLORTANKER.”
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  • HazMat Experts and Firefighters petition Dow Chemical and Union Pacific for safe rail tank cars transporting gas chlorine. Secondary containment is a necessary improvement that must be implemented. See--PETITION C KIT for First Responders Comments.
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  • Transcript of "Chlorine Hazards 2009"

    1. 1. Chlorine Production and Uses 1
    2. 2. Objectives This web seminar will enable the participant to • identify the hazards of chlorine (Cl2) • describe chlorine transfer and water disinfection processes and other equipment common in chlorine service • recognize common causes and signs of failures in chlorine systems, along with current compliance policy 2
    3. 3. References Many key safety related publications are available for download free of charge from The Chlorine Institute (Ci), a major industry trade group, at http://www.cl2.org The Ci also produces valuable RAGAGEP on chlorine system design and operation ($$) OSHA’s chlorine guidelines are at http://www.osha.gov/SLTC/healthguidelines/ chlorine/recognition.html 3
    4. 4. Chlorine Production • Most Cl2 is produced at large facilities by electrolysis of salt brine: 2 NaCl + 2 H2O  Cl2↑ + 2 NaOH + H2↑ • 1.1 tons of caustic are co-produced with every ton of chlorine • The hydrogen may be vented, or captured and purified for sale • 15 million tons produced in the US in 2005, using 1.2% of total US electricity supply 4
    5. 5. Chlorine Production Hydro Power Major Adapted from Kirk-Othmer, Encyclopedia of petrochemical Chemical Technology, 5th ed, Vol. 6, p. 191 users 5
    6. 6. Chlorine Production • Much chlorine consumed close to production sites to make chlorinated intermediates, e.g., vinyl chloride for plastics. These are shipped world-wide • Chlorine shipped nationally by rail as liquefied gas under pressure at ambient temperature • Repackaged into trucks, ton containers, cylinders for local delivery to small users 6
    7. 7. Chlorine Consumption Chlorinated Organics, 27% Inter., 8% Pulp & Paper, 3% Water Treatment, 4% Vinyls, 39% Others, 19% • By volume, most consumed producing other chemicals and intermediates and in pulp & paper (bleaching) • Smaller quantities used very widely as biocide for municipal, industrial, and waste water treatment 7
    8. 8. Chlorine Helps Make… • Vinyl chloride  PVC plastic • Phosgene  Polycarbonates, pharmaceuticals • Chlorine Dioxide / Hypochlorite  Bleaching • Chlorinated intermediates  polysulfone, nylon, polyurethanes (foams), coatings, pesticides • Germ-free (disinfected) drinking water 8
    9. 9. Chlorine Properties 9
    10. 10. Physical / Chemical • Yellowish-green gas at room temperature • Boiling Point -29 F • Gas specific gravity 2.4 (at room temperature), ~2.9 at boiling point • Pungent, irritating smell • Sparingly soluble in water: 6.9 pounds / 100 gallons at 60oF • Not flammable 10
    11. 11. Physical / Chemical • Stable • A powerful oxidizer – supports combustion of many materials • “Dry” chlorine has no free water present - < 100 ppm at 41oF, <300 ppm at 86oF • Generally stored and shipped as a liquid under pressure 11
    12. 12. Physical / Chemical • Reactive with many materials ● Steel preferred as material of construction for dry Cl2 below 250oF ● However, steel ignites above 480oF ● Many metals react violently with dry Cl2 (e.g., titanium at ordinary temperatures) ● Wet chlorine is highly corrosive; FRP, PTFE, titanium (must be wet) are resistant ● Many organics react, some violently ● Special cleaning required for steel in Cl2 service 12
    13. 13. Release Properties • Liquid releases boil (auto-refrigerate) releasing flash vapor • Vapor heavier than air – releases tend to stay near the ground, fill low lying areas, and to disperse slowly • Applying water to liquid Cl2 adds heat, increases vaporization • Cl2 and water form corrosive HCl (hydrochloric) and HOCl (hypochlorous) acids - water spray on release points can worsen releases 13
    14. 14. Properties of Chlorine – Vapor Pressure 550 500 450 Gage Pressure, psig 400 350 300 250 200 150 100 50 0 -50 0 50 100 150 200 250 Temperature, F 14
    15. 15. Properties of Chlorine – Liquid Density 100 95 Liquid Density, lb/ft^3 90 85 80 75 70 65 60 -50 0 50 100 150 200 250 Temperature, F 15
    16. 16. Health Effects of Chlorine • Chlorine is extremely irritating and can burn the 0 skin and eyes • If inhaled, chlorine causes 3 0 OXY respiratory distress, and can be fatal • Liquid chlorine releases will form an immediate cloud (flash vapor) and will cool to -29 F. • Exposure to liquid can cause frostbite, as well as chemical burns. 16
    17. 17. Health Effects of Chlorine Exposure Concentration Health Effects (ppm in air) 1-3 ppm Mild mucous membrane irritation 5-15 ppm Upper respiratory tract irritation Immediate chest pain, vomiting, shortness of breath 30 ppm (dyspnea) and cough Inflammation of lung tissues (toxic pneumonitis) and 40-60 ppm fluid accumulation (pulmonary edema) 430 ppm Death within 30 minutes 1,000 ppm Death within a few minutes 17
    18. 18. Exposure Limits for Chlorine Standard Permissible Setting Exposure Description Body ppm NIOSH 0.5 Recommended Exposure Limit (REL) OSHA 1 Permissible Exposure Limit (PEL) NIOSH 1 Short Term Exposure Limit (STEL) Emergency Response Planning Guideline AIHA 3 Level 2 Immediately Dangerous to Life or Health NIOSH 10 (IDLH) Emergency Response Planning 20 AIHA Guideline Level 3 18
    19. 19. Chlorine Transfer Operations 19
    20. 20. Chlorine Transfer Operations • Major users may take delivery directly from Cl2 producers via railcar • Cylinders and containers for smaller users are usually filled locally/regionally by chlorine “repackagers” • All transfer operations share common aspects • Refer to Ci Pamphlet 17, Packaging Plant Safety & Operational Guidelines 20
    21. 21. Chlorine Transfer Operations 21
    22. 22. Chlorine Re-packagers xx x x x x x x x x x x x x x x x x x x x x x xx x x x x x x x x xx x x x x xx x x x x x xx x x x xx x xx x x xx xx Data from Chlorine Institute Pamphlet 10 - 2005 x 22
    23. 23. Chlorine Transfer Operations Container being filled (on scale) Dry air or N2 Scrubbing solution Chocked rail car (usually caustic) From CSB DPC-Glendale Report
    24. 24. Chlorine Transfer Operations • Liquid Cl2 is displaced from the railcar using dry gas (air or nitrogen) • Liquid Cl2 flows into receiving container • Cl2 vapor plus air/N2 present is vented through a throttling valve to keep the container pressure high to suppress flash vapor formation • Hose connections should have emergency isolation valves on both ends 24
    25. 25. Chlorine Transfer Operations • Cl2 vapor flows to a scrubber, typically filled with NaOH solution • The reaction produces bleach – sodium hypochlorite – plus salt and heat Cl2 + 2 NaOH  NaOCl + NaCl + H2O • The scrubbing solution is usually circulated through an eductor (aka, a venturi) – High liquid velocity ensures good contacting – Maintains a slight vacuum on the Cl2 line 25
    26. 26. Chlorine Transfer Operations • Scrubbing is normally ~100% efficient • The scrubbing solution is monitored using redundant oxidation-reduction potential (ORP) meters – These alarm and/or shut off chlorine flow if the scrubbing fluid becomes depleted • A heat exchanger removes the heat of reaction using air or cold water 26
    27. 27. Chlorine Transfer Operations • The bleach produced may be sold as a product • Some (~0.5 – 1.0%) residual caustic must remain in solution to maintain scrubbing effectiveness and prevent decomposition of the bleach • Depletion of the caustic can cause the scrubber to fail & the bleach to decompose, emitting toxic gases 27
    28. 28. Chlorine Transfer Operations When isolation valves fail – Festus, MO, August 2002 • Ci Pamphlet 57 has details on emergency shut- off systems for bulk Cl2 transfer
    29. 29. Water Disinfection with Chlorine 29
    30. 30. Chlorine in Water Treatment • Excellent sanitizing agent • Forms hypochlorous acid in solution – active biocidal material Cl2 + H2O  HOCl + HCl • Good residual action – bacteriostatic at 1-5 ppm Cl2 in water • Can form undesirable chlorinated organic materials, e.g., chloromethanes • Ci Pamphlet 155 – Water & Wastewater Operators Chlorine Handbook 30
    31. 31. Chlorine in Water Treatment • Facilities tend to be lightly staffed • May be located in populated areas • Key components: – Chlorine cylinders / containers – Piping – Chlorinator – Water eductor 31
    32. 32. Chlorine in Water Treatment To injection point Chlorine Ton Containers in Water Treatment System (usually in separate building / Vacuum Chlorinator room, with independent Cabinet ventilation. May exhaust to scrubber) 32
    33. 33. Chlorine in Water Treatment Ventilation In Storage Shed Loss of Vacuum Clean Water Shut-off Source Vapor PSL 1-Ton Cl2 PY Container PE Eductor Spare To Water Container(s) Chlorinator System Drain Trap AAH Heater HTR Chlorine Sensor / Ventilation Out (may Alarm go to scrubber) 33
    34. 34. Chlorine Incident History 34
    35. 35. IMIS* Chlorine Incidents • ~ 175 total incidents – All SICs – Since 1984 * Based on review of IMIS data only (i.e. no further analysis). Incident = Cl2 release and acute exposure where injury or fatality is noted. 35
    36. 36. IMIS* Fatal Chlorine Incidents • 11 total fatal incidents related to chlorine release and acute exposure – 5 fatal incidents related to cleaning/disinfecting • Inadvertent mixing of sodium hypochlorite and formic acid resulting in reaction w/Cl2 gas generation • Cleaning storage (e.g. CTMV and tank) * Based on review of IMIS data only (i.e. no further analysis) Incident = Cl2 release and acute exposure where injury or fatality is noted. 36
    37. 37. IMIS* Fatal Chlorine Incidents • 2 fatal incidents related to chemical processing facilities (SIC 28) – Bleed valve not closed resulting in trapped pressure between valve and cap. When operator began removing cap to bleed Cl2 line, Cl2 released. During incident respirator pulled off and employee was exposed and dies later. – Purging Cl2 from cylinder to prepare it for pressure test, used 3,000 psi nitrogen resulting in catastrophic failure of the cylinder. There was no pressure regulator or pressure relief device on the filling system between the 3,000 psi nitrogen system and the 480 psi chlorine cylinder. 37
    38. 38. IMIS* Chlorine Incidents Related to Chemical Manufacturing (SIC 28) • 37 total incidents (fatalities + others) – Chlorine was connected by manifolds to a bleach manufacturing process as well as to a chlorine repackaging process. The manifolds were equipped with air and electric operated valves. The compressed air was introducing debris into the system which caused the actuators to stick and prevent the valves from closing. • Result – Cl2 release, 5 employees hospitalized. – A block valve under 300 psi chlorine failed • Factors contributing to release included lack of maintenance and inspection program for smaller valves. • Result – Cl2 release, 10 employees hospitalized. 38
    39. 39. IMIS* Chlorine Incidents Related to Chemical Manufacturing (SIC 28) • Subcontract employees were working ~ 50 ft from a tank, which held chlorine. The tank PSV opened and released due to tank overpressure. – RV discharge was designed to release into the work area. – Result – Cl2 release, 2 employees hospitalized. • Brine coolant got into the dry chlorine production stream – Resulted in accelerated corrosion and production piping failure. – Fire fighters, responded to the incident, and were exposed to liquid chlorine hazards when they secured the incident scene – Result – Cl2 release: 60 tons of liquid chlorine were released from a 150-ton production storage tank , 6 firefighters hospitalized & 42 others non-hospitalized injuries 39
    40. 40. Cl2 Release DPC Enterprises •A hose used to transfer Cl2 from a railroad tank car suddenly burst and released thousands of pounds of Cl2 liquid and gas •DPC is a Cl2 repackager •Automatic and manual shutdown systems failed to work, and the release continued for about three hours. ● Moisture into dry system resulting in corrosion 40
    41. 41. CSB Issues with DPC Cl2 Release • Emergency training and drills were inadequate • Facility Siting of the Cl2 protective gear – gear stored in the chlorine packaging building too close to the tank car unloading station • Employees could not get to gear as it was engulfed in Cl2 cloud • Develop MI QA program to ensure that chlorine hoses are made of the correct materials of construction – Positive Material Identification (PMI) – chlorine transfer hose should have an inner Teflon lining reinforced by an exterior metal braiding made of Hastalloy C-276 • Need MI for ER systems and chlorine- related corrosion 41
    42. 42. Chlorine Specific PSM Issues 42
    43. 43. 43
    44. 44. Process Safety Information 1910.119 (d): Piping • Do materials for piping and components comply with Ci recommendations – for metallurgy, schedule, and welding? – Ci 6 Sec 2 • Are materials for threaded connections PTFE tape or non-reactive pipe dope? - Ci 1 and 6 Sec. 3 44
    45. 45. Process Safety Information (d) (Piping) cont. •Are gaskets compatible with liquid and gaseous chlorine? – Ci 95 Sec 3 45
    46. 46. Process Safety Information (d) (piping) cont. • Is piping adequately supported and braced? – Ci 6 Sec 10 • Is piping system protected from vehicular traffic? – Ci 6 Sec 10 • If piping is underground, is it continuously leak monitored? – Ci 60 Sec 3 46
    47. 47. Process Safety Information (d) (Piping) cont. • Are there expansion pots where liquid Cl2 can be blocked in? – Ci 5 Sec 5 • Is the expansion pot isolated by rupture disk and monitored? – Ci 6 Sec 5 47
    48. 48. Process Safety Information (d) (Piping) cont. • Are liquid valves designed to prevent trapping Cl2 in the body? – Ci 6 Sec 4 • When Cl2 pressure is lower than process pressure, is there backflow prevention? – Ci 9 Sec 4 and 5 48
    49. 49. Process Safety Information (d) (Vaporizers) • Is the vaporizer heating medium non-organic and limited to 250 F? – Ci 9 Sec 3 • Is the heating medium pressure lower than the chlorine supply pressure? – Ci 9 Sec 3 • Is the vaporizer designed for a minimum metal temperature of -40 F? – Ci 9 Sec 3 • Does the vaporizer outlet have a pressure relief valve? – Ci 9 Sec 4 • Is there a program in place to monitor NCl3 levels? – Ci 9 Sec 5 and Ci 152 Sec 5 49
    50. 50. Process Safety Information (d) (Bulk Container Unloading) • Are there a remotely operated or automatically actuated emergency shutoff valves to isolate both sides of flexible hoses? – Ci 57 Sec 3, Ci 66 Sec 9 • Are there at least 2 remote shutoff valve operators? – Ci 57 Sec 3 • Is there a tank motion detector that closes shutoff valves? – Ci 57 Sec 3 51
    51. 51. Process Safety Information (d) (Bulk Container Unloading) cont. • Does the padding system include backflow prevention? – Ci 49 Sec 7 • Are Cl2 hoses constructed of compatible materials? – Ci 6 App A 53
    52. 52. Process Safety Information (d) (Storage Systems) • Is the Cl2 tank protected with a pressure relief device? – Ci 5 Sec 5 • Are there emergency shutoff devices on the liquid lines? – Ci 5 Sec 5 • Is there a pressure sensing device on the tank? – Ci 5 Sec 5 • Does the tank have a reliable level device? – Ci 5 Sec 5 • Are all tank openings (nozzles) on the tank top? – Ci 5 Sec 4 • Does the tank have sufficient spill protection? – Ci 5 Sec 6 54
    53. 53. Process Safety Information (d) (General Process) • Are process areas monitored for chlorine? – Ci 1 Sec 7 • Are indoor chlorine areas properly ventilated? – Ci 1 Sec 7 • Are process vessels equipped with relief devices? – Ci 9 Sec 5 55
    54. 54. Process Safety Information (d) (Scrubbers) cont. • Is there a means to process chlorine gas vented from equipment and piping? – Ci 89 Sec 1 • Can the scrubber handle the most probable release scenario? – Ci 89 Sec 3 • Does the scrubber have passive capability or emergency power? – Ci 89 Sec 4 • Is the scrubbing medium appropriate? – Ci 89 Sec 2 57
    55. 55. Process Safety Information (d) (Scrubbers) cont. • Is the scrubbing solution monitored to confirm continued capability? – Ci 89 Sec 2 • Is the scrubbing vent monitored? – Ci 89 Sec 4 • Is there adequate backflow prevention? – Ci 89 Sec 4 58
    56. 56. Process Safety Information (d) (Packaging / Processing) • Are there chlorine monitors in packaging and processing areas with appropriate limits? – Ci 1 Sec 7 • Are the materials for the sodium hypochlorite piping appropriate? – Ci 96 Sec 4 59
    57. 57. Process Hazard Analysis 1910.119 (e) • Is there chlorine monitoring at the railcar unloading site? – Ci 64 Sec 3 • Has the facility investigated the potential for nitrogen trichloride to accumulate? – Ci 9 Sec 5, Ci 152 Sec 5 60
    58. 58. Operating Procedures 1910.119 (f) (Bulk Container Unloading) • Do procedures include the following: – PPE for chlorine loading/unloading/line breaking? – Ci 1 Sec 5, Ci 85 Sec 12 – Requirements for unloading lines and air padding lines purged to a scrubber, evacuated, disconnected, and capped? – Ci 1 Sec 3, Ci 49 Sec 11, Ci 66 Sec 9, Ci 79 Sec 79 61
    59. 59. Operating Procedures (f) (Packaging / Processing) • Do procedures include the following: – Appropriate steps for evacuating and filling cylinders and ton containers? – Ci 162 Sec 6 – Leak testing containers before filling? – Ci 17 Sec 3 – Proper evacuation of lines before disconnecting? – Ci 17 Sec 3 – Appropriate torque setting of valves and packing nuts? – Ci 17 Sec 4 62
    60. 60. Training - 1910.119 (f) (employees and contractor) • Have employees been trained on (Ci 1 Sec 5): – Operation of chlorine equipment and container handling – Properties and physiological effects of chlorine – Equipment failure and leak reporting procedures 63
    61. 61. Training (g) (Employees and Contractor) cont. • Location, purpose and use of emergency equipment, fire fighting equipment, fire alarms, and shutdown equipment. • Use of emergency kits A, B, or C if used at the site • Locations, purpose and use of safety equipment • Location, purpose, and use of specialized first aid equipment. 64
    62. 62. Pre-startup Safety Review 1910.119 (i) • Is new or replacement piping properly cleaned and inspected for chlorine service? – Ci 6 Sec 11 65
    63. 63. Mechanical Integrity 1910.119 (j) • Do procedures require leaks to be repaired before allowing operations to begin or continue? – Ci 1 Sec 4, Ci 49 Sec 11, Ci 66 Sec 9 • Have lubricants been checked for compatibility ( j(6))? – Ci 6 Sec 3 • Is the emergency shut-off system tested routinely? – Ci 57 Sec 3 • Are chlorine hoses tested and replaced on a preventive maintenance basis? – Ci 6 App A 66
    64. 64. 67
    65. 65. Mechanical Integrity (j) • Is the piping system routinely inspected? (Ci 6 Sec 12) – Flange bolt condition and tightness – Valve packing leaks – Valve operation – Insulation condition – Paint condition – Condition of supports – NDT for piping inspections 68
    66. 66. Mechanical Integrity (j) • Are underground piping systems protected by cathodic protection? – Ci 60 Sec 3 • Are chlorine storage tanks scheduled for inspection? – Ci 5 Sec 8 • Are pressure relief valves scheduled for periodic inspection? – Ci 5 Sec 9 • Are there procedures for inspection of valves? – Ci 17 Sec 4 69
    67. 67. Mechanical Integrity (j) • Are there scheduled routine external and detailed internal inspections of the vaporizer? - Ci 9 Sec 8 – Gaskets and valves for leaks – Insulation for damage and signs of leaks – Proper function of steam traps – Proper function of all instruments – Condition of supply equipment – Coating condition – General housekeeping to guarantee safe evacuation 70
    68. 68. Honeywell - Baton Rouge Incident Timeline • Chlorine cooler failed • Liquid chlorine entered the coolant system • Coolant pumps failed • Chlorine is released to atmosphere 72
    69. 69. Honeywell Baton Rouge Incident Timeline cont. • 3:05 am – Operator notices leak, Cl2 gas enters the control forcing operators to leave • 3:25 am – Plant evacuated, authorities notified • 3:30 am – Vapor cloud mitigation water sprays turned on • 7 am – Equipment secured and release stopped 73
    70. 70. 74
    71. 71. 75
    72. 72. 76
    73. 73. Honeywell Citations • j(4)(i) – failure to inspect, test, or otherwise evaluate air supply pipes for the control room ventilation system • e(3)(i) – PHA did not address possible failure of the brine pumps • e(3)(iii) – PHA did not address the engineering and admin controls such as providing a device to monitor for chlorine in the control room 77
    74. 74. Honeywell Citations (cont.) • e(3)(iv) – PHA did not provide description of the consequences for deviations • d(3)(i)(e) – PSI did not include design info on the control room positive pressure system • d(3)(i)(f) – PSI did not contain info on the RAGAGEP for the ventilation system 78
    75. 75. Honeywell Citations (cont.) • f(1)(i)(D) – Operating procedures did not address emergency shut down procedures and condition that would require an emergency shut down related to the coolant system • f(1)(ii)(B)- Operating procedures for the coolant system did not cover how to handle the deviation for chlorine entering the system 79
    76. 76. Honeywell Citations (cont.) • l(1) – MOCs were not completed for a previous coolant change or when the positive pressure ventilation system was installed in the control room • m(4) – There was no investigation report for a previous failure of heater tubes that lead to contamination of the brine system 80
    77. 77. Closing 81
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