Chlorine Production and Uses

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

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 ($$) OSHAs chlorine guidelines are at http://www.osha.gov/SLTC/healthguidelines/ chlorine/recognition.html
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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
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Chlorine Production
Hydro Power

Adapted from Kirk-Othmer, Encyclopedia of Chemical Technology, 5th ed, Vol. 6, p. 191

Major petrochemical users

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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
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Chlorine Consumption
Chlorinated Inter., 8% Pulp & Paper, 3% Water Treatment, 4% Others, 19% Organics, 27%

Vinyls, 39%

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
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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

Chlorine Properties

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

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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

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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
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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
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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
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Temperature, F

Properties of Chlorine Liquid Density

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Liquid Density, lb/ft^3

95 90 85 80 75 70 65 60 -50 0 50 100 150 200 250

Temperature, F
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Health Effects of Chlorine

Chlorine is extremely irritating and can burn the skin and eyes

If inhaled, chlorine causes respiratory distress, and can be fatal

3 0 OXY

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.
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Health Effects of Chlorine Exposure

Concentration (ppm in air)
1-3 ppm
5-15 ppm 30 ppm 40-60 ppm 430 ppm 1,000 ppm

Health Effects
Mild mucous membrane irritation
Upper respiratory tract irritation Immediate chest pain, vomiting, shortness of breath (dyspnea) and cough Inflammation of lung tissues (toxic pneumonitis) and fluid accumulation (pulmonary edema) Death within 30 minutes Death within a few minutes
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Exposure Limits for Chlorine

Standard Permissible Setting Exposure Body ppm
NIOSH OSHA NIOSH AIHA NIOSH AIHA 0.5 1 1 3 10 20

Description
Recommended Exposure Limit (REL) Permissible Exposure Limit (PEL) Short Term Exposure Limit (STEL) Emergency Response Planning Guideline Level 2 Immediately Dangerous to Life or Health (IDLH) Emergency Response Planning Guideline Level 3
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Chlorine Transfer Operations

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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
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Chlorine Transfer Operations

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Chlorine Re-packagers
x x x x x x x x x x x x x xx
Data from Chlorine Institute Pamphlet 10 - 2005

x x x x x x x x x x x x x x x x x x 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
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Chlorine Transfer Operations

Container being filled (on scale)

Dry air or N2 Chocked rail car

From CSB DPC-Glendale Report

Scrubbing solution (usually caustic)

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
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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
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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

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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
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Chlorine Transfer Operations

When isolation valves fail Festus, MO, August 2002
Ci Pamphlet 57 has details on emergency shutoff systems for bulk Cl2 transfer

Water Disinfection with Chlorine

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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
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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

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Chlorine in Water Treatment

To injection point

Chlorine Ton Containers in Water Treatment System

(usually in separate building / room, with independent ventilation. May exhaust to scrubber)

Vacuum Chlorinator Cabinet

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Chlorine in Water Treatment

Ventilation In
Storage Shed
Vapor

Loss of Vacuum Shut-off

PSL PY PE

Clean Water Source

1-Ton Cl2 Container

Eductor

Spare Container(s) Trap

AAH

Chlorinator
Drain

To Water System

Chlorine Sensor / Alarm

Heater

HTR

Ventilation Out (may go to scrubber)

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Chlorine Incident History

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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.
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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.
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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.
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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.
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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
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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
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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 chlorinerelated corrosion

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Chlorine Specific PSM Issues

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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

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Process Safety Information (d) (Piping) cont.

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

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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

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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

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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
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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
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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

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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

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Process Safety Information (d) (Storage Systems)

Is the Cl2 tank protected with a pressure relief device?
Ci 5 Sec 5
Ci 5 Sec 5

Are there emergency shutoff devices on the liquid lines? 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

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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

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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
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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

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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

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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

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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
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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
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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
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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.
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Pre-startup Safety Review 1910.119 (i)

Is new or replacement piping properly cleaned and inspected for chlorine service? Ci 6 Sec 11

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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
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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
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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
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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
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Honeywell - Baton Rouge Incident Timeline

Chlorine cooler failed Liquid chlorine entered the coolant system Coolant pumps failed Chlorine is released to atmosphere

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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
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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
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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

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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
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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

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Closing

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