Environmental, Health, and Safety Overview

Numerous environmental and safety concerns exist in the proposed production route of
tetraphenylethylene (TPE). All reactants and intermediates pose some significant health risk to
both employees and the environment. The consequences of any chemical release in the proposed
production route was identified. Toxicity values and PPE requirements highlight the deadly
chemical exposure hazards. Additional health and safety hazards are identified to outline areas
where measures can be established to decrease injury and incidence rates. Industrial,
environmental, and product safety codes relevant to TPE production are identified. The codes
identified are not a comprehensive list, but indicate codes unique to the proposed TPE
production, or of significant industrial importance. Finally, a specific hazard scenario has been
analyzed to identify risks to health and safety of people and the environment inside and outside
the plant.
Environmental Concerns
Waste Stream Identification and Treatment
The proposed TPE reaction pathway has no waste streams. Phosphorous oxychloride
(POCl3) exits the diphenyldichloromethane (DPCM) Reactor and is separated via distillation.
POCl3 exits the packed distillation column at a purity of 99.7 wt% allowing for the possibility of
sale as a byproduct. With no chemical waste streams, no waste treatment must be implemented
in the proposed TPE production process.
Environmental Release Consequences
The raw materials and reactive intermediates of the TPE production pose a significant
environmental risk in the event of an accidental release. Unplanned releases of Cl2, PCl3, and
benzophenone all pose a documented environmental toxicity risk. Table 1 below shows a list of
the chemical species, and the LC50 concentrations after 96.0 hours for fish.
Table 1: Documented Aquatic Toxicity
Species Concentration and Test Time
Cl2 0.014 mg/L 96.0 h [1]
PCl3 >1000 mg/L 96.0 h [2]
Benzophenone 14.2 mg/L 96.0 h [3]
Additionally, some chemicals used in proposed TPE production route pose an inhalation toxin to
the environment should a release occur. Table 2 shows all documented inhalation LC50 and
times, oral LD50, and dermal LD50 for each chemical species.
Table 2: Chemical Species Acute Toxicity Information
Toxicity Test Cl2 [1] PCl3 [2] PCl5 [4] Benzophenone [3] POCl3 [5]
LC50 Inhalation 293 ppm 0.586 ppm 24 ppm - 32 ppm
1 hour 4 hours 4 hours 4 hours
LD50 Dermal - - - 3,535 -
(mg/kg)
LD50 Oral - 18 660 >10,000 36
(mg/kg)

The documented low lethal toxicity concentrations and times on many of the chemicals
emphasize the need for proper release control measures, and the severe consequences of any
small quantities of chemical release.
Neither DPCM nor the nickel-glyme catalyst have toxicity data available in their SDS
sheets but may still pose a significant untested environmental hazard. DPCM has the potential to
cause respiratory irritation as well as skin burns and potential eye damage if exposed [6]. The
nickel-glyme catalysts SDS identifies the compound as very toxic to aquatic life with long
lasting effects [7]. Additionally, the nickle-glyme catalyst is identified as a potential carcinogen
if exposed. With all chemicals in the proposed production route having profound environmental
impacts, any unknown spill of any size will be treated as extremely dangerous to both employees
and the environment.
The highly toxic nature of the chemicals in this process mandate establishing measures in
the event of an accidental release. Even a small amount of chemical release poses a risk to have
disastrous and long term ramifications on the health of the environment. Solid and liquid
components which are released must be quarantined immediately to prevent run off into ground
water or exposing animal life to the toxins. The chlorine compounds in this process are generally
reactive components. If one of the chlorine based compounds is released, it must be initially be
quarantined and then neutralized to facilitate clean up. Spill kits to neutralize the chlorine
compounds stationed throughout the plant will reduce the toxicity of the spill and expedite clean
up. Additionally, a high capacity HVAC system with chemical filters will be installed to remove
any hazardous chemicals and reduce release and exposure risks. Any unplanned releases will be
cleaned and quarantined to the extent possible by on-site environmental services. Environmental
remediation services and professional waste disposal companies will be contacted immediately
following any release regardless of quantity.
Health and Safety
Primary Health and Safety Hazards
TPE production also possesses risks to the health and safety of all people working in and
around the plant. Chemical exposure hazards are severe and significant risks to the health and
safety of anyone in the immediate area of the plant. Projected acute toxicity in humans based on
testing with rates is listed in Table 2. Low concentration exposure to almost any chemical in the
TPE production route has a chance to be lethal within a very short amount of time. Table 3
below, lists the fatal and carcinogenic hazard statements to highlight the severity of exposure to
each chemical in short and long term exposure.
Table 3: List of Substantial Chemical Exposure Hazards
Hazard Code Hazard Meaning Relevant Chemicals
H300 Fatal if swallowed PCl3 [], POCl3 []
H301 Toxic if swallowed Nickel-Glyme []
H330 Fatal if inhaled PCl3 [], PCl5 [], POCl3 []
H331 Toxic if inhaled Cl2 []
H350/H351 May cause cancer Nickel-Glyme [], Benzophenone []
H372/H373 Damage to organs through repeated exposure PCl3 [], PCl5 [], POCl3 []

The list of hazard codes is not a comprehensive list of all hazards of the chemicals associated
with this process, but highlights the most severe hazard codes with the potential to cause
substantial health problems or may be fatal.
To mitigate the health and safety risks of workers and anyone in the surrounding area,
several steps to increase safety will be taken. Constant air quality monitoring and rigorous
engineering controls will be implemented to keep air free of chemicals should release occur. A
large HVAC system with redundant chemical filters installed will reduce the airborne chemical
exposure and reduce the risk of toxic releases. As a last measure of safety, PPE will be required
for all employees working in the plant. The SDS for many of the chemicals call for a chemical
resistant suit, nitrile gloves, a face shield and a breathing apparatus. Anyone walking on the plant
floor will be required to wear all PPE to keep every person at the lowest exposure levels
possible.
Several other hazards also exist, many of which are common in all industrial processes.
As in many processes, there is a significant fire hazard risk. During TPE production natural gas
is burned. Chlorine gas and nickel-glyme catalyst may fuel the fire and allow it to spread
uncontrollably. Foam fire suppression systems subject to periodic testing are stationed
throughout the plant. Noise hazards also risk the health of all workers. Decibel measurements
will be taken regularly throughout the plant to continue to provide all employees with necessary
hearing protection. Additional hazards from slips and falls, and potential heavy equipment strike
or pinch hazards may also exist. These hazards will be addressed by appropriate engineering
controls to reduce the risks of slips and falls with non-slick floors and hand rails. To prevent
strikes or pinches, areas with large moving parts or pinch hazards, such as the magnetic drum
and centrifuge will be safety guarded and a lock out tag out procedure implemented on all plant
equipment.
OSHA Codes
To maintain worker safety the Occupational Safety and Health Association (OSHA)
codes will be stringently followed. Part 1910 of OSHA is the primary top-level code to be
addressed in most industrial processes []. Code 1910.1030 refers to effective hazard
communication []. This is essential for the effective communication of the potential hazards of
the chemicals and process streams. To comply with this code all chemicals will be clearly
labeled and any electrical or mechanical hazards will also be defined and labeled. Appropriate
training and educations for working and interacting with any chemical processes will also be
conducted to keep worker safety paramount. Code 1910.132 refers to the personal protective
equipment minimum requirements in industrial processes []. This code requires employees at a
minimum to wear safety goggles, long pants and shirts, and possibly noise cancelling ear buds to
meet code 1910.95 on occupational noise exposure []. Additional PPE will be required and
supplied in consultation with hazard and precautionary statements in chemical SDS sheets.
Subpart H of code 1910 refers to the precautions in handling hazardous materials. All process
steams are considered hazardous due to the potential health and environmental risks, requiring
sufficient engineering controls and sufficient PPE. Code 1990.119 Appendix A identifies the
threshold quantity (TQ) of the specific chemicals []. The TQ value is the amount of a substance
which when released could potentially cause serious danger within a short amount of time if
released. Two chemicals in the proposed TPE production route have TQ values listed within
Appendix A. Chlorine and phosphorus trichloride have TQ values of 1500 and 1000 pounds
respectively []. The presence of these chemicals on this list further highlight the need to reduce
and prevent the release of even small amounts of any chemical in TPE production.
NFPA Codes
The second significant set of codes in this process are codes outline by the National Fire
Protection Association (NFPA). NFPA codes provide recommendations to improve fire safety
measures within a process. NFPA code 1 describes fire codes including fire suppression and fire
alarms in industrial processes []. Natural gas, chlorine and the nickel-glyme catalyst are all
species which could ignite and spread rapidly. Areas containing these chemicals require a fire
suppression system to extinguish any fire before it can propagate. NFPA code 30 refers to the
storage, handling, and use of flammable and combustible liquids []. Within the TPE production
process DPCM, nickel-glyme catalyst, and benzophenone are flammable compounds. While not
considered by NFPA 30 to be classified as a highly flammable chemical, similar caution and care
will be taken, to reduce any risks in working with these chemicals. Natural gas codes are
presented in NFPA 54 []. Natural gas is used to heat the reboiler of the distillation column and
heating of the DPCM reactor. Additional codes for the handling of natural gas are found in
NFPA 329, which describes recommended practice for handling flammable and combustible
fluids [].
In addition to fire codes, NFPA also provides codes dealing with explosions and process
vessel safety in industrial applications. NFPA 69 provides standards on explosion prevention
systems which in all reaction vessels is a significant risk []. Other explosion prevention standards
can be found in NFPA 8502, which describes prevention of furnace explosions/implosions.
NFPA 8502 applies to the reboiler in the distillation column as well as the natural gas heating
system for the DPCM reactor []. This code highlights practices to reduce the chances of
explosions leading to destructive situations within these operations. Guidelines on safe heat
exchanger operation are available in NFPA 87 []. This code provides safety guidance for fluid
heaters to minimize process hazards.
 NFPA also addresses hazardous material identification and necessary engineering
controls. Due to the toxic qualities of most of the chemicals in the system, NFPA 90A and 306
will be addressed. NFPA 90A deals with air conditioning and ventilation systems which are
important to keep the air clean of any potential toxic chemicals that may be in the air []. NFPA
306 refers to gas hazards on vessels to ensure any toxic liquids, vapors, gases, or chemicals are
safe for entry work []. The combination of both codes ensure no scenarios arise where a worker
is trapped in a confined space with hazardous chemical vapors, and that any hazardous vapors
are removed from the air to keep employees safe. Codes for hazardous materials important to
this process are in NFPA 400 and 704. NFPA 400 pertains to the storage, use, and handling of
hazardous and toxic solids and liquids such as PCl5, PCl3, and DPCM. NFPA 400 provides
guidance on safe interaction with hazardous solids and liquids to keep employees safe []. The
final significant code, NFPA 704, provides information for appropriate identification of the
health, flammability, and reactivity hazards of all chemicals []. This code provides the NFPA
Hazard Diamond, a simple and easily understood system to identify the hazards of materials.
The diamond allows for emergency personnel to have quick knowledge of the potential hazards
of a chemical or process. All process equipment and raw materials will be identified per NFPA
704 guidelines to give both employees and emergency personnel concise knowledge of potential
hazards within the process.
EPA Codes
To remain in compliance with all federal regulations of industrial process and to keep
environmental sustainability and preservation paramount, several EPA acts will be followed
throughout the life of the plant. While these acts are not standard numbered codes as with NFPA
and OSHA, they are equally important for safe operation. The Clean Water Act ensures pollution
of the worlds water resources are not carelessly polluted by industrial processes []. Periodic
water testing will be conducted to ensure cooling water is not contaminated and releases of toxic
materials are addressed immediately. Discussions with local water treatment organizations to
ensure they are adequately prepared to handle water pollutants. Additionally, the TPE production
will comply by the EPA Clean Air Act. Compliance with the act maintains community safety,
reduces greenhouse gas emissions to maintain federal compliance []. Following of these acts is
necessary to maintain federal compliance and maintain high public confidence in the product.
Product Safety Codes
The final two acts for this process ensure high product quality are the Product Safety
Code from the American Chemistry Council, and the Food and Drug Administrations
Biomarker Qualification Program. The American Chemistry Council publishes a set of standards
for consumer product safety. These standards consist of rigorous testing on raw materials as well
as on finished products to maintain high quality of final product []. The FDA guidelines for
Biomarker Qualification would not be mandated in production of the fluorescent TPE backbone,
but production goals would include satisfying as many qualifications as possible []. This will
allow an increased level of confidence to customers on product safety as well as decreasing the
possibility of issues with TPE fluorescent backbones causing issues during use in the medical
field.
Hazard Scenario and Response
Chlorine gas evolved from the TPE reactor recycled back to the PCl5 reactor poses a risk
of clogging and creating a hazardous scenario without proper engineering controls. If a clog
occurs in the chlorine recycle line, the pressure behind the clog would initially begin to increase
significantly as gas is evolved from the TPE reactor. Assuming the chlorine gas is transported in
a 4-inch Schedule 40 Hastelloy C276 pipe the pressure behind the clog could build up to over
7000 psig []. This pressure build up would be observed in the reaction vessel to decrease line
pressure. As pressure within the system continues to build the maximum allowable pressure of
the system would be exceeded and the reaction vessel subject to bursting.
If the reaction vessel bursts, the rupturing of the vessel threatens the life and health of all
plant operators and all people within the surrounding community. The sudden release of 7000 psi
of pressure provides a significant amount of energy which could launch projectiles at an
extremely high rate of speed. Reactor shrapnel has the potential to destroy process facilities
potentially increasing the magnitude of damage and leading to additional destructive events such
as fires and destruction of surrounding property. Nickle-glyme catalyst is known to release
flammable gases in the presence of water which in the event of fire would make firefighting
applications more difficult and dangerous. The chlorine gas has the potential to act as oxidizer
for any fires, further increasing the magnitude and destruction. Pressure releases, shrapnel from
reactors, and fire pose a substantial risk of loss of life or severe injuries for all employees as well
as any people in the surrounding area.
 Additionally, the rupturing of the TPE reactor or the destruction of any other vessel and
piping from fire or shrapnel poses significant chemical risk. The hazardous health nature of all
chemicals in this process expose operators, civilians, and the environment to substantial chemical
risk. Numerous components in the proposed TPE production will cause severe damage to the
environment even at low concentrations. Low LD50 and water toxicity values pose risks of long
lasting environmental and societal damage. Large scale releases of these chemicals risk the lives
of any employee working in the plant and any civilians near the disaster immediately following
release of chemicals. As chemicals are released waste water, ground water, and nearby streams
may be exposed to chemical run-off causing long lasting and detrimental effects of anyone
working with water downstream or of any biological life which interacts with any water [Nickel-
Glyme] [Benzophenone]. All biological life which is exposed to even extremely low levels of
chemical exposure could be damaged for years to come.
To prevent the catastrophic long-lasting destruction pressure monitoring and process
control measures will be implemented. Pressure monitoring via a differential pressure gauge
along the chlorine recycle is utilized to provide early identification of a clog developing.
Significant pressure increases and decreases in a section of pipe are indicative of a clog. In the
event of a clog and pressure differential increasing in the line, an electric signal to switch a three-
way valve at the inlet of the chlorine line will divert chlorine gas flow to an auxiliary pipeline
with similar monitoring implemented. The auxiliary pipe allows for continued operation even in
the event of a clog, and allows for maintenance personal properly equipped with PPE to perform
necessary maintenance and remove a clog before a crisis can emerge. If the auxiliary line would
become clogged while maintenance was being conducted on the main line, an emergency plant
shut off procedure would be initiated to allow for the repair of both pipelines before any
operation can commence.
References
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