Chemical security v5

OPCW
Chemical Security
Dr Alan Millington
August 2018 (v5)
POCW © C A Millington 2017

Chemical Security
World wide chemical industry produces large quantities
of many materials which could be used as chemical
weapons i.e. Chlorine, Hydrogen Cyanide etc. The
security of these materials , must be considered within
the following contexts
• Manufacturing – safe operation and containment
• Storage – how we store and how much
• Transport – how do we get product to consumer
• End user – how can we control use of our products

Chemical Manufacturing (1)
Scale of Operation
• Chemical Industry operates over a very large
range of scale
– Large tonnage chemicals
• 35000 tonne/day Oil Refinery
• 1750 tonne/day Ammonia plant
• 750 tonne/day Vinyl Chloride plant
– Moderate scale more specialised chemicals
• 200 tonne/day Hydrogen Cyanide plant
• 100 tonne/day Refrigerant plant
– Small Scale
• 5 tonne/day Fine Chemicals/Catalysts
• 100 kg/week Pharmaceutical chemicals

Continuous vs. Batch operation
• Continuous
– Most large production processes
– Low residence time
– Steady state operation
– Continuous 24x7 operation – often 4 years between shutdowns
• Oil refining, Ammonia, Chlorine etc.
• Batch
– Most small scale production
– High residence time
– Non steady state operation (day work or 24x7 operation)
– Multipurpose plants
• Fine Chemicals, Pharmaceuticals

Plant Complexity
• Often Multistep Processes
– Ammonia plant
• Furnace
• 6 different reactors
• 2 distillation & absorption columns
• Multiple heat exchangers/steam generators
• 4 compressors (2 very large)
• Refrigeration system
• Emergency flare system

Factory Environment (a)
• Production processes rarely stand alone
• Several different processes on a single factory
site
– Unified utilities/offsites/management
• Centralised steam generation, cooling water and flare
systems
• Centralised electricity import/export, waste treatment
• Centralised storage, maintenance, fire, medical and
laboratory facilities
• Common highly skilled flexible labour force

Factory Environment (b)
• Adjacent processes often uses, as a feed, the
product from neighbouring processes
– Vinyl Chloride plant uses Chlorine for a Chlorine
plant and sends product to a PVC plant
• Manpower
– Processes computer controlled so staffing level
very low
• Fawley FCCU has only 6 operatives per shift (5 shift
teams)
• All operatives trained on multiple process plants

Site Security (a)
• PEOPLE
– Controlled people entry & exit via small number of gates
– Random searches of all people entering and leaving site
– No private cars on site – external parking
– Occasional workers/visitors require special procedure
– Individual process plant access via “permit to work
system”
• MATERIALS
– All road/rail deliveries/exports to/from specified gates
separate to “People Gates”
– Material entry/exit via road, rail, ship, pipeline etc.

Site Security (b)
• REGULATION
– Sites controlled via statutory instruments
• CoSHH
• CoMAH
• H&SaWA(1974)
• MH&SaWR (1999) etc.
– Special regulations for site with high risk processes
and chemicals
– Security via double fencing, CCTV, Doppler radar

Process Design
• Design & operation influenced by statutory
instruments and CoP (DOW, CoMAH etc.)
• DOW properly applied influences plant layout
(safe unit separation, zoning, electrical safety)
• Can design
– To stop uncontrolled emissions (closed buildings)
– For effective effluent treatment (incineration etc.)
– For emergency shutdown to prevent material lost to
the environment (emergency scrubbing towers)
– For effective on-site or off-site waste treatment

Internal Plant Inventory (a)
• Continuous plant operation long term steady state with
significant short term perturbations
• Exact internal inventory at any point in time is
impossible to measure directly
• Inventory calculated on time averaged flow rates &
vessel levels
• Internal inventory in pipes, vessels, columns, pumps,
heat exchangers etc. can be significant
– FCCU fractionator contains about 130 tonne hydrocarbon
when throughput is 450 tonne/h
– Entire process contains about 250 tonne when throughput
is 450 tonne/h

Internal Plant Inventory (b)
• Sellafield often reports an annual loss of
Plutonium (circa 1 kg last year) which simply
reflects internal inventory variations
• Plant Inventory depends on measurement
accuracy which is seldom better than ±0.5%.
– It is important to know how variables are
measured.

Flow Measurement (a)
• Flow Measurement
– For liquids and gases usually volume based
• Orifice plate, Turbine meters etc.
• Some mass flow devices available but calibration
difficult
– For volume based devices
• Calibration depends on stream density which is
composition, temperature and sometimes pressure
dependent ( a change in any one affects reading
accuracy)

Flow Measurement (b)
– For solids mass flow measurement via strain
gauges on conveyers or weighed material
introductions and extractions
• Calibration temperature dependent
– For mixed streams (liquid/vapour/gas, solid/liquid)
accurate measurement very difficult
• Calibration is phase fraction, temperature and pressure
dependent
• Phase fraction evaluation for multicomponent systems
composition, temperature and pressure dependent

Temperature Measurement
• Temperature Measurement
– Via thermocouple, platinum resistance
thermometer or IR meter
– Reading can be inaccurate if device covered by
condensation or precipitated solid
– Reading is a point value so position of probe
critical is mean values is to be indicated

Composition Measurement
• Composition Measurement
– Measurement usually via discrete sample for
laboratory analysis (may take some hours)
– Can be measured by on-line gas chromatograph
• Device needs special containment (sample cabin)
• Ensuring sample injected is characteristic of material being
analysed often difficult (long sample lines)
– Some continuous component specific devices
available (O2 CO2 H2S etc.) but again sampling difficult
or must scan whole stream
– Outputs can be directly linked to control computer

Depth Measurement
• Depth Measurement (Tanks/Vessels)
– Measuring static head by determining pressure at
base of vessel
• Pressure diaphragm cell fitted with strain gauges
– Measuring head directly
• Floating indicator with magnetic follower and positional
conversion
• -ray detectors (Co60 plus Geiger-Müller counters)
• Dipping rods

Storage (a)
• Why store
– Check purity before sale
– Allow for batch blending (shift tank)
– Buffer to meet import and export batch
requirements
• Ship export may require 5000 tonne batch
• Road export may require 38 tonne batch
– Buffer to meet import and export delivery delays
– To allow off-spec products and slops to be
recycled

Storage (b)
• How much to store
– Minimise to meet offsite operational requirements
– Minimise using pipeline export to adjacent facilities for
most dangerous chemicals
• Chlorine, Hydrogen Cyanide, Ammonia, Vinyl Chloride, Phosphine
etc.
– CoMAH suggests storage be minimise
– QRA and HAZOP essential to determine quantity stored
– Storing implies a cost
• Loss of income – product made but not yet sold

Storage (c)
• How to store
– Gases
• Depends on Tcrit
– T> Tcrit
» Compressed (gas phase HP bulk storage unusual)
– T< Tcrit
» Liquefy to V/L mixture at atmospheric temperature (High Press -
Propane)
» Liquefy to V/L mixture at atmospheric pressure (Low Temperature
insulated tank refrigerated storage with vent condenser,
Ammonia -33°C), Chlorine (-25°C), Ethylene (-105°C))
– Liquids
• Depends on phase above liquid
– Under own SVP in sealed vessel at low pressure
– Under atmospheric air/inert gas blanket (“breathing” tank with vent
condensers)

Storage (d)
– Solids
• Depends on export transport
• Silo or bunker (under atmospheric air, inert gas)
• Semi bulk pre-weighted containers/bags (under atmospheric air,
inert gas)
• Shared Storage
– Factory sites
• Mostly dedicated tanks but some “swing” tanks which can
be used for a range of products
• Shared warehouse facilities for solids and smaller quantities
of liquids.
• Pressurised and refrigerated storage usually dedicated to
one product or feed

Storage Inventory (a)
• Compressed Gases
– Temperature & Pressure in and volume of container
(PV=zRT)
• Liquids and Liquefied Gases
– Usually measured by volume (tank depth x area) with
depth measured via static head
• Converting depth to mass depends on density is both
temperature and composition dependent
• Large tank stratification
• Inventory often dynamic as tank can be fed and material
withdrawn at different rates at the same time

Storage Inventory (b)
• Solids
– Semi-bulk containers/bags weighed on filling
– Silo inventory usually measured by volume (solid
depth x area) with depth measured directly or
from pressure exerted on bottom of silo
– Mass conversion via packed density (depends on
voidage [particle shape, size] and particle density)

Feed and Product Transport (1)
• Chemical Import/Export Bulk Transport
– Road tanker
• Liquid, Solid, Liquefied Gas, Compress Gas (multiple small units)
• Maximum load circa 38 tonne
• Frequency – with multiple loading points could be maximum of a
tanker every 3-5 minutes
– Rail tanker
• Circa 100 x 20 tonne trucks/train
• Liquid, Solid, Liquefied Gas, Compress Gas (multiple small units)
• Maximum load circa 2000 tonne/train
• Frequency – with empty containers delivered to site and
automated loading/unloading could be one train every 15 minutes

– Pipeline
• For liquids, suspended solids in liquid and gases
• Can be very long length (1000+ miles with booster pumps)
• Can be designed for very high pressure (200 bar supercritical
CO2 for EOR)
• Can be used for multiple liquid product with buffer material
and destination slops tankage
• Used for large product packages (5000+ tonne lots)
• Stopping flow was cause problems (pressure surge causing
“hydraulic hammer”)

– Ship
• For solids, liquids and refrigerated liquefied gases (LNG,
Chlorine, Ammonia etc.)
• Requires jetty with loading and off-loading facilities
– Very large vessels may need off shore transfer facilities
• Large package sizes (5000 tonne minimum package size but
500,000 tonne vessels common)
• Ships with multiple tanks can carry several different products
• Cleaning tanks to stop cross contamination can be difficult

Chemical Transport Security (1)
• Road Transport
– Satellite tracking of lorry
– Police/Army escort for dangerous materials
– Many materials banned because QRA indicates unacceptable
risk (liquid Chlorine etc.)
– Many materials have package size limits (CHIP)
– Theft possible at driver stops
• Rail Transport
– Satellite tracking of train
– Police/Army escort for dangerous materials
– Special crash resistant containers (radioactive fuel rods)
– Theft possible by disrupting signalling but removal of large
quantities to road/ship transport difficult

• Pipeline
– Often on surface or just subsurface
– Difficult to keep under continuous observation
– Theft relatively straight forward with technical knowledge
– If theft rate small compared with flow in pipe very difficult
to detect
– In 2016-17
• Nigerian LPG/Petrol/Diesel pipeline annual thefts estimated at
1x1011 $ US
• Nigerian Crude Oil pipeline thefts estimated at 7x109 $ US
• Mexican annual petrol/diesel thefts estimated as 1x109 $ US from
6873 illegal pipeline taps
• £M1.0 petrol/diesel from Esso Central pipeline

• Ship
– Difficult to steal other than complete load
– Warship escort for the most dangerous cargoes
– Some piracy off horn of Africa for ransom
– Major environmental contamination if ship sinks
– Difficult but not impossible to transfer cargoes at
sea

End-User Security (1)
• Seller can impose conditions on end user BUT
– Difficult to check because supplier need access to
customer operating/sales records
– Difficult to check exactly what customer is doing
with product
– Customer may sell on to third party and enforcing
conditions along a sales chain very difficult
– Difficult to impose conditions across national
boundaries

End-user Security (2)
• Some materials covered by special
government regulation and/or international
treaty which imposed manufacturing and
sales conditions
– Chemical weapons precursors
• Can only manufacture under license
• Government controls on end use
• OPCW Inspections

End-user Security (3)
• Some materials have both an acceptable and
unacceptable uses
• Potassium Nitrate used widely as a fertiliser but can
also be used make bombs (Potassium Nitrate + Diesel
oil + Detonator)
• Potassium Cyanide used widely in Electroplating but
can be used as mass poison
• Gamma Hydroxybutyrate (GHB) can be used as a
chemical tracer or as “date rape” drug
• Security forces check all new customers and intended
end use of such materials before dispatch

Summary
• Chemical industry produced many dangerous
material which could be used for offensive
purposes
• Control of accurate process inventory difficult
• Material theft from process plant difficult
• Transport of product is controlled but theft is
possible and long pipelines particularly
vulnerable
• End-user security particularly difficult across
national boundaries

Questions
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Chemical security v5

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