Transcript ChemAlliance

Improving Chemical Plant Security
via Greener Process Technologies
TUR Continuing Ed Conference
April 12, 2007
Scott Butner
Director, ChemAlliance
Pacific NW National Laboratory
[email protected]
Overview of Presentation
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Quick intro to ChemAlliance
Chemical Plant Security – why it’s an
issue
Policy & Industry responses to the issue
Reducing the risks
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inherently safer chemical manufacturing
“green” chemistry
process intensification
Where do we go from here?
What is ChemAlliance?
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ChemAlliance (www.chemalliance.org)
is an EPA-OECA supported
Compliance Assistance Center.
Our mission is to help small chemical
manufacturers (and allied industries)
improve their environmental
performance
We serve as a clearinghouse for
compliance and P2 information
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access to tools and training
emphasis on cost-effective
compliance strategies
technical assistance programs
trade & professional associations
peer-to-peer mentoring
ChemAlliance is about Partnerships
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ChemAlliance works closely with key
regulatory and industry partners
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National Association of Chemical Distributors
Synthetic Organic Chemical Manufacturers Assoc
American Chemistry Council
American Institute of Chemical Engineers
US EPA (OECA, OPPT, OPEI)
Texas Commission on Environmental Quality
Michigan Department of Environmental Quality
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Improving Chemical Plant Security
via Greener Technology
Phillips Petroleum (October 1989)
image courtesy of Dennis Hendershot, Rohm & Haas (used with permission)
This was not done by terrorists…
image courtesy of http://www.acusafe.com/Incidents/PasadentTexas1989/incident-pasadenatexas1989.html
…but the threat is real…
FBI warns
petrochemical plants
on Gulf of Mexico
TEXAS CITY, Texas (AP) —
Security was tight early
Thursday at
petrochemical plants
along the Gulf of Mexico
following a caution
issued by the FBI.
An agency official said
that the Texas Coastal
Regional Advisory
R&D for Domestic Attacks?
Chemical Manufacturing Facilities
Represent Real Threats for Terror Attacks
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Routinely process large quantities of
materials that are:
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toxic
volatile
flammable
stored under extremes of pressure, temperature
Often close to population centers
Vulnerable to attack
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relatively low security
numerous
critical to the economy
The Scope of the Threat is Large…
“…according to EPA, 123 chemical facilities
located throughout the nation have
accidental toxic release ‘worst-case’
scenarios where more than one million
people…could be at risk of exposure”
Source: US EPA
Industry Responses to Terror Threats
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Industry response stresses site security,
“voluntary” action
“Site Security Guidelines for U.S. Chemical Industry”
issued October 2001
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Joint effort by ACC, SOCMA, and the Chlorine Institute
emphasis on site and operational security via
“rings of protection”
Security Vulnerability Assessment (SVA)
and related Prioritization Methodologies
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AIChE/CCPS
Sandia National Lab
SOCMA
Many private companies
(BASF, Air Products, G-P)
Federal Chemical Facility Security
Regulations are Evolving Rapidly
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Recent DHS Actions
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October 2006 – Congressional direction to
DHS to develop regulations addressing
chemical plant security
December 2007 – DHS issues draft interim
rule for comment
April 2, 2007 – DHS issued “Chemical
Facility Anti-Terrorism Standards Interim
Final Rule”
First federal legislation to specifically
address plant security (vs. safety,
environment, etc)
Chemical Facility Anti-Terrorism Standards
Interim Final Rule (aka "Section 550")
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Promulgated by DHS on April 2, 2007
(2 days ahead of Congressional deadline)
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Self-identification of facilities to DHS triggered by chemical
inventory thresholds
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Currently accepting comments on list of reportable chemicals
First reporting deadlines are 60 days after final Federal
Register announcement of final list
List of chemicals drawn from RMP, CWC, DOT regs
Screening done online via "Top Screen"
Additional facilities may be required to identify, essentially
upon Secretary's discretion
Depending upon initial risk assessment, may require:
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Security Vulnerability Assessment
Site Security Plan
Security Vulnerability Assessments
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Required of all high-risk facilities (per Top
Screen)
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Must include
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Tier 4 (lowest risk) facilities may submit an Alternative
Security Program (ASP) in lieu of SVA
Asset characterization
Threat assessment
Vulnerability assessment
Risk assessment
Countermeasures analysis
Updates required by schedule, or on direction of
DHS
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2 year cycle for Tier 1 & 2
3 year cycle for Tier 3 & 4
Site Security Plans
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Required of all high-risk facilities
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SSP must:
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ASP may be acceptable for all tiers
Address each vulnerability identified in the
SVA
Identify and describe security measures
and their impact on risk reduction
Emphasis in DHS guidance is on
"guns, gates and guards"
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Inherently safer design is not mentioned in
the rule
Rule expected to impact
~5,000 US Facilities
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Initial reporting (Top Screen)
SVA development
Site Security Plans
Periodic updates for each of these
documents
Record keeping burden
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Reporting documentation
Training records
Security incidents
Threats against facility
But this probably isn’t the final word…
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The issue (and the rule) has drawn attention from
major presidential contenders (Clinton, Obama)
Likely to be a platform plank – possibly for both
parties
Potential exists for conflict w/ state laws that are
more stringent (e.g., NJ, NY)
Current law expires in 3 years. What will take its
place?
Even if rule remains intact: will it drive adoption
of IST?
Connecting Plant Security and TUR
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Protecting the public from deliberate attacks on chemical
plants shares many characteristics with pollution prevention:
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Short-term responses focus on plant security
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need to balance short-term and long-term responses
non-obvious and often intangible benefits to industry
Non-obvious, and sometimes counterintuitive “right” answers
likely to be an evolutionary, rather than revolutionary response
“Guns, Gates and Guards”
Long-term responses are likely to have much
in common with P2 strategies
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inherently safe chemical processing
“green” chemistry
process intensification
Strategies for Reducing Risk While
Improving Your Process
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Inherently Safer Design
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Green Chemistry
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Making the chemistry safer
Process Intensification
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Making the process safer
Reducing chemical inventories
These strategies often overlap
Each provides the opportunity for direct
benefit to businesses that adopt them
Inherently Safer Chemical Processing
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Has it’s roots in process safety discipline, dating back
many decades
Traditional safety placed an emphasis on operational
procedures, process control, and root cause analysis
Inherent safety adds an emphasis on reducing potential
for, and risks of, catastrophic or uncontrolled releases
Underlying principles are common to P2
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use less hazardous materials when possible
reduce inventories of hazardous materials
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reduce inherent risks of reactions
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generate “just in time”
reactor designs, operating schemes to reduce possibility of “runaway”
reactions
reduce severity of processing/storage
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(lower pressure, lower temperature)
Examples of Inherently Safer
Chemical Processing
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DuPont Edgemoor Plant
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Refrigerant solvent substitution of aqueous calcium
chloride solution for methylene chloride, a carcinogen
and haz waste
Eliminated fugitive methylene chloride emissions – was
20,000 lbs/yr at each of 4 domestic TiO2 plants
Continuous addition, flow reactors
instead of batch reactors
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Applicable to fast, highly exothermic reactions
Allows heat of reaction to be controlled in more than
one way
Often allows for better temperature control
Keep this in mind, though…
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Inherently safer is not necessarily safer!
~ 0.17 deaths/billion passenger miles
~10 deaths/billion passenger miles
Photos used via Creative Commons license
http://www.flickr.com/photos/davipt/165533374/
http://www.flickr.com/photos/spike55151/187677818/
DHS Guidance on IST
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"Section 550 prohibits the Department
from disapproving a site security plan
'based on the presence or absence of
a particular security measure,'
including inherently safer
technologies. Even so, covered
chemical facilities are certainly free to
consider IST options, and their use
may reduce risk and regulatory
burdens"
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DHS Response to comments, Interim Rule
And although the federal law is
mostly silent on the issue…
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Section 550/Chemical Facility
Anti-Terrorism Standards have implicit
drivers for some forms of IST
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Provides "escape clause" for firms that can
drop out of high-risk category
NJ Chemical plant security regulations
require firms to investigate IST
alternatives
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Other states may follow suit
“Green” Chemistry
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Emphasis of green chemistry tends to be
on synthesis routes and solvent
selection, rather than equipment
engineering
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biologically-catalyzed reactions
low-toxicity reactants and solvents
aqueous and solvent-less reaction processes
EPA’s approach to green chemistry
stresses early assessment and reduction
of chemical risks
12 Principles of Green Chemistry
• Prevent Waste
• Maximize Atom Economy
• Design Less Hazardous Chemical Synthesis
• Design Safer Chemicals and Products
• Use Safer Solvent/Reaction Conditions
• Increase Energy Efficiency
• Use Renewable Feedstocks
• Avoid Chemical Derivatives
• Use Catalysts, Not Stoichiometric Reagents
• Design Chemicals and Products that Degrade After Use
• Analyze in Real Time to Prevent Pollution
• Minimize the Potential For Accidents
Anastas, P. T.; Warner, J. C.
Green Chemistry: Theory and Practice,
Oxford University Press: New York, 1998, p.30.
Green Chemistry in
Catalyst Manufacture
Conventional Precipitation
Na2CO3,
Process
NH3
NOx
metal
HNO3
Precipitation
nitrate
metal
Proton
source
hydroxide/
carbonate/
nitrate
(Na)
(NH4 ) NO3 H2O
Separation
hydroxide/
carbonate/
nitrate
Catalyst production scheme
Oxidizer
Süd-Chemie Wastewater
Free Process
Precipitation
Me3+
H2O
oxide
CO2
H2 O
oxide hydrate
Dehydration
Metal
Hydroxide
H2O
NOx
CO2
Activation
Metal
Oxide
Catalyst
Benefits
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Sud-Chemie received 2003 Presidential
Green Chemistry Challenge Award
Metal oxide catalyst production process
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Alternative process chemistry for metal oxide
Uses 16 times less water and eliminates
wastewater and NOx generation
Eliminates generation of by-product
ammonium nitrate (explosive!)
Savings of nearly $12 million annually
Process Intensification
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Process intensification = “…strateg[ies]
for achieving dramatic reductions in the
size of the [manufacturing] plant at a
given production volume”
specific strategies may include
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unit integration (combining functions)
field enhancement (using light, sound,
electrical fields, or centrifugal force to alter
process physics)
micro-scale technology
Combining Unit Operations –
Reactive Distillation
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Combines
reaction,
distillation
in single
unit
Can be very
effective in
equilibrium
limited
reactions
Andrzej I. Stankiewicz, Jacob A. Moulijn,
Process Intensification: Transforming Chemical Engineering
Field Enhancement
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Uses field
enhancement to
effect intensification
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Gravity/centrifugal
force
Ultrasonic
Electromagnetic
Most commercial or
near-commercial
work involves
centrifugal force
fields to improve
mass transfer
efficiency
Higee Separator
image courtesy UCSD
Field enhancement can be used in
reactions as well
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Ramshaw (Univ. of Newcastle) reports significant
reductions in cell voltage for electrochemical
reactions conducted under high G-forces
 0.4V improvement on chlorine cells
 0.7V improvement on water electrolysis
 Results at ~180g
Spinning disk reactor image c/o Protensive
Microscale Technology
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Uses
microchannel
devices to alter
flow
characteristics
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Dramatic
improvements in
heat tranfer, mass
transfer efficiency
Driving forces in microchannel heat
exchanger performance
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High surface area/volume
ratio increases volumetric
efficiency
High heat transfer coefficient
increases area efficiency
Net result:
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Large heat transfer per unit
volume allow compact
devices, small temperature
gradients within fluid
High transfer coefficient
allows closer temperature
approaches
Q  h  A  T
Nu  k
h
d
Heat Exchanger Comparison
Shell &
Tube
Surface Area per 50-100
Unit Volume
(m2/m3)
Heat Transfer ~5000
Coefficient (l) (tube
(W/m2/K) side)
Heat Transfer 20-100
Coefficient (g)
(W/m2/K)
Approach Temps ~20 °C
Compact HX
Microchannel
850-1500
1500
3000-7000
7000
50-300
400-2000
~10 ° C
< 10 ° C
Microchannel technology has
applications to other unit operations
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Separations
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Reactors
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Thin liquid phase, control over gas phase
provides for compact, energy efficient
distillation
Efficient heat exchange provides for tight
control over reaction conditions, especially
in fast, exothermic reactions
Mixing
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Preliminary work on emulsion formation
suggests much more monodisperse
emulsions
Examples of Process Intensification
(PI) in Industry
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GlaxoSmithKline has demonstrated 99%
reduction in inventory and 93% reduction in
impurities by using spinning disk reactors
Studies show that process integration on the
Bhopal facility could have reduced MIC
inventories from 41 tons to < 10 kg.
ICI has demonstrated byproduct reductions of
75% by using integral heat exchange (HEX)
reactors
Use of HEX reactors can result in ~100-fold
reductions in chemical inventory!
Some Caveats
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Process modification is non-trivial for the
chemical industry
Some strategies tend to shift risks, rather than
reduce them
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Even if all risk could be eliminated from chemical
manufacturing facilities, other targets exist
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e.g., reducing inventories may increase transportation
only 18% of facilities required to report under RMP were
chemical manufacturing facilities!
underscores importance of moving towards safer
products, not just safer processes
The “risk vs. efficiency” equation has
implications for sustainability.
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beware of “easy answers!”
Summary
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Chemical manufacturing facilities have a
heightened awareness of process risks since
9/11
Increasing visibility of the threat is likely to lead
to additional regulatory action and/or increased
public pressure
Many of the strategies for reducing risk are also
effective sustainable process strategies
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inherently safer design
process intensification
“green” chemistry and engineering
References
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US EPA, Chemical Accident Risks in US Industry, September 2000
US General Accounting Office (GAO), Voluntary Initiatives are Under
Way at Chemical Facilities, but the Extent of Security Preparedness
is Unknown. US GAO Report GAO-03-439, March, 2003.
Ragan, P.T., Kilburn, M.E., Roberts, S.H. and N.A. Kimmerle
Chemical Plant Safety - Applying the Tools of the Trade to New Risk
Chemical Engineering Progress, February 2002, Pg. 62
Royal Society of Chemistry, Note on Inherently Safer Chemical
Processes, 03/16/2000
Bendixen, Lisa, Integrate EHS for Better Process Design
Chemical Engineering Progress, February 2002, Pg. 26
Stankiewicz, A and J.A. Moulijn, Process Intensification, Ind. Eng.
Chem. Res. 2002, vol. 41 pp 1920-1924.
Note: Chemical Engineering Progress articles are available
online to registered users, via http://www.cepmagazine.org/
Selected Resources: Plant Security
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GAO Report: Protection of Chemical and Water Infrastructure
http://www.gao.gov/new.items/d05327.pdf
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Congressional Research Service: Chemical Facility Security:
Regulations and Issues for Congress (January 31, 2007)
http://www.fas.org/sgp/crs/homesec/RL33847.pdf
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Chemical Facility Anti-Terrorism Stds Interim Final Rule
http://www.dhs.gov/xlibrary/assets/IP_ChemicalFacilitySecurity.pdf
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DHS Chemicals of Interest
http://www.dhs.gov/xprevprot/laws/gc_1175537180929.shtm
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ACC’s Responsible Care Security Code
http://www.americanchemistry.com/s_acc/bin.asp?CID=373&DID=1255&DOC=FILE.PDF%22
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New Jersey DEP Chemical Plant Security Downloads
http://www.state.nj.us/dep/rpp/brp/security/secdown.htm
Selected Resources: Green Chemistry,
Inherently Safer Design, and Process Intensification
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A Checklist for Inherently Safer Chemical Reaction
Process Design and Operation
http://www.aiche.org/uploadedFiles/CCPS/Publications/SafetyAlerts/CCPSAlertChe
cklist.pdf
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Inherently Safer Process Design
http://www.sache.org/links/Pike21Jul2004/Inherently%20Safer%20Design.ppt
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Green Chemistry (Wikipedia version)
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Center for Green Chemistry at UML
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ACS Green Chemistry Institute
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Process Intensification Network
http://en.wikipedia.org/wiki/Green_chemistry
http://www.greenchemistry.uml.edu/
http://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC=greenchemistryinst
itute%5Cindex.html
http://www.pinetwork.org/whatsnew/whatsnew.htm
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Process Intensification: Transforming Chemical Engineering
http://www.citg.tudelft.nl/live/binaries/5fbfd71c-e196-49a8-bc78-853600f8d710/doc/CEP%20paper.pdf
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Process Intensification and Green Chemistry
http://rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=gc990g15&JournalCode=GC