Improving Chemical Plant Security via Improving Chemical Plant Security via Greener Process Technologies Greener Process Technologies

TUR Continuing Ed ConferenceApril 12, 2007

Scott ButnerDirector, ChemAlliancePacific NW National Laboratoryscott.butner@pnl.gov

Overview of PresentationOverview of Presentation

Quick intro to ChemAlliance Chemical Plant Security – why it’s an

issue Policy & Industry responses to the issue Reducing the risks

inherently safer chemical manufacturing “green” chemistry process intensification

Where do we go from here?

What is ChemAlliance?What is ChemAlliance?

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 access to tools and training emphasis on cost-effective

compliance strategies technical assistance programs trade & professional associations peer-to-peer mentoring

ChemAlliance is about PartnershipsChemAlliance is about Partnerships

ChemAlliance works closely with key regulatory and industry partners 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

Key Features of ChemAllianceKey Features of ChemAlliance

Virtual Plant Tour regulatory overview best management tips p2 case studies

ChemAlliance News updated semi-weekly 40-50 items/month focused on process

industries Plain-English overviews

of key regulations

ChemAlliance on your Desktop!ChemAlliance on your Desktop!

Google now allows you to add ChemAlliance content to your Google home page Online

regulatory glossary and search-aid

ChemAlliance news

More to come…

Improving Chemical Plant Security Improving Chemical Plant Security via Greener Technologyvia Greener Technology

Phillips Petroleum (October 1989)Phillips Petroleum (October 1989)

image courtesy of Dennis Hendershot, Rohm & Haas (used with permission)

This was This was notnot done by terrorists… done by terrorists…

image courtesy of http://www.acusafe.com/Incidents/PasadentTexas1989/incident-pasadenatexas1989.html

……but the threat is real…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?R&D for Domestic Attacks?

Chemical Manufacturing Facilities Chemical Manufacturing Facilities Represent Real Threats for Terror AttacksRepresent Real Threats for Terror Attacks

Routinely process large quantities of materials that are: toxic volatile flammable stored under extremes of pressure, temperature

Often close to population centers Vulnerable to attack

relatively low security numerous critical to the economy

The Scope of the Threat is Large…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 ThreatsIndustry Responses to Terror Threats

Industry response stresses site security, “voluntary” action

“Site Security Guidelines for U.S. Chemical Industry” issued October 2001 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 AIChE/CCPS Sandia National Lab SOCMA Many private companies

(BASF, Air Products, G-P)

Federal Chemical Facility Security Federal Chemical Facility Security Regulations are Evolving RapidlyRegulations are Evolving Rapidly

Recent DHS Actions 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 Chemical Facility Anti-Terrorism Standards Interim Final Rule (aka "Section 550")Interim Final Rule (aka "Section 550")

Promulgated by DHS on April 2, 2007 (2 days ahead of Congressional deadline) Currently accepting comments on list of reportable chemicals First reporting deadlines are 60 days after final Federal

Register announcement of final list Self-identification of facilities to DHS triggered by chemical

inventory thresholds 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:

Security Vulnerability Assessment Site Security Plan

Security Vulnerability AssessmentsSecurity Vulnerability Assessments

Required of all high-risk facilities (per Top Screen) Tier 4 (lowest risk) facilities may submit an Alternative

Security Program (ASP) in lieu of SVA Must include

Asset characterization Threat assessment Vulnerability assessment Risk assessment Countermeasures analysis

Updates required by schedule, or on direction of DHS 2 year cycle for Tier 1 & 2 3 year cycle for Tier 3 & 4

Site Security PlansSite Security Plans

Required of all high-risk facilities ASP may be acceptable for all tiers

SSP must: 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" Inherently safer design is not mentioned in

the rule

Rule expected to impact Rule expected to impact ~5,000 US Facilities~5,000 US Facilities

Initial reporting (Top Screen) SVA development Site Security Plans Periodic updates for each of these

documents Record keeping burden

Reporting documentation Training records Security incidents Threats against facility

But this probably isn’t the final word…But this probably isn’t the final word…

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 TURConnecting Plant Security and TUR

Protecting the public from deliberate attacks on chemical plants shares many characteristics with pollution prevention: 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

Short-term responses focus on plant security “Guns, Gates and Guards”

Long-term responses are likely to have much in common with P2 strategies inherently safe chemical processing “green” chemistry process intensification

Strategies for Reducing Risk While Strategies for Reducing Risk While Improving Your ProcessImproving Your Process

Inherently Safer Design Making the process safer

Green Chemistry Making the chemistry safer

Process Intensification Reducing chemical inventories

These strategies often overlap Each provides the opportunity for direct

benefit to businesses that adopt them

Inherently Safer Chemical ProcessingInherently Safer Chemical Processing

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 use less hazardous materials when possible reduce inventories of hazardous materials

generate “just in time” reduce inherent risks of reactions

reactor designs, operating schemes to reduce possibility of “runaway” reactions

reduce severity of processing/storage (lower pressure, lower temperature)

Examples of Inherently Safer Examples of Inherently Safer Chemical ProcessingChemical Processing

DuPont Edgemoor Plant 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 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…Keep this in mind, though…

Inherently safer is not necessarily safer!

Photos used via Creative Commons licensehttp://www.flickr.com/photos/davipt/165533374/

http://www.flickr.com/photos/spike55151/187677818/

~ 0.17 deaths/billion passenger miles

~10 deaths/billion passenger miles

DHS Guidance on ISTDHS Guidance on IST

"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"

DHS Response to comments, Interim Rule

And although the federal law is And although the federal law is mostly silent on the issue…mostly silent on the issue…

Section 550/Chemical Facility Anti-Terrorism Standards have implicit drivers for some forms of IST Provides "escape clause" for firms that can

drop out of high-risk category NJ Chemical plant security regulations

require firms to investigate IST alternatives Other states may follow suit

““Green” ChemistryGreen” Chemistry

Emphasis of green chemistry tends to be on synthesis routes and solvent selection, rather than equipment engineering 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

• Prevent Waste

• Design Less Hazardous Chemical Synthesis

• 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

• Design Safer Chemicals and Products

• Maximize Atom Economy

12 Principles of Green Chemistry12 Principles of Green Chemistry

Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice,

Oxford University Press: New York, 1998, p.30.

ActivationDehydrationPrecipitation

Me3+ MetalOxide

CatalystMetal Hydroxide

Catalyst production schememetal oxide

HNO3

NOx metalnitrate

hydroxide/carbonate/

nitrate

hydroxide/carbonate/

nitrate

Dissolutio

n Precipitation Separation Dry/Calcine

Conventional Precipitation Process Na2CO3,

NH3

NO3(Na)

(NH4)H2O H2OH2ONOxCO2

oxide hydrate

Digestion and precipitation

Süd-Chemie WastewaterFree Process

Protonsource Oxidizer

Dry/Calcine

CO2

H2O

Green Chemistry in Green Chemistry in Catalyst ManufactureCatalyst Manufacture

BenefitsBenefits

Sud-Chemie received 2003 Presidential Green Chemistry Challenge Award

Metal oxide catalyst production process 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 IntensificationProcess Intensification

Process intensification = “…strateg[ies] for achieving dramatic reductions in the size of the [manufacturing] plant at a given production volume”

specific strategies may include unit integration (combining functions) field enhancement (using light, sound,

electrical fields, or centrifugal force to alter process physics)

micro-scale technology

Combining Unit Operations – Combining Unit Operations – Reactive DistillationReactive Distillation

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 EnhancementField Enhancement Uses field

enhancement to effect intensification 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 Field enhancement can be used in reactions as wellreactions as well

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 TechnologyMicroscale Technology

Uses microchannel devices to alter flow characteristics Dramatic

improvements in heat tranfer, mass transfer efficiency

Driving forces in microchannel heat Driving forces in microchannel heat exchanger performanceexchanger performance

High surface area/volume ratio increases volumetric efficiency

High heat transfer coefficient increases area efficiency

Net result: Large heat transfer per unit

volume allow compact devices, small temperature gradients within fluid

High transfer coefficient allows closer temperature approaches

TAhQ

d

kNuh

Heat Exchanger ComparisonHeat Exchanger ComparisonShell & Tube

Compact HX Microchannel

Surface Area per Unit Volume

(m2/m3)

50-100 850-1500 1500

Heat Transfer Coefficient (l)

(W/m2/K)

~5000 (tube side)

3000-7000 7000

Heat Transfer Coefficient (g)

(W/m2/K)

20-100 50-300 400-2000

Approach Temps ~20 °C ~10 ° C < 10 ° C

Microchannel technology has Microchannel technology has applications to other unit operationsapplications to other unit operations

Separations Thin liquid phase, control over gas phase

provides for compact, energy efficient distillation

Reactors Efficient heat exchange provides for tight

control over reaction conditions, especially in fast, exothermic reactions

Mixing Preliminary work on emulsion formation

suggests much more monodisperse emulsions

Examples of Process Intensification Examples of Process Intensification (PI) in Industry(PI) in Industry

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 CaveatsSome Caveats Process modification is non-trivial for the

chemical industry Some strategies tend to shift risks, rather than

reduce them e.g., reducing inventories may increase transportation

Even if all risk could be eliminated from chemical manufacturing facilities, other targets exist 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. beware of “easy answers!”

SummarySummary

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 inherently safer design process intensification “green” chemistry and engineering

ReferencesReferences 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. KimmerleChemical Plant Safety - Applying the Tools of the Trade to New RiskChemical 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 SecuritySelected Resources: Plant Security

GAO Report: Protection of Chemical and Water Infrastructurehttp://www.gao.gov/new.items/d05327.pdf

Congressional Research Service: Chemical Facility Security: Regulations and Issues for Congress (January 31, 2007)http://www.fas.org/sgp/crs/homesec/RL33847.pdf

Chemical Facility Anti-Terrorism Stds Interim Final Rulehttp://www.dhs.gov/xlibrary/assets/IP_ChemicalFacilitySecurity.pdf

DHS Chemicals of Interesthttp://www.dhs.gov/xprevprot/laws/gc_1175537180929.shtm

ACC’s Responsible Care Security Codehttp://www.americanchemistry.com/s_acc/bin.asp?CID=373&DID=1255&DOC=FILE.PDF%22

New Jersey DEP Chemical Plant Security Downloadshttp://www.state.nj.us/dep/rpp/brp/security/secdown.htm

Selected Resources: Green Chemistry, Selected Resources: Green Chemistry, Inherently Safer Design, and Process IntensificationInherently Safer Design, and Process Intensification

A Checklist for Inherently Safer Chemical Reaction Process Design and Operationhttp://www.aiche.org/uploadedFiles/CCPS/Publications/SafetyAlerts/CCPSAlertChecklist.pdf

Inherently Safer Process Designhttp://www.sache.org/links/Pike21Jul2004/Inherently%20Safer%20Design.ppt

Green Chemistry (Wikipedia version)http://en.wikipedia.org/wiki/Green_chemistry

Center for Green Chemistry at UML http://www.greenchemistry.uml.edu/

ACS Green Chemistry Institutehttp://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC=greenchemistryinstitute%5Cindex.html

Process Intensification Networkhttp://www.pinetwork.org/whatsnew/whatsnew.htm

Process Intensification: Transforming Chemical Engineeringhttp://www.citg.tudelft.nl/live/binaries/5fbfd71c-e196-49a8-bc78-853600f8d710/doc/CEP%20paper.pdf

Process Intensification and Green Chemistryhttp://rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=gc990g15&JournalCode=GC