Improving Chemical Plant Security via Greener Process Technologies

TUR Continuing Ed Conference April 12, 2007

Scott Butner Director, ChemAlliance Pacific NW National Laboratory scott.butner@pnl.gov

Overview of Presentation

Quick intro to ChemAlliance Chemical Plant Security why its 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?

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 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 ChemAlliance

Virtual Plant Tour

regulatory overview best management tips p2 case studies

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

ChemAlliance News

Plain-English overviews of key regulations

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 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

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

according to EPA, 123 chemical facilities located throughout the nation have accidental toxic release worst-case scenarios where more than one million peoplecould be at risk of exposure

Source: US EPA

Industry 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 Regulations 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 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 Security Vulnerability Assessment Site Security Plan

Depending upon initial risk assessment, may require:

Security 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 Asset characterization Threat assessment Vulnerability assessment Risk assessment Countermeasures analysis

Must include

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 Plans

Required of all high-risk facilities

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

SSP must:

Emphasis in DHS guidance is on "guns, gates and guards"

Inherently safer design is not mentioned in the rule

Rule expected to impact ~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 isnt 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 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
Guns, Gates and Guards

Short-term responses focus on plant security

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 Improving Your Process

Inherently Safer Design

Making the process safer

Making the chemistry safer Reducing chemical inventories

Green Chemistry

Process Intensification

These strategies often overlap Each provides the opportunity for direct benefit to businesses that adopt them

Inherently Safer Chemical Processing

Has its 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

(lower pressure, lower temperature)

reduce severity of processing/storage

Examples of Inherently Safer Chemical 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

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

"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 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 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

EPAs 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 NH 3 NOx metal HNO Precipitation nitrate 3
H2O (Na) (NH ) NO3 H2O 4 Separation

hydroxide/ carbonate/ nitrate

hydroxide/ carbonate/ nitrate

H2O NOx CO 2

metal

Catalyst production scheme

oxide

Proton source

Oxidizer

Sd-Chemie Wastewater Free Process

oxide hydrate

CO2 H2 O

Precipitation Me3+

Dehydration Metal Oxide

Activation Catalyst

Metal Hydroxide

Benefits

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 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 Reactive 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 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 reactions 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 Technology

Uses microchannel devices to alter flow characteristics

Dramatic improvements in heat tranfer, mass transfer efficiency

Driving forces in microchannel heat exchanger performance

High surface area/volume ratio increases volumetric efficiency High heat transfer coefficient increases area efficiency Net result:

Q h A T
Nu k h d

Large heat transfer per unit volume allow compact devices, small temperature gradients within fluid High transfer coefficient allows closer temperature approaches

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
1500

850-1500

3000-7000

7000

50-300

400-2000

~10 C

< 10 C

Microchannel technology has applications to other unit operations

Separations

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 Preliminary work on emulsion formation suggests much more monodisperse emulsions

Reactors

Mixing

Examples of Process Intensification (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 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!

Summary

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

References

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

GAO Report: Protection of Chemical and Water Infrastructure

http://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 Rule

http://www.dhs.gov/xlibrary/assets/IP_ChemicalFacilitySecurity.pdf

DHS Chemicals of Interest

http://www.dhs.gov/xprevprot/laws/gc_1175537180929.shtm

ACCs Responsible Care Security Code

http://www.americanchemistry.com/s_acc/bin.asp?CID=373&DID=1255&DOC=FILE.PDF%22

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

A Checklist for Inherently Safer Chemical Reaction Process Design and Operation Inherently Safer Process Design

http://www.aiche.org/uploadedFiles/CCPS/Publications/SafetyAlerts/CCPSAlertChe cklist.pdf

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

Green Chemistry (Wikipedia version) Center for Green Chemistry at UML

http://www.greenchemistry.uml.edu/

http://en.wikipedia.org/wiki/Green_chemistry

ACS Green Chemistry Institute

http://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC=greenchemistryinst itute%5Cindex.html

Process Intensification Network

http://www.pinetwork.org/whatsnew/whatsnew.htm

Process Intensification: Transforming Chemical Engineering

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

Process Intensification and Green Chemistry

http://rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=gc990g15&JournalCode=GC