Improving Chemical Plant Security via Greener Process Technologies

1. Improving Chemical Plant Security via Greener Process Technologies TUR Continuing Ed ConferenceApril 12, 2007 Scott ButnerDirector, ChemAlliancePacific NW National Laboratoryscott.butner@pnl.gov

2. Overview 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?

3. 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

4. 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

5. Key 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

6. 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…

7. Improving Chemical Plant Security via Greener Technology

8. Phillips Petroleum (October 1989) image courtesy of Dennis Hendershot, Rohm & Haas (used with permission)

9. This was not done by terrorists… image courtesy of http://www.acusafe.com/Incidents/PasadentTexas1989/incident-pasadenatexas1989.html

10. …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

11. R&D for Domestic Attacks?

12. 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

13. 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

14. 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)

15. 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)

16. 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 • Depending upon initial risk assessment, may require: • Security Vulnerability Assessment • Site Security Plan

17. 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 • 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

18. Site 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

19. 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

20. 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?

21. 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 • 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

22. Strategies for Reducing Risk While Improving 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

23. Inherently 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)

24. 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

25. 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 licensehttp://www.flickr.com/photos/davipt/165533374/http://www.flickr.com/photos/spike55151/187677818/

26. 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

27. 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

28. “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 • EPA’s approach to green chemistry stresses early assessment and reduction of chemical risks

29. 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.

30. Conventional Precipitation Process (Na) NO H O (NH ) 3 2 H O H O Na CO , 4 2 2 2 3 NOx NH CO 3 hydroxide/ hydroxide/ 2 NOx metal carbonate/ carbonate/ nitrate HNO Precipitation Separation nitrate nitrate 3 Dissolution Dry/Calcine Catalyst production scheme metal oxide Dry/Calcine Digestion and precipitation Proton CO source 2 Oxidizer oxide hydrate H O 2 Süd-Chemie Wastewater Free Process Green Chemistry in Catalyst Manufacture Precipitation Dehydration Activation Metal Hydroxide Metal Oxide Me3+ Catalyst

31. 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

32. 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

33. 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

34. 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 Separatorimage courtesy UCSD

35. 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

36. Microscale Technology • Uses microchannel devices to alter flow characteristics • Dramatic improvements in heat tranfer, mass transfer efficiency

37. Driving forces in microchannel heat exchanger 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

38. Heat Exchanger Comparison

39. Microchannel technology has applications 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

40. 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!

41. 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!”

42. 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

43. 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. 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 DesignChemical 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/

44. Selected 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

45. Selected Resources: Green Chemistry, Inherently 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 UMLhttp://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