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Bradbury, J., K. Branch, J. Heerwagen, and E. Liebow. 1994. Community Viewpoints of the Chemical Stockpile Disposal Program. Washington, D.C.: Battelle Pacific Northwest Laboratories.

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ECO LOGIC. 1996b. Report by ECO LOGIC, Inc., on Public Consultation Activities. April 4, 1996. Submitted to National Research Council, Panel on Review and Evaluation of Alternative Chemical Disposal Technologies. Rockwood, Ontario: ECO LOGIC.

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Gill, D.M. 1996. Letter from D.M. Gill, business development manager, Defense Land, AEA Technology, U.S. DOD Chemical Demilitarization Project-Alternative Technology Program. April 4, 1996.

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Harvey, S.P. 1994. Report to the U.S. Army Program Manager for Chemical Demilitarization, Agent Neutralization. I. Hydrolysis of Sulfur Mustard. March 1994. Aberdeen Proving Ground, Maryland: Edgewood Research, Development and Engineering Center and Geo-Centers, Inc.

Harvey, S.P., T.A. Blades, L.L. Szafraniec, W.T. Beaudry, M.V. Haley, T. Rosso, G.P. Young, J.P. Earley, and R.L. Irvine. 1996. Kinetics and toxicological parameters of HD hydrolysis and biodegradation. Presented at NATO Advanced Research Workshop on Chemical Problems Associated with Old Arsenical and Mustard Munitions, March 17-19, 1996. Lodz, Poland.

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M4 Environmental L.P. 1996c. Correspondence to Michael Clarke, study director, from T.J. Abraham, M4 Environmental L.P. May 10, 1966.

M4 Environmental L.P. 1996d. Alternative Technologies for Chemical Demilitarization: National Program Plan. Submitted to U.S. Army Chemical, Biological and Defense Command. Oak Ridge, Tennessee: M4 Environmental L.P. May 31, 1996.

M4 Environmental L.P. 1996e. Chemical Demilitarization Utilizing Catalytic Extraction Processing: Hazard Analysis. Prepared by H&R Technical Associates, Inc., Oak Ridge Tennessee. Submitted to U.S. Army Program Manager for Chemical Demilitarization. Oak Ridge, Tennessee: M4 Environmental L.P. March 1996.

M4 Environmental L.P. 1996f. Public Participation Document. Submitted to National Research Council Panel on Review and Evaluation of Alternative Chemical Disposal Technologies. Oak Ridge, Tennessee: M4 Environmental L.P. April 4, 1996.

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Nunn, J. 1996b. Letter from John E. Nunn, III, cochair of the Maryland CAC, to the AltTech Panel. April 11, 1996.

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U.S. Army. 1995b. Concept Design Package: Stand-Alone Neutralization. 21 November 1995. Aberdeen Proving Grounds, Maryland: U.S. Army Program Manager for Chemical Demilitarization.

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1. The U.S. Army, through the Office of the Program Manager for Chemical Demilitarization is responsible for the demilitarization and disposal of chemical agents and munitions. Eight demilitarization facilities are proposed for construction and operation in the continental United States.
2. The Army has demonstrated the operational effectiveness of incineration at its Johnston Atoll Chemical Agent Disposal System facility. The first demilitarization facility for the continental United States has been constructed at Tooele Army Depot and is scheduled to be operational in 1995. In the spring of 1981, the Army began testing at the Chemical Agent Munitions Disposal System (CAMDS) at Tooele, Utah. The mission of CAMDS is to test and evaluate equipment and processes proposed for chemical agent munitions demilitarization facilities.
3. The National Research Council's (NRC) Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (Stockpile Committee) was formed in 1987 at the request of the Undersecretary of the Army to monitor the disposal program and to review and comment on relevant technical issues. The Stockpile Committee is a standing committee which remains in service with rotating membership until the demilitarization program is completed.
4. As a consequence of public concern over the use of incineration for chemical warfare agent disposal, the Army commissioned in November 1991, the National Research Council to conduct a study to evaluate alternatives to the reverse assembly (baseline) incineration process for use in destroying the U.S. chemical stockpile. In January 1992, the National Research Council established the Committee on Alternative Chemical Demilitarization Technologies (Alternatives Committee) to develop a comprehensive list of alternative technologies and to review their capabilities and potential as agent and munitions disposal technologies. The Defense Authorization Act for FY93 directed the Army to submit to Congress a report on potential alternative technologies.
5. The NRC report on recommendations for the disposal of chemical agents and munitions was published in 1994. The NRC recommended that the Army continue the current baseline incineration program, since, at that time, no other technologies were mature enough to meet the Army's requirements. However, the NRC did recommend that the Army investigate alternative technologies based on chemical neutralization for the bulk-only sites.
6. In August 1994, the Army initiated an aggressive RDT&E program to investigate, develop, and support testing of two technologies based on chemical neutralization for the destruction of mustard (agent HD) at Aberdeen Proving Ground, MD, and nerve agent VX at the Newport Chemical Activity at Newport, IN. The two alternative technologies are stand-alone chemical neutralization and neutralization followed by biodegradation. The purpose of the RDT&E program is to determine whether an alternative technology warrants pursuing a pilot-scale facility based on one or both technologies. The decision to proceed to pilot-testing will be made by the Defense Acquisition Board (DAB) in October 1996.
7. The NRC also was aware that there would be ongoing development of the various research programs involving

7. potential alternatives subsequent to the publication of the NRC report in 1993 on alternative technologies. Thus, the NRC recommended that the Army continue to monitor research developments.
8. The Army agrees with this NRC recommendation, and the Army has been exploring developments in technologies with potential application to chemical demilitarization as part of the RDT&E program.
9. The Army will be conducting a survey to determine if there are any technologies other than the two already being evaluated by the Army as part of the Alternative Technology Program which are capable, within the Chemical Stockpile Disposal Program (CSDP) schedule of meeting chemical demilitarization requirements for the HD (mustard) and VX (nerve) agents stored at the Aberdeen Proving Ground, MD, and Newport Chemical Activity, IN storage sites, respectively. This announcement requests information from industry on any alternative technology that a firm believes is mature enough to meet the needs of the Army program. The Army will conduct a preliminary 30 day screening to determine whether any of the technologies identified pursuant to this announcement warrant further review by the NRC. The Army will identify up to a maximum of three of the most promising technologies in addition to neutralization and neutralization followed by biodegradation. The evaluators will determine whether the technology meets the following screening criteria.
• Any proposed alternative technology should not resemble incineration (high temperature oxidation) or produce effluents characteristic of incineration;
• The technology must utilize processes and equipment that are developed or capable of being developed in time to meet the requirements of the Chemical Weapons Convention;
• Laboratory-scale testing must have been completed with agent or chemicals with similar properties to agent. Data must be available to provide an initial indication of performance characteristics and destruction efficiency.

10. Interested firms are asked to provide information in the form of a conceptual design package within 60 days from the date of this announcement. The purpose of the conceptual design package is to demonstrate the feasibility of using an alternative set of process unit operations to conduct the total activities that are required to complete the program, and to provide a basis for its comparison with the baseline system. At a minimum, it should include the following:
• Process description. The information package should include a description of the total process, detailing how actual experience or test results have been used to project equipment performance, and how the various agent destruction, decontamination, and waste processing steps are conducted. The description should also provide an adequate basis for establishing that the process has a high probability of success, after pilot-testing, to perform the necessary agent destruction and waste disposal functions.
• Process data. Chemical and physical properties of all process materials should be provided to the extent that data is needed to design each unit operation in the overall process.
• Flow sheets, showing all proposed equipment, piping, and general control methods, including:
• Material and energy balances, projections showing all material flow rates, and energy requirements, such as heat generation and removal rates for each step of the process
• Process monitoring and control, showing all proposed process monitoring instrumentation and describing the methods used to control the process
• A description and characterization of all process waste streams.
• A description of storage facilities for all feed materials and all wastes prior to the final disposition.
• A description of facilities for packaging and handling wastes prior to off-site shipping.
• Utility requirements, including process requirements for both fuel and electricity. Also include need for backup requirements to allow for emergency shutdown of the process and related pollution control systems.
• Feed materials requirements, including both quantities and qualities of all chemicals that are required, and the need for any special feed preparation.
• Equipment lists for all major pieces of equipment for the destruction process, secondary treatment systems, and pollution control systems.

• Any data generated from agent or simulant tests or data resulting from destruction of similar chemicals by the proposed processes.
• Equipment designs, including design sketches, sizing calculations and materials of construction for all major pieces of process equipment.
• Plant layout. The design should show the layout and working space for the major pieces of equipment, plot plans for the current storage facilities, and planned means for transport of agent containers from the storage area to the destruction facilities.

11. On written request, firms will be provided with information on: the baseline incineration system; the chemical stockpile disposal program schedule; and the current program for developing neutralization and neutralization followed by biodegradation. Firms may write or fax their requests to Dr. Francis W. Holm, Science Applications International Corporation, 9 Aberdeen Shopping Plaza, Aberdeen, MD 21001. Fax: (410) 273-1001.
12. The NRC will review those promising alternative technologies, if any, identified by the Army as well as neutralization and neutralization-biodegradation. Concurrently, proponents of technologies identified by the Army will be asked to furnish a notional program plan including: a rough, order of magnitude estimate of the projected cost and schedule and chemical agent destruction test data. Firms must perform testing to obtain actual chemical agent test data at an Army approved surety laboratory at the firm's expense. The test data must be available to the NRC for review by 31 May 1996.
13. As a note of caution, those considering participation should understand that chemical agents and munitions are significantly more toxic than many substances normally referred to as "hazardous and toxic material." Therefore, high standards of employee, public, and environmental protection are required.
14. This announcement is meant to offer industry the opportunity to make the Army aware of potential alternative technologies which can meet the needs of the chemical demilitarization program. The process outlined herein will not necessarily lead to any request for proposals (RFP) or contract awards. The government does not intend to reimburse firms for the cost of providing data originally submitted pursuant to this request.
15. Mr. Eric W. Braerman, Procurement Directorate, CBDCOM, is the point of contact for this announcement, (410) 671-4469.

Chapter 9 discusses the rationale for public involvement in the panel's deliberations and describes interactions with the communities neighboring the Newport and Aberdeen sites and meetings with regulators. This appendix includes samples of the letters of invitation sent to individuals and organizations in Indiana and Maryland prior to the public forums and summarizes the categories of stakeholders contacted.

The Army Program Office, located in Maryland with established communications links to stakeholders interested in the chemical demilitarization process, assisted with the notification process within Maryland. Because of the independent notification by the Army, the panel sent fewer letters to Maryland stakeholders than to Indiana stakeholders.

The National Research Council (NRC) has been asked by the Army to evaluate alternative technologies (alternatives to the Army's baseline incineration process) for the destruction of bulk chemical warfare agents stored at facilities near Aberdeen, Maryland and Newport, Indiana.

In August through October, 1995, the Army conducted an evaluation of chemical destruction processes that resulted in the selection of three technologies, plus the Army's two neutralization technologies, to be evaluated by the NRC. A Panel on Review and Evaluation of Alternative Chemical Disposal Technologies, called the AltTech Panel, was formed by the NRC. The AltTech panel will provide a report to the Army in August, 1996 that will make recommendations on whether any of the five technologies is suitable for pilot plant demonstration. In the Fall of 1996, the Army will present its recommendations to the Defense Acquisition Board (DAB) on which, if any, of the technologies should move forward to the pilot plant demonstration phase.

On Tuesday, March 12 at 7:00 p.m. representatives of the AltTech Panel will be present at North Vermillion High School, RR 1, Cayuga, Indiana, to solicit the public's views on these technologies. As Chairman of the AltTech Panel, I am writing to inform you of this information-gathering meeting. In the past, public meetings like this have added greatly to the knowledge base of other NRC committees and have ensured views of all interested parties are heard and considered.

At the meeting you will be provided an opportunity to state your views about the five technologies. The AltTech panel has been informed that the Army provided information on the alternatives during its earlier meeting, and that you have also had the opportunity to review vendor-provided information and information placed by the Army in libraries. Therefore, the panel will not spend valuable time describing the technologies again at this meeting so that the time can be applied to the most important objective, hearing your input.

I will begin the public meeting by making a short presentation that describes the NRC panel schedule and data gathering methodology. After my presentation, you may make your statements. To enable as many as possible with an opportunity to speak, you will be asked to limit your remarks to five minutes or less. If you intend to speak, please ensure you have signed in prior to the meeting. You are also encouraged to submit your statements in written form at the meeting, whether you speak or not. If you cannot attend the meeting, and you wish the AltTech panel to consider your views, please provide a written statement to the National Research Council, 2101 Constitution Avenue, N.W., Washington, DC 20418, Attn.: Mr. Michael A. Clarke, HA258, by March 31, 1996

The sole purpose of this meeting is to provide the public an opportunity to state its insights, observations, concerns, and feelings about the various technologies under consideration. You should also know that the panel will not share its assessment of the technologies with you at this meeting. That would be premature and is reserved for the panel's final report in August. Therefore, it is very important that you state only your views when you address the panel. Please do not address questions to vendor or Army personnel present. This meeting is intended to be a dialog between the NRC and the public. Conversations with the Army or vendors present should take place in other locations than the formal meeting.

Your opinions on these important local and national issues are important to us. The panel members and I look forward to hearing from you.

The National Research Council (NRC) has been asked by the Army to evaluate alternative technologies (alternatives to the Army's baseline incineration process) for the destruction of bulk chemical warfare agents stored at facilities near Aberdeen, Maryland and Newport, Indiana.

In August through October, 1995, the Army conducted an evaluation of chemical destruction processes that resulted in the selection of three technologies, plus the Army's two neutralization technologies, to be evaluated by the NRC. A Panel on Review and Evaluation of Alternative Chemical Disposal Technologies, called the AltTech Panel, was formed by the NRC. The AltTech panel will provide a report to the Army in August, 1996 that will make recommendations on whether any of the five technologies is suitable for pilot plant demonstration. In the Fall of 1996, the Army will present its recommendations to the Defense Acquisition Board (DAB) on which, if any, of the technologies should move forward to the pilot plant demonstration phase.

On Friday, March 15 at 8:00 p.m. representatives of the AltTech Panel will be present at the Kent County Courthouse, County Commissioner's Room, 103 Cross Street, Chestertown, MD and on Saturday, March 16, 1996 at 10:00 a.m. at Edgewood High School, Willoughby Beach Road, Edgewood, Maryland, to solicit the public's views on these technologies. As Chairman of the AltTech Panel, I am writing to inform you of this information-gathering meeting. In the past, public meetings like this have added greatly to the knowledge base of other NRC committees and have ensured views of all interested parties are heard and considered.

At the meeting you will be provided an opportunity to state your views about the five technologies. The AltTech panel has been informed that the Army provided information on the alternatives during its earlier meeting, and that you have also had the opportunity to review vendor-provided information and information placed by the Army in libraries. Therefore, the panel will not spend valuable time describing the technologies again at this meeting so that the time can be applied to the most important objective, hearing your input.

I will begin the public meeting by making a short presentation that describes the NRC panel schedule and data gathering methodology. After my presentation, you may make your statements. To enable as many as possible with an opportunity to speak, you will be asked to limit your remarks to five minutes or less. If you intend to speak, please ensure you have signed in prior to the meeting. You are also encouraged to submit your statements in written form at the meeting, whether you speak or not. If you cannot attend the meeting, and you wish the AltTech panel to consider your views, please provide a written statement to the National Research Council, 2101 Constitution Avenue, N.W., Washington, DC 20418, Attn.: Mr. Michael A. Clarke, HA258, by March 31, 1996

The sole purpose of this meeting is to provide the public an opportunity to state its insights, observations, concerns, and feelings about the various technologies under consideration. You should also know that the panel will not share its assessment of the technologies with you at this meeting. That would be premature and is reserved for the panel's final report in August. Therefore, it is very important that you state only your views when you address the panel. Please do not address questions to vendor or Army personnel present. This meeting is intended to be a dialog between the NRC and the public. Conversations with the Army or vendors present should take place in other locations than the formal meeting.

Your opinions on these important local and national issues are important to us. The panel members and I look forward to hearing from you.

Panel Meeting: October 11-12, 1995

Washington, D.C.

Participants. Panel chair: Richard S. Magee. Panel members: Joan B. Berkowitz, Gene H. Dyer, Frederick T. Harper, Joseph A. Heintz, David A. Hoecke, David S. Kosson, Walter G. May, Alvin H. Mushkatel, Laurance Oden, George W. Parshall, L. David Pye, William Tumas; BAST liaison: Robert A. Beaudet; NRC staff members: Bruce Braun, Michael Clarke, Jacqueline Johnson, and Deborah Randall. Briefers.

Objectives. Welcome and introduce new members; complete administrative matters; complete composition and balance discussion; discuss and develop prototype criteria checklist; organize panel into subpanel teams; perform historical review for new members; receive status briefings from applicable Army officials on call for alternative technologies; and discuss November meeting requirements.

Panel Meeting: November 20-21, 1995

Washington, D.C.

Participants. Panel members, NRC staff, and briefers

Objectives. Welcome and introduce two new members; complete administrative matters; complete composition and balance discussion; discuss and develop prototype criteria checklist; develop and approve report concept; organize panel into technology assessment teams; receive briefings from applicable Army officials on alternative technology selection process; receive briefings from technology proponent company finalists; and discuss future meetings/vendor visits.

Site Visit: January 8-9, 1996

Fall River, Massachusetts

Participants. Panel members: Gene Dyer, and Laurance Oden. BAST liaison: Robert Beaudet.

Objectives. Receive presentations and information from technology proponent company for catalytic extraction process technology and perform site tour.

Site Visit: January 8-9, 1996,

Ontario, Canada

Participants. Panel members: Walter May, Roger Staehle, and William Tumas

Objectives. Receive presentations and data from technology proponent company for gas-phase reduction technology and perform site tour.

Site Visit: January 14-16, 1996

Aberdeen/Dounreay, Scotland

Participants. Panel members: Roger Staehle, Joan Berkowitz, and Walter May. NRC staff member: Michael Clarke.

Objectives. Receive information from AEA and SubSea on the status of the electrochemical oxidation process.

Site Visit: January 18-19, 1996

Oak Ridge, Tennessee

Participants. Panel members: Gene Dyer and Laurance Oden. NRC staff member: James Zucchetto.

Objectives. Receive presentations and information from technology proponent company for catalytic extraction process technology and perform site tour.

Site Visit: January 18-19, 1996,

Edgewood, Maryland

Participants. Panel members: George Parshall and David Kosson. NRC staff members: Bruce Braun and Donald Siebenaler.

Objectives. Receive presentations and data from Army and Army contractors on neutralization technologies.

Panel Meeting: February 1-2, 1996

Irvine, California

Participants. Panel. NRC staff members: Bruce Braun, Michael Clarke, Deborah Randall, and Shirel Smith.

Objectives. Welcome and introduce three new members; complete administrative matters; complete composition and balance discussion; receive Army briefing on AltTech program status; receive briefings from team leaders on vendor assessment visits; discuss plan for public meetings and meetings with state and federal agencies; and discuss report status and future activities.

Panel Meeting: March 14-15, 1996

Washington, D.C.

Participants. Panel chair: Richard S. Magee. Panel members: Joan B. Berkowitz, Gene H. Dyer, Frederick T. Harper, Joseph A. Heintz, David A. Hoecke, David S. Kosson, Walter G. May, Alvin H. Mushkatel, Laurance Oden, George W. Parshall. BAST liaison: Robert A. Beaudet. NRC staff members: Bruce Braun, Michael Clarke, and Deborah Randall.

Objectives. Complete composition and balance discussion for three new members; receive panel assessment team briefings on chapter draft status and data requirements; discuss comparison criteria for chapter 8; assemble first full message draft of report; discuss results of Newport public and regulator meetings and plan for Aberdeen meetings; discuss AltTech program status; and discuss future report activities and goals for April meeting.

Site Visit: March 16-17, 1996

Oak Ridge, Tennessee

Participants. Panel chair: Richard S. Magee. Panel members: Joseph Heintz, David Hoecke, and Laurance Oden.

Objectives. Receive follow-up information on status of catalytic extraction process technology.

Site Visit: April 2, 1996

Ontario, Canada

Participant. Panel member: Frederick Harper

Objectives. Receive presentations data from technology proponent company for gas-phase reduction technology and perform site tour.

Site Visit: April 8-9, 1996

Edgewood, Maryland

Participants. Panel members: David Kosson and George Parshall

Objectives. Receive follow-up information from Army and Army contractors on the status of neutralization technologies.

Writing Session: April 11-12, 1996

Washington, D.C.

Participants. Panel members: Alvin Mushkatel and Richard Magee. NRC staff member: Michael Clarke.

Objectives. Organize report and draft community and regulator chapter of report.

Panel Meeting: April 18-20, 1996

Washington, D.C.

Participants. Panel chair: Richard S. Magee. Panel members: Joan B. Berkowitz, Gene H. Dyer, Frederick T. Harper, Joseph A. Heintz, David A. Hoecke, David S. Kosson, Walter G. May, Alvin H. Mushkatel, George W. Parshall, L. David Pye, William Tumas. BAST liaison: Robert A. Beaudet. NRC staff members: Bruce Braun, Michael Clarke, and Deborah Randall.

Objectives. Assemble first full message draft of report; develop a strategy for the rapid development of a concurrence draft; discuss AltTech program status, including final data acquisition and surety testing; review preliminary hazard and operability report status; settle panel indemnity issue; and set goals for the May meeting.

Site Visit: April 26, 1996

Oak Ridge, Tennessee

Participants. Panel member: Frederick Harper

Objectives. Tour facilities and orient risk assessment panel member; discuss risk issues with the technology proponent company.

Site Visit: May 5-8, 1996

London, England

Participants. Panel members: Joan Berkowitz and Walter May

Objectives. Evaluate and assess the electrochemical reduction alternative technology as a candidate for pilot-

plant demonstration by the U.S. Department of the Army for destruction of chemical agents; receive presentations from the technology proponent company on that technology and perform site tour.

Panel Meeting: May 15-17, 1996

Washington, D.C.

Participants. Panel chair: Richard S. Magee. Panel members: Joan B. Berkowitz, Gene H. Dyer, Frederick T. Harper, David A. Hoecke, David S. Kosson, Walter G. May, Alvin H. Mushkatel, Laurance Oden, William Tumas. BAST liaison: Robert A. Beaudet. NRC staff members: Bruce Braun, Michael Clarke, and Deborah Randall. Technical writer/consultant: Robert Katt.

Objectives. Assemble and sign off on concurrence draft of report; discuss AltTech program status and methodology for including surety testing data; settle panel indemnity issue; and discuss milestones leading to report review and publication.

When HD is treated in the Silver II process, 75 kg·mols will be decomposed during the course of a campaign as the source of oxygen for agent oxidation. An additional amount of water will be lost by the parasitic reaction in which water is decomposed and 02 gas evolves. Approximately 176 kg·mols of water will be carried from the anode compartment to the cathode compartment by electrical diffusion of hydrated hydrogen ions. The total of these water losses, more than 251 kg·mols, should be compared to the initial water content of the anode compartment of 2.5 m³ or 139 kg·mols. Part of the loss, as yet unquantified, is made up by spontaneous osmotic diffusion from the cathode compartment back to the anode department, induced by the large difference in acid concentration between the two. (The anolyte is maintained at 8 molar in nitric acid, the catholyte at 4 molar.)

When VX is treated, the water losses are about 116 kg·mols from agent oxidation and 307 kg·mols from the transport of hydrated hydrogen ions. Total losses therefore exceed 423 kg·mols during the course of a VX campaign, compared with the initial water content in the anode compartment of 139 kg·mols. As in the HD case, there is an as yet undetermined osmotic flow of water back from the cathode compartment to the anode compartment.

Tables E-1 and E-2 provide an elemental analysis of the mass balance data provided by the TPC for the Silver II process for treating VX and HD, respectively.

The ECO LOGIC process is described as a gas-phase chemical reduction process in which waste materials react with hydrogen and steam at high temperature. The reaction conditions are very different from the reaction conditions in industrial hydrogenation processes, which are usually carried out at much higher hydrogen pressure and lower temperature than the ECO LOGIC conditions and require a catalyst because of the lower temperature. In this appendix, the AltTech Panel has used thermodynamic data to examine likely chemical reactions and reaction products that will result from processing agent.

Data on free energy of formation were used for these calculations. The data were taken primarily from the JANAF Thermochemical Tables (JANAF, 1985); a few of the data are from Perry's Chemical Engineers Handbook (Perry et al., 1984). Data at 1100 K were used as representative of reactor conditions; data at 298 K were used as representative of quenched reactor products.

Feed material in the main reactor is at a high enough temperature for cracking (breakup of the carbon chain into smaller fragments) to occur rapidly. Molecular fragments can then react with the hydrogen and steam in the reactor environment. The end products indicated by thermodynamic considerations are discussed below for carbon and for each of the heteroatoms.

Methane is the only hydrocarbon with significant thermodynamic stability at 1100 K in the presence of hydrogen as illustrated by the following possible product reactions:

The panel concludes that at this, reaction temperature and with this hydrogen content in the main reactor, these hydrocarbons would react almost completely to form methane. Methane itself, however, is not expected at high concentration; reaction with hydrogen should result in solid carbon and only low concentration of methane.

With a hydrogen content of 70 percent in the product gas, the equilibrium methane concentration is calculated to be only 1.7 percent. This does not conform to experimental observation, however. The observed methane content, which is reported to be as high as 15 percent, probably represents a nonequilibrium, rate-controlled product. A possible alternative explanation is that carbon formed in high temperature reactions sometimes has a higher free energy than graphite (so-called "Dent" carbon). At 500°C, the free energy of this carbon form may be 15 KJ above the free energy of graphite. This difference would lead to a larger equilibrium constant for the reaction (K_{1100 K} = 0.1859) and a possible equilibrium methane content of 9 percent.

This calculation suggests that high methane content is probably a result of the reaction sequence during the decomposition process. It also suggests that solid carbon should be expected as a product. The TPC assumes that 10 percent of the carbon in the feed will show up as solid elemental carbon in the reactor effluent gas. Precursors to the solid carbon, such as polycyclic aromatics, would then also be expected.

Steam can also react with carbon (and methane), and in fact thermodynamic equilibrium would result in complete conversion.

However, reaction rates with industrial carbon at 1100 K are very slow and are inhibited by the presence of hydrogen (Gadsby et al., 1946; May et al., 1958).

Reaction with carbon from a decomposing hydrocarbon could be faster, however, and significant CO would be expected.

Much of the CO produced would react via the water gas shift reaction to form CO₂.

The rate for this reaction is high enough to approach equilibrium.

Chlorine (in mustard) should react almost completely to HCl.

Sulfur should go primarily to H₂S in the reactor.

A very small amount of H₂S could react with steam.

A small amount of sulfur should be expected in the quench of the product stream-probably in the HCl product solution.

Phosphine and oxides of P(II) and P(IV) do not appear to be very stable relative to elemental phosphorus at either reactor (1100 K) or quench (298 K) conditions; only very small concentrations would therefore be expected. For example:

Higher-valence oxides, P₄O₆ in particular, are much more stable under both reactor and quench conditions.

The trivalent oxide appears to be the most stable oxide under the reducing conditions of the process. It is considerably more stable than the divalent and tetravalent oxides, as well as the pentavalent oxide, at both reactor and quench conditions.

It appears likely that the phosphorus species produced in the reactor will be the oxide of trivalent phosphorus, P₄O₆.

A number of phosphorus acids might form in solution when the reactor vapor is quenched. The stable one appears to be the orthophosphorous acid (Moeller, 1952).

This form is unstable in an oxidizing atmosphere and would presumably convert to the pentavalent orthophosphoric acid, H₃PO₄. The rate of conversion to the higher oxide is not known.

Nitrogen would be expected in the form of molecular nitrogen, ammonia, and possibly some N-oxide species. An interesting possibility that will need further examination is the potential to produce hydrogen cyanide (HCN). At reactor conditions, this material would be expected at parts per million concentration, though at virtually zero concentration at room temperature.

The rates of reaction are unknown. Because nitrogen is associated with carbon (in VX), HCN would probably be formed in the reactor. Whether it will be at its equilibrium level and whether it will persist (at above equilibrium level) during the quench are questions that will need evaluation.

Two sets of material and energy balances were submitted by the TPC, the first on January 30, 1996, the second on April 4, 1996. The panel has examined the balances for HD. The two balances differed in the feed rate of HD: 5.0 liter/min. for the first, 2.736 liter/min. for the second. The numbers that follow are taken from the second balance unless otherwise stated. The feed rate of 2.736 liter/min. corresponds to a destruction rate of 5 metric tons per day (5.5 English tons per day).

The feed to the reactor consists of four streams: feed HD; gas from the steam reformer; waste steam; and waste water. A stream from the SBV (sequencing batch vaporizer) would also go to the reactor when the SBV is operating. Some product gas from the product gas blower might also be recycled directly back to the reactor, bypassing the catalytic reformer.

The largest gas stream is the reformer gas, which constitutes approximately 85 percent of the total gram-mols of feed. This gas is at a high temperature (775°C) and has a large H₂ content.

Table F-1 shows flow rates and compositions into and out of the reactor. The hydrogen content of the product gas is kept high, above 55 percent (wet basis) in this case. There may also be trace quantities (parts per million) of other materials not shown in the product gas analysis above are possible (SO₂, for example).

The TPC assumes that 10 percent of the carbon in the HD feed will be solid carbon in the product. Most of the TPC's experience has been with aromatic feed stocks, such as PCBs (polychlorinated biphenyls), which would presumably yield relatively large carbon residues. The carbon residue from HD (or VX) might be lower than 10 percent.

The methane content of the product gas is well above the thermodynamic equilibrium value. It may simply represent a nonequilibrium product limited by the reaction rate. The methane presumably forms from CH₂ radicals (see section on Thermodynamic Calculations).

Most of the gas feed to the reactor is at high temperature; the reformer gas, which is 85 percent of the total, is at 775°C, and the direct recirculation gas is heated to

600°C. The electric heaters in the reactor then supply energy to raise the gas mixture to between 850 and 900°C. The reaction itself is a combination of hydrocracking (to produce methane), which is exothermic, and steam reforming (to produce CO), which is endothermic. Overall the reaction appears to be slightly exothermic (about 1,400 kJ/kg of HD processed, equivalent to less than 10 percent of the heat of combustion of HD).

The product gas from the reactor is quenched with water to produce an HCl solution of moderate concentration together with suspended carbon. The quench will also dissolve some of the H₂S (and the possible low concentration [ppm range] of SO₂), as well as some CO₂. The suspended carbon must be filtered out before disposal of the HCl solution. The TPC has estimated that the quench will remove 43.8 g-mols/min. of HCl and 5.5 g-mols/min. of CO₂. (On the assumption that the HCl solution will be fairly concentrated, perhaps 30 percent, the CO₂ removal rate appears too high.)

The H₂S and most of the CO₂ will be recovered in the methanolamine scrubber. The product gas from this scrubber will be:

The scrubbed gas will have the following composition (dry basis).

In the material balances submitted by the TPC, no aromatic hydrocarbons are shown for the product gas, and the submitted design makes no provision for hydrocarbon scrubbing. The TPC does recognize that some high-molecular-weight hydrocarbon may be present (a precursor to solid carbon) and that a scrubber for removal may be necessary.

Part of the scrubbed product gas is recycled (mostly via the catalytic reformer); part is burned to supply steam. Overall, the material balance indicates that approximately 17 percent of the scrubbed gas will be burned. The products of HD destruction then show up in the streams shown in Table F-2. The scrubbed product

gas, which consists mainly of hydrogen (83 percent) and methane (10 percent), should burn cleanly, that is, with negligible products of incomplete combustion.

Gadsby, J., C.N. Hinshelwood, and K.W. Sykes. 1946. Kinetics of the Reactions of the Steam-Carbon System. Proceedings of the Royal Society, London, Series A. 187: 129-151.

JANAF. 1985. JANAF Thermochemical Tables. 3^rd Ed. Journal of Physical and Chemical Reference Data 14, Suppl.1.

May, W.G., R.H. Mueller, and S.B. Sweetser. 1958, Carbon steam reaction kinetics from pilot plant data. Industrial and Engineering Chemistry 50: 1289-1296.

Moeller, T. 1952. Inorganic Chemistry. New York: John Wiley and Sons, Inc.

Perry; R. H., D.W. Green, and J.O. Maloney (eds). 1984. Perry's Chemical Engineers Handbook. 6^th Ed. New York: McGraw-Hill.

This appendix contains mass balance matrices for the four HD neutralization configurations. For each configuration, there is a matrix for process inputs and one for process outputs. The stream numbers in the column headings are keyed to the numbered input and output streams shown in the process diagrams preceding each set of matrices. Each process diagram consists of two sheets: sheet 1 is the left side of a full diagram, sheet 2 is the right side. Input streams are numbered from 1; output streams are numbered from 100.

The diagrams and the mass balance data are derived either from the April 4, 1996, design package submitted by the Army Alternative Technology Program or from more recent data.

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