WSRC-MS-95-0518

Vitrification of Ion-Exchange (IEX) Resins: Advantages and Technical Challenges

bv C. M. Jantzen Westinghouse Savannah River Company Savannah River, Site Aiken, South Carolina 29808 D. K. Paster

G. A. Cicero

A document prepared for AMERICAN CERAMIC SOCIETY ANNUAL MEETING, NUCLEAR DIVISION at Indianapolis frorrt 04/14/95 - 04/17/95.

DOE Contract No. DE-AC09-89SR18035 This paper was prepared in connection with work done under the above contract number with the U. S. Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper. DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed,.or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. This report has been reproduced directly from the best available copy. Available to DOE and DOE contractors from the Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831; prices available from (615) 576-8401. Available to the public from the National Technical Information Service, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161. USfiC-fns-IS-*31*

VITRIFICATION OF ION-EXCHANGE (IEX) RESINS: ADVANTAGES AND TECHNICAL CHALLENGESt

Carol M. Jantzen David K. Peeler Connie A. Cicero Westinghouse Savannah Westinghouse Savannah Westinghouse Savannah Technology Center (SRTC) River Technology Center River Technology Center Aiken, SC 29808 Aiken, SC 29808 Aiken, SC 29808 (803)725-2374 (803)725-8435 (803)725-5306

ABSTRACT I. INTRODUCTION

Technologies are being developed by the US Spent ion exchange (EX) resin wastes are Department of Energy's (DOE) Savannah generated from a variety of waste treatment River Site (SRS) in conjunction with the processes in the DOE complex and in Electric Power Research Institute (EPRI)t and commercial nuclear facilities. The spent IEX the commercial sector to convert low-level resins are generated during the radioactive ion exchange (IEX) resin wastes decontamination of liquid or aqueous process from the nuclear utilities to solid stabilized streams. The contaminants which are waste forms for permanent disposal. One of removed from the aqueous streams and sorbed the alternative waste stabilization technologies on the IEX resins can be radioactive, is vitrification of the resin into glass. Wastes hazardous, or both. Thus, spent resins exist can be vitrified at elevated temperatures by as High Level Waste (HLW),* Low Level thermal treatment One alternative thermal Waste (LLW),** and Mixed Low Level Waste treatment is conventional Joule heated+t (MLLWJ.ttt melting. Vitrification of wastes into glass is an attractive option because it atomistically bonds both hazardous and radioactive species highly radioactive material resulting from the in the glass structure, and volume reduces the reprocessing of spent nuclear fuel, including liquid waste by 70 - 80%. The large volume waste produced directly in reprocessing and any reductions allow for large associated savings solid material derived from such liquid waste that in disposal and/or long term storage costs. contains fission products in sufficient concentration (Nuclear Waste Policy Act of 1992) waste that is not high-level radioactive waste, spent nuclear fuel, transuranic waste, or by-product material as defined in section 1 le(2) of the Atomic Energy Act of 1954 (Nuclear Waste Policy Act of 1992) ttt waste that contains source, special nuclear, or byproduct material subject to regulation under the Atomic Energy Act and hazardous waste species Westinghouse Savannah River Cooperative subject to regulation under the Recource Research and Development Agreement (CRADA) Conservation and Recovery Act waste as defined in No. CR-94-002 40 CFR 261 (U.S. Code Title 42, Section 2011); tt Joule heated melters vitrify waste in a refractory- if the hazardous species are on the U.S. lined vessel containing diametrically opposed Environmental Protection Agency (EPA) list of electrodes. The electrodes are used to heat the hazardous wastes as oudined in 40 CFR261.31, glass by passing an electric current through the .32, .33 then the waste is considered a "listed" material. This process is called Joule heating. MLLW

DISTRIBUTION OF THIS DOCUMENT IS UNLIMITED'yo 0 USfit-ms^f-fclX

EX resins are used in defense and commercial - the Environmental Protection Agency power reactors to remove hazardous anions (EPA) has declared vitrification the and cations, particularly low levels of fission Best Demonstrated Available products such as Cs137, Sr9», Co60, C14 and Technology (BDAT) for high-level Tc". In addition, some tritium contamination radioactive waste3 or suspect tritium contamination is usually present. The EX resin wastes from " the EPA has produced a Handbook of commercial power reactors typically use Vitrification Technologies for organic resins with sulfonated or chlorinated Treatment of Hazardous and groups. The resin wastes, ashes or residues Radioactive Waste4 resulting from thermal treatment of such resins are, therefore, usually high in sulfur or - the DOE Office of Technology chlorine. Development (OTD) has taken the position that MLLW should be The resin wastes from Boiling Water Reactors stabilized to the highest level (BWR) are enriched in constituents such as reasonably possible to ensure that the Fe3C>4 while wastes from Pressurized Water resulting waste form will meet both Reactors (PWR) are enriched in borate used as 7 current and future regulatory a homogeneous moderator and in Li used for specifications pH control. In addition, these wastes are 137 60 usually contaminated with Cs and Co . • vitrification allows glass to have a high Both dry and wet wastes from BWR/PWR potential to meet the EPA characteristically reactors can be combined, e.g. EX resins, hazardous and/or listed Land Disposal waste sludges, filter aids, slurries, and other Restrictions (LDR's)tt spent decontamination solutions.1 Approximately, 100,000 lbs of BWR EX • glass formulations are flexible and easily waste and 30,000 lbs of PWR EX waste are accommodate process chemistry variation generated per reactor per year.t Large volumes of EX waste must, therefore, be • waste pretreatment is often minimal; waste converted to a solid stabilized waste form for can be dry or slurry fed to a melter permanent disposal. • high throughput melters which are low in cost, compact and have simple n. RATIONALE FOR VITREICATION maintenance features are readily available from commercial vendors and can be made One alternative EX resin waste stabilization transportable option is to vitrify the hazardous and radioactive species into glass.2 The rationale • commercially available melters have the for the vitrification of EX resin wastes are the ability to handle high concentrations of following: sulfate • glass is a very durable and • vitrification allows for large volume environmentally acceptable waste form reductions, sometimes up to or greater because both hazardous and radioactive than 97%5-6 species are atomistically bonded in the glass tt vitrified waste forms have the highest probability t EPRI consultant, Jene N. Vance of being "delisted"

-2- [^6 AC- mnS-15-6

• large reductions in volume minimize long- forming potential" of the waste. Stabilization term storage or disposal costs of heavy metals in glass has been shown to be enhanced by use of reactive additives* • minimization of long-term storage costs such as diatomaceous earth, perlite (perflo), makes vitrification cost effective on a life rice husk ash, and/or precipitated silica.5"6 cycle basis Use of highly reactive silica was determined to lower vitrification temperatures, increase • vitrification is a well developed technology waste loadings, maximize volume reductions, minimize melt line corrosion, and produce • vitrification and resin destruction avoid EPA acceptable glasses. hydrogen generation of "resin only" storage or disposal in cement7 Vitrification via the Reactive Additive Stabilization Process (RASP) can be used to The US DOE Savannah River Site (SRS), vitrify the following types of wastes: which is operated by Westinghouse Savannah River Company (WSRC), is currently • spent filter aids from waste water investigating vitrification for disposal of treatment various low-level and mixed wastes.4'6'8 The first hazardous/mixed wastes vitrified in • waste sludges laboratory studies at SRS have been (1) simulated incinerator wastes (ash and • combinations of spent filter aids from blowdown) and (2) actual listed nickel plating waste water treatment and waste sludges line (RCRA F006) waste water sludges admixed with spent filter aids. Additional • combinations of supernate and waste studies have concentrated on sludges produced sludges from various waste water treatment facilities at the Oak Ridge Reservation (ORR) and on • incinerator ash cementitious waste forms that were incompletely stabilized. The current study • incinerator off-gas blowdown investigates the use of vitrification for IEX resin wastes from commercial power reactors • combinations of incinerator ash and off- via Cooperative Research and Development gas blowdown Agreement (CRADA CR-94-002) between WSRC and the Electric Power Research • cement formulations in need of Institute (EPRI). remediation into glass

• inorganic filter media III. VITRIFICATION PROCESS • ion exchange (IEX) resins or zeolites Vitrification into simple glass compositions is achieved by tailoring a glass composition to • asbestos or glass fiber filters take advantage of the common glass constituents in the waste. This allows for • radioactive materials including TRU maximum waste loadings to be achieved, e.g. wastes wastes high in borate and lithium, like the PWR wastes, would be stabilized in the alkali-boro-silicate glass forming system. Reactive additives are chosen or a glass- making frit is developed based on the "glass Reactive Additive Stabilization Process (RASP), U.S. Patent 5, 434,333 ^AC- ms- ^5-6 51%

• contaminated soils, mill tailings, and expected to volatilize during vitrification, e.g.

other geologic media H2O, CO2, NOx, organics, etc. This information assists in determining the amount Glass fluxing agents are added, if necessary, and composition of the anticipated off-gas to lower melt temperatures and minimize produced by a given waste stream.tt volatilization of hazardous and/or radioactive species. The wastes plus additives are mixed The major cationic species left after calcining and slurry fed to a melter where they are (drying at temperatures sufficient to drive off reacted at temperatures of 1150°C or greater. all anions except oxygen, e.g. > 800°C) are used to determine the "glass forming potential" of the waste. Wastes high in B2O3 would be IV. GLASS FORMING POTENTIAL OF A formulated preferentially in the alkali-boro- WASTE silicate system, e.g. in the known region of durable homogeneous glasses formulated for In order to determine the "glass forming HLW (Figure 1). Wastes high in CaO on a potential" of a waste, an approximate chemical dry calcine oxide basis, would be formulated composition should be determined by either a in the Soda-Lime-Silica (SLS) system due to variety of wet chemical techniques,* by x-ray the large known immiscibility gap in the CaO- fluorescence (XRF), or by process history. B203-Si02 system.9 Wastes high in Fe203 For slurries or aqueous solutions a wt% solids could be formulated in either glass forming should be determined after drying at 110°C. system. However, alkali-boro-silicate glasses Additional information can be obtained about the species that will volatilize by analyzing the sio2+AI2O3 waste after drying at 110°C, 350°C, 650°C, and 1150°C. This allows determination of the waste composition on a dry calcine, e.g. glass forming, oxide basis. Dried sludge can also be analyzed by x-ray diffraction (XRD) to determine the major crystalline phases present.

The cation, anion, and XRD analyses are coupled together to determine if the various analyses are consistent, e.g. a mass balance analysis is calculated using the pooled waste analyses. Mass balance calculations are useful to verify the accuracy of the waste analyses. Mass balance analyses using the phases analyzed by XRD allows for a semi• quantitative determination of the species Figure 1. Composite diagram of the alkali- boro-silicate system indicating t The EPA SW846 Method 3050 is not aggressive regions where homogeneous and enough to determine the concentrations of major inhomogeneous (phase separated) glass forming species such as AI2O3 and Si02 in glasses form.10 wastes and use of this technique should be restricted to determination of the hazardous constituents of the waste; analysis by XRF or more aggressive chemical methodologies should tt Volatiles can also be determined by Differential be used to determine the major inorganic cationic Thermal Analysis (DTA) coupled with Gas species. Chromatography and Mass Spectrometry (GCMS)

-4- bisRC- ms-^S-o are preferred10 when volatilization of A. Product Control hazardous and radioactive constituents is a concern since the borosilicate glasses are The most important glass product property is known9 to melt at lower temperatures than the glass durability.10"11 The durability of a SLS glasses. waste glass is the single most important variable controlling release of radionuclides and/or hazardous constituents to the V. SYSTEMS APPROACH biosphere. A systems approach to glass formulation is The chemical durability of glass is a complex used to simultaneously evaluate product phenomenon that depends on a variety of performance and processing considerations.10* kinetic and thermodynamic parameters. 11 Glass formulation includes the However, the long-term durability of a wide simultaneous optimization of the following variety of glasses has been determined to be a process and product constraints: function of the glass composition. A model, the Thermodynamic Hydration Energy • product control Reaction MOdel (THERMO) has been developed to relate glass composition to glass - chemical durability 11 13 - homogeneity durability test response. ' THERMO is - thermal stability based on the calculation of the thermodynamic hydration free energy which is calculated from * process control glass composition (including the redox) and/or - viscosity die melter feed composition. The model - liquidus expresses the thermodynamic tendency of - volatility species (components) in a glass to hydrate. - melt temperature - melt corrosivity The reduction-oxidation (redox) equilibria of waste solubility alkali borosilicate glasses used for waste disposal is important because glasses which This "systems approach" requires that have large concentrations of reduced iron are parameters affecting product performance and known to be poorly durable.13 In addition, processing considerations be optimized glasses which are too reduced or too oxidizing simultaneously. The "systems approach" can cause processing problems. ensures that the final product safeguards the public, and that the production process used is B. Glass Homogeneity safe to operate. During the development of glass formulations First principles process and product quality for HLLW, known alkali borosilicate phase models were developed at SRS11 for diagrams were compiled to determine the vitrification of HLW in a borosilicate glass homogeneous glass composition envelope. matrix. These process/product models directly The composite diagram is shown in Figure 1. relate process and product parameters to glass Glasses in the region of phase separation form and/or feed composition.11 This statistical two separate glass phases, e^g. glass-in-glass process control methodology12 provides for phase separation. One phase is usually borate fabrication of durable waste glasses which are rich and is more soluble and the second phase processable. This statistical process control is usually silicate rich and more insoluble. methodology is direct applicable to vitrification The durability of phase separated glasses is of resin wastes in borosilicate glasses. often poorer than that of homogeneous glasses because the durability test response is

-5- ws*c-m5-

Tmeit do not readily pour. Moreover, too high Glass durability can also be adversely affected a viscosity can reduce product quality by by crystallization. Crystallization can causing voids in the final glass. A 14 sometimes cause accelerated leaching. conservative range of 20-100 poise at Tmeit, is However, some isometric crystals such as recommended as optimal. spinel do not disturb the glass matrix and do not cause accelerated leaching.14 Although, electrical resistivity of waste glasses is not a process model constraint, the electrical resistivity of a glass is highly correlated with C. Thermal Stability Considerations its viscosity. The ability to predict the electrical resistivity of a glass from its composition, or Crystallization in glass can be eliminated, if alternatively from its viscosity, is important to desired, by defining the regions of thermal startup and/or restart of Joule-heated electric stability for the glass. This can be melters. At low temperatures, glasses are accomplished by determining the time- good insulators, while at high temperatures temperature-transformation (I'll) diagrams they conduct electric current relatively well so for the waste glass.14-15 Avoiding the time that the glass melt may be heated by direct and temperature conditions that cause passage of electric current. The electrical crystallization during processing and storage resistivity is, therefore, the single most will eliminate concerns about the thermal important variable affecting the establishment stability and crystallization of the glass as well of Joule heating in an electric melter. as any adversely effects on product performance. Models11 exist for relating borosilicate glasses compositions to melting and establishment of Joule heating. VI. PROCESS CONTROL B. Glass Liquidus11 A. Glass Viscosity (and Resistivity)11 Formation of crystals in the melt during The viscosity of a glass melt, as a function of processing in a Joule heated melter can cause temperature, is the single most important problems with processing and discharging of variable affecting the melt rate and pourability the glass. If a waste glass is not properly of the glass. The viscosity determines the rate formulated, the insoluble species can form of melting of the raw feed, the rate of glass crystals during melting which settle to the

-6- (x}£>Ac- ms-l^d-^^ floor of the melter and form viscous layers. The RASP process was also determined to Formation of a viscous layer is highly minimize accelerated melt line corrosion.5-6 undesirable because the viscosity of the melt In addition, melt line corrosion and general increases sharply and this can cause difficulty refractory corrosion can be minimized by in melting and discharging the glass. formulating glasses with viscosities >20 poise. C. Species Volatility/Melt Temperature

Waste glasses formulated for wastes VII. TECHNICAL ADVANTAGES containing radioactive or hazardous volatile species should be optimized at melt A. Optimization of Vitrification Advantages temperatures of ~1150°C or below in order to minimize volatility. As discussed in Section II and summarized in Table 1, there are many advantages to support D. Melt Corrosivity and Waste Solubility vitrification as a means of IEX resin waste Considerations stabilization. Although glass formulations are flexible and will easily accommodate a wide For HLLW vitrification, finely reactive glass chemistry variation of feed material, a systems forming "frits" have been developed as the approach should be utilized to optimize glass forming additives in order to maximize parameters that affect both product glass homogeneity, simplify process control, performance and processing considerations. and lower melt temperatures which minimize Optimization leads to maximum waste loading volatility. For LLMW wastes, the RASP (or volume reduction) which translates into process defined previously can be used to minimized storage volumes and life cycle enhance the solubility and retention of costs. hazardous, radioactive, and heavy metal species in glass.5-6

Table 1. Vitrification Advantages of Ion Exchange Resins.

Vitrification Advantages Processing Solution(s)

Volume Reduction Maximize waste loading (minimize storage volume) Cost Savings Maximize waste loading (storage costs, lower life cycle costs, etc.) High Durability Known glass formulating region of high durability Radionuclides Atomistically Stabilized Low temperature glass formulation for volatiles, SPC and/or models Flexible and easily accommodate process chemistry SPC and/or models variation Developed Technology Not Applicable (processing and product performance) Avoid Hydrogen Generation Not Applicable of "Resin Only" Storage and/or Cement

-7- UJ^/?C- ws-^z-dsiz

VIII. TECHNICAL CHALLENGES when thermally treating organic-based resins. Table 2 lists some of the major Although vitrification of IEX resin wastes technical challenges and potential processing offers many advantages, it is not without solutions. technical challenges that must be addressed

Table 2. Technical Challenges of Vitrification of Ion Exchange Resins.

Technical Challenges Processing Solution(s)

Redox Pretreatment, Bubbler, Oxidizers Accumulation in cold cap Mechanical Stirring Cesium Volatility/Retention Low Temperature Glass Formulation (1150°Q, Moderate Cold Cap Coverage, Fairly Viscous Melt, No Excessive Bubbling

Off-Gas Emissions Resin Prelreatment and Glass Formulation

Salt Solubility Limits Glass Formulation, Off-gas System, and "Salt Drain"

Materials Corrosion Glass Formulation Containment of tritium

A. Redox high organic content of these IEX resin wastes, transition metals in the glass could A primary processing and product precipitate as metallic species. Conductive, performance issue is redox equilibria. The metallic species have the potential to redox equilibria of a glass is a function of anny electrically short melter electrodes if settling oxidizers (nitrates, oxygen), or reductants occurs in a flat bottom, Joule heated melter. (formic acid, resorcinol or other organic Precipitated metals can be drained if the Joule resins, coal, charcoal) present in the waste or heated melter employed has a sloped bottom added during processing. In the absence off and a bottom metals drain. excess oxidizers or reductants, the prevailinng oxygen fugacity of a melt is a function of melt 16 lelt Glass durability can also be affected by temperature. The experimental data indicatate redox.13 An increase in the glass that oxygen fugacities in melters at 1150°C Fe(II)/Fe(total) ratio can decrease durability should be maintained at oxygen fugacities 2 9 because Fe(II) acts as a network modifier, between 10" and 10" to simultaneously avoiroid while Fe(IH) can be a network former. foaming and metal precipitation. Due to thej Processing solutions to mitigate potential negative redox issues include bubbling oxygen

-8- ^flC-^-lB^SiS through the melt,17 adding oxidizers such as Processing solutions that address volatilization nitrates to the melter feed which would react concerns include minimizing processing with the organic at melt temperatures,2 temperature and maintaining moderate cold cap mechanically stirring the melt to increase the coverage. Proper glass formulation can oxygen exchange between the melt and vapors minimize the required melting temperature above the melt, and/or pretreatment of the while maintaining product performance resin to destroy carboneous materials via criteria. Maintaining moderate cold cap chemical destruction or wet oxidation. A coverage is more of a challenge since it is combination of these processing solutions may primarily a function of feed rate and melting be utilized as well. rate.

B. Volatilization C. Off-Gas Emissions The volatilization of cesium and other semi- Vitrification of wet BWR/PWR type ion volatile radioactive metals sorbed onto the exchange resins causes the formation of NOx, resin poses another processing concern. COx, and SOx creating off-gas emissions 17 Cs137 is vaporized from borosilicate type glass concerns. Also mixed alkali salts, borates, melts as CsB02 18 and/or gaseous Cs 19"21 at and chromates are semi-volatile off-gas species at 1150°C which can vaporize from temperatures between 800 - 1150°C. 24 26 Volatilized cesium must be removed by the borosilicate glass melts. " Destruction of off-gas system which generates (or increases) organics in a melt forms volatile CO and CO2 secondary contamination stream handling. while nitrates, if added as melt oxidizers, Retention efficiencies vary with the type of cause formation of NO and NO2. Low radioactive metal being considered and are temperature glass formulations and/or highly dependent upon processing pretreatment or destruction of the organic temperature. resins ex-situ of the melter will minimize off- gas emissions. Cold cap coverage for Joule heated melters plays an integral role in controlling D. Salt SolubiUty Limits volatilization. Preliminary pilot-scale testing by Bibler showed a tendency of a resorcinol Many common salts (sulfates, chlorides, phosphates, and chromates) have limited ion exchange resin to accumulate in the cold 24-28 cap.22 This increased the time necessary for solubility in glass. Solubility limits may the feed to become incorporated in the melt. It be optimized through proper glass also lengthened the time species, such as Cs formulation. However, if solubility limits are and organics, were exposed in the melter exceeded, both processing and product plenum for volatilization. Mechanical stirring performance problems may arise. In (via an impeller) and/or use of lid heaters in particular, if molten salts are allowed to the melter plenum may eliminate or minimize accumulate, steam explosions within the accumulation of the resin within the cold cap melter may occur. Removal of insoluble salt as the crust is continuously drawn into the accumulation from the melter can occur by use melt. As described previously, mechanical of a "salt drain". Melters have been designed which have a separate drain to pour off alkali agitation can also mitigate negative redox 29 effects of a reduced melt by increasing oxygen salts floating on top of the melt The salt exchange. A more oxidized melt could also phase becomes a secondary waste stream that lower the amount of cesium volatilized as well can be immobilized via another alternative, as other metals.23 e.g., sulfur polymer cement. Entrainment of the salt phases in the off-gas line should be

-9- WSAC- ™S~

"I" Jantzen patent pending

-10- wstc-ms^Z-a-SiZ

confirmation of the processability of once dried at 110°C, 50% of the resin glass compositions optimized in waste is volatile, e.g. lost on ignition at crucible studies the melt temperature

determination of off-gas emissions as a function of melt temperature XII. CONCLUSIONS verification of melter behavior as a Vitrification of ion-exchange resins to stabilize Continuously Stirred Tank Reactor a wide variety of PWR/BWR wet resin wastes (CSTR) to ensure that waste and glass and sludges is feasible. Although vitrification formers are homogenized during melting of EEX resin wastes poses many potential technical challenges, viable processing demonstration of recycle of secondary solutions exist. These include proper waste condensate produced compositional development, resin pretreatment (chemical destruction or wet oxidation), melter predictability of process/product models design (bubblers, stirrers, salt tap, etc.), and/or batch additives (oxidizers). evaluation of melter refractory and electrode corrosion Glass compositions can be designed to accommodate both the hazardous and radioactive species in the wastes. The wastes XL VOLUME REDUCTIONS appear to be soluble in borosilicate glass which takes advantage of the glass forming Preliminary "proof-of-principle" testing with potential of high borate and lithium containing wet PWR/BWR resin wastes indicates that PWR wastes. Therefore, the Statistical waste loadings of-50 wt% PWR and 35 wt% Process Control (SPC) system developed for BWR wet resin are achievable in high-level waste borosilicate glasses is homogeneous borosilicate type glasses applicable. The glass compositions for IEX (Figure 1). The reduced waste loadings of the wastes can, therefore, be designed to be both BWR resins occurs because Fe304 crystals durable and processable. Waste loadings of form during melting, e.g. the liquidus is 35-50 wt% provide volume reductions of 66- violated, at the melt temperature of 1150°C 77 volume percent. for the higher waste loadings.

Waste loadings of 50% for PWR resin wastes XIII. REFERENCES and 35% for BWR resin wastes convert to volume reductions of 77 and 66 volume 1. H.E. Filter, "Polymeric Solidification of percent, respectively. For calculational Low-Level Radioactive Wastes from purposes the volume reduction calculations are Nuclear Power Plants," Toxic and based on several assumptions. These include Hazardous Waste Disposal, Vol. 1, R.B. the following: Pojasek (Ed.), Ann Arbor Science, Ann Arbor, MI, 167-188 (1979). wet resin wastes are 50% solids and 50% water N.E. Bibler, J.P. Bibler, M.K. Andrews, specific gravity of the resin wastes is and CM. Jantzen, "Initial Demonstration -1.26 kg/liter of the Vitrification of High Level Nuclear Waste Sludge Containing an Organic Cs- density of the glass is 2.7 kg/liter Loaded Ion Exchange Resin," Sci. Basis for Nuclear Waste Management, C.L.

-11 - biS£C- m£-*\Z-65l%

Interrante, et.al. (Eds.), Materials 10. CM. Jantzen, "Systems Approach to Research Society, Pittsburgh PA, 81-86 Nuclear Waste Glass Development," J. (1993). Non-Crystalline Solids, 84,215-225 (1986). 3. Federal Register, "Land Disposal 11. CM. Jantzen, "Relationship of Glass Restrictions for Third Third Scheduled Composition to Glass Viscosity, Wastes, Final Rule," 55 FR22627 (June Resistivity, Liquidus Temperature, and 1, 1990). Durability: First Principles Process- Product Models for Vitrification of 4. U.S. Environmental Protection Agency, Nuclear Waste," Nuclear Waste Mgt IV, "Handbook: Vitrification Technologies for G.G. Wicks, D.F. Bickford, and L.R. Treatment of Hazardous and Radioactive Bunnell Waste," EPA/625/R-92/002 (May, 1992). 12. CM. Jantzen and K.G. Brown, 5. CM. Jantzen, J.B. Pickett, and W.G. "Statistical Process Control of Glass Ramsey, "Reactive Additive Stabilization Manufactured for the Disposal of Nuclear Process (RASP) for Hazardous and Mixed and Other Wastes," Am. Ceramic Society Waste Vitrification,". Proceed. Second Bulletin, 72, 55-59 (May, 1993). Inter. Symp. on Mixed Waste, A.A. Moghissi, R.K. Blauvelt, G.A. Benda, 13. CM. Jantzen and M.J. Plodinec, and N.E. Rothermich (Eds.), Am. Soc. "Thermodynamic Model of Natural, Mech. Eng., p.4.2.1 to 4.2.13 (1993). Medieval, and Nuclear Waste Glass Durability," J. Non-Cryst. Solids, 67, 6. Jantzen, CM., Pickett, J.B. and Ramsey, 207-233 (1984) W.G., "Reactive Additive Stabilization Process (RASP) for Vitrification of 14. CM. Jantzen, and D.F. Bickford, Hazardous and Mixed Waste," "Leaching of Devitrified Glass Containing Environmental and Waste Management Simulated SRP Nuclear Waste," Sci. Issues in the Ceramic Industry, Ceramic Basis for Nuclear Waste Mgt, VIIL CM. Transactions, 39, American Ceramic Jantzen, et. al. (eds.), Mat. Res. Soc., Society, Westerville, OH, 91-100 (1994). Pittsburgh, PA 135-146 (1985).

7. C.L. Crawford and N. E. Bibler, 15. CM. Jantzen, D.F. Bickford, and D.G. "Radiolytic Hydrogen Production During Karraker, "Time-Temperature- the Long-Term Storage of Spent Organic Transformation Kinetics in SRL Waste Ion Exchange Resins," Waste Glass," Adv. in Ceramics, 8, Am Ceram. Management 95 Proceedings (1995). Soc, Westerville, OH, 30-38 (1984).

8. CM. Jantzen, N.D. Hutson, T.M. 16. H.D. Schreiber, C.W. Schreiber, M.W. Gilliam, A. Bleier, and R.D. Spence, Riethmiller and J.S. Downey, "The Effect "Vitrification Treatability Studies of Actual of Temperature on the Redox Constraints Waste Water Treatment Sludges," Waste for the Processing of High-Level Nuclear Management 95 Proceedings (1995). Waste into a Glass Waste Form," Sci. Basis for Nuclear Waste Management, 9. M.B. Volf, "Chemical Approach to XIII, V.M. Oversby and P.W. Brown Glass," Glass Science and Technology, 7, (Eds.), Materials Research Society, Elsevier, NY (1984). Pittsburgh, PA 419-426 (1990).

-12- teSRC-ms-iZ-aSJS 17. M. Brandys, R. Mohr, H. Hojaji, S.S. Savannah River Company, Savannah Fu, P.B. Macedo, and W. Greenman, River Site, Aiken, SC (March, 1991). "Vitrification of Wet Waste Resin", Waste Management 95 Proceedings (1995). 25. CM. Jantzen, A.S. Choi, and CT. Randall, "Remediation of Off-Gas System 18. H. Kamizono, S. Kikkawa, Y. Togashi, Deposits in a Radioactive Waste Glass and S. Tashiro, "Volatilization of 137Cs Melter," Proceedings of the 1991 Joint and 106Ru from Borosilicate Glass International Waste Management Containing Actual High-Level Waste," J. Conference, Volume 2, Seoul, Korea, American Ceramic Society, 72 [8], 1438- 1991. 1441 (1989). (1989) 26. CM. Jantzen, "Glass Melter Off-gas 19. G.W. Wildes, "Vaporization of Semi- Pluggages: Cause, Significance, and Volatile Components from Savannah River Remediation," Ceramic Transactions, Plant Waste Glass," U.S. DOE Report Volume 23, 621-630, 1992 DP-1504, Savannah River Laboratory, E.l. duPont deNemours & Co., Aiken, 27. D.F. Bickford, A. Applewhite-Ramsey, SC (August, 1978). CM. Jantzen, and K.G. Brown, "Control of Radioactive Waste Glass Melters: I. 20. J.W. Hastie, E.R. Plante, and D.W. Preliminary General Limits at Savannah Bonnell, "Vaporization of Simulated River," J. Am. Ceram. Soc., 73 [10] Nuclear Waste Glass," NBSIR 83-273 lm 2896-2902 (1990). National Bureau of Standards, Washington, DC (June, 1983). 28. J.C Marra, M.K. Andrews, and R.F. Schumacher, "Vitrification in the Presence 21. D.W. Bonnell, E.R. Plante, and J.W. of Molten Salts," Ceramic Transactions, Hastie, "Vaporization of Simulated Volume 45,401-408 (1994). Nuclear Waste Glass," J. Non-Crystalline Solids, 84, 268-275 (1986). 29. J.C. Whitehouse, CM. Jantzen, F.R. Van Ryn, and D.H. Davis, "Design and 22. N.E. Bibler, Bibler, J.P., Andrews, Fabrication of a Transportable Vitrification M.K., and Jantzen, CM., "Initial System for Mixed Waste Processing," Demonstration of the Vitrification of Proceed. Third Inter. Symp. on Mixed Nuclear Waste Sludge Containing an Waste, A.A. Moghissi, B.R. Love, and Organic Cs-Loaded Ion Exchange Resin," R.K. Blauvelt (Eds.), Am. Soc. Mech. WSRC-MS-91-465, Westinghouse Eng., p.8.3.1 - 8.3.8, (1995). Savannah River Co., Aiken, SC (1991). 30. CM. Jantzen, "Vitrification of Low Level 23. T.N. Sargent, D.M. Bennert, T.J. and Mixed (Radioactive and Hazardous) Overcamp, D.F. Bickford, and C.A. Wastes: Lessons Learned from High Level Cicero, "Vitrification of Ion Exchange Waste Vitrification," Proceedings of Resins," Proceedings of the 95th Annual Spectrum 94 Nuclear and Hazardous American Ceramic Society Convention, Waste Management International Topical Symposium, VIII, April 19-22, 1993. Meeting, Am. Nuclear Soc., 487-492 (1994). 24. CM. Jantzen, "Glass Melter Off-gas Pluggages: Cause, Significance, and Remediation," U.S. DOE Report WSRC- TR-90-205, Rev. 0, Westinghouse

-13-