ayes ono - digital library/67531/metadc733375/... · hnf-sd-cp-ocd-040 revision 3 ecn basis...

*%%e d,

ENGINEERING CHANGE NOTICE o'&-

I .ECN 657667' ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. ECN Category (mark one) Supplemental 0 N. E. Wilkins, NlB10000, T5-55, 373-3685 Direct Revision

3. Originatots Name, Organization, MSIN. and Telephone No.

I R Risenmay T5-55 i M Stubbs T5-55 : A Larkin T5-55 i E Nunn T5-11 < A Burk T4-20

4. US0 Required? 5. Date

ayes oNo 3/16,,oo

I____.

4-7900-013-2 (10/97) A-7900-013-1

0 Change ECN

0 Temporaw

Standby

Supersedure 0 Canca Woid 0

Yes (fill out Elk. 12b)

{2c, 12d)

2a. Modification Work

o NA Elks. 12b,

6. Project TitlelNo.Mlork Order No.

Thermal Stabilization/110893

9. Document Numbers Changed by this ECN (includes

WHC-SD-CP-OCD-040, Rev. 2 0 N/A N/A 12b. Work Package No.

N/A N/A N/A

7. Bldg./Sys./Fac. No. 8. Approval Designator

234-5Z/PFP S I O . Related ECN No@). 11. Related PO No.

sheet no. and rev.)

12c. Modification Work Completed 12d. Restored to Ori inal Condition (Temp. or Standby E C i s only)

Design AuthoritylCo Engineer Signature 8 Design Authority/Co Engineer Signature 8 &e Bite

4a. Justification (mark one)

Criteria Change 0 Designlmprovement

0 Environmental

Facility Deactivation

As-Found

Facilitate Const. 0 Const. ErrorlOmission 0 Design ErrorlOmission

14b. Justification Details Pu Metal will be processed through the HC-21C furnaces. A technical justification of the heating cycle (Section 3.71 and previous experimental results from heating Pu Metal in a furnace (Attachment F) are being added to the document. The section concerning the fire suppression system activation temperature is being deleted because the responsibility for maintaining this system lies with the Hanford Fire Department, not Thermal Stabilization.

tq vw Pagezof g 7 ENGINEERING CHANGE NOTICE

. Design Verification 17. Cost Impact Required ENGINEERING CONSTRUCTION

0 Yes Additional 0 t N/A Additional 0 $ N/A

[XI No Savings 0 $ N/A Savings 0 $ N/A

Environmental Permit 0 Inventory Adjustment Request 0 OtherAffected Documents: (NOTE: Documents listed below Will not be revised by this ECN.) Signatures below indicate that the signing organization has been notified of other affected documents listed below.

1. ECN (use no. from pg. 1)

657667 18. Schedule Impact (days)

Improvement 0 N/A

Delay 0 N/A

Document NumberIRevision

OSD-Z-184-00006/D-6 Document NumberIRevision Document NumberlRevision

Anorovals Signature Date

Design Authority

Cog. Eng. 3/23 .zBeo 3 f3Dl Do 3-10 uo

Environ

Other

Date

Design Agent .5 /16/&9

Safety

Design

Environ

Other

PFPARTME NT OF FNE RGY Signature or a Control Number that tracks the Approval Signature

A-7900-01 3-3 (10197)

~~~~~ ~ -.

Identification Number ZO-160-038 A-0 0-160-039 A-O,OSD-Z-184-00006 D-7 IIHC-SD-CP-OCD-040 Rev 3

!SCRIPTION

USQ SCREENING

ctions are being added to the OSD and OCD for thermal stabilization to describe the heating cycle for utonitiiii metal. Section 6.6.1 of the OSD, "Fire Suppression System Activation Temperature", will be leted. New procedures are being written for furnace charge preparation for plutonium metal and oxidizing thi utoniiim metal in Glovebox HC-21C.

TRODUCTION

iult personnel have begun a program of radiographing plutonium metal cans. Metal that appears to be corroded will be xessed through the furnaces in Glovebox HC-21C. The fire suppression system activation temperature will be deleted cause it is not maintained by PFP Stabilization.

'FECTED SSC

2 1 C glovebox and furnaces, HC-21A glovebo:;

JPHORiZATlON BASIS

le authorization basis documents considered for review included those listed in FSP-PFP-5-8, Section 2.23, Appendix A. iose applicable are:

HNF-SO-CP-SAR-021, Rev. 1 Letter FDH-9954877 R1, which includes HNF-4823, Rev. 0, "Hazards Evaluation of Plutonium Metal Opening and Stabilization" and USQ Evaluation PFP 99-017, "Pu Metal Reaction Upon Opening Item with Paneled Inner Container" (Approved by DOE Letter 99-TPD-326)

HNF-4823 and Pu metal as a feed stream into the HC-21C furnaces is scheduled to be incorporated into the next update of the FSAR (DOE Letter 99-TPD-326).

ONCLUSION

lese changes will not affect the plant's safety envelope in any way.

EFERENCES

NF-SD-CP-SDD-010, "Definition and Means of Maintaining the Fire Protection System Portion of the PFP Safety

.6000-615 (10195) GEF319

ldentificallon Number 20-160-038 A-0 10-160-039 A-O,OSD-Z-l84-00006 0-7 NHC-SO-CP-OCD-040 Rev 3

WESTIONS

USQ SCREENING

l.Ooes the proposed change or occurrence represent a change to the facility or procedures as described in the Authorization Basis? [I NIA [X] No [] YeslMaybe

BASIS: A hazard analysis was done of the activities involved with stabilizing Pu metal in the HC91C furnaces (HNF-4823) which was included in the Authorization Basis for PFP. The procedures for Pu metal include only the activities evaluated (as listed on pages 2 and 3 of HNF-4823). USQ 99-017 has an evaluation of the various accidents that can be associated with stabilizing plutonium metal in the HC-21C furnaces, and it concluded that thermal stabilization of plutonium metal was not outside the Authorization Basis, as long as certain operating restrictions were lifted. DOE Letter 99-TPD-326 lifted the operating restrictions. These procedures do not represent a change to thermal stabilization activities as described in the Authorization Basis.

In SDD-010, Section 5.2.1, it states that the Hanford Fire Department is responsible for testing, maintenance, and inspection of the dry chemical and Halon fire suppression systems. Thermal stabilization personnel are not responsible for the correct operation of the fire suppression system, and this section is being removed from the OSD.

2.Does the proposed change or occurrence represenl conditions that have not been analyzed in the Authorization Basis? (1 NIA (XI No [I YesIMaybe

BASIS: See answer to question 1. These procedures do not represent conditions that have not been analyzed in the Authorization Basis.

3.Does the proposed change represent a test or experiment NOT described in the Authorization Basis that may aHect the safe operation of the facility? (XI NIA (1 No [I YeslMaybe

BASIS: This is not a test or experiment

4.Does the proposed change or occurrence represent a change to the Technical Safety Requirements or a reduction in the margin of safeiydelined in

(1 NIA [XI No [] YesiMaybe

BASIS: These changes do not propose a change to any technical safety requirements, and PFP has no safety limits in

the Technical Safety Requirements?

OSR-010. Therefore, no margin of safety is applicable.

$.6000-615 (10195) GEF319

UNREVIEWED SAFETY QUESTION (USQ)

1 . Identification Number: 20-160-038 A-0 20-160-039 A-O,OSD-Z-l84-00006 0-7 WHC-SD-CP-OCD-040 Rev 3

w- USQ SCREENING Page jo f 3 5-5- %

(Print Name) (PridName)

If there is a YESIMAYBE response to queslions 1, 2, 3, or 4 , then a USQ Evaluation must be completed

The following guidance should be considered when compleling lhis screening. This guidance should not be considered all-inclusive; additional faclors may need lo be considered depending on the nalure of Ihe proposed change.

Does Ihe proposed change:

Modify, add, or delete a safely class function of a structure, system or component slated in Ihe aulhorization basis? Alter Ihe design of a structure, syslem or component as described in the authorization basis? Modify. add, or delete Ihe descriplion of operalion, operating environment, or analyses of any system or component described in the aulhorization basis? Modify, add, delele or conllicf with any of !he design bases slaled in Ihe aulhorizalion basis? Conflict wilh the principle or general design crileria slaled in the aulhorizalion basis? Modify add, or delete any plant design features described in !he authorization basis? Modify add, or delele a flow diagram or facilily drawing provided in the authorizalion basis? Create Ihe polential for new system or componenl interactions (e.g , seismic, electrical breaker caordinalion)7

7

~ ~

A-6000-615 (10195) GEF319

.. .

HNF-SD-CP-OCD-040 Revision 3

Basis Document for Sludge Stabilization

Prepared for the U.S. Department of Energy Assistant Secretary for Environmental Management Projed Hanford Management Contractor for the US. Department of Energy under Contract DEAC06-96RL13200

Fluor Hanford P.O. Box 1000 Richland, Washington

Approved for public release; further dissemination unlimited

-

HNF-SD-CP-OCD-040 Revision 3

ECN

Basis Document for Sludge Stabilization

Date Published April 2000

Prepared for the U.S. Department of Energy Assistant Secretary for Environmental Management Project Hanford Management Contractor for the U S Deoarlmenl of Energy under Conlrad DE-AC06-96RL13200

Fluor Hanf ord P.O. Box 1000 Richland, Washington

I - '

eas Approval - Release Stamp

Approved for public release: further dissemination unlimited

. _ _ _ _

TRADEMARK DISCLAIMER Reference herein to any specfc cmmerc al prwucl. procBss or service by tram 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 or its contractors or subcontractors.

This report has been reproduced from the best available copy.

* i Total Pages:

RECORD OF REVISION

1 Basis Document for Sludge Stabilization ,* (1) Document Number

HNF-SD-CP-OCD-040 P a w AI

I A-7320-005 (10197)

HNF-SD-CP-OCD-040 REV . 3

BASIS DOCUMENT FOR SLUDGE STABILIZATION

TABLE OF CONTENTS

1 . INTRODUCTION .................................................... 4

2 . Feed Specifications ............................................. 4 2.1. Feeds Permitted ............................................ 4

2.3. Charge Size ................................................ 5 2.2. Feeds NOT Permitted ........................................ 5

3 . Controller Specifications ....................................... 6 3.1. Furnace Ramp Rate Settings ................................. 6 3.2. Furnace Temperature Deviation Band Settings . . . . . . . . . . . . . . . . 1 3.3. Heating Cycle PFtF Sludge Settings .......................... 7 3.4. Heating Cycle Pu Oxalate (Oxycarbonate) Settings . . . . . . . . . . . 8 3.5. Heating Cycle Fu Oxide Setting .............................. 9 3.6. Heating Cycle Reactive Incinerator Ash Setting . . . . . . . . . . . . . . 9 3.7. Heating Cycle for Pu Metal .................................

High Furnace Temperature Setting ........................... Glovebox High Temperature Alarm Setting ....................

4.1. Off-gas Flow Rate .......................................... 1 0 4.2. Filter Differential Pressure ............................... 11

5.1. Purge Flow Rate ............................................ 12

6.1. Combustible Material ....................................... 12

I . Product Specifications .......................................... 13

9 1 0 10

10

3.8. 3.9.

4 . OFF-GAS SYSTEM ..................................................

5 . PURGE SYSTEM .................................................... 12

6 . FIRE SAFETY ..................................................... 12

7.1. Particle Size .............................................. 13

2

HNF-SD-CP-OCD-040 REV. 3


TABLE OF CONTENTS (continued)

ATTACHMENT A: SLUDGE STABILIZATION STUDIES ............................ 14

ATTACHMENT B

ATTACHMENT C

ATTACHMENT D

ATTACHMENT E

ATTACHMENT F

TEST PERFORMED BY PLUTONIUM PROCESS SUPPORT LABORATORIES 1994 .................................... 26

INTERNAL MEMO (15530-94-DMB-070) "D. M. BERSHAW TO W. S. LEWIS, "PRESSURE DROP ANALYSIS FOR FILTER ON 26 IN VACUUM LINE IN GLOVE BOX HC-21'2" . . . . . . . . . . . . . . . 35 MASS W C E ......................................... 41

REACTIVE INCINERATOR ASH OFF GAS FLOW RATE CALCULATIONS .......................................... 49

BURNING PLUTONIUM METAL BUTTONS USING AN IGNITER .............................................. 55



1. INTRODUCTION

The HC-21C and HA-211 gloveboxes will be used to stabilize plutonium bearing material. This will be accomplished by heating PRF and other orqanic (tributvl phosphate) bearinq sludaes, plutonium oxide, reactive- incinerator ash, plutonium metal, and piutonium oxalate conversion product (oxycarbonate). Heating to a temperature of 1000°C in an air stream will drive off residual volatile components and convert residual plutonium-organic materials to PuO,.

This technical basis covers the Operation Specification Document (OSD-Z-184-00006) and explains the limits necessary for criticality prevention, protection of personnel and environmental safety, minimizing equipment damage, and attempting to maximize process efficiency.

The following equipment, along with associated instrumentation, interlocks, piping, etc., is covered.

Equipment

Furnace Temperature Controller Temperature Alarm Switches Off-gas Filter Sieve

2. Feed Specifications

2.1. Feeds Permitted

Limit: PRF sludge and sludges from other wet process gloveboxes, plutonium oxide, plutonium oxalate (oxycarbonate), plutonium metal and incinerator ash. Glovebox HA-211 cannot be used to process plutonium metal or any material that may have organic content, i.e., PRF sludge and sludges from other wet process gloveboxes that may contain tributyl phosphate (TBP).

Basis: Processing has been limited to the above feeds because analysis has shown the off-gases produced will not be a safety hazard. Glovebox HA-211 is not equipped with a C02 purge system, and therefore, it cannot be used to process any item that may contain organic material (TBP). The Authorization Basis does not allow plutonium metal to be processed in Glovebox HA-211.

Over time the Pu Oxalate will degrade to PuOC03-2H20 (plutonium oxycarbonate) with a reaction half-life of 64 days. Considering the length of time the oxalate has been in storage (in excess of 4 years), this results in essentially all of the oxalate having degraded to the carbonate form. (Reference: The Chemistry of Plutonium, J. M. Cleveland, pages 407-408)

Incinerator ash is primarily made of material from the Rocky Flats incinerator. A small portion of the material is from the 232-2 incinerator. The ash contained an average of 22% carbon and therefore was reburned in glovebox HA-40F to remove the carbon. A

4



portion of the material was not processed in HA-40F and this material will be stabilized in the muffle furnaces.

The material that came from Rocky Flats is broken into three categories, Old, Middle and Current. The Old material typically has the high carbon content (up to 4 2 % ) and the lowest plutonium content. The Current material typically has the lowest carbon content and the highest plutonium content.

A potential concern with the incinerator ash from Rocky Flats is the presence of lead in the form of lead nitrate which can react violently with graphite. TGA/DTA testing performed with lead nitrate in the presence of graphite indicated that only a small exothermic reaction occurred between 340°C and 420°C (Appendix H). The material was heated to over 450°C prior to being shipped to Hanford, therefore the presence of lead nitrate is not expected.

Any other feeds will be evaluated by PFP Stabilization engineers on a case by case basis.

2 . 2 . Feeds NOT P e r m i t t e d

L i m i t : Plutonium bearing materials (PBM) with greater than 10 grams maximum organic in each charge.

Basis: Feed items that originated in PRF have a potential to contain tributyl phosphate (TBP). One of the decomposition products of TBP is butene. Butene, in certain concentrations, can be flammable. Controlling the organic content to 510 grams is one of the barriers which prevents butene generation from reaching flammable levels. [See Attachment A, Table 1 and Figures 1 and 2 . )

The 10 gram organic limit is specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, "Plutonium Finishing Plant Final Safety Analysis Report", 1999, Section 5.2.2.

2.3. C h a r g e S i z e

L i m i t : Shall not exceed a mass of 2400 g of Pu for feed material except organic bearing sludge and reactive incinerator ash, 1% inches depth in the boat and a maximum amount of 10 grams organic in the charge

Basis: Charge size (depth) was determined to allow for oxidation of the material in the boat and to allow for safe operation of the process. Safety calculations have been done using 20 grams TBP. If the charge size is limited to 10 grams organic, then the amount of butene gas generated during processing will be within safe limits (below flammability limits).

Laboratory tests showed that charges containing oxalate (oxycarbonate) liquefied and foamed. The charge must fit into the boat, which has been designed to fit inside the furnace without interference with thermocouples o r purge and vent lines. The boat allows generous free board to avoid boil over. CSER 94-007 and 94-008 assess

5



the boat size for criticality and allows material to fully load the boat.

Feed material charges other than organic bearing sludges and reactive incinerator ash are limited to 27259. total weight with a restriction of 2400g Pu. The criticality limit for glovebox HC-21C is 5000g Pu when processing feed material with a H/X < 20. Reducing the boat charge size to 24009 from the CPS allowed 2500g allows 2009 for the glovebox holdup. Typical glovebox holdup is around 50g Pu.

To eliminate the necessity of doing calculations to determine the allowable charge that meets the 2400g Pu limit that can be placed in a furnace boat during charge preparation, the maximum charge size will be based on a product quality oxide that contains about 88% Pu. This results in a maximum charge size of 27259 of material in each boat for stabilization.

3. Controller Specifications

3.1. Furnace Ramp Rate Settings Limit: Maximum Furnace Ramp Rate Temperature Range @ Ramp Rate (C/hr) SCR Output (Amps)

25 - 500 300 13 500 - 700 200 13 700 - 900 125 13 900 - 1000 75 13

Basis: The furnace is ramped up slowly to avoid damaging the furnace heating coils. The manufacturer recommends that the furnace should not be operated at full power ( 1 7 amps) for extended periods of time (over 4 hours). Process tests indicate that complying with the specified ramp rates will prevent overloading the heating coils. (See Attachment C), "Scrap Stabilization Furnace Test Results", WHC-SD-CP-TRP-059, J. A. Compton, April 5, 1994) Consideration was also given to optimize process time within the safety envelope and to protect the furnace heating coils from overheating causing failure and short lifetime . These ramp rates are a safety feature and are programmed into the controller, The specified ramp rates ensure that gases will be exhausted as they are generated so combustible mixtures will not be accumulated. (See Attachment A, Table 1 and Figures 1 and 2) The ramp rates cited are maximum rates. Ramp rates can be adjusted to avoid overshooting the soak temperatures.



3.2. Furnace Temperature Deviation Band Settings

Deviation Limit: i 20°C

Basis: Low deviation alarm can detect a removed thermocouple, burnt out heater element, poorly tuned controller, etc. High deviation alarm will detect too high a ramp rate by activating when temperature exceeds the expected ramping temperature. Exceeding the ramp rate could generate excess butene gas when processing an organic charge or overheat the heating coils causing failure and short lifetime. The deviation band alarm will also detect soak temperatures either above or below the set point. The butene curves in Figures 2 and 6 of Attachment A show the effect of exceeding the soak temperature set point of 175°C by 20 degrees.

3.3. Heating Cycle PRF Sludge Settings

Limit : 1st Soak - 1% hr at 175°C 2nd Soak - 2 hr at 1000°C

Basis : The ramp rate and temperature limit for the first soak time was selected because this parameter keeps the rate of butene generation outside of the flammable range. The one and a half hour soak time was determined by calculating the amount of time it would take to thermally decompose 20 grams of TBP to butene. Twenty grams is double the amount of TBP allowed in a batch. (See Attachment A, Table 1 and Figures 1 and 2).

Laboratory test results were used to determine the temperature limit and one hour soak time for the second soak. The tests showed that by heating material at 1000°C for one hour, essentially all of the volatiles will be removed, thus meeting the vault storage specification. In addition, the higher temperature reduces the absorptivity of the processed sludge making it more stable. (See Attachment B)

These soak rates are specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, "Plutonium Finishing Plant Final Safety Analysis Report", 1999, Section 5.2.2.



3 . 4 . Heating Cycle Fu Oxalate (Oxycarbonate) Settings

L i m i t : 1st Soak - 1 hr at 110°C 2nd Soak - 1/2 hr at 175'C 3rd Soak - Minimum - 2 hrs at 1000°C

B a s i s : 1st Soak - Before start of operation, laboratory tests with oxalate (oxycarbonate) showed that it became liquid above 100°C. A soak at this temperature removes the water of hydration and allows the evaporation of the free liquid portion of the charge to evaporate without foaming over the edge of the boat. Operating experience has shown that boil-over was not avoided at the previous soak setpoint of 175°C. Upon further research it was found that the dehydration temperatures start at 90'C (Reference: J.M. Cleveland, The Chemistry of Plutonium, 1979, p. 403, 404). In order to evaporate water, the soak temperature must exceed the boiling point of water. To avoid boil-over and still evaporate water, a new setpoint of 110°C was selected for the first soak. Even with the lower soak time, some of the material may boil over. This is not a major concern in that the material can be easily scraped and brushed out of the furnace. The material is then placed in a can with the rest of the charge material in HC-18M.

2nd Soak - Laboratory test results were used to determine the temperature limits for the second and third soaks. The second soak separates the remaining water of hydration from the oxycarbonate (oxalate) and continues evaporation of free liquids.

3rd Soak - The DOE Standard 3013-96, Long Term Storage Criteria for >508 Pu oxides, requires that materials be heated to 950°C or higher for 2 hours and meet a <0.5% LO1 @ 1000°C. Tests showed that by heating material at 1000°C for one hour, essentially all of the volatiles will be removed, thus meeting the vault storage specification of <0.5% LO1 for material less than 50% Pu. In addition, the higher temperature reduces the absorptivity of the processed sludge making it more stable. (See Attachment B J



3.5. Heating Cycle Eu Oxide Setting

Limit : Soak - Minimum 2 hrs at 1000°C

Basis: Laboratory test results were used to determine the temperature limit and soak time. The DOE Standard 3013- 96, Long Term Storage Criteria for >50% Pu oxides, requires that materials be heated to 950°C or higher for 2 hours and meet a cO.58 LO1 @ 1000°C. Tests showed that by heating material at 1000°C for one hour, essentially all of the volatiles will be removed, thus meeting the vault storage specifications of <0.5% LO1 for material less than 50% Pu. In addition, the higher temperature reduces the absorptivity of the processed sludge making it more stable. (See Attachment B)

3.6. Heating Cycle Incinerator Ash Setting

Limit : Reactive Ash Soak - 4 hr at 1000°C Nonreactive Ash - Minimum 2 hrs at 1000°C

Basis : Process testing indicates that a 4 hour soak time at 1000°C along with a one and one half inch depth in the boat will allow oxidation of sufficient carbon to meet vault specifications. (Reference: WHC-SD-CP-TP-087 Rocky Flat Ash Test Procedure (Sludge Stabilization), 9/14/95).

The 2 hrs at 1000°C heating cycle is to be used with nonreactive incinerator ash that has been processed through HA-40F or the stabilization furnaces. Because the material was previously processed to 600"C, 2 hours at 1000°C is sufficient to meet the Long Term Storage Criteria.

3 . 7 Heating Cycle for PU Metal

Limit : 1"' Soak - 550°C for 6 hours 2"'Soak - 1000°C for 2 hours

Basis : A laboratory experiment heated a metal button to 550°C in a crucible furnace. Oxidation of the button was completed in 6 hours. (Reference: SD-CP-PTR-008, Burning Plutonium Metal Buttons Using an Igniter, 10/23/85) The second soak is identical to the soak performed on other plutonium oxide items.

The soak temperature of 550°C was selected for the first soak because it is below the melting point of plutonium metal. If the metal melts, it will form an alloy with the Hastelloy boat and ruin the boat.



3 . 8 . H i g h Furnace T e m p e r a t u r e Setting

L i m i t : 1050°C

Basis: The high furnace temperature alarm system provides an independent backup to prevent over-heating the furnace if the Controller fails. The maximum furnace temperature recommended by the manufacturer is 1093°C. Operating the furnace at the full output of power required to maintain this temperature for an extended period of time (>4 hours) can shorten the lifetime of the furnace element and cause failure.

Specification limit is set to allow for over-shooting during ramp time. The set point changed from 1025°C to 1050°C in September, 1995 because the lower temperature was found to be more conservative than required and caused unnecessary process cycle shut-downs. There were no safety reasons for the lower limit of 1025°C and the new setpoint of 1050°C is still well below the manufacturers recommended guidelines.

3.9. Glovebox H i g h T e m p e r a t u r e A l a r m Setting

L i m i t : 70°C (158°F)

B a s i s : This alarm is in place to provide sufficient warning of off-standard conditions which could cause the glovebox to heat up and reach the Fire Suppression System activation temperature of 93°C (200"Fl.

Glovebox HC-21C has a Halon fire suppression system, and Glovebox HA-211 has a dry chemical suppression system. It is desirable that activation of the Halon system in Glovebox HC-21C be avoided unless there is an uncontrolled fire in the glovebox, because once the Halon has been released, there will be no fire suppression system for the glovebox. Halon is a regulated material and may be difficult to replace. (Reference drawing H-2-97481, sheets 26, 27, 28, 29.1

4 . OFF-GAS SYSTEM

4 . 1 . O f f - g a s Flow Rate

L i m i t : 120 to 180 std. ft3/hr. for Sludge/oxalate 60 to 90 std. ft3/hr. for Oxide/MOX/Pu Metal

A flow rate of 60 - 90 std. ft3/hr shall be used when processing reactive incinerator ash.

Exception:

Off-gas flow was specified for sludge charges because of the possibility of butene which could be generated when PRF Sludge containing tributyl phosphate ( T B P ) is

10



processed. Its purpose is to dilute and remove flammable off-gases during the period butene can be generated. This period is ended before the furnace reaches a temperature of 250°C. The same flow rate was specified for oxalate charges to aid the evaporation of free liquids.

Basis : In glovebox HC-21C. off-gases are vented to the 26" Hg vacuum system. In glovebox HA-211, off-gases are vented to the 5" Hg vacuum system. A flow rate of 120 - 180 std. ft3/hr will provide enough circulation to dilute the flammable gases generated when processing PRF Sludge to within safe concentrations. It will also provide greater air circulation through the furnace to aid oxidation and remove volatiles from the charges. (See Attachment A, Figures 3, 4, 5, and 6 and associated tables. )

During stabilization of reactive incinerator ash, carbon will oxidize to both CO and C02. CO is flammable (though not explosive) in concentrations greater than 12%. Calculations were performed which indicated that CO concentrations will remain below 128 as long as sufficient oxygen is present (0.6 scfm is sufficient to convert almost all carbon to COz) (Attachment E).

The incinerator ash is very flighty and therefore is susceptible to being pulled into the off gas line and plugging the filter. The off gas flow rate will be reduced to 60 - 90 scfh while processing this material.

The sludge/oxalate and oxide/MOX off-gas flow rates are specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, "Plutonium Finishing Plant Final Safety Analysis Report", 1999, Section 5.2.2.

4.2. Filter Differential Pressure

Limit: - < 10 psi for Glovebox HC-21C

- < 50 in.-H20 for Glovebox HA-211

Exception

PFP Stabilization engineers can allow continued operation of a cycle with greater dP as long as the required exhaust flow is maintained.

A filter is instailed in the exhaust line after it leaves the furnace. The filter's function is to remove airborne particulate matter in the off-gas.

Basis: Any particulate matter remaining in the filter can absorb moisture at the beginning of the cycle. Once the particulate matter absorbs moisture, it hardens into a solid piece. This reduces the permeability of the filter which decreases the air flow rate through the furnace. Low air flow increases the possibility of combustible gas build-up. (See Attachment C, Internal Memo 15530-94-DMB-070, D. M. Bershaw to W. S. Lewis, "Pressure Drop Analysis for Filter on 26 Inch Vacuum Line in Glove Box HC-21C", Westinghouse Hanford Company,

.. 11

. .-



Richland, Washington, June 1, 1994). The limit for Glovebox HC-21C is also specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, ”Plutonium Finishing Plant Final Safety Analysis Report”, 1999, Section 5.2.2.

5. PURGE SYSTEM

5.1. Purge Flow Rate

> 45 std. ft3/hr C02

The carbon dioxide purge flow will be used only for charges originating in PRF or other wet process gloveboxes with a potential for containing TBP. The C02 purge is only available in Glovebox HC-21C.

L i m i t : -

B a s i s : Carbon dioxide was chosen because it was found to be more effective on a molar basis. Minimum purge flow with carbon dioxide during the ramp and soak times (about 2% hours) for PRF sludge charges, assures flammable gas concentration in the furnace remains below minimum safe limit. (See Attachment A, Figures 3, 4, 5, and 6 and associated tables).

The 45 scfh CO, flow rate is specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, ”Plutonium Finishing Plant Final Safety Analysis Report“, 1999, Section 5.2.2.

6 . FIRE SAFETY

6.1. Combustible Material

L i m i t : Glovebox gloves near furnace fixed in position with bungi cord during processing cycle.

Minimal non-engineered combustible materials such as plastic bags, polyjars, or rags in Gloveboxes HC-21C and HA-211 during the heating cycle.

B a s i s : This limit is set both to prevent contacting of combustible materials with hot surfaces and accumulating of significant quantities of combustibles. Surface temperatures of the lines exiting the furnace can exceed 400°C during the heating cycle. The exhaust line which carries the hot gasses is insulated to the offgas filter which is a significant heat s i n k . The CO, line is not insulated and portions of the line near the furnace could reach temperatures over 400°C. Radiant heat transfer should reduce the line temperature to below 200°C by the time the line exits the glovebox. Combustible materials contacting these surfaces may ignite and the resulting fire may breach glovebox containment if these materials are present in sufficient quantity.

These requirements are specified in the Addendum to WHC-SD-CP-SAR-021, Revision 0-K, “Plutonium Finishing Plant Final Safety Analysis Report”, 1999,Section 5.2.2.

12



7. Product Specifications

7.1. Particle Size

Limit: Particles must go through 4 mesh sieve

Exception: PFP Stabilization engineers can allow larger chunks of material to be canned with the concurrence of the Product Handling and Storage Cognizant Engineer.

Basis: A fairly uniform particle size is required to assure that samples taken for LO1 are representative. Larger chunks also may not be completely dried. If no large chunks of material are present in product, sieving will not be required.

hh’f-SD-CP-OCD-040 REV. 3


ATTACMENT A: SLUDGE STABILIZATION STUDIES

1 4

fw -5 D -C P -0C 0- 0 4 0 REV. 3

BASIS DOCUI.. .T FOR S L U D G E STABILIZATION

ATTACHMENT A PAGE A - 1 Of A - 1 1

S L U D G E STAB1 LI Z ATION STUD1 ES

T h i s series o f f i g u r e s was d e v e l o p e d from d a t a o b t a i n e d from l a b o r a t o r y tests p e r f o r m e d w i t h Urany l n i t r a t e - t r i h u t y l p h o s p h a t e a d d u c t ( " B e h a v i o r of T r i b u t y l P h o s p h a t e i n A-Line P r o c e s s e s " , DP-1416, August 1976, H.D. Harmon, e t a l ) . The p h y s i c a l and c h e m i c a l p r o p e r t i e s were s t u d i e d t o d e f i n e o p t i n u m , s a f e o p e r a t i n g c o n d i t i o n s fo r d e n i t r a t i o n o f u r a n y l n i t r a t e s o l u t i o n s c o n t a i n i n g l o w c o n c e n t r a t i o n s o f a d d u c t . A c o n s e r v a t i v e k i n e t i c f a c t o r ( K F ) of 3 was used when t h e d a t a h"as a p p l i e d t o p l u t o n i u m b e a r i n g m a t e r i a l , which w i l l b e used i n t h e s l u d g e s t a b i l i z a t i o n process, t o a c c o u n t f o r t h e f a c t t h a t p l u t o n i u m n i t r a t e has two t imes a s nuch n i t . r a t e a s u r a n y l n i t r a t e .

F i g u r e s 1 and 2 shot! t h e c x p e c t e d r e s u l t s c a l c u l a t e d i f t h e p r o c e s s is o p e r a t e d a t c o n d i t i o n s d e f i n e d i n t h e O p e r a t i n g S p e c i f i c a t i c n Document. F i g u r e 1 shows the r e l a t i o n s h i p of t h e d e c o m p o s i t i o n curve o f 2 0 grams of T E P and t h c b u t e n e g e n e r a t i . c n c u r v e t o t h e t e m p e r n t u r e c y c l c . F i g u r e 2 shows the f l n n i u n b i l i t y CuL-ves. The b u t e n e c o n c e n t r a t i o n i s w e l l below t l r c los,,,er flanmahility l i r , , i t .

Changes i n i n p u t s f.or T a b l e 2 and re f1cc te : l in F i g u r e s 3 2nd 4 a r c : (1) i: hold t e n p e r a t u r c of 1 5 5 ' C , w h i c h i s 2 0 ' C l e s s t h z n s e t p o i n t t empcraLurc b u t :?:ill v i t h i i : t h e GSl? 1iwit.s; ( 2 ) f - r n a c c p u r y e f l o w rates a t 5% less thnn p S 0 1it:iits; z;:? (3) the o f f - a % s flo:; r a t e of 90 s c f h , which is 2 5 % lcss t i ian O S D l i r , i t s . FigurL: 3 $;:,x:*; c?. ;,::rL of t h e b u t e n e i s g c n e r a t e c l a t rl t e n p e r a t u r c o f irbout 1 5 0 ' C an? d i s s i p a t e d s l .oc / ly d u r i n g t h e h o l ~ d ti??. '??.c r r i~:?e:- i s g c n e r ? t e d at t h e time of L L l i i . scco:rd L-ar?? UCI. F:o:\'f~er, a:; c a n b e seen i n F i z u t - e .: t h e c o n c e n t r a t i o n l e v e l b f t!le hi9hest ~ c r ; : i s xtich i e s s t h z n t h e lower f l a m m a b i l i t y l i m i t . These r e s u l t s i n d i c a t e t h a t t b . e czz-bon d i o x i d e p u r g e f low n e e d s t o c o n t i n u e f o r a t l e a s t l c , O m i n u t e s 'io co:.pensate f o r t h i s d e v i a t i o n .

F i g u r e s 5 and 6 r e f l e c t t h e i n p u t c h a n c ; e s , a s fo l lo ' d s : (1) t h e h o l d t e m p e r a t u r e of 1 9 5 ' C , which i s 2 0 ' C g r e a t e r t h a n s e t c o i n t t e m p e r a t u r e , b u t s t i l l w i t h i n t h e OSD l i m i t s ; ( 2 ) t h e f u r n a c e purge r a t e a t 5% l e s s t h a n 0513 l i m i t s : and ( 3 ) t h e o f f - g a s flow r a t e of 90 s c f h , which is 2 5 % less t h a n O S D l i m i t s . T h e b u t e n e peak for t h e s e con+.Ltior,s r e a c h e s i ts h i g h e s t c o n c e n t r a t i o n a t t h e s e t p o i n t ( S e e F i g u r e 5 ) . T h i s is t h e p o i n t mos t l i k e l y t o have a n o v e r s h o o t s o t h e upper d e y i a t i o n l i m i t s h o u l d n o t e x c e e d t h i s t e m p e r a t u r e . T h e h i g h e s t b c t e n e c o n c e n t r a t i o n ( a s shown i n F i g u r e 6 ) is a b o u t 755; of t h e f l a r r a b l e l i m i t . T h i s c o n c e n t r a t i o n is a c c e p t a b l e d u e t o t h e f o u r o t h e r c o n s e r v a t i v e i n p u t s u s e d i n t h e c a l c u l a t i o n s .

T e m p e r a t u r e o v e r - s h o o t s of 3 t o 13 d e g r e e s were obse rved i n t h e i n i t i a l f u r n a c e t es t s . T h e r e f o r e , a h o l d t e m p e r a t u r e of 2 0 'C l e s s t h a n t h e u p p e r d e v i a t i o n band w i l l b e s e t t o a l lo i , f o r o v e r s h o o t w i t h o u t a c t i v a t i n g t h e f u r n a c e shu tdovn i n t e r l o c k .

15

http://generati.cn

H~N'F: -S D-CP-OC D-0 4 0 REV. -3

B A S I S DOCU13ENT FOR SLUDGE STABILIZATION

B A S I S DOCUMENT FOR SLUDGE S T A E I L I Z A T I O M ATTACHMENT A

Page A-2 Of A - 1 1

Calculations to show the lo:.ier flammability limit for butene compared to normal operating conditions.

Butene is generated at 0.658 mol/hr (Table $1. Row 9, Colunns 1 and 2 )

Offgas flow rate is 1 3 9 . 0 0 6 mnl/hr (Table $1, Last Row, Columns 1 and 2)

0.646 m ol/hr butene = 0 /0046 x 100 = 0.46% butene 139.006 mol/hr offgas total o f f g a s

For conservatism, calculations were made for a double batch, with the amount of TDP (20 grams) Scc T a b l e #l, Rov 1, Columns 3 a n d 4 .

Kormal operations will process a charge of 500 grams with a naximum of 2 % TBP which equals 10 grams TRP. The percent butene is divided by 2 .

0.$6 = 0.23% 2

The ~ O W S L - fla::,xztii?ity 1ini.t. 2 : ? 5 ' C ;is rhu'vn in Ficjurf 2 is from Figure 6 0 on page 54 of Fi::.23'-1 of X i n c s Bulletin 6 2 7 , "Flammability Characteristics of Combustible Gases and ; 'i?pors", ? , I . G. Zabetakis, 1965.

,._, i n e ;.u'+.er. ilanaability linit a t 250'C is calculated by using the temperature correction cyati.on on page C-67 of A I C h E Today Series, "Fundamentals o f Fire ard Er.plo3ion i l aza rds Evaluation", C. Grclecki, 1 9 7 6 .

L, / h1 = 1 - 0.000721 (t - 25) where

L, LZr = lower limit of gas mixture at 25'C t = temperature of interest

= lower limit of gas mixture at temperature of interest

Lz5 = 1 - 0.000721 (250 - 2 5 ) (2)

LZ5 = 1.675

The percent of butene which could be generated at normal conditions as compared to the lower flanmability limit at 2 5 0 ' C .is as follows:

0.23 = 0.1373 x 100 i3.73% 1.675

16

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~ ~ - S D - C P - O C D - O ~ O R E V . 3


ATTACKHENT B TEST PERFORHED BY PLUTONIUM PROCESS SUPPORT LABORATORIES 1994

26

a r -

c

fi’t -S D - C P -0CD- 0 4 0 REV. 5

BASIS D O C W E I I r FOR SLUDGE STABILIZATION

ATTACKMENT C INTERNAL WEHO (15530-94-DMB-070) “D. H. BERSKhW TO W. S . LEWIS, “PRE5S12’?..:” DROP ANALYSIS FOR F I L T E R ON 26 IN VACUUH LINE IN GLOVE fi3:X HC-ZTC”

35

Westinghouse Internal Hanford Company Memo

BASIS OOCUMENT FOR SLUDGE STAB[LIZATION REV. 0 From: PFP P r o c e s s Engineering 15jjS-S4-OM3.070 Phone: 373-5092 T 5 - 5 5 Date: June 1. 1994 Subject: PRESSURE OROP A N A L Y S I S F3fi F I L T E R ON 26 I N C H VACUU.'I LI:,E IN C L O V E

BOX HC-ZlC

_ _ _ _ To: W . S. Lewis I:-::

._ .- c c : , L. Oayley I > - > : N. W . Gibson%k i S - ! 5 131.18 File/tB

( I ) C R A I I E Co. F l o w o f Fluids : : u t . h l v e s . Fittincs. and Pice. Technical P a o c r No. 410.- Crane C G . i : icc; G! Prussia, P A . 19%.

(2) Rockw?ll Hanford Dperat ic:.;, F:!~-+GJ i u m Fini5hir.q Plant Safe:, Analvsis fieport (SO-HS-SAR-0071. f :q~"- 5. : ! thr-ough 5 - 2 6 . 1987.

This neno documents a n a n a l y s i s o f C i ' , ? 25'' vacui;m line and f i l t i . - ir g l o ? ? box t ! C . Z ! C . A t:ir:iI?c-, flo,,r I' c i .' ~C'J throlqh : h z V?CI:U: i i r , ~ d u r i r , g s l u d q e s t d S i 1 i z d t i o r i i s ~:Ec+: :; ti . : : ! s u r 2 ti?? g l o v ? t a x is p r c ; r r l y -ientsd. A diffet-entia1 press; : r - . q : I.? ibis b:?,i in::alled zc1-08: :n? 2 6 ' ' ,,>:NJ:::I 1 i:)? f i l t e r . Thz nor, ; ~.:-:;s ';: .i c:-c; ;crass t 7 . s cet'2t~ic F i l t e r - is I p s i . I t i s expec t : , : L i d : ... i t h U S E t h e prEsscr-i IIX; : : ~ . G S S :hz f i i t c i ' :.ri!i i n i t . c z S e , t h v r reL!::in,- ..I th:.cc?h t h ? line. f y izzroximating hovi much vacuum is rlecessary :: YJ m y be established to c e t t r .-: filter s h c u i d b e c h > r , q i r 3ut.

Fnalysis of this system ir.d ..:tuum requirsd f o r 2 i cf- Closi througi: t h e vacuum line is !5 in. f ig) . Eo,,iever, t h i r analysis 6 3 e s not talce i n t o account ti;? ; r ? : s - ' . ? d r o p for ali t h e pipins f -x th+ glove box t o the 26" vacuulil ~u:rr ; 3 : . ! ~ d in building 2 9 1 - 2 . i k i - e f o r e a safe operaticg linit for the c":.:s:," , : ' . G ~ I a c r o s s the filter VIO,J'L be in the 8-10 psi (16-20 in. Hg) r a n $ € .

In order t o calculate t h e presr:!re .:-:a a flow rate o f 2 c f m (12; cfh). observed 5 ft. f r o m the end o f 3 I/?'' 5 . 5 . pipe, w a s plugged intc a version of the Bernoulli equation f o r c m p t . ? : s l b l e fluid f l c w i n pipe. i!? ideal g a s law and a temperature o f 7 6 ' ; 'b?:-? Lsed to determine the denrity o f a i r under a 26" vacuum. Correctio? fat::;.: f o r the conpressibility cf air u?r.?

. L.,: ,. . imitii?iux flq:., r;:c, 2 ;:.idel

. .. . . ....

36 . , .

CTTACHXEN? Q. PA5E L - 2 o f 5 5

B A S I S DOCUHENT FOR SLULIGE S T A B I L I Z A T I O N R E V . 3 u. S . Lewis (+fi?< -SD-CP-0C0-040 . 1 S 53C. 9 4 -DM8 -07 0 Page 2 June 1, 1994

f o u n d in t h e Crane b l a n u a l . f l o w equat ion and then were r e f i r , e i a f t e r sever21 iterations.

Any q u e s t i o n s concerning. t h i s a : ~ l ; s i 8 nay b e addressed t o Owayn? E e r s h a w r t

Th?:@ factcrs w e r e approximated t o sc lve t h a

373-5092 ( T 5 - 5 5 ) .

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C 5 E

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, , . , -. . .. . ., _ . _ _. I. . . . . . . . .. .

. . ATTACJ'UENT E-

PfiGE LI-3 O f a-5 BASIS OOCUMENT FOR.SLUDGE STABILIZATION R E V . 3

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B A S I S DOCUMENT FOR SLUDGE STABILIZATION

ATTACKnENT D NASS BALANCE

4 1

A T i A C t l r i i t I T PAGE E-1 o f b7

BASIS OO$UEliNT F O R SLUDGE STABILIZATIOM VfiT40-CF-OCG-040 R E V . 3

HC-21 C Material Balaoce

rCiTfiCB:.!E:IT PACE 5 2 O F 87

B A S I S OOCU'lEiIT FCR SLUDGE S T A B l $ I Z A T I O N ~ ~ f - s o - c ? - o c o - o 4 o REV.

Feed 1 (Pu Oxalate)

heat PuOC03 * 2 H 2 0 - - - > PuO2 + 2 H20 (4: + CO2 (9)

95% "03 driven off as acid

"03 - - - - --- - > " 0 3 (9)

5% Reacts as follows:

2 " 0 3 - - - - - - - > H20 (9) + NO (Q) + K 3 2 (9) + 0 2 (9)

Feed 2 (PRF Siadge)

i T T A C H N E P I T D PAGE 8 3 o f 8-7

E4515 O O C U M i l i T FOR SLUOtE STABILIZATION ldf -SO-CP-OCD-040 R E V ,

(C4H90)3PO + Heat - - -

H4P207 -k Heat - - - > 2 H20 (9) + P205 (9)

2 Fe(N03)3 * 2H20 - --- Fe203 + 4 H i 1 0 3

3 C4H8 (9) + 112 H 4 0 2 0 7 + 1/2 H20 (9)

NO (3 ) f NO2 (9) + 0 2 (g)

P ~ ( N 0 3 ) 4 ” H 2 0 - - - - > 2 “03 + NO (3 ) + 1102 (9) + PuOZ + 0 2 (9)

954’. ”03 driven off as acid

W N 0 3 - - - - - - - - > HN03(g)

5% Reacts as follows:

2 “03 - --- - - > H2O (9) + NO (9) + NO2 ( 3 ) -C 02 (9)

Charge Size (grams) 500

YY

B€ST AVAILASLE COPY

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B A S I S DOCUMENT FOR SLUDGE S T A B I L I Z A T I O N REV ... ?

ATTACMENT E REACTIVE 1HCINI:RATOR ASH OFF GAS FLOW RATE CALCULATIONS

4 9

. .;J ,.. .:+ fldf-50 - L P - ~ C D - 8 y z R a j j I ;,

Westinghouse Internal Hanford Company Memo

From: PFP Process E n g i n e e r i i j Phone: 373-3685 T5-55

15530-95-LTC-039

bate;. May IO, 1995 Subject: A I R FLOW REqUIREIIEEITS F O R STABILIZATION OF P.OCKY F L C i S ASH

To : I.I.S. Lewis i 5 - 5 5

c c : H . W . Gibson i 5 - 5 5

The purpose o f t h i s ~ S , - J i : t o p r e s e n t t h e r e s u l t s o f c a l c u l a t i o n s f o r d e t e r m i n i n g t h e a i r f l o w r e q u i r e d t h r o u g h t h e HC-21C m u f f l e f u r n z c e s when s t a b i l i z i n g Rocky F l a t s A s h . The a i r f l o w n u s t be g i - e a t e n o u g h t o p r o v i d e s u f f i c i e n t o x y g e n t o o x i d i z e tk; r?rbs:i i n t h e a s h .

O b s e r v a t i o n s f m n J ? , ' dc:,? t;. t h e PFSL w i t h grz- , t2 lz r a c t i v a t e d c a r b o n ir.d LL' t h a t s m i n i m a r e a c t i o n t i m o f 1.9 h o u r s i s r e q u i r e 1 o x i d i z e a carbon c h a r g ? . T h i s tims was u s e d t o p e r f o h il: i r c i n i n g c a l c u l a t i o n s ..

As s e e n i n Attach:xr:: ! , c a l c u l a t i o n s show t h a t an Zir flo;g o f 0 .679 scFn i s r e q ' - i : . d ti? o x i d i z e 2 c h a r g e o f SO3 grams w i t h 37% c a r b o n t o ci;.t>::n d i o x i d e (CO,).

F o r m a t i o n o f i a r b o r i r j r l > x i d r ( C O ) due t o d e f i c i e r , t s u p p l y o f osyce-:) is ufic!?sirdblk I i nce C O c o n c e n t r a t i o n s of 1 2 . 5 % t o 7C.7.:: ?.)-e f l a m z b l e . I , ~ a l : i a t i o n o f tb,e P P S I anal:;s;s d o e s r i o t shoi i f o r m a t i o n o f PI w i t h zn a i r flak/ o f 20 c c / n i n . T h i s i s e q u i v a l e n t t.? s i r f l o ' d o f 1 s c f n t h r o u s h t h e m u f f l e f u r n a c e s i r i !!:-: :C u s i n 3 t h e c a r b o n m a s s t:. a i r - r a t i o u s e d f o r t h e TGA a:. ,?;, . ; s .

Even i f t h e ca rbon i i ' c cti-ii.g? + , e re t o f o r m e x c l c s i v e l y C O , t h e a i r f low c a n b? lc ' . t o ensure the CO c o n c e n t r z t i o n i s b e l o w t h e low.?? f l a x z k i l i t y l i m i t o f 1 2 . 5 % . An Z i r f l o w o f 0 . 8 6 scfn w a s found 1 9 r i a i r i t a in t h e CO leve l belo,! the L F L .

T h e r e f o r e , an a i r f low o f 1 scfm i s s u f f i c i e n t f o r c h a r g e s o f Rocky F l a t s Ash. T l i s C1o:r r a t e i s a d e q u a t e t o o x i d i z e t h e c a r b o n t o CO, a n d 2 1 8 0 ensures t h a t CO c o n c e n t r z t i o n s w i l l remain below t h ? i F L f o r CO of 12.5%.

L . T. C u n n h g h a m PFP Process Engineet

a t t

kt.ti.ch,z:.eni 1

Carbon f lonoxidc G e n e r a t i o n C a c u l a t i o n s

Page 1 o f 2

Assumptions: - Charge w e i g h t i s 5 5 9 g r a n r b u l k we igh t - Elaxirnum c a r b o n ct.n:ent i s 37% ( a v e r a g e i s 2 ~ ) - Carbon h o n o g e n i o : . ; 1 j n i x e d t h roughou t cha rge - Oxygen d i f f u s i o : i r . t o c h a r s e i s s u f f i c i e n t t o m a i n t a i n

c a r b o n o x i d a t i o r l 3 : m a x i c a m r a t e - E f f i c i e n c y o f ~ : . : , g t n u t i l i z a t i o n i s 75'4 - S t a n d a r d Tenpera :u . e a n d ? r e s s u r e

1 . C a l c u a t e t he r a t e a t which t:ar-bon v i11 oxidize.

=> Used the TGA run o f g r j . c . , z r >c t i : . a ted carbon (GAC) d o n 2 in t h e PFSC l a b o r t t o r y . TG.? 1' :I :i@ii.: h i t h 130.8 ng GAC and from 2 O ' C t o 1ooo'C a t 5'Cjnin.

* Find t h e g r e z t e s t s l o p e i i ' . r ,? TG c u r v e .

D a t a p o i n t s : 10% w e i g h t 1 0 5 , :.I 5SO'C and 24% weight l o s s a t 670'C

100% 1 - u-- 0a.c- * IOO'L 1 = 116 n i n d (Weigh t L o s s ) 5 'C/rn i r ! , : ' : X i : ? igh t l o s s [ 5'C/nin

* dT

2 . Calculate t h e m o u n t O F c a r - . g - t i n a c h a r g e .

-> The m a x i m u m c a r b o n ccii: .r, ~ i r i t i , ? Rocky F l a t s Ash i s 3 7 % . Thc a v e r a g e c a r b o n c o n t e n t 5 .?211. Charge s i z e i s curren:ly l i n i t e d t o 500 g r a m s .

I . ! ~ X ~ C ; U , > . c a ~ t s n ir, cb?::

500 q * 0 . 3 7 g C/g m a t c r i ; ' ~ - !S5 :I c a r b o n o r 15 .417 g - m i e s

,? , ;~I- ,?T? c a r b o n ir, ci.?:-ai-:

500 g * 0 . 2 2 9 C / g r ,a te r i? l 7. 110 9 r a v b o n o r 9 . 1 6 7 9 -no lc s

c a r b o n d i o x i d e .

=> =; =;

Oxvqen n e e d e d :

-

3 . C a l c u l a t e t h e f l o w r a t e G F ::i n c c ~ ~ ! ~ i t o o x i d i z e carbon c c n p l e t i y t o

R e a c t i o n : C + 0, - - 3 CC, Assume e f f i c i e n c y of 0, 3:: a s 75:; 0, u s e d p roduces an ~ q l . ! . ~ i , ;olune o f CO,

1 5 . 4 1 7 q -moles C I 1 q - m l c Q , = 20.556 9-moles 0, 1 1 9 - n o l c c

A i r n e e d e d :

2 0 . 5 5 6 q-moles 0, a i r I 100 a-mo'les a i r 7 7 . 4 3 f t3 a i r I 2 1 g-moles 0,

/------- -7 7 77.43 ft' a i r = 40.76 ft'!? 3 0.679 scfrn , , 1 . 9 h o u r s --.

.. . --_ ~.~

.. . .

Carbon Manoxid; S e n e r a t i o n Caculations

4 . C a l c u l a t e the a i r ' f l o w r ? t e :- m a i n t a i n t he CO level below the L F L i f o n l y CO i s p r a d u c e d .

-5 R e a c t i o n : 2C + 0 --i 2': 1

->

Oxvqen needed t o make C O :

=> L F L o f co i s 12.5% 0, u s e d produces t w i c e t i ; volurie o f CO

J5.417 s -moles C t 1 a - w i e L ? I = 10.278 g-moles 0, 1 2 g - z o l e c I . 7 5

Air needed t o a r o d u c e C O :

1 0 . 2 7 8 q-moles 0,- 2 2 . 4 l i c2 .21e a i r 1 100 q-moles a i r = 3 8 . 7 2 f t ' a i r l m - / i L ' I 21 g-moles 0,

3 8 . 7 2 f t 3 a i r = 20.38 f t ' / h r = 0.3;O s c f n 1 . 9 hours

Carbon Monoxide oroduced.;

1 5 . 4 1 7 a-r,oles C 1 I C I - Z ~ ] : . ~ ~ ~ ~ . ' ~ l / s - n ; o l c a i r = 6.4? f t s / h r CO 1 . 9 h o u r s I 1 9 - 7 ~ 1 . - : 1 2 8 . 3 1 6 l / f t '

Air f low r a t e needed tq_i.:,~i. J . ; x & J _ c o n c e n t r a t i o n b c l o w l i . 5 X : '.

m N

\

.. , . . . . . . . . . - - . . . . . . .

54 . , . .

h'rl" / -SD-CP-OCD-040 REV. 3


ATTACHMENT F PROCESS TEST REPORT: BURNING PLUTONIUM METAL BUTTONS USING AN IGNITER

S5-

__ _- -.-

SUPPORTING DOCUkiENT

P R O G R A M . CHEMICAL PROCESSING -

~ Document Titla: I i PROCESS TEST REPORT: Burning Plutonium Metal i Buttons Using An Igni ter

. . ..

P e v . Chp. L f r J NO. Fap: A riumoar

0 1 7 SD- CP-FTK-008 Tola1 Page,

I

I

Baseline Document C l e v ;8 N o

! WWS W O . 0, W o r k Packaga h O .

Four ( 4 ) process t e s t s were performed in Glovebox

[tie f i r s t t h ree process t e s t s involved i g n i t i o n i r d Hoskins cr i ic ible furnace . Because o f poor' d i r ' supply t o the burning oxide and the awkward haricll i n y o f h o t c ruc ib l e s u s i n g t o n s s , imzrovenwnt in s a f e t y and opera t ing time were needed. a l t e r n a t i v e prccessing method, a button i g n i t e r , w a i Fabricated fo r the four th process t e s t . The i g n i t e r eras designed t o s i t on the button sur face and supply s u f f i c i e n t heat to i n i t i a t e oxidat ion. Besides reducing processing time f roni approximate! 9 hours t o approximately 2 hours, no t r a n s f e r r i n g of hot a u t e r i a l was necessary.

An

* P . . J . Brown * / 5 . I?. Davis

I

2 3 4- 5 Z) 2!~1 27 36 -28; 2!1

234-52/2!.1 231 -2/21d

23a-5Zjz!~i 2 34 - 5 Z/ 21.4 2 3a - 5 Z,' 21.1

j I i j

The procedure a n d equipment out l ined in the fourth/ process t e s t . PTP-Z-995-0004, "Oxidation Process" w i l l be used a s a b a s i s f o r f u t u r e plutOniUm oxidat ion orocessing i n Glovebox IC-21-C.

/

Rockwell Hanford Operations Number

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T A B L E OF C O N T E N T S

I N T R 0 0 U C T I O N

D E S C R I P T I O N OF T E S T

T E S T M E T H O D A N D T E S T E Q U I P M E N T

T E S T R E S U L T S

R E C O M M E N D A T 1 0 NS/C 0 N C L US10 NS

R E F E R E N C E S

A P P E N O I X A

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Rockwell Hanford Operations SUPPORTING DOCUMENT

Number IRev. Ltr.lChp. No. P a y e -

1.0 INTR 0 0 U CTIO N

- SD- CP-PTR-008 i 0

Four (4) process tests were performed to determine the safest and most efficient method of oxidizing plutonium metal. T h e third process test was also run t o verify P u but ton calorimetry results for Nuclear Material Inventory Control ( N MIC) . The tests were established by Z-U-T-S Process Engineering and performed by Plutonium Operations in Glovebox H A-21-1. The process tests PTP-Z-995-0004, Rev. 0 - 2, were performed on July 7, 1985, July 18, 1985, July 19, 1985 and August 27, 1985 on buttons 0 26-45-06-384, -426, -425, and -401, respectively.

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SO- CP-PTR-008 I 0 SUPPORTING DOCUMENT

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DESCRIPTION OF TEST

Plutonium (Pu) me ta l oxidat ion i s accomplished b y contact ing a heat source t o t h e metal, which raises t h e surface tempera ture o f t h e bu t ton t o approx imate ly 550OC. A t t h i s temperature, ign i t ion occurs and in i t ia tes the ox idat ion o f Pu meta l t o Pu oxide.

A series o f f o u r (4) tests, total , ?*ere per fo rmed t o evaluate processing t i m e and ease o f operation. The processing detai ls f o r each t e s t are described below.

2.1 F i r s t Test

The first tes t examined but ton ign i t ion and oxidat ion o f Pu n e t a l i n a cruc ib le furnace. Besides successful oxidat ion o f the plutonium m eta1 i n a cruc ib le furnace, t he processing t ime, ign i t ion tem perature, and cool ing times, associated w i th th is apparatus 'was a question answered by th is process test.

2.2 Second Test

The second tes t was an a t tempt t o i gn i te the plutonium meta l but ton using a soldering i r o n as an a l ternat ive heat source t o t h e crucible furnace. The but ton was placed in a 6" x 6" x 1" burning pan and the soldering it-aa b - i d c? t h ? but ton surface. C! hei t he sglderir;> i ron fa i led t o i gn i te the plutonium metal, t he but ton was placed i n t h e cruc ib le furnace, heated t o igni t ion, and t ransferred t o the burning pan t o comolete conversion t o the oxide form.

2.3 Thi rd Test

Ver i f icat ion o f N M I C ca lo r imet ry resul ts and increasing the a i r supply t o the burning plutonium meta l were t h e object o f th is process test . The bu t ton ign i t ion was accomplished i n t h e crucible furnace and then t ransferred t o the 6" x 6" x 1" burning pan t o oxidize. A f t e r about 30 minutes the burning meta l was t ransferred t o an 11" x 11" x 1-1/2" Dan which was being tested t o see if processing t i m e could be reduced. When su f f i c ien t t i m e was al lowed t o complete cool ing o f ths oxide product, it was transferred t o packaging cans.

Number /Rev . Ltr./Chg. NO. SUPPORTING DOCUMENT

2.4 Four th Test

Page

An addi t ional heat source, an i g n i t e r designed and fabr ica ted f o r th is process test, i n i t i a t e d oxidat ion o f t h e plutonium bu t ton without t h e use o f a Hoskin furnace. The bu t ton was placed i n an 11" x 11" x 1-1/2" burning pan and t h e i g n i t e r rested on t h e button surface supplying enough heat through a c i rcu lar shaped element t o i n i t i a t e oxidation. The plutonium oxide product, once fo rmed i n t h e pan, was al lowed t o cool and then packaged. A s w i th t h e other tests, c r i t e r i a such as t o t a l processing t i m e and ease of operation were considered.

In addition, heat dissipation f rom the burning button was measured using heat crayons. The results o f these observations w i l l be discussed i n the " tes t results" section o f th is docum ment.

.

Number iRw. Ltr./Chg. NO.

SD- CP-PTR-008 0 SUPPORTING DOCUMENT Page

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3.0 TEST M E T H O D A N D T E S T E Q U I P M E N T

All four (4) process tests involved plutonium metal oxidation in Glovebox HA-21-1. T h e followning summarizes equipment used in each test.

Test 1

Furnace (Hoskins model

Crucible

8.8. sheathed chrom-alumel

F D-104

Electronic balance

Leather gloves

Test 2 Test 3 Test 4

Furnace Furnace Igniter (Hoskins model (Hoskins model (H-2-95860)

Crucible Crucible S.S. stirrer

S.S. sheathed S.S. sheathed Electronic balance

F 0-104 F 0-104

chro m-alu m el chro m -alu m el S.S. l l " x l l " x l - 1 / 2 " pan

Electronic Electronic Leather gloves balance balance

He2.t cravons Soldering iron S.S.

l l "x l l "x l -1 /2" S.S. Pan 6"x6"x1" pan

Leather gloves Leather gloves

*S.S. = Stainless steel

i+dt-sD-cPQ& D -GYP Re.v 3

Roc kwel I H an f o rd Ooera t ions SUPPORTING DOCUMENT

Nuinuer :Rev Ltf . /Chp Na. PW. ,

4.0 TEST RESULTS

- SD- CP-PTR-008 0

Processing t i m e and operator sa fe ty were major c r i t e r i a f o r choosing the most desirable processing method. The resul ts f o r processing t i m e i n te rms o f ignition, burning, and cool ing t imes are summarized i n F igure 1. A s ign i f icant decrease i n processing t i m e between t h e first and fou r th run i s i l l us t ra ted by t h e drop f rom 8.75 hours t o 2.25 hours. This i s a decrease o f 74%, which t ranslates t o a 200% - 300% increase i n processing capabil ity. For Runs 1, 2, and 3, t he use o f t he fu rnace increased ign i t ion t i m e because o f o f poor a i r supply t o t h e metal. In Run 1, since t h e conversion o f Pu meta l t o oxide was per formed comple te ly in t h e cruc ib le furnace, the a i r supply problem was even more evident b y t h e drast ic increase i n react ion t ime. For tests 2 and 3, t ransferr ing Pu meta l and oxide i n a ho t crucible was awkward and ign i t ion t i m e took longer because of a i r supp ly problems. F o r these reasons, Process Tests 2 and 3 took longer than the fou r th process test.

6

In te rms o f sa fe ty and ease o f operation, Process Test 4 was the best processing al ternat ive. The resul ts are presented i n tabular f o rm on Table 1. I n sum mary, Run 4 was the safest and easiest process tes t t o perform because the ign i ter , instead o f t he crucible, was the heat source. There was no t ransferr ing o f thermal ly hot material, no awkward and heavy crucible handling and no a i r c i rcu la t ion problems around the burning Pu m e t a l . The f i ;t t.::? $v:.s t h e next best al ternat ive, since a l l t ransfers were made while the plutonium was cool. The worst a l ternat ives were Runs 2 and 3. Because o f operat ing d i f f i cu l t ies and transferrance o f ho t plutonium metal, these t w o operat ing schemes were considered poor choices.

Using the heat crayons during Process Test 4 revealed no heat dissipation problems around o r above the burning pan. Temperatures close t o normal were observed because o f good a i r c i rculat ion. However, t h e area o f con tac t below the pan, which sa t d i rec t l y on t h e glovebox f loor , became qui te hot, reaching approximately 400OC. Because o f th is finding, a change i n the burning pan design was incorporated which added 1” legs. The in t roduct ion o f an insulat ing layer o f a i r between the pan and glovebox should prevent fu tu re h o t spots on the glovebox.

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Rockwell Hanford Operations Number / R e v . Ltr.lChg No.

SO- CP-PTR-008 I 0 SUPPORTING DOCUMENT Page

9

5.0 R E C 0 M M E N D AT10 N S / C 0 NCLUSIO N S

I n t e r m s o f safety, ease o f operation, and processing t ime, using the i gn i te r t o i n i t i a t e burning was the optimum al ternat ive. The cruc ib le furnace made t ransfers o f p lutonium metal, o r oxide, a problem and lengthened processing t ime. This was due t o t h e awkward handling o f t h e cruc ib le with tongs and t o t h e poor a i r supply available t o the burning meta l i n t h e crucible. Using the furnace alone, as i n the first process test, t h e operat ion was both safe and easy t o perform, b u t t he processing t i m e was too long and therefore unacceptable.

The second and t h i r d process tests were acceptable i n te rms o f processing t ime, bu t were considered nei ther safe n o r easy t o perform.

Since the f o u r t h process test, which evaluated the igni ter , m e t al l the c r i t e r i a deemed essential f o r but ton burning, t he process t e s t procedure PTP-Z-995-0004, "0 xidat ion Process" w i l l be t h e basis f o r f u tu re plutonium oxidat ion processing i n Glovebox H C-21-C. The operat ing procedure which w i l l provide inst ruct ions f o r processing is: 20-160-033, Rev 3.

A s f o r h e a t dissipatioii, continued i,i o r , i x r i n g o f t t jc c?;ra:i>n i s pl2nned. I n i t i a l operat ion w i l l invo lve t w o (2) but tons burning simultaneously i n H C-21-C. With the avai lab i l i ty o f addi t ional heat sources and increased operator f a m i l i a r i t y w i th the but ton burning process, Z-Plant Process Engineering can approve simultaneous ign i t ion o f up t o f o u r (4) buttons.

Numb., Rev. Ur.lChg. No. SUPPORTING OOCUMENT SD- cp-PTR-008 0

6.0 R E F E R E N C E S

Papi

10

Process Test Plans

PTP-Z-995-0004, Rev. 0 - Rev. 2, "Oxidation Process''

Operatinq Procedure

20-160-033, Rev. A-0, "Oxide P u Metal in Glovebox H C - 2 1 - C "

Process Specification

OS D-A -184-00005, "Miscellaneous Treatment"

Drawinqs

H-2-95660, Button Igniter Assembly

Rockwell Hanford Operations 1Nurnb.r IRsv. Lcr.lCho. No. I P a w

SD-CP-PTR-008 I I 0 SUPPORTING DOCUMENT 11

I A P P E N O I X A

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Rockwell Hanford Operations Number

DOCUMENT so-CP-PTR-008

Rrv. Llr lChg NO. Page

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OXIDATION PROCESS T E S T D A T A SHEETS

D Z A-45-06-384 (07-09-85)

1. Weight of button/%240: content: 2064.3

2. Time of starting furnace: 1 0 5 0 a m

3. Time oxidation begins: 11:25 am

4. Temperature oxidation begins: 5 5 0 O C

5. Time oxidation is complete: 5:45 pm

6. Time furnace i s cooled to 5 0 O C : 6:45 pm

7.

8. Gross weight of can(s): 1432.4 - 1172.0 grams

5. i ie: wsight (8-7) : 1344.7 - 1078.0 y a m s w t . gain: 359.4 grams

10.

11.

Tare weight o f slip lid can(s): 87.7 - 94.0 grams

Estimated plutonium value t o can(s): (0.88 x net w t . (9.))

Pleasured P u value (calcrimeter/N D A I A )

2132 grams

N O T E S : o Once oxidation started, the metal burned slow due to lack of oxygen.

o Material stuck t o the sides of pot crucible; operators had t o reheat crucible to clean o u t remaining metal

Metal would arc when temperature reached 2ZOOC o

N"rnI?W

SD- CP-PTR-008 SUPPORTING DOCUMENT

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Rev. Ltf.lChg. No. Page

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O X I D A T I O N P R O C E S S T E S T D A T A S H E E T

D ZA-45-06-426 (07-18-85)

Weight of button/%240 content:

Time soldering iron turned on:

Time oxidation begins: 10:43 am

Temperature oxidation begins: 575OC

Time oxidation complete: 1:30 pm

Tare weight o f slip lid can(s):

Gross weight o f can(s):

Net weight (8-7):

Estimated plutonium value to can(s):

(0.88 x net weight (9.)) Total: 2122.4 g

Measured P u value (calorimeter/NDAIA)

2054 grams

1O:OO am

88.2 g/91.3 g

1331.1 g/1260.2 g

1242.9 g/1168.9 g

1093.8 g/1028.6 g

f f ~ C 5 P - h ; P - Q C P -040 Rew4

Rockwell Hanford Operations Number /Rev Ltr./ChP. No.

SUPPORTING DOCUMENT CP-PTR-008 0

Page

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O X I D A T I O N P R O C E S S TEST D A T A S H E E T

D ZA-45-06-425 (07-19-85)

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

Weight o f b u t t o n l X 2 4 0 content:

T ime soldering i r o n turned On: furnace t ime: 10:15 am

T ime oxidation begins: 10:55 am

Temperature oxidat ion begins: 5500C

Time oxidat ion i s complete: 1 2 4 5 pm

Tare weight o f s l ip l i d can(s): 128.0 g

Gross weight o f can(s):

Net weight (8-7): 2347.3 g

Estimated plutonium value t o can(s):

(0.88 x ne t weight (9.))

Measured Pu value (calor imeter/N D A I A )

2068.8 grams

2475.3 g

2065.6 g

/ i~-%~--eP-cXJ-J-@o jqaj 3

Rockwell Hanford Operations Number /RN. Lir.iChg. No.

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I 0 SUPPORTING DOCUMENT so- CP-PTR-008

Page

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OXIDATION PROCESS TEST DATA SHEET

D ZA-45-06-401 (08-27-85)

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

Weight of but ton /%240 content:

T ime r i n g heater turned on:

T ime ox idat ion begins: 1200 pm

Temperature ox idat ion begins: 5500C

T ime ox idat ion i s complete: 1 2 5 5 pm

Tare weight of s l ip l i d can(s): 124.5 g

Grass weight o f can(s):

N e t weight (8-7): 2336.5 g

Est imated plutonium value t o cads):

(0.88 x net weight (9.))

Measured Pu value (ca lor imeter /NDAIA)

Heat Crayon Types Melt? (y/nl Time

2037 grams

11:30 am

2461.0 g

2056.12 g

520 C N

1 5 0 O C Y

2 6 0 O C Y

3 7 1 0 C Y

4270C N

1 2 3 0

1 2 3 0

1 2 3 5

1240

1 2 4 5

Locat ion

1’ f r o m pan inside glovebox Under glovebox, under pan Under glovebox, under pan Under glovebox, under pan Under glovebox, under pan

71