ML20137K532
| ML20137K532 | |
| Person / Time | |
|---|---|
| Site: | Trojan File:Portland General Electric icon.png |
| Issue date: | 09/05/1996 |
| From: | Roberts R, Row C SCIENTIFIC ECOLOGY GROUP, INC. |
| To: | |
| Shared Package | |
| ML20137K508 | List: |
| References | |
| SEG-TRJ-PRO-006, SEG-TRJ-PRO-006-R00, SEG-TRJ-PRO-6, SEG-TRJ-PRO-6-R, NUDOCS 9704070050 | |
| Download: ML20137K532 (9) | |
Text
. , _ . . -. - . . _
l i
l l
s i
l
( 1 l
1 l
1 Attachment 3 ,
1 I
Hydrogen Analysis of Residue Protocol SEGffRJ/ PRO-006 !
September 5,1996 i
l l
l l
l 1
I 9704070050 970331 i PDR ADOCK 05000344 P PDR, !
l
-EM
._M. _E_ l l
l l
SEG/TRJ/ PRO-006 l l
l Hydrogen Analysis of Residue !
,,,,1m,o Protocol GENERAL ELECTRIC COMPANY (TRJ-PRD-162) 36m ,.5FPDP Norfl3.26-23-0 nw % SFPQP-o11-97 L. .
$UPPUEEt 00 Cut 4EstT STA40P .
e < F_ilter Media Processing System wk may proceed. SutwnN Sn.f docu-3 *:7 ,d , - Wo,, m., ,,o Trojan Nuclear Plant T "'*""" ~ " * * ""'~ Spent Fuel Pool Debris Project 4 a Hawise .nd reeubmit Wort may riot pro.
w not required. Wort eney proce.d. l 5 o F4 6801w '
-- ~ - DATEOFISSUE
==". c .'f::::r = FEB 111997 5!M, i ", "*.***.,llT.,"l'.".,';l; c- ; . ; sp10, centractual . hag. des,s.
t ~3INFMMATION ONLY ,,a
' ar.o. .o TA'h Scientific Ecology Group,Inc.
['i,,#g$ (3~
1234 Columbia Drive SE Richland, WA 99352
, 3. TA he. A7 xi w =>
Project Quality Project Originator ,Engineel Assurance Managern Date Rev. DCN No.
o -
RDWAL6L onkAL ,Islu
"[f 5FPDP-NGIsl3Afo-A3-0 Page1of8
l i
l SEG/TRJ/ PRO-006, Hydrogen Ana / sis of Residue Protocol @
TABLE OF CONTENTS ,
1 l
Section Page i n .,
i l
1.0 P URPOS E AND SCOPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 l 2.0 RE FERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1 1
1 i
3.0 DE FINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 4.0 RESPONSIBILITIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 5.0 P ROCED URE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.1 Safety P reca u tions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.2 P rereq uisites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.3 An alysis Protocol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.4 Q A/QC Pro tocol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 ,
5.5 An alysis o f Da ta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 6.0 RE C O RD S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 7.0 ENCL OS URES . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 7.1 Temperature Choice for Quartz Furnace Operations . . . . . . . . . . . . . . . . 6 Page 2 of 8
l l
SEGfrRJ/ PRO-006, Hydrogen Analysis of Residue Protocol l.0 PURPOSE AND SCOPE ,
The purpose of this procedure is to provide the necessary procedural steps for the IT Lab l analysis of the dry, steam reformed residue from the Trojan Proof-of- Principle Test.
t The residue created from the steam-reforming of surrogate filter waste (feed ranging from i 2 to 6 lbs) will likely involve about 30 to 100 grams ofpowdered material consisting of a i heterogeneous and anisotropic collection ofinorganic solids, salts, clays, carbon black, l and small amounts ofincompletely processed feed plus 8 lbs of dross. !
This residue remalaing will contain some unknown amount of hydrogenous materials !
where the hydrogen is chemisorbed (i.e. waters of hydration, bound water, mineralized ;
water, etc.), hydrogen chemically bonded in the organics (i.e. plastics, polymers, oils, . ;
. rubbers, and small residual solvents), hydrogen bonded to inorganic salts (NaHSO., j
. Ca(HSO.) , CaOH, etc.), and finally hydrogen in physically adsorbed moisture (mostly j associated with the clays and inorganic salts). j i
There is a minimum acceptable residual amount of hydrogen left in th- final residue that I will, in the actual operation at Trojan, eventually be placed into the can capsule for -
ultimate disposal in a repository. Hydrogen limits for the residue are prescribed in SEGfTRJIR-001, Trojan ProofofPrinciple Test Plan.
i
2.0 REFERENCES
2.1 SEGfTRJIR-001, Trojan ProofofPrinciple Test Plan 2.2 SEGfTRJIPRO-005, TROJANProofofPrinciple Test Procedure 3.0 DEFINITIONS 3.1 Dross; Fine metallic and metallic oxide particles from filing, grinding, or polishing stainless and carbon steel.
3.2 STP: Standard. temperature and pressure 4.0 RESPONSIBILITIES 4.1 IT Analytical Manager: Supervise analyses, oversees QA for laboratory analysis in the form of procedures, blanks, instrument calibration, and sample chain-of-custody.
4.2 IT Quality Assurance Manager: Provides QA for laboratory analysis in the form of procedures, blanks, instrument calibration, and sample chain-of-custody.
4.3 IT Project Engineer: Set up and operate the quartz furnace in an argon purged glove box.
Page 3 of 8
.e e ..
SEG/TRJ/ PRO-006, Hydrogen Analysis of Residue Protocol @@@
4.4 IT Senior Chemist: Prepare residue samples for placing in quartz fumace. Analyze I argon gas exiting quartz fumace for remaining H2 content. l
. 5.0 PROCEDURE 5.1 Safety Precautions Laboratory safety procedures are specified in IT Laboratories safety procedures. l l
5.2 Prerequisites !
5.2.1 IT Corporation's Technology Development Laboratory shall prepare a :
detailed project work plan providing a description of the process, details of l I
the testing procedure, sampling and analysis plan and quality assurance activities. l I
5.3 Analysis Protocol 5.3.1 Testing will be performed at IT's Technology Development Laboratory in-Knoxville, TN. The testing system that will be used will be a heated quartz tube reactor that will hold 5-10 grams of waste char. The tube will be heated by a controlled tube furnace to a temperature of 1100*C. The i tube will be fitted with an argon gas purge and controller on the front end.
The back end or down flow end of the quartz tube will be connected to a ,
gas collection system, such as a Tedlar bag. The flow of purge gas will be low (1-10 ml/ min) to minimize cooling needs and maximize sensitivity, but will be high enough to collect a usable sample within a reasonable reaction time of 4-6 hours. The flow of gas will be recorded and timed to determine the volume of gas used in the test. An ice bath or cooling system may be required between the heated tube and the gas collection system. The quartz reaction tube may also contain quartz or ceramic packing material in the heated zone down-flow from the sample placement zone to increase heat transfer to the effluent gases and ensure reaction.
The entire system will be enclosed in a glove box and operated in an argon gas environment to minimize contamination from atmospheric hydrogen and moisture. All sample handling will also be performed in the glove box. At the conclusion of the reaction time the collected effluent gas will be analyzed by a micro GC/TCD continuous analyzer for hydrogen and water. The total gram-moles of potential hydrogen gas from a sample will be considered the total of the gram-moles of water and hydrogen produced during the test. The gram-moles of the analytes will be determined from the analyzed concentration and the measured volume of gas as well as assuming ideal gas conditions. For each test, the purge gas and the glove box atmosphere will also be sampled and analyzed for hydrogen and water to determine background levels.
Page 4 of 8
.o e..,
SEG/TRJ/ PRO-006, Hydrogen Analysis of Residue Protocol 5.3.2 Calculations based on testing a material containing the maximum allowable hydrogen,0.25 gram-moles of potential elemental hydrogen per amount of material contained in a process can capsule, show that the expected resultant hydrogen concentration in the effluent gas from a test would be 56,000 ppm. These calculations assume a sample loading of 13.6 kg (30 lbs) per process can (i.e. 5 process cans per process can capsule) and that a 90 percent reduction in weight will occur during steam reformation, producing the char to be tested. It is also assumed that 10 grams of the char would be used in the test and that a total of one liter of effluent gas would be collected. The proposed analytical method is capable of determining hydrogen at a level of 10" of the critical hydrogen concentration calculated for the test. The expected analytical detection limit for hydrogen is 5 ppm.
5.3.3 By similar calculations, the critical hydrogen content of a char will be achieved by the presence of 0.41 percent of water in the sample. Even though water should be decomposed to hydrogen during the test, some water may be obtained and will need to be determined to assuie accountability of hydrogen. In addition, background levels of water in the purge gas and glove box will also need to be determined as proposed.
Problems with water determination are not anticipated. The expected analytical detection limit for water is 100 ppm.
5.3.4 The advantages of the described system is its simplicity to measure total hydrogen by thermal decomposition of water, organics and other combined forms of hydrogen to produce hydrogen gas for collection and analysis.
The challenges presented will be in minimizing moisture contamination of the sample in handling and assuring that complete decomposition of organic compounds and other compounds containing combined forms of hydrogen occurs in the tube reactor.
5.3.5 Moisture contamination will be minimized by performing the work in an (argon) atmosphere controlled glove box and will be assessed by analyzing a trip blank of anhydrous sodium or calcium sulfate. The degree of decomposition of compounds containing hydrogen will be maximized by rapid heating of the sample to the reaction temperature and controlling the purge gas flow to begin after the sample has reached temperature. This will minimize loss of water and organics by thermal desorption before the final temperature is attained. The degree of decomposition of organice or accountability for hydrogen will be assessed by analyzing a blank sp%e and a matrix spike of benzoic acid and/or other suitable spike matenal and detennining the recovery of hydrogen.
Page 5 of 8
. v .. . .. .
SEGrrRJ/ PRO-006, Hydrogen Analysis of Residue Protocol 5.4 QA/QC Protocol r
Eight test runs or analyses will be conducted in all:
5.4.1 A system blank run will be performed initially to assure that the system is contaminant controlled to an acceptable level.
5.4.2 Next, a blank spike of benzoic acid or other suitable compound will be run as described above to assure recovery of hydrogen by the analysis system.
5.4.3 Following these tests, a trip blank, as described above will be analyzed to assure control of moisture contamination.
5.4.4 If the system demonstrates itself to be in control, then three samples of surrogate char, provided by SEG, will be run.
5.4.5 A duplicate analysis will be performed on one of the three char samples.
5.4.6 Finally, the sample material will be spiked with benzoic acid or other -
suitable spiking material to assess hydrogen recovery from the sample matrix.
5.5 Analysis of Data 5.5.1 At the conclusion of testing a final report will be completed containing a summary of activities, description ofprocess and procedures used, analytical results, summary of QC activities and results, conclusions and recommendations.
6.0 RECORDS IT Laboratory shall produce data forms to document the data required by this procedure in accordance with IT Laboratory's standard procedures. The completed forms and the final report shall be delivered to SEO and shall become permanent records to be stored in accordance with SEG Procedures, SEG/QA-17.1, Quality Recordt Management, and SEGlQA-17.2, Preparation andStorage ofRecords.
7.0 ENCLOSURES 7.1 Temperature Choice for Quartz Furnace Operations Page 6 of 8
o o . .. ,
1 SEG/TRJ/ PRO-006, Hydrogen Analysis of Residue Protocol N@@@
M GCOLOGv omour. oc l
ENCLOSURE 7.1 Temperature Choice for Quartz Furnace Operations !
To ensure that all hydrogen is removed while samples are processed in the quartz fumace reactor, a study of required temperatures was conducted. There are four sources of hydrogen in a given l waste stream: (1) hydrogen as part of hydrocarbons, (2) hydrogen in waters of hydration, (3) !
hydrogen in inorganics, and (4) hydrogen in moisture. The thermal decompositions of each of these hydrogens can be found in the CRC Handbook of Chemistry & Physics. 75th Edition,1994
- 1. Hydrogen as Part of Hydrocarbons:
Hydrocarbons are made up of hydrogen bonded to carbon atoms. The decomposition temperature of organics varies depending on the volatility of the organics and strength of 1 I
hydrogen-carbon bonds. In the Trojan project the can feed evaporator must get hot enough that i
the organics are volatilized, at which point the gas-phase organics are fed into the steam-reformer main reactor where they are almost completely destroyed. So the critical first step is the volatilization. The CRC Handbook (pp. 3-1 to 3-330) lists known organics compound by number as indicated as follows: Examples of heaviest, stable organics known are fluoranthene (C16H10) with a boiling point of 384*C,5- phenyl-1,l',3',l" terphenyl (#11598 C24H18) with a.
boiling point of 462 C, and 2-naphthalenamine (#7727 C20H15N3) with a boiling point of 471'C. Since the can feed evaporator will operate around 593'C (1100 F), all of the most refractory organics will evaporate e.nd volatilize.
I
- 2. Hydrogen in Waters of Hydration:
The CRC Handbook also lists temperatures at which the waters of hydration are released (pp. 4-36 to 4-114). Two of the strongest bonded compounds are lime which releases its H2 0s at 580 C, and lithium iodide-trihydrate losing its last water at 300*C. ;
- 3. Hydrogen in Inorganics:
Two compounds which require the highest temperatures to release hydrogen from inorganics are NaOH boiling at 1390*C and LiOH decomposing at 980*C (pp. 4-36 to 4-114). Even though NaOH boils above 1100*C, there is enough vapor pressure that the liquid melt will continually evaporate and be carried away in the 1100*C test; besides NaOH is soluble in water and is not expected to occur as crystalline solids in the waste.
- 4. Hydrogen in Moisture:
The hydrogen associated with the water moisture in salts will be released at lower temperatures than the water of hydration for each salt; thus, the above #2 case is more limiting than the presence of moisture.
The quartz fumace is capable of reaching i100*C maximum. Since all forms of hydrogen can be driven off at this temperature,1100*C was chosen as the operating temperature for IT Corporation's Technology Development Laboratory's quartz furnace reactor. For the can feed evaporator, the processing temperature will be limited to 539'C by the stainless steel Page 7 of 8
I o o .. . ,
SEGrrRJ/ PRO-006, Hydrogen Analysis of Residue Protocol @@@
construction materials. Since the Spent Fuel Pool waste is not expected to contain measurable amounts of inorganic hydrogen compounds which require higher than 539'C to drive off the hydrogen, this temperature limitation should be acceptable. The results of the Proof of Principle Test will confirm the choice of the can feed evaporator operating temperature.
Page 8 of 8