Autonomous Gas Chromatograph System for Thermal Enhanced Vapor Extraction System (TEVES) Proof of Concept Demonstration

Transcription

1 OCT O 1998 SANDA REPORT SAND UC-21 Unlmted Release Prnted September 1996 Wg'CEV&() OCT OST a Autonomous Gas Chromatograph System for Thermal Enhanced Vapor Extracton System (TEVES) Proof of Concept Demonstraton Frank J. Peter, George R. Laguna

2 d ssued by Sanda Natonal Laboratores, operated for the Unted States Department of Energy by Sanda Corporaton. NOTCE: Ths report was prepared as a n account of work sponsored by a n agency of the Unted States Government. Nether the Unted States Government nor any agency thereof, nor any of ther employees, nor any of ther contractors, subcontractors, or ther employees, makes any warranty, express or mpled, or assumes any legal lablty or responsblty for the accuracy, completeness, or usefulness of any nformaton, apparatus, product, or process dsclosed, or represents that ts use would not nfrnge prvately owned rghts. Reference heren to any specfc commercal product, process, or servce by trade name, trademark, manufacturer, or otherwse, does not necessarly consttute or mply ts endorsement, recommendaton, or favorng by the Unted States Government, any agency thereof or any of ther contractors or subcontractors. The vews and opnons expressed heren do not necessarly state or reflect those of the Unted States Government, any agency thereof or any of ther contractors. Prnted n the Unted States of Amerca. Ths report has been reproduced drectly from the best avalable copy. Avalable to DOE and DOE contractors from Offce of Scentfc and Techncal nformaton PO Box 62 Oak Rdge, TN Prces avalable from (615) , FTS Avalable to the publc from Natonal Techncal nformaton Servce US Department of Commerce 5285 Port Royal Rd Sprngfeld, VA NTS prce codes Prnted copy: A4 Mcrofche copy: A1

3 S A N D Unlmted Release Prnted September 1996 Dstrbuton Category UC-2 1 Autonomous Gas Chromatograph System for Thermal Enhanced Vapor Extracton System (TEVES) Proof of Concept Demonstraton Frank J. Peter, George R. Laguna Manufacturng Control Subsystems Department 2338 Sanda Natonal Laboratores Albuquerque, NM Abstract An autonomous gas chromatograph system was desgned and bult to support the Thermal Enhanced Vapor Extracton System (TEVES) demonstraton. TEVES s a remedaton demonstraton that seeks to enhance an exstng technology (vacuum extracton) by addng a new technology (sol heatng). A plot scale unt was set up at one of the organc waste dsposal pts at the Sanda Natonal Laboratores Chemcal Waste Landfll (CWL) n Tech Area 111. The responsblty for engneerng a major part of the process nstrumentaton for TEVES belonged to the Manufacturng Control Subsystems Department. The prmary msson of the one-of-knd hardwarehoftware system s to perform on-ste gas samplng and analyss to quantfy a varety of volatle organc compounds (VOCs) from varous sources durng TEVES operatons. The secondary msson s to montor a varety of TEVES process physcal parameters such as extracton manfold temperature, pressure, humdty, and flow rate, and varous subsurface pressures. The system began operaton n September 1994 and was stll n use on follow-on projects when ths report was publshed. 1 _.

4 Table of Contents 1. OVERVEW VEW OF E V E S STE WHAT S EVES? TEVES BLOCKDAGRAM hhnufacturng CONTROL SUBSYSTEMSDEPART~ENT CONTUBVnON TARGETANALYTES QUALTY CONTROLE/EASURES HARDWARE SUBSYSTEMS Vew of Autonomous GC nsde Lab buldng Hardware Subsystem Block Dagram SAMPLETRANSFER LNES Sample Transfer Subsystem Desgn Layout SAMPLER Sample Sources Sampler Desgn Zayout Nafonm Dryer Desgn Layout Sample Loop Volume Sample Rate GASCHROMATOGRAPH Flame onzaton Detector EXTRACTON MANFOLD AND SU~SURFACE PRESSURE N S T R V M E N T... A~ON Extracton Manfold & Subsurface Pressure nstrumentaton COMPUTER AND DATAACQUSTON 2.5. Computer & Data Acquston Hardware Block Dagram Computer Electrcal nterface GASSUPPLES SUMMARY OF OPERATON N AND O NSTALLATON 3.2 UNATENDEDOPERATON TE YES Samplng Schedule CHROMATOGRAPHC METHOD Column Oven TemperatureProfe GCgmflow rates GC Results CALBRATON & VERFCATON LABORATORY CALBRATON FELDVERFCATON RPCAL CALBRATON CHROMATOG RAM... REPORT TCAL CALERATON SOFTWARE SomARE ARCHTECTURE Labvew Vrtualnstruments GC Star WorkstatonApplcaton VsualBasc Applcatons EXCEL Spreadcsheet _

5 DSCLAMER Portons of ths document may be llegble n electronc mage products. mages are produced from the best avalable orgnal document.

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7 5.2 SOFWARE SEQUENCE OF OPERATON SUMMARY DATAFLE TASKFLES DATAFLE AND DATADRECTORY ORGANZATON LESSONS LEARNED. PROPOSED SYSTEM MPROVEMENTS HARDWARE 6.2SOFWARE APPENDX A: SYSTEM NSTALLATON & TURN-ON LGHTNG FLAMEONZATON DETECTOR... computer/electrcal SYSTEM RTRN.ON COMPRESSED GAS SYSTEM RTRN.ON SE'TNG GC FLOW RATES... APPENDX C: COMPRESSED GAS ASSEMBLY DAGRAMS... APPENDX B: GAS SUPPLY HOOKUPS (BACK PANEL OF GC) HYDROGEN ZEROAR CALBRATON GAS HELUM APPENDX D: CALBRATON CALBRATON STANDARDPREPARAnON CALCULATONS CALBRATON TABLE... APPENDX F POWER REQUREMENTS... APPENDX G: ROUTNE MANTENANCE... APPENDX E: CALBRATON STANDARD CERTFCATE OF ANALYSS COMPRESSED GASREPLACEMENT... GASFLTERS... PARTCLE FLTE RS... FD DETECTOR CLEANNG APPENDX : VOC MASS REMOVAL RATE CALCULATONS... APPENDX J: WATER MASS REMOVAL RATE CALCULATONS... APPENDX K:PARTS LST (ARRANGED BY SUBSYSTEM)... APPENDX H MANFOLD AR FLOW RATE CALCULATONS CHROMATOGRAPH SAMPLER... MANFOLD NSTRVMENTA~ON... COMPRESSED GASES& PLVMSNG... COMPUTER & DATAACQUSTON HARDWARE... SAMPLE TRANSFER SVSSYSTEM

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9 1. Overvew t Department 2338 has developed an autonomous gas chromatograph system for Department 6621 to support the Thermal Enhanced Vapor Extracton System (TEVES) experment. The prmary msson of ths one-of-knd hardwarehoftware system s to perform on-ste gas samplng and analyss to quantfy a varety of volatle organc compounds (VOCs) from varous sources durng TEVES operatons. The secondary msson s to montor a varety of "EVES process physcal parameters such as extracton manfold temperature, pressure, humdty, and flow rate, and varous subsuface pressures. The system s located n a portable, temperature-controlled buldng at the chemcal waste landfll n Area 11 and was n contnuous operaton from September 1994 through June Vew of TEVES Ste 1.2 What s TEVES? The Thermal Enhanced Vapor Extracton System (TEVES) s a demonstraton that seeks to enhance an exstng technology (vacuum extracton) by addng a new technology (sol heatng). A plot scale unt was set up at one of the organc waste dsposal pts at the Sanda Natonal Laboratores Chemcal Waste Landfll (CWL) n Tech Area 111. A vacuum blower pulls untreated vapors from the ground va two boreholes nto an extracton manfold. The vapors (contanng ar,a complex mx of volatle organc compounds and water) are dred and then ntroduced nto a catalytc oxdaton (cat-ox) unt whch converts the vapors nto water, carbon doxde, and smple acds. The treated vapors, rendered non-hazardous are vented nto the ambent ar. A more detaled descrpton may be found n: Resource Conservaton and Recovery Act, Research Development, and Demonstraton Permt for Thermal Enhanced Vapor Extracton System. ssued by the New Mexco Envronment Department, Santa Fe, New Mexco, May 26,

10 1.3 TEVES Block Dagram landfll area affected by - heat - - &- vacuum borehole #1.. u_ a extracton & _ 1 : Pre cat-~... condenser r jf ; : ; ; ; :. borehole #2 f sample #1 ; : -b _ G vent to ambent ar b... Autonomous Gas:Chromatograph j System fl responsblty......engneerng... ; ~ + catalytc oxdaton. unt... temperature, pressure, humdty, flow rate subsurface pressure measurements, 12x ~ - moble lab 1.4 Manufacturng Control Subsystems Department Contrbuton The msson of the autonomous GC system s to collect data to help characterze several aspects of the TEVES experment. These nclude: VOC concentratons n the untreated borehole effluent extracton manfold flow rate extracton manfold temperature, pressure, and relatve humdty mass removal rates for a select lst of VOCs mass removal rates for water effcency of the catalytc oxdaton system mass dscharge rates of VOCs nto the ambent ar subsurface pressure profle. 1.5 Target Analytes The gas chromatograph method quantfes the followng compounds wth nomnal detecton lmts rangng from 2 ppm to 1, ppm calbrated, but wth the capablty to extend lower and hgher. 2

11 -Pentane Tetrachloroethylene (PCE) l,l,l-trchloroethane (TCA) Trchloroethylene (TCE) Xylene (-somer) Xylene (m- somer) * Xylene (p- somer) * * m-xylene & p-xylene coelute 1.6 Qualty Control Measures The system s operated n accordance wth the QC/QA requrements descrbed n: Resource Conservaton and Recovery Act, Research Development, and Demonstraton Permtfor Thermal Enhanced Vapor Extracton System. ssued by the New Mexco Envronment Department, Santa Fe, New Mexco, May 26, To ths end the followng were ncorporated: twce daly calbraton verfcaton wth a NST-traceable calbraton gas twce daly zero ar certfcaton to establsh lower detecton lmts perodc measurement of parameters that mpact data qualty (moble lab temperature, gas supply pressures, valve states, sample flow rate). 3

12 2. Hardware Subsystems The autonomous GC system conssts of sx hardware subsystems: sample transfer lnes sampler gas chromatograph extracton manfold nstrumentaton computer and data acquston hardware gas supples Vew of Autonomous GC nsde Lab buldng 4

13 2..1 Hardware Subsystem Block Dagram Gas +- Sampler Chromatograph nnn Sample Transfer Lnes 4 ' Manfold & Subsurface Pressure nstrumentaton Gas Supples TEVES 111 l 1l U U Computer & Data Acquston & Control Hardware t Sample Transfer Lnes The sample transfer lnes (Fgure 2.1) are desgned to delver a small fkacton (4%) of TEVES vapors to the moble lab where the autonomous GC s located. Three TEVES vapor sources are montored: extracton manfold (untreated borehole effluent) pre-cat-ox (dred vapors before catalytc oxdaton treatment) post-cat-ox (vapors after catalytc oxdaton treatment) Each source has t's own ndependent transfer subsystem wth the followng major components: heated TeflonTMtubng PUP partcle flter A tee between the pump and heated lnes s the access pont for the sampler subsystem. The 25 foot long TeflonTMlnes are heated to 1 C to prevent condensaton of VOCs and water vapor. The orentaton of the components prevents condensaton fkom enterng the sampler and frtted flters prevent partculates fkom enterng the sampler subsystem.. The unsampled porton s vented through a charcoal flter to the outsde ar. 5

14 Sample Transfer Subsystem Desgn Layout borehole extracton oxdaton unt borehole #2 6 heated tranfer lne - 3X outsde of moble lab 1/4" teflon, 25 ft long, lopc nomnal, 3x + vent tp outsde au, 3x 4 9Opm flter, 3 x 5-1 to sampler, 3x 2.2 Sampler The sampler (Fgure 2.2) selects the sample source of nterest and condtons the sample for njecton onto the column. The major components are Valco 6 port swtchng valve Nafonmdryer Tylan FC-26 precson mass flow controller rotaryvanearpump 1 cc sample loop 1 port, 2 poston njector valve. The mode of operaton s to nject a repeatable volume of sample usng constant flow rate samplng through a sample loop. The sample loop volume was carefully selected so that no sample dluton or preconcentraton s requred to meet the target detecton lmts for the GC. The sample flow rate was selected to be hgh enough to elmnate errors due to dfson effects whle keepng pressure drops reasonably low. n addton, a volumetrc purge of about 5x s performed between sample changes to mnmze carryover. Because of the extremely hgh relatve humdty of the samples, a Nafonm membrane dryer s used for dryng all samples upstream of the mass flow controller and sample loop. The rotary vane pump contnuously crculates whchever sample source s selected n order to purge the lnes and mnmze carryover between runs. The sample source of nterest s selected by the sx port valve, whch dverts the sample stream through the NafonTMdryer, mass flow controller, then through a 1 cc sample loop. The mass flow controller regulates flow rate at a 6

15 constant, preset level (1 cc/mn) ndependent of source pressure. After a 2 mnute purge tme (a volumetrc purge of 2 tmes), the 1 port valve changes poston, njectng the contents of the sample loop (whle flow rate s held constant) onto the chromatographc column. After sample njecton, the 6 port swtchng valve s reset to poston 1 to purge the sampler wth relatvely clean room ar) Sample Sources There are fve vapor sample sources, three fkom the TEVES ste and two used for qualty control. extracton manfold (untreated borehole effluent) pre-cat-ox (dred vapors before catalytc oxdaton treatment) post-cat-ox (vapors after catalytc oxdaton treatment) NST-traceable calbraton verfcaton standard (to montor GC calbraton stablty) UHP zero ar (to establsh lower detecton lmts) Sampler Desgn Layout Because of the extremely hgh relatve humdty of the samples, a Nafonm membrane dryer s used for dryng all samples upstream of the mass flow controller and sample loop. n the worst case desgn condton, the dryer s desgned to reduce sample dew pont to O C or lower. Although we have attempted by desgn to mnmze the potental for condensaton of water and or VOCs, we have no means for verfjrng that condensaton does not occur.

16 "wet" sample n "wet" ar out 4 NAFON Dryer, Perma we #MD-1&-24S + "dry" sample out 2cc/mn mass flow control ultra zero ar thc <.1 p$m dp<-4 C Sample Loop Volume The sample loop sze (1 cc) was selected so that the concentraton of any of the target analytes n a 1 cc sample would fall wthn our target detecton lmts (1 ppm to 1, ppm) and also fall wthn the range bracketed by the FD mnmum detecton lmt and the maxmum column capacty. Mnmum sample volume s drven by the detecton lmt of the flame onzaton detector (FD). The detecton lmt for the FD s conservatvely estmated to be about 1 nanogram, although much less may be possble for some compounds. Maxmum sample volume s lmted by the capacty of the column. The capacty of the.53 mm D capllary column s conservatvely estmated to be 1 nanograms per component, but much more s probable for most compounds Sample Rate A sample rate of 1 cc/mn was chosen because t s low enough to keep pressure drops wthn reasonable lmts hgh enough to elmnate errors due to dffuson hgh enough to keep purge tmes reasonably short. 2.3 Gas Chromatograph The gas chromatograph (GC) s a Varan model CX34 wth the followng features. wde bore capllary column (Restek MXT-vol), desgned specfcally for volatle organc compound separaton. flame onzaton detector (see below) programmable column temperature fom ambent to 25 C carrer gas = Helum makeup gas = Helum 8

17 FD fuel = Hydrogen The chromatographc method s descrbed n secton Flame onzaton Detector A flame onzaton detector (FD) was used because t s responsve to almost all organc compounds, and has more than enough senstvty for the TEVES applcaton. FD response s greatest to hydrocarbons and decreases wth ncreased substtuton of other elements. The FD has the advantages of a wde dynamc range (1 O7), low senstvty to water and most norganc compounds, and requres essentally no mantenance. 2.4 Extracton Manfold and Subsurface Pressure nstrumentaton tem erature/ temperature --+ hum 1 sensor humdty =?! manfold L pressure, 4x pressure subsurface pressure, 12x scanner - A A RS232, barometrc ressure sensor + asala #PTA427) (3 dfferental pressure sensor (Setra #264) flow #21X) +# 2.5 Computer and Data Acquston Hardware All system h c t o n s are controlled by a DEC model 466d2 MT computer. To runthe software wth acceptable response tme a 66 M H z 486 &th at least 16 M3 RAM s requred. A Natonal 9

18 nstruments A./D board wth sgnal condtoners and a Hostess 8 channel RS232 port board are used for data acquston and control. S o h a r e s dscussed n detal n Secton Computer & Data Acquston Hardware Block Dagram helum pressure gage hydrogen pressure gage y lab sensor sampler 1 massflow controller Jl p1 pressure gage sgnal!' controller temperature &hhndty transmtte 6 port valve 4 manfold ressure ptot delta-pressure 11 barometrc pressure 11 subsurface pressures 41.r-;;e swtch mouse 1..,' Chromatograph

19 2.5.2 Computer Electrcal nterface 486 PC AD ch AD ch 1 ADch2 8 channel RS232 card (COM 2,3,6,7,8 not used) f, - HMP 235 humdty/,vasala temperature transmtter Galco seral valve -)1 6portvalve nterface 4datalogger COM4 4 COM2 f-) COMl 4 4 ~ 2.6 Gas Supples Fve gases are used. Gas U H P Helum U H P Hydrogen Compressed Ar UHP Zero Ar Calbraton Gas purpose carrer & makeup gas for GC FD fuel FD ar calbraton blank & NAFON drer NST-traceable calbraton verfcaton standard cvlnder compressor cylnder The GC back panel gas hookups are shown n Appendx B. Assembly dagrams for the helum, hydrogen, calbraton gas, and zero ar supples are shown n Appendx C. The helum and hydrogen supples are scrubbed pror to delvery to the GC by water/oxygen/hydrocarbon flters. Compressed ar s suppled by an ar compressor. All compressed gas cylnder pressures are montored by the computer to ensure adequate gas supples. Each manfold was leak tested usng Snoop up to the pressure set pont (1 ps) of the pressure relef valves. 11

20 3. Summary of Operaton The autonomous GC system collects data to characterze several aspects of the TEVES experment. The system operates contnuously 24 hours a day, startng a new operatng cycle (or task) every two hours. Durng each task, the followng operatons occur automatcally: one of fve vapor sources (calbraton gas, zero ar, extracton manfold, pre catalytc oxdaton unt, post catalytc oxdaton unt) s selected for samplng the sample s prepared for njecton nto the GC the sample s analyzed usng a wde bore capllary gas chromatography and 9 specfc analytes are quantfed parameters that mpact data qualty (traler temperature, gas supply pressures, valve states, sample flow rate) are montored. extracton manfold physcal condtons are montored (temperature, pressure, relatve humdty) the mass removal rates for VOCs and water are calculated a summary data fle s generated. Ths s desgned to be mported nto an EXCEL spreadsheet whch wll provde a quck and easy platform for data analyss and presentaton a backup copy of the TEVES subdrectory n made onto a Bernoull dsk. 3.1 nstallaton and Turn-on Pror to unattended operaton, the system needs several manual adjustments, descrbed n detal n Appendx A. Subsequently, all operatons run unattended under computer control. Software s dscussed n Secton Unattended Operaton Fve types of tasks are performed each day. Each task follows the same procedure as any other task wth one excepton - the choce of sample source. There are fve sample sources, three from the TEVES and two used for data qualty control. A scheduler program calls one of the fve tasks to execute startng at a gven tme of day accordng to the followng schedule: 12,

21 3.2.1 TEVES Samplng Schedule (dp<-4 C, THCKO.1 ppm) extracton manfold after condenser zero ar (dp<-4 C, THC<O.l ppm) exhaust stack NST-traceable cal gas zero ar (dpc-4 C, THC<O.l ppm) extracton manfold 22:OO post cat-ox after condenser zero ar (dp<-4 C, THCXO.1 ppm) exhaust stack purpose calbraton verfcaton establsh lower detecton lmt & measure carryover quantfy vapors n untreated borehole effluent pre cat-ox value establsh lower detecton lmt destructon verfcaton calbraton verfcaton establsh lower detecton lmt & measure carryover quantfy vapors n untreated borehole effluent pre cat-ox value establsh lower detecton lmt destructon verfcaton The sequence of operaton for a typcal cycle s: 1. ntalze valve postons, GC settngs, sample flow rate 2. read lab temp, pressures, flow rate 3. select sample source 4. drythesample 5. purge sample loop 6. nject sample 7. run chromatographc method to measure concentratons of target analytes 8. calculate VOC mass removal rate, water mass removal rate, manfold flow rate 9. ntegrate and archve data 3.3 Chromatographc Method The chromatographc method uses a sngle wde-bore capllary column and flame onzaton detecton. The column s a Restek model MXT-VOL (3 meters long, 3. mm thck flm,.53 mm D) desgned specfcally for volatle organc compound separatons. A chromatogram s generated by njectng the sample loop contents drectly on column, then readng the FD output whle the oven temperature s controlled to a specfc temperature versus tme profle. The profle was selected to resolve as many VOCs as possble gven the followng constrants: the GC does not have sub-ambent temperature capablty only a sngle general purpose column s used cycle tme must be 2 hours or less. 13

22 After the heavest dentjed compound (Dchlorobenzene) elutes from the column, the column s baked out to condton the column and to remove any undentjedheavy compounds that mght otherwse carry over nto the next chromatography cycle. Ths s ncorporated nto every run by rampng the column temperature to 2 C for a short perod of tme. A cool down perod of approxmately 35 mnutes s requred to allow the oven to return to ts ntal temperature after the bakeout. The traler nto whch the GC s placed must be capable of mantanng the temperature less than 2 C Column Oven Temperature Profle - 2 column bakeout dd) \ cooldown looo 3' tme after njecton, mnutes (not to scale) GC gas flow rates The GC requres helum as a carrer and makeup, hydrogen and ar for the FD. The flow rates are: 3 cc/mn 14

23 3.3.3 GC Results After a chromatogram s generated, retenton tme, peak area, and concentraton of each compound are calculated by the Varan GC Applcatons software. A typcal report s shown here: Ctle un Fle 4ethod Fle Sample D : TEVES analyss : D:\TEVES\941115\OOOO.RUN : C:\STAR\STARTUPl.MTH : TEVES calbraton run Cnjecton Date: 15-NOV-94 :2 AM >perator : Jorkstaton: [nstrument : Zhannel : FJ Peter DECPC Varan Star #1 B = B Detector Type: ADCB (1 Volts) : 16 Sample Rate : 2.5 Hz Run Tme : 8.7 mn Bus Address tun Mode : Analyss?eak Measurement: Peak Area Zalculaton Type: External Standard?eak Retenton Tme Tme Offset (mn) (mn) Peak Name PEN FRE TCA TCE PCE EBZ XMP x- DCB _ Totals : 'otal Undentfed Counts : etected Peaks: counts Rejected Peaks: 4 hnount Standard: Area Sep. (counts) Code dentfed Peaks: 9 Multpler: 1. Dvsor: 1. 3aselne Offset: -7 mcrovolts Jose (used): 3 mcrovolts - montored before ths run e**** 15 Wdth 1/2 (sec) -_

24 4. Calbraton & Verfcaton The relatvely hgh expected concentratons (up to 1 ppm by volume) of some compounds places restrctons on unattended calbraton of the GC. The problem s that compounds wth low vapor pressures cannot be volatlzed at even modest cylnder pressures (1 Os of ps). The consequence s that calbraton mxtures that bracket the hgh end of our concentraton range of nterest cannot be made n suffcent quantty, practcally speakng, to support a long-term unattended applcaton. For ths reason, calbraton and verfcaton was dvded nto two groups: laboratory calbraton and feld verfcaton. 4.1 Laboratory Calbraton All laboratory GC calbraton ms were performed pror to the feld tests and used the dentcal samplng procedure and hardware at the ste. Mult-pont calbratons (,2,2,2, 1 ppm by volume) were performed n order of ncreasng concentratons wth three replcates at each level for each compound. Absolute retenton tme on the column s used for compound dentfcaton and peak area s used for quanttaton. All results are expressed as parts per mllon by volume (ppmv) at2 C, 76 mm Hg. The calbraton procedure and calculatons are descrbed n detal n Appendx D. 4.2 Feld Verfcaton To ensure data qualty, two types of qualty control samples are taken. Frst, the calbraton stablty of the GC s verfed on 12 hour ntervals usng a NST-traceable gas standard (nomnally 2 ppm) from Scott Specalty Gases. The certfcate of analyss s gven n Appendx E. Second, the lower detecton lmt s measured and carryover quantfed by perodcally analyzng zero &' blanks. 16

25 4.3 Typcal Calbraton Chromatogram Typcal Calbraton Chromatogram.25.2 A 2k 2.15 Y y1 W B 3 fs.1 L aj 4 d B Retenton Tme (mn)

26 4.4 Typcal Calbraton Report Ptle %un F l e gethod F l e Sample D : : : : TEVES a n a l y s s D:\TEVES\941115\OOOO.RUN C:\STAR\STARTUPl.MTH TEVES c a l b r a t o n run n j e c t o n Date: 15-NOV-94 :2 AM 3perator : Vorkstaton: nstrument : 2hannel : FJ P e t e r DECPC Varan S t a r #1 Detector Type: : Bus Address Sample Rate : Run T m e : B = B ADCB (1 V o l t s ) Hz 8.7 mn 3un Mode : Analyss Peak Measurement: Peak Area 2 a l c u l a t o n T y p e : E x t e r n a l Standard Peak go Retenton Tme (rnn) Peak Name PEN FRE TCA TCE PCE EBZ XMP x- 1 DCB Tme O f f set (mn) Area ( counts ) Totals : R e j e c t e d Peaks: 4 knount Standard: d e n t f e d Peaks: 9 M u l t p l e r : 1. D v s o r : 1. 3aselne O f f s e t : -7 mcrovolts gose ( u s e d ) : 3 mcrovolts - montored b e f o r e t h s run ***** counts r o t a 1 U n d e n t f e d Counts : l e t e c t e d Peaks: 16 Sep. Code Wdth 1/2 (sec)

27 5. Software The major software elements, all operatng under Mcrosoft Wndows, are: 1) Labvew vrtual nstruments for nstrument montorng and control 2) the Varan GC Star Workstaton software for controllng the GC method 3) several Vsual Basc programs to provde tmng synchronzaton between the Labvew VS and the Star Workstaton and for creatng the summary data fle used by the EXCEL spreadsheet 4) an EXCEL spreadsheet for data manpulaton and graphcal presentaton 5.1 Software Archtecture / c Excel 5. -\! f! s c h e d y 1!! data 1ogger.V GC Star f Workstaton 3.! 1 Varan summary f1e.w 1 Vsual Basc fle hand1er.w t pressure.v]: \ 3. %! GCsleep.exe.,./ J Most nstrument control functons are wrtten as Labvew vrtual nstruments (VS). All VS and ther respectve functons are lsted below: 19.

28 vrtual nstrument name startall.v scheduler.v Task manager.v GC.V H2P.V calgas.v carrer.v TRH.V RTD.V mass flow controller.v valves.v datalogger.v fle handlng.v backup.v descrnton starts the two man controllng VS: scheduler.v & task manager.v. reads a schedule fle contanng the tme of day based sequence fles to pass to the task manager and sgnals the task manager to begn sequence executon. trggers specfc events (such as readng temperatures, pressures, actuatng valves) based on tmes contaned n task fle. calls GC Star Workstaton software reads hydrogen gas cylnder pressure reads calbraton gas cylnder pressure reads helum gas cylnder pressure reads the temperature and relatve humdty fom the Vasala nstrument. reads lab temperature sets and reads sampler flow rate & zero ar flow rate for Nafonm dryer controls and reads poston of Valco electrcally actuated valves reads and save datalogger data names & stores data fles backup to 9 Mbvte Bernoull dsk GC Star Workstaton Applcaton The GC s controlled by the Varan Star Workstaton. Functons nclude calbraton, column oven temperature control, sample nject valve control, FD output measurement, chromatographc analyss, and report generaton Vsual Basc Applcatons There are three Vsual Basc applcatons: Gcawake.exe GCsleep.exe summary.exe opens and operates GC Star Workstaton applcaton closes Star Workstaton applcaton generates a comma delmted data fle, yymmdd.csv whch ntegrates all data fles up to and ncludng the gven day nto a sngle ASC text fle for uses bv an Excel smeadsheet EXCEL Spreadsheet The summary data fles, yymmdd.csv, contan all relevant TEVES data n a form drectly mportable to a customzed EXCEL spreadsheet. The spreadsheet provdes a sngle ntegrated platform for analyss and presentaton of all TEVES data. TEVES data may be accessed at any 2

29 tme (up to the most recently completed operatng cycle) by removng the Bernoull dsk used for backups and mportng the summary data fle nto the EXCEL spreadsheet. 5.2 Software Sequence of Operaton After all the hardware (GC, data acquston, samplng system, etc.) s turned on (see Appendx A), the software can be run. The sequence of software operaton s: 1. the machne boots from the hard dsk wheren CONFG.SYS s executed, AUTOEXEC.BAT s executed. 2. the STARTAL,L.V program opens all Labvew Vrtual nstruments 3. the scheduler.v wats for the system clock to trgger the approprate task fles at the approprate tmes. 4. the task manager.v wats for the system clock to trgger the hardware and data collecton events at the approprate tmes. 5. the GC method runs 6. at the end of each task, a set of data fles contanng all data acqured durng that task (nstrument readngs, raw chromatograms, datalogger data, etc.) s saved to hard dsk. 7. a summary data fle s updated on the hard dsk 8. all data fles are backed up to the Bernoull dsk 9. wat for next task 5.3 Summary Data Fle The summary data fle contans the followng data: datehme of sample collecton sample locaton (zero ar, calbraton gas, extracton manfold, cat-ox nlet, or cat-ox exhaust) extracton manfold temperature, pressure, relatve humdty, and ptot tube pressure dfferental speces concentraton for each target analyte (n unts of ppm by STP). GC state of health measurements data logger pressure scanner data 5.4 Task Fles For the TEVES project, there are fve task fles, one for each sample source: task fle name manfold.txt pre cox.txt postcox.txt calgas.txt zeroar.txt ~~~~~ contans Extracton Manfold sample sequence Pre cat-ox sample sequence Post cat-ox sample sequence Calbraton sequence Zero ar seauence 21-7

30 5.5 Data Fle and Data Drectory Organzaton Each subdrectory named as yymmdd s ntended to hold the data fles (chromatograms and other nstrumentaton data fles) for the day defned by the subdrectory name. The data fle name format s hhmm.ext where hhmm represents mltary tme. The.ext s an extenson dentfyng the contents of the datafle. SubdrectoryName C:\ c:\dos c:\wndows Flename@) autoexec.bat DOS 6.2 fles Wndows 3.1 fles C:\STAR C:LABVEW Star fles C:LABVEWTEVES C:\W c:\teves C:\TEvES\yymmdd Labvew fles *.V GCawake.exe GCsleep.exe summary.exe schedl.txt manfold.txt pre-cox.txt postcox.txt calgastxt zeroar.txt yymmdd.csv hhmm.rtd hhmm.dat hhmm.hep hhmm.h2p hhmm.cg hhmm.trh fle type batch see DOS manual see Wndows manual see Star manual see Labvew manual *.V *.exe ASC text ASC text descrpton set PC envronment operatng system operatng system GC control Labvew applcaton Vrtual nstruments GC Star Workstaton control creates summary data fle schedule fle manfold sample task fle pre cat-ox sample task fle post cat-ox sample task fle cal gas sample task fle zero ar samde task fle * summary data thru current day RTD temperature readng chromatogram report Helum pressure Hydrogen pressure readng cal gas pressure readng manfold temperature &......relatve humdty readngs

31 6. Lessons Learned, Proposed System mprovements 6.1 Hardware Sample Flterng. The mass flow controller on the post cat-ox sample lne needed to be replaced several tmes because t was fouled by the drty samples downstream of the cat-ox unt. A gravty trap for heavy partculates, followed by a graduated flter (multple step, wth fner flterng at each stage) s recommended. Hydrogen Source. The compressed Hydrogen cylnder should be replaced by a Hydrogen Generator, whch generates H2fom dstlled water on demand. Ths has two benefts: 1. t would enhance fre safety by lmtng the volume of stored hydrogen and by elmnatng the possblty of ntroducng a leak durng cylnder changeout. 2. there would be no need to nterrupt testng to replace empty cylnders. Ar Compressor. The current compressor s extremely loud and has mnmal storage tank volume. nvestng n a queter compressor wth a larger storage tank would have two benefts: 1. a more comfortable work space by sgnfcantly reducng nose. 2. n the event of an electrcal power blackout, the larger storage tank would reduce the rsk of the FD flamng out due to lack of ar flow. 6.2 Software The system test schedule and methods are currently coded as text fles. Ths requres that the user has some faclty wth a text edtor and requres an understandng of the requred text fle syntax. A graphcal user nterface (GU) schedule edtor that nsulates the user from the detals s hghly recommended f frequent changes n test schedule and methods are requred. 23

32 Appendx A: System nstallaton & Turn-on ComputerBZlectrcal System Turn-on make sure all equpment, pumps, computer, and nstruments are plugged n turn on power to all nstruments turn on the GC, press the RESET button run software (see s o h a r e secton) Compressed Gas System Turn-on ' 1. close all valves n the manfold 2. open valve at gas cylnder fully 3. make sure t s open by readng pressure gauge on nlet of regulator 4. adjust regulator output pressure settngs (h2 ps) to the followng: helum: 8 ps hydrogen: 4 ps zero ar: 1 ps calgas: 1Ops 5. open all shut-off valves 6. at ntal turn-on, the excess flow valve on the hydrogen tank wll lkely trp due to the ntal surge of flow, requrng that t be reset. Reset t by smply pressng the red button. 7. leak check vsually usng "Snoopll leak detecton flud. 8. recheck pressure gauges for proper pressure and adjust regulator f necessary. Settng GC Flow Rates All gas flow rates were preset n the laboratory usng a bubble flow meter. See the GC manual for nstructons. The nomnal flow rates are: helum carrer = 7 cc/mn helum makeup = 2 cc/mn hydrogen = 3 cc/mn: FD ar = 3 ml/mn: Lghtng Flame onzaton Detector 1. make sure hydrogen and ar flow rates are properly set 2. press Shzj? and gnte B on font panel of GC and hold for 5 seconds. 3. make sure FD s lt by holdng a cool shny object next to exhaust port of FD. f lt, mosture wll condense on the object. f not, recheck gas supply and flow rate settngs. mportant: f loss of electrcal power occurs for more than a few mnutes, the FD flame wll go out because the ar compressor wll stop supplyng ar. Although the software wll begn to run when power returns, the FD may need to be relt per above nstructons. 24

33 Appendx B: Gas Supply Hookups (back panel of GC) AUX FD AR 3 cdmn FD Hz CARRER 3 cc/mn HC trap 32trap 4) ar compressor >5 6ps UHP Hydrogen MAKEUP 1 cc/mn 2 cc/mn

34 Appendx C: Compressed Gas Assembly Dagrams Helum 2 starre reguktor 8 ps pressure relef valve, 1 ps setpont b relef vent bellows valve b to system snubber ( m aflow = ps) UHP Helum 249 ps, 244 cu ft Hydrogen pressure relef valve, 1 ps setpont 2 stage regulator 4 ps CGA 35 \ bellows valve relef vent (maxflow = ps) excess flow valve (1 lter/mn trp pont) 215 ps, 73 cuft 26 to system

35 Zero Ar ressure relef valve, TOO ps setpont 2 stace regultor 1 ps m bellows valve P C X 59& b relef vent b to system.. snubber (maxflow = ps) Zero Ar 22 ps, 225 cu ft Calbraton Gas pressure relef valve, 1 ps setpont 2 stane regukor 1 ps bellows valve snubber (maxflow = ps) Cal Gas 275 ps, 1.5 cu f 27 b relef vent + to system

36 Appendx D: Calbraton Calbraton Standard Preparaton Vapor phase calbraton standards were prepared usng the followng procedure: 1. A Scott Specalty Gases Acculfe alumnum cylnder (sze CL) was cleaned by purgng wth dry UHP Zero Ar, then evacuated to 1-4 torr. Ths process was repeated three (3) tmes. 2. Each VOC of nterest was ntroduced nto the evacuated cylnder by njectng a measured volume of each through a slcone septum at the cylnder valve. A gas-tght mcrolter syrnge was used to nject the compounds of nterest, one at a tme, n lqud phase. The syrnge was cleaned between njectons by purgng twce wth methanol and once wth the VOC to be njected next. 3. After all compounds were njected, the cylnder was flled wth a metered volume of UHP Zero Ar usng a precson mass flow controller. Flow rate was 5 cclmn and fll tme was dependent on what volume of dluton gas was needed to acheve the desred VOC vapor concentraton. Calculatons All chromatographc results are calculated as parts per mllon by volume (ppmv) at 2 C, 76 mm Hg. Vapor concentratons for each VOC are calculated as follows: step 1) calculate mass njected: mx = v x rx step 2) calculate volatlzed vapor mass densty: dx = mxn step 3) convert mg/m3 to ppmv: cx= dx= mx = V= r, = V= Z= M= cx = dx x Z/M concentraton of x concentraton of x mass njected lqud volume of VOC x njected lqud densty of VOC x volume of dluton gas (zero ar) molar volume of perfect 2 OC, 76 mm HE molecular weght of x PPmv mg/m3 mllgrams mlter g/d cubc meters 24.4 lters/mole gramdmole 28

37 Calbraton Table conc* CAS number. level 1 Dchlorobenzene (ly2-) Ethyl benzene Freon Pentane Tetrachloroethene Trchloroethane (1,1,1-) Trchloroethylene Xylene (m-) Xylene (-) Xylene (p-) balance UHP Zero Ar da -----UHP Ntrogen da conc* = ppm by 2 C,76 rny1hg Compound Level 1: made by mxng.5 mlter lqud of each compound and 5 lters ar Level 2: NST-traceable standard fom Scott Specalty Gases, Scott #CAL9245 Level 3: made by mxng 1 mlter lqud of each compound and 1 lters ar Level 4: made by mxng 5 mlter lqud of each compound and 1 lters ar (compounds wth VP > 1 mm Hg) 29

38 Appendx E: Calbraton Standard Certfcate of Analyss Scott Specalty Gases, nc. --. ~ Shpped From: 5 WEAVER PARK RD LONGMONT Phone: CO ~...-- Fax: C E R T F C A T E O F A N A L Y O P... PROJECT n: PO%: AK-711E) TEM a: 8 2 D A 1 1 A L DATE:1/31/94 SAND A NAT ONAL LABS U.S.O.E. BLDG EUBANK BLVD SE ALBUQUERQUE NM REQUESTED GAS COMPONENT CONC MOLE5 2. PPM 1.2-DCHLOROBENZENE ETHYLBENZENE HALOCARBON N- PENTANE TETRACHLOROETHYLENE.1,l-TRCHLOROETHANE TRCHLOROETHYLENE M-XY LENE -XY LENE P-XY LENE N TROGEN CGA PSlG N l S T TRACEABLE BY WEGHT QCn PPM PPM PPM P PM PPM PPM PPM PPM PPM BALANCE ANALYS S --[WCY ---LEBL, PPU PPM P PM PPM P PM PPM P PM PPM P PM PPM BALANCE EXPOSURE TO TEMPERATURES B E L ~ W32 DEG F MAY CAUSE COMPONENTS TO L Q U F Y. KEEP CYLNDER ABOVE 7 DEG F FOR 1-2 DAYS OR HEAT FOR 1-2 HOURS. ROLL CYLNDER FOR 15 MNUTES BEFOR USNG.... DO NOT HEAT ABOVE 12 DEG F. ALWAYS USE ADEQUATE TEMPERATURE CONTROL.... B&kw A ANALYST: DANA EEHLER PLUMSTEADVLLE. PENNSYLVANA TROY, MCHGAN HOUSTON. TEXAS DURHAM. NORTH CAROLNA SOUW PWNFELD. NEW JERSEY FREMONT. CALFORNA WAKEFELD. MASSACHUSETS LONGMONT. COLORADO BATON ROUGE. LOUSANA

39 Appendx F: Power Requrements All nstruments operate usng 12 VAC. The followng s a conservatve estmate of amperage requred. nstrument Current Gas Chromatograph computer montor Bernoull drve A/D, dgtal YO,etc valves mass flow controllers ar cornmessor sample pump crculatng pumps (2. A x 3 each) heated sample lnes (3.6 A x 3 each) Total amperage estmate o 2. 1.o 1.o

40 Appendx G: Routne Mantenance The only mantenance requred s perodc replacement of compressed gases and gas flters. Cleanng of the FD electrode s not antcpated, but may be requred f the samples are extremely drty. Compressed Gas Replacement The helum, hydrogen, or zero ar cylnders should be replaced when the tank pressure gauge reads 1 ps or less. Lfe expectances for the gases are gas quantty hydrogen helum zero ar 2 15 ps, 73 ftj 2 ps, 22 f t j 2 15 ps, 225 f j Cal gas 275 ps, 1 ftj use rate cc/mn, duty cycle 3 cc/mn, 1% 3 cc/mn, 1% 1 cc, 1% 2 cc/mn, 4% 1 cc/mn,.2% lfetme 4 days 66 days 3 days 15 days Gas Flters f the chromatogram baselne starts to look "drty", the carrer gas flter should be replaced. Flter lfe expectancy wth our system s expected to be many months of contnuous usage. Partcle Flters f a drop n sampler flow rate (as read by the sampler mass flow controller) takes place over tme, the cause may be a clogged partcle flter. f ths s the case, the 2 mcron stanless steel frt must be replaced. FD Detector Cleanng f a reducton n FD response s notced over a perod of tme, as ndcated by the twce daly feld calbratons, t may be necessary to clean deposts from the FD electrode. See the GC manual for gudance on dsassembly and cleanng.

41 Appendx H: Manfold ar flow rate calculatons Extracton manfold flow rate s calculated from three measurements: ptot tube dfferental pressure manfold statc pressure manfold temperature The calbraton curve for the Omega #FPT-613 ptot tube s: Q= flowrate Dp = K= dfferental pressure ptot tube flow coeffcent ppe dameter manfold statc pressure specfc gravty of ar temperature D= P= s= T= 6 F, 76 rnm H s nches H2 dmensonless (calculated) (measured).665 (known) nches ps absolute 3 (known) relatve to 6 F "F 1. (known) (measured) (measured) To convert flow rate Q at 6 F (15.6"C = K) to flow rate 2 C (293 K): Q' = 1.15 x Q 33

42 Appendx : VOC mass removal rate calculatons VOC mass removal rate s smply the product of manfold ar flow rate and mass densty of VOC per volume ar. t s calculated from two parameters: extracton manfold ar flow rate Q' (calculated per Appendx H) VOC concentraton as measured by the GC step 1) convert chromatographc result, parts per mllon by volume (ppmv) at 2 C, 76 mm Hg to mg/m3 at 2 C, 76 mm Hg for each VOC: PPmv mdmj 22.4 lterdmole Mx = concentraton of VOC x concentraton of VOC x molar volume of perfect O'C, 76 mm Hg molecular weght of T= P= local ar temperature local ar pressure "K mm Hg Cx = D, = 2= voc x grandmole At 2 C, 76 mm Hg, ths reduces to: Dx = cx Mx 24.4 VOC mass removal rate converted to lb/hr s: lb m m n

43 Appendx J: Water mass removal rate calculatons Water mass removal rate s smply the product of manfold ar flow rate and mass densty of water per volume ar. t s calculated fom four parameters: extracton manfold ar flow rate Q (calculated per Appendx 3) manfold relatve humdty (measured by Vasala humdty transmtter) manfold temperature (also measured by Vasala humdty transmtter) manfold pressure (measured by the pressure scanner) ReZatve humdty s defned as the rato of water vapor pressure to the saturaton water vapor pressure at the gas temperature. Total pressure does not enter the defnton. step 1) calculate saturaton water vapor pressure: Over the temperature range to 2OOC, saturaton water vapor pressure (psa) can be approxmated (<.38% error) by: Pws =.885 x lo( X T/( T)) T =temperature, "C step 2) calculate water vapor concentraton by volume: Water vapor concentraton by volume s equvalent to the rato of water vapor partal pressure to total (manfold) pressure. Cw = water vapor concentraton, ppmv H = relatve humdty, % Pws= saturaton water vapor pressure, psa Pt= total (manfold) pressure, psa step 3) convert ppmv to mg/m3 at 2 C, 76 mm Hg: c, = Dw= z= Mw= T= P= concentraton of water concentraton of water molar volume of perfect 2"C, 76 mm Hg molecular weght of water manfold temperature manfold pressure PPmv mg/mj ar 24.4 lterdmole 18.2 grandmole "K mm Hg

44 step 4) convert water mass removal rate to lbh: c 36

45 Appendx K: Parts Lst (arranged by subsystem) Chromatograph descrpton gas chromatograph FD nterface card for above wde bore capllary column, 3 meters long, 3. mm thck fl,.53 mm D lqud calbraton standards, 1 ml each suppler Varan Restek part number (2x34 comes wth above comes wth above MXT-VOL Accu-standmd custom order Sample Transfer Subsystem descrpton suppler Techncal Heaters heated samplng lne, Teflon, 25 ft long daphragm ar pump, 1.1 cfm, 12 VAC Fsher Scentfc partcle flter, 9 mm SS frt Nupro part number ss-4tf-9 Sampler descrpton 6 port valve, electrcally actuated RS232 Seral valve nterface, for above sample loop, 1 cc Nafon Dryer mass flow controller readout box for above rotary vane ar pump, 1.5 cfm, 12 VAC suppler valco Valco Valco Perma-pure Tylan Tylan Thomas part number ESF6P SV SL1KC1OUW MD-19-24s FC-26 RO-28 SR-15-VP suppler Vasala part number HMP235 Manfold nstrumentaton descrpton Humdty/Temperature transmtter data logger ptot tube dfferental pressure sensor (*5" H2) 1 1 Campbell Scentfc 21X FPT-6 13 Omega 264 Setra 37

46 Compressed Gases & Plumbng descrpton rjhphelum kjj2 Hydrogen rjhp Zero ar Calbraton Verfcaton Standard pressure transmtter, -25 psg, 4-2 ma output,excessflow valve, CGA 35, 11 lter/mn trp pont lpressure regulator shut off valve, metal bellows type pressure relef valve, 1 ps gas purfer cartrdge ar compressor,.6 6 ps suppler. Tr-Gas Tr-Gas Tr-Gas Scott Specalty Gases PS-tronx part number SGUHPHE243M SGUHPHY73M SGUZCA239M Cylnder #ALM5149 PG-4/2 ABQ V&F 6L-E4-HA-3 5-VR4 Concoa ABQ V&F ABQ V&F Alltech Thomas SS-4BG-VSl SS-RL3M4-S4-MO LGH-21 ~~ Computer & Data Acquston Hardware part number descrpton suppler 466d2 MT computer, 8486, 66 MHz, 16 Mb RAM DEC PCXBV-DE 15' montor DEC NHX835A RS232,8 channel expander Hostess 1Bernoull drve, 9 Mb Lberty 19OPRO Natonal nstruments ADFO 16 A/D, D/A 1/board Natonal nstruments 5B1 16 channel back plane Natonal nstruments 5B34 RTD to 5 volt module Natonal nstruments 5B41 +5 V to 5 volt module Natonal nstruments 5B32 4/2 ma to 5 volt module 38