### HCL CEMS Edul Chikhliwala \Chikli\ to: Keith Barnett 05/28/2010 10:24 AM Show Details

Dear Keith:

Here is a "brain dump" regarding our existing HCL CEMS and issues related to the low levels associated with the Cement application. I provide a short discussion on the important aspects and have attached numerous supporting documents. I have intentionally kept this discussion informal but if need be, it can be converted into an appropriate technical document. Please review and give feedback.

Thank you

Edul Chikhliwala ("Chikli") EcoChem Analytics 202 Reynolds, League City, TX 77573, USA 281-338-9888 chikli@ecochem.biz

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---- TYPE OF SYSTEM The EcoChem CEMS is based on HOT-WET MULTICOMPONENT TECHNOLOGY. The basic premise is to keep ALL surfaces that contact the flue gas to be above the dew point of the flue gas. Specifically, the probe, the sample line, the pump and the sample cell within the analyzer are maintained at 185 degC (365 degF) or higher. This ensures that there is no condensation of the

### reactive vapors leading to a reliable system and minimal downtime. In addition, we use a MULTICOMPONENT GAS ANALYZER -- a single analyzer measures up to 8 components. It is infra-red technology based instrument with an optional in-built Zirconium Oxide oxygen sensor.

Specifically we use GAS FILTER CORRELATION (GFC) for measuring HCl. This technique uses an HCl gas filled cell along with an appropriate interference filter (centered around 3.6 micron and 4% band width). This allows us to be very specific to HCL and possible interference from other components is eliminated. The technique is simple and yet specific to HCL. This technique is described in detail in the book "Continuous Emission Monitoring" by James A. Jahnke and we have attached an relevant pages (note, in this book the emphasis of GFC is for CO detection but it can be equally applied towards HCl detection). In addition we have attached Proposed Test Method 322 which describes also the use of the Hot-Wet GFC technique for HCl monitoring at a Cement Kiln. This document also summarizes very well the EcoChem approach described in this email.

--- CALIBRATION RELATED ISSUES HCl calibration gas can be difficult to obtain at higher accuracy levels. Typically +- 5% is the normal accuracy associated with HCl calibration gas. For lower concentrations, it is proposed that the HOVACAL (Hot Vapor Calibrator) be used for generating HCL vapors of known concentration. The HovaCAL has been certified and a paper describing the HovaCAL has been attached. The HovaCAL is widely used by EPA scientists and engineers for oxidized mercury calibration. In addition the HovaCAL has also been used for calibrating FTIR analyzers.

--- BUDGETARY SYSTEM COST Attached please find an EcoChem quote for a HCL monitoring system which was purchased recently. This system will go online in two or three months. This system has dual range HCl (0-20 PPM and 0-200 PPM).

---- MANPOWER REQUIRED TO RUN THE SYSTEM Our systems are designed for running 24 hours 365 days with minimal human intervention. More frequently, once a day a technician will check the calibration and make a visual check of the system. Every quarter maintenance is performed. The labor needs for our HCL system is no more than what is needed for a standard CEMS.

--- SYSTEM INSTALLATIONS Attached please find a document which provides a list of installations using the EcoChem MC3 analyzer and measuring HCl as one of the components.

--- CERTIFICATION BY REGULATORY AUTHORITIES The MC3 analyzer has been tested and approved by regulatory bodies in Europe. Attached please find the review reports of these evaluations (TUV in Germany and MCERTS in UK). Note, these studies were done several years ago and subsequently developments/optimization of the analyzer has occurred. For example, the TUV evaluation found cross-interference of >4% between the HCL signal and high SO2 levels. Subsequently by fine-tuning

### the optics and better choice of the interference filters this cross-interference has been eliminated.

--- RELEVANCE TO EPA TEST METHODS AND DOCUMENTS As mentioned previously, EPA Proposed Test Method 321 (attached) is identical to the technology used by EcoChem. In addition, Eli Lilly has developed Performance Specification and QA/QC procedures for HCl CEMS which are posted on the EPA's website. These were developed for the Lilly incinerator T149 which uses an EcoChem MC3 analyzer.

---- FUTURE ENHANCEMENTS The present MC3 analyzer has been certified for 0-9 PPM HCl by the TUV. The present MC3 analyzer has a 5.6 meter path length. So far customers have never requested lower ranges since there was no regulation. However for the cement application, we propose a MC3 analyzer with a range of 0 to 5 PPM HCL. This will be achieved by doing the following: --- Increasing the path length to 11.2 meter to increase the sensitivity

## A Po rtable Calibration Gas Generator f o r H 2 

## O, HCl, NH 3 

## and Mercury Peter Wilbring 1



### , M a r t i n S c h m a e h 2

1 

### TÜV Immissionsschutz und Energies ysteme Gm bH, Am Grauen Stein, D-511 05 Köln
2 

### IAS Gm bH, Heddernheim er Landstraße 13A, D-60 439 Frankf urt am Main
presented at CEM 2001 International Conference on Em issions Monitorin g 25 – 27 April 200 1 in Arn h eim
, Netherlands



### Abstract

The cal i b rat i o n of em i ssi on m easurem ent sy st em s for wat e r va po r, hy d r og en c h l o ri de, a m m oni a and m e rcu r y i s diffic u lt and s p an gas is not available for every com p one nt . O n t h e pr i n ci pl e o f t h e dy nam i c evaporat i o n o f l i qui ds an d t h e co nt i n u o u s a d di t i on o f car ri e s gas , a p o rt a b l e cal i b rat i o n g a s ge nerat o r w a s de vel o pe d. Li neari t y , accuracy a nd t h e re produci b i lity is com p arable with t h e quality of ce rt ified cylinde r spa n gas or even better. B e si des a num ber of ad va nt ages o v er e x i s t i ng cal i b rat i on m e t hods , t h e sy st em provi de s a cal i b rat i o n gas wi t h si m ilar co n s tit u tio n as fl u e gas esp ecially fo r water con t en t. Mercury ch lorid e h a s b e en in v e stig ated up to a
conce n t r at i o n of 15 0 μ g / m 3. B e si des car ri er gas fl ow va ri at i on, al s o t i m e con s t a nt an d t h e speci at i on o f m e rcury
un de r t h e i n fl u e nce of eva p or at or t e m p erat ur e has bee n e x a m i n ed.



### Introductio n

Th e calib ration o f em issio n measu r in g syst e m s for H2O, HCl, NH3 and me rcu r y sho w s a few d i fficu lties: H2O is no t av ailab l e as test g a s u p to th e requ ired c once n t r at i o ns and t h e ha ndl i n g o f HC l nee d s ap pr o p ri at e expe rience [1]. The wall a d sorption e ffects of HCl, NH3 a n d als o HF e v e n on heated surfaces of gas fee d ing

com pone nt s re sul t i n t i m e l a g, a dra g gi n g r u nni ng be ha vi o u r an d de vi at i ons of t h e rea d i n g , es peci al l y at l o w
conce n t r at i o ns

. M e rcu r y as H g ° i s avai l a bl e as t e st gas

. B u t i t

i s k n o w n, t h at t h e be ha vi o u r of H g C l 2 i s
co m p letely d i fferen t i n term s o f ad sorp tion [2 ]. Moreo v e r Hg° test g a s is o n l y su itab l e t o ch eck th e pho to m e ter

o f

th e Hg -em i s s io n m easu r in g syste m , b u t not th e sam p le con d ition i ng syst e m . Th is d e m a n d h a s led to t h e devel opm ent o f t h e cal i b rat i o n gas ge nerat o r H O VAC AL.



### Principle o f operation

The de vi ce w o rks o n t h e pri n ci pl e o f t h e dy nam i c evapo r at i on o f l i q ui ds a n d t h e c o nst a nt ad di t i on o f ca r r i e r gas. A co n tinuo us flo w of liqu i d is in j ected i n an ev apor ato r and mix e d w ith a co n tinuo us carr i er g a s f l ow

. Bo th l i qui d a n d gas fl o w are m oni t o re d as m a ss fl ows an d t h ere f ore i n depe n d en t of t e m p erat ur e an d pres su re. The

resu lting co ncen tration s can be calcu lated wi th th e m i x i n g eq u a tion s g i v e n b e low. Th e b a sic eq uatio n for water v a pou r con c en tratio n is:



###      

• + =

liquid gas O H



### v f v c 1 100

2 ( 1)

whe r e c H2O is t h e water v a p our co n c en tration in % V/ V, v liqu id t h e l i q ui d fl ow i n g/ m i n, v gas the carrier gas flow in m l / m in b a sed o n stand a rd co nd itio ns an d f th e v o l u m e fact or fr om l i qui d t o ga s; t h e n u m eri cal val u e f o r

wat e r is 12 44 ,53

.

1/ 7The use o f a q u e ou s s o l u t i o ns of hy dr o g en c h l o ri de, am m o ni a or m e rcury chl o ri de i n pl a ce o f pu ri fi ed wat e r resul t i n ga s va po u r m i xt ures. The c o ncent r at i on o f t h e gas c o m pone nt s i n t h e a que o u s s o l u t i o n i s a n a ddi t i onal p a ram e ter to the mix ratio s of liq u i d and g a s flows. Th is liqu i d con cen t r atio n is u s u a lly g i v e n in m o l/lite r. The basi c e q u a t i on fo r a que o u s sol u t i o n s of c o m pone nt s l i k e HC l
, NH 3 an d H g C l 2 u p t o c once n t r at i o ns o f app r oxi m a t e 1 m o l/ l , base d o n wet ga s i s :

6 

### 10 •        
+ •

=

liquid gas

K K K



### v v f n

M c (2 )

whe r e c K i s t h e co ncent r at i o n of gaseo u s co m ponent i n m g /m 3 , M K th e mo lecu lar m a ss o f th is co m p o n en t, n K is th e liq u i d con c en tration in m o l/li ter and f is t h e vol um e factor for water.

Is th e con c en tratio n b a sed o n d r y g a s, th e volu m e facto r in eq u a tion (2 ) h a v e to b e o m itte d :

6 

### 10 •         •

=

liquid gas K K K



### v v n M c ( 3 )

Principle of the device

Th e calibration g a s g e n e rat o r co nsists of a po rtab le supp ly u n it, an ev apo r a t o r and an e l ec tr on ic b a lan c e. Su pp ly unit a n d eva porator are conne c ted via electrical powe r ca bles, tem p erature si g n al , car ri er gas a n d l i q ui d sup p l y lin es. Th e con s tru c tion is shown in d i agrammatic fo rm in Fig

. 1

.

Ele c tron ic bal a nce Ca rrier g a s Tem p era t ure c ontro ller Liq u i d 

### Vap o ri z e r

Su pp ly un it Ga s-V a p o r Mi xture Ca

rrier g a s

Pum p MF C

Fig. 1: Sche m a tic re presentati on of the c a libration gas generator

A p e ristaltic pu m p is u s ed to p u m p th e li q u i d in t o th e ev apo r at o r fro m a liq u i d reservo i r. Th e liqu i d is passed th ro ugh a fin e filter to k e ep the ev ap orator an d g a s v a pou r mix t u r e free of con t amin atio n. The m a ss of l i qui d pum ped i s d o se d usi n g a p r eci si on bal a nce. The l i qui d fl o w i s det e rm i n ed p r i m ari l y by t h e spee d of r o t a t i o n an d t ube di a m et er of t h e p u m p. The ca rri e r gas i s fe d t o t h e su ppl y uni t at

a n ove r p ress ur e an d a m a ss f l ow con t ro lle r inje cts a continuous and constant fl ow into t h e e v aporator.

2/ 7The e v a p orator can be set up s o m e m e ters away from th e su ppl y uni t

. It ha s a car ri er gas con n ect i o n a n d a l i qui d supply port. T h e te m p erature of the e v a p orat or can be co n t ro lled on the tem p eratu r e co n t ro ller i n tegrated in t o th e su pp ly un it. Th e g a s v a p our m i x t u r e m u st b e ex tracted wh ile still h o t to p r ev en t cond ensatio n and associated lo sses of g a s
com pone nt s or wat e r va p o u r

. Thi s i s d one by ei t h er c o nnect i ng a heat e d pi pe t o t h e e v a p o r at or o r
accomm odating the entire eva p orator in a larger heate d unit
, e.g. a m easuring ga s s u pply unit.

Due t o t h e l i q u i d m e t e ri ng wi t h a n el ect r oni c bal a nce an d t h e gas m e t e ri ng wi t h a m a ss fl o w c ont rol l e r, b o t h flu i d flows are mass flows and th e resu lting co n c en tration i s ind e p e nd en t o f tem p eratu r e an d pressu re.

The e v a p orator can operate d up to tem p eratures of 240 °C. T y pical a te m p e r atu r e of 18 0 °C is u s ed

. A t th is te m p erature most of t h e sam p ling lines are operate d . T h e tem p erature of t h e v a porisatio n is no t critical, b u t t

h e
o n l y criterion i s th at th e tem p eratu r e is well ab ov e t h e te m p erat ure o f de w poi nt

. Wi t h 1 8 0 °C t h i s c o n d i t i on i s fulfilled for wa ter in a n y case and also for com ponents like HCl, HF a n d NH 3 in conj un ctio n with water v a pou r.

The w o r k i n g r a nge f o r

ge ne r a t i ng wat e r va po u r i s defi ned i n t e rm s of t h r ee pa ram e t e rs and l i m i t e d by t h e
m a xim u m pow er of t h e e v ap o r at or ( 8 00 W) . The p r ese n t e d devi ce has cha r act eri s t i c , s h o w n i n Tabl e 1.

T a bl e 1: Ch ar acteri s t i c o f H O V A C A L e v a p or at or

Par a m e t e r M i n i m u m M a x i m u m O p t i m u m Li qui d fl ow rat e i n g/ m i n 0, 05 6 0, 1 – 4 C a rri er gas fl o w i n l / m i n 3 10 4 - 7 Vap o r i s at i on t e m p erat ure i n ° C 15 0 24 0 18 0 - 2 00
Wat e r va po ur conce n t r at i o n % V/ V 0, 6 70 1, 7 - 55

Th us wat e r va po u r c once n t r a t i ons bet w ee n 0 a n d 4 0 % V/ V a r e gene rat e d i n t h e o p t i m u m worki n g ra n g e. Fo r dem a n d of h i gh er w a ter v a pou r con t en t or h i gh er car r i er g a s f l ow , t h e po w e r o f th e ev apor ato r can b e enha nce d

. 

### Results and analysis

A l a b o r at ory t e st an d a fi el d t r i a l have bee n m a de t o e x am ine the acc urac y and lin earity for th e co m p onen t s H 2 O, HCl, N H 3 and H g Cl 2 [3 , 4] . F o r ve ri fi cat i o n of t h e c o ncent r at i on i n l a b o rat o ry , co n v ent i o nal m e t hods ha ve been

use d

. I n t h e fi el d t r i a l
, cal i b r a t e d c ont i n u o u s em i ssi on m easuri n g sy st em s have bee n use d

.
Accur a cy In Table 2, the accuracy of the calib ration gas ge nerat o r for t h e diffe re nt com ponents is shown. T h e carri er gas flow was set at 300 l/h, t h e te m p eratur e of t h e e v aporator at 180 °C. The no m i n a l v a lu e, calcu lated wit h ab ov e mix i n g eq uation s , was set at t h e calibratio n g a s g e n e rator, th e an alytical resu lt was ach ieved b y th e sp eci fic

con v e n t i onal m e t hod.
Table 2: Accuracy of HOVA CA L in t e rms of mea n dev i at io n

Com p o n e n t M e a s u r i n g R a n g e Number o f

measure ments Stand a rd deviation % Slope

Wat e r va po ur 0 – 40 % V/ V 27 1, 62 1, 00 2 Hy dr o g e n c h l o ri de 0 –5 0 0 m g /m 3 27 0, 88 0, 99 8 Am m oni a 0 – 50 0 m g /m 3 27 0, 97 0, 99 9 M e rcu r y chl o ri de 0 – 15 0 μ g / m 3 11 1, 79 0, 94 1

The sta nda rd deviation as a re sult of a linear regression , sho w s h i g h statistical security a n d a sl ope of nearly one fo r eac h c o m pone nt

. The er ro r of t h e c o n v e n t i onal m e t hod has n o t bee n c o m p ensat e d.

Linea r ity

In Fi g

. 2 , 3 a n d 4 t h e l i n eari t y check f

o r

t h e d i ffere nt c o m ponent s are sh o w n. A cal i b rat e d
, co nt i n uo us F T IR

anal y s er (C E M AS F T IR , A B B Aut o m a ti on P r o d u ct s) wa s use d t o m oni t o r t h e t e st gas, gene rat e d by

3/ 7HO V A C A L

. T h e sam p l i ng sy st em and m easuri n g cel l of t h e analyser was heated t o 1 80 °C also tem p erature of evaporator and test gas. T h e e v aporat or wa s placed i n t h e heated m easurin g gas s u pply unit of the analy s er. The carrier g a s fl ow was set at 360 l/min

. As ca rri er gas p u r i f i e d ai r o r ni t r o g e n was use d

.

0 5 10 15 20 25 30 35 40 45 50

0 5 10 15 20 25 30 35 40 45 50 C E M A

S A

n al yser S i g n al [ V

o l

. - % ]NominalValue HOVACAL [Vol.-%]

W a t e r

Vapour

R

egr

es

si on C u r v e

C

onf i denc e A

r e a

T o l e r anc

e A

r ea

Fi g. 2: L i ne ar i t y c h eck of w a ter v a p o ur

At

8 m easuri n g poi nt s, 3 3 m easurem ent s w e re m a de. By lin ear r e g r ession a slop e o f 1,002 an d a stan d a rd devi at i o n of 0 , 54 4 % V/ V wa s f o u n d

.

0 20 40 60 80 100 120 140 160 180

0 2 0 4 0 6 0 8 0 100 120 140 160 180 C E M A

S A n al yser Si g n a l [ m g / m 3 ]NominalValue HOVACAL [mg/m3]

H y dr

ogen C h l o r i de

R

e gr

es

si o n C u r v e

C

o nf i denc e A

r ea

T o l e r anc

e A

r ea

Fi g. 3: L i ne ar i t y c h eck of h y dr oge n chl o r i de

At

6 m easuri n g poi nt s, 2 4 m easurem ent s w e re m a de. By lin ear r e g r ession a slop e o f 0,982 an d a stan d a rd devi at i o n of 4 , 43 6 m g /m 3 w a s fo und

.
4/ 70 5 10 15 20 25 30

0 5 10 15 20 25 30 C E M A S A n al yser S i g n al [ m g / m 3 ]NominalValue HOVACAL [mg/m3]

A m m oni a

R egr es s i on Cur v e

C onf i denc e A r e a

T o l e r anc e A r ea

Fi g. 4: L i ne ar i t y c h eck of a mmoni a

At

6 m easuri n g poi nt s, 2 3 m easurem ent s w e re m a de. By lin ear r e g r ession a slop e o f 0,997 an d a stan d a rd devi at i o n of 4 , 4. 83 3 m g /m 3 w a s fo und

.
Due t o t h e l o w va po u r press u re of wat e r an d aq ueo u s hy dr o g en chl o ri de s o l u t i on, t h e han d l i n g o f t

h i s s o l u t i ons i s very si m p l e . Aq ue ous am m oni a sol u t i ons , especi al l y at hi ghe r c o ncent r a t i ons, can n o t h a ndl e d i n an op en b o ttle. A flex ible b a g system was d e sign ed fo r storag e and h a nd ling them

.
In Fi g

. 5, t h e l i n eari t y chec k f o r

m e rcury i s s h o w n ove r a ra nge o f 1 0 0 μg/ m 3 . Th e HOVACAL ev apo r ato r ou tlet

was c o nnecte d to a MERCEM analyser (Sic k UPA). T h e ga s tube betwee n the e v aporator and the analys er inlet was t h o r o u ghl y heat ed u p t o 18 0 °C t o p r ev ent col d bri dge s an d wal l ads o rpt i o n.

0 20 40 60 80 100 120 140

0 2 0 4 0 6 0 8 0 100 120 140 M E RCE M A n al yser S i g n a l [ μ g / m3 ]NominalValue HOVACAL [μg/m3]

Me r c u r y

R egr es s i on Cur v e

C onf i denc e A r e a

T o l e r anc e A r ea

Fig. 5: Line ar ity c h eck of m ercury At 11 m easuri n g points
, 11 measurem ents were m a de. By lin ear r e gr essi o n a sl o p e of 0,99 5 and a stand a rd devi at i o n of 0 , 70 9 μ g / m 3was f o u n d

.

5/ 7Fi g. 6 s h ow s t h e speci at i o n a n al y s i s . Th e ratio betwee n ele m entary Hg a n d HgCl 2 i s bet w een 2 0 a n d 3 0 % , depe n d i n g on t h e t e m p erat ure o f t h e eva p ora t or [5]

.

0, 0 10
, 0 20
, 0 30
, 0 40
, 0 50
, 0 60
, 0 70
, 0

23 0 °C 23 0 °C 22 0 °C 22 0 °C 20 0 °C 20 0 °C
T e m p er at ur e of Evap or at orHg-Concentration (μg/m3)

Hg( C l 2 )-Con c e nt ra t i on Hg( 0 )- C o ncen t r ati o n Nom i n a l Val u e HO VA CA L

Fig. 6: Speciation anal ysis of HOVACAL mercury tes t gas

At lower tem p eratu r es, t h e ratio Hg °/Hg Cl 2 d ecreases. A h i n t , th at t h erm a l d e co m p o s itio n of Hg Cl 2 may occur at highe r tem p eratures . T h e l o we r limit of tem p eratu r e inv e stig atio ns is 1 8 0 °C, d u e to st ron g wall ads o rption effe cts of m e rcury chloride.



### Conclusions

The HC l

- a n d NH 3-t e st gas , pr o duce d wi t h t h e ca l i b rat i o n gas ge nerat o r HO V A CAL is co m p arab le with cylin d e r test g a s. Th e h u m id ity o f th e HOVACAL test g a s can b e ad ap ted to th e water co n t en t of t h e measu r ing g a s. Th erefore, calib ration and m easu r ing con d ition s can b e m a d e v e ry similar, esp ecially in th e case, when instead of nitrogen or air, a span gas m i xture of typical flue gas c o m pone nt s is use d . An a dditional a dva ntage of th e ho t an d wet sp an g a s, is the red u c ed ad sorp tion wall effect. The ran g e o f w a t e r va p o u r c o vers t h e t y pi cal ap pl i cat i ons i n co nt i n u o u s em i ssi on m oni t o ri ng fo r cal i b rat i on a n d

cro s s sen s itiv ities ch eck

. The h u m i di ty of t h e ge nerat e d m e rcury s p a n gas ca n al s o adapt e d t o t h e hum i d i t y of fl u e gas an d al l o ws besi des th e calib ration o f Hg -an a lysers also t h e ch eck o f th e sa m

p lin g system . Fu rth e r i n v e sti g atio n s will b e m a d e in defi ned cha n ge o f t h e rat i o bet w een H g ° an d HgC l 2 .

6/ 77/7 

### References

[1] W. Jockel, C. Gökcek, H. Bollmacher: Stabilitäts untersuchungen an HCl- und HF-Prüfgasen in Druckgasflaschen . Staub 47 (1987) 280 – 282 [2] H. Braun, A. Gerig: Einfluß von Materialien bei der Beprobung quecksilberchlorid-haltiger Abgase. Staub 54 (1994) 167 – 170 [3] P. Wilbring, Bericht über die Prüfung des Kalibriergasgenerators HOVACAL des Ing.-Büro Dr. Schmäh, Frankfurt, (1997), TÜV-Bericht 936/970001A [4] P. Wilbring, C. Röllig, Bericht über die Prüfun g des Kalibriergasgenerator s HOVACAL des Ing.-Büro Dr. Schmäh Frankfurt, für die Komponente Quecksilber, (1998) TÜV-Bericht 936/980001A [5] P. Wilbring, C. Röllig, Bericht über die Prüfun g des Kalibriergasgenerator s HOVACAL des Ing.-Büro Dr. Schmäh Frankfurt, für die Komponente Quecksilber, (2000) TÜV-Bericht 936/000001A


### Biographical detail of the authors

Dr. Martin Schmäh, Physicist, IAS GmbH, Manufacturer of the calibration gas generator HOVACAL located in Frankfurt am Main, Germany . He works since 1987 in the area of gas analysis and since 1997 Manager of IAS. Dr. Peter Wilbring, Chemist, TÜV Immissionsschutz und Energiesysteme GmbH, D-51101 Köln, Germany. He works since 1990 in the field of environmental protection especially in the area testin g of continuous emission measurement and ambient ai r measurement systems.EcoChem References and Installations 

# EcoChem Installations Third Generation Multicomponent Systems (since 2002)
Beginning late 2001 and early 2002 EcoChem Analyt ics began installation of the updated, 3 rd Generation multicomponent Infrared Analyzer Systems. Thes e systems utilize the MC3 multicomponent analyzer. Aside from the process monitoring applications ident ified as such, the CEMS installed in the US have all been certified to US EPA Part 60, Part 75 and many state regulations including seven systems under PADEP (Pennsylvania Department of Environmental Pr otection) performance specifications. The following listing provides details of MC3 systems which have been placed into service.

# Name Location Application Components EA-239 US EPA Research Triangle Park, NC Combustion Research HBr, HCl, NH3, SO2, NO, CO2, H2O, O2 EA 229-238 CF Industries / Tyco Donaldsonville, LA Nitric Acid Plant NO, NO 2, N2O, NH3, CO, H2O, O2 EA 228 Schuylkill Energy Resources Shenandoah, PA Coal-Fired Power Plant NOx, SO2, CO2, H2O, O2

EA 227 Wheelabrator Chambers Anahuac, TX Medical Waste Incinerator NOx, SO2, CO, H2O, O2

EA 226 Wheelabrator Westchester Peekskill, NY Waste-to-Energy NOx, SO2, CO, H2O, O2

EA 221-225 Ocean State Power Harrisville, RI Gas Turbine with SCR NO, NO2, CO, CO2, SO2, O2, H20

EA 219 Rentech Midwest Energy East Dubuque, IL Nitric Acid / Ammonium Nitrate NO, NO2, N2O, SO2, CO, H2O

EA 218 Wheelabrator Westchester Peekskill, NY Waste-to-Energy NOx, SO2, CO, H2O, O2

EA 217-218 PCS Geismar, LA Nitric Acid NO, NO2, N2O, SO2, CO, H2O EA 216 Albemarle Pasadena, TX Chemical Facility NOx, NH3, CO, H2O
EA 214-215 Wheelabrator Lisbon Lisbon, CT Waste-to-Energy NOx, SO2, CO, H2O, O2

EA 213 Rentech Midwest Energy East Dubuque, IL Nitric Acid / Ammonium Nitrate NO, NO2, N2O, SO2, CO, H2O

EA 212 Covanta Philippines Quezon, Philippines Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, O2

EA 211 PCS Lima, OH Nitric Acid NO, NO2, N2O, SO2, CO, H2O
EA 187 -210 Xcel Power Texas facilities Coal and natural Gas Fired Facilities NOx, SO2, CO, CO2, H2O, O2

EA 186 Rosebud Power Plant Colstrip, MT Coal-Fired Power Plan t NOx, SO2, CO, CO2, H2O, O2

EA 185 Eli Lilly Shadeland, IN Waste Inci nerator SO2, NOx, CO, CO2, H2O, O2
EA 184 Ash Grove Cement Clancy, MT Cement Kiln SO2, NOx, CO, CO2, H2O, O2

EA 182-183 Wasatch Integrated Waste Management District Layton, UT Waste-to-Energy NO x, SO2, CO, CO2, H2O, O2

...Table continues on next pageEcoChem References and Installations

Third Generation Systems (continued)

# Name Location Application Components

EA 181 Sunnyside Cogeneration Sunnyside, UT Coal-Fired Power Pl ant NOx, SO2, CO2, H2O, O2

EA 180 Panther Creek Energy Facility Nesquehoning, PA Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, O2

EA 179 Panther Creek Energy Facility Nesquehoning, PA Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, O2
EA 178 Onyx Environmental Sauget, IL Waste Incinerator HCl, CO, O2

EA 177 Onyx Environmental Port Arthur, TX Process Monitor CO, CO2, H2O, O2

EA 176 Onyx Environmental Port Arthur, TX Process Monitor CO, CO2, H2O, O2

EA 175 Pollution Control Department Bangkok, Thailand Mobile Van NOx, CO, CO2, SO2, H2O, O2, HCl, NH3, H2S, TRS

EA 174 GCC Dacotah Rapid City, SD Cement Kiln SO2, O 2 , H 2 O

EA 173 Eli Lilly Shadeland, IN Waste Incinerator NOx, CO, SO2, HCl, O2, H2O

EA 172 Gilberton Power Frackville, PA Coal-Fir ed Power Plant NOx, SO2, CO2, H2O, O2

EA 171-170 Onyx Environmental Sauget, IL Waste Incinerator NOx, CO, CO2, H2O, O2

EA 169-167 Atlas Equipment Taipei, Taiwan Wa ste Incinerator NOx, CO, SO2, H2O, O2, HCl

EA 166-163 Wheelabrator Falls Township Morrisville, PA Waste-to-Energy NOx, SO2, CO, HCl, H2O, O2

EA 162 SE Analytics Kazakhstan Waste Incinerator NOx, CO, SO2, HCl, O2, H2O

EA 161 SE Analytics Mozambique Waste Incinerator NOx, CO, SO2, HCl, O2, H2O

EA 160 Eli Lilly Shadeland, IN Waste Incinerator NOx, CO, SO2, O2, H2O

...Table continues on next pageEcoChem References and Installations

Third Generation Systems (continued)

# Name Location Application Components

EA 158- 157 Atlas Equipment Taipei, Taiwan Waste In cinerator NOx, CO, SO2, H2O, O2, HCl

EA 156 Fodisch Korea Process HCl, NO, NO 2 , CO, NH 3 , H 2 O

EA 155- 154 GCC Dacotah Rapid City, SD Cement Kiln NOx, CO, O 2 , H 2 O

EA 153- 152 Atlas Equipment Taipei, Taiwan Waste In cinerator NOx, CO, SO2, H2O, O2, HCl

EA 151- 50 Sartec, Italy Sardinia, Italy Waste Incinerator NOx, CO, SO 2 , HCL, O 2 , H 2 O

EA 149- 148 Eli Lilly Shadeland, IN Regenerative Thermal Oxidizer NOx, CO, SO 2 , HCL, O 2 , H 2 O, THC

EA 147 Measurementation Coldspring, TX Process Unit HCl

EA 146 Graymont (QC) Inc Bedford, Quebec Lime Kiln NO, NO2, SO2, CO2, O2, H20

EA 139- 136 Ocean State Power Harrisville, RI Gas Turbine with SCR NO, NO2, CO, CO2, NH3, O2, H20

EA 135 Onyx Environmental Sauget, IL Waste Incinerator SO2, CO, CO2, H2O, O2, HCl

End of TableEcoChem References and Installations



## First and Second Generation Multicomponent Systems

The following is a summary of First and Second Genera tion multicomponent IR analyzer based CEMS that were designed, installed, and supported by the staff of EcoChem Analytics. The list goes back to 1989, covering the complete gamut of applications...from Ga s Turbines to Cement Plants. The industries are broken out for clarity. A total of 52 second genera tion and 390 first generation systems were installed. A comprehensive list or specific references ca n be supplied for any of these industries.



### First Generation Multicomponent Systems (1989 – 1997)

Industry Installations

Cement Industry 64
Coal Fired Utility 48
Diesel Fired Utility Boiler 4

Gas & Oil Utility Boiler 67

Industrial 82
Process Monitoring 6

Waste Incineration 119



### Second Generation Multicomponent Systems (1998 - 2001)

Industry Installations

Cement Industry 2
Utility (Coal, Gas, Oil, Wood) 12

Industrial 6

Waste Incineration 32EcoChem References and Installations



## Installations in Europe
EcoChem Messtechnik has an exclusive arrangemen t with Dr Fodisch Umweltmesstechnik AG for supplying systems in Germany. Additionally, some of these systems have also been provided to several international locations. The MCA-04 Emission analyzer pr ovided by Dr Fodisch is identical to the standard EcoChem MC3 analyzer but is a private label brand na me. Attached please find a list of the installations done by Dr Fodisch.EcoChem References and InstallationsEcoChem References and InstallationsEcoChem References and InstallationsEcoChem References and Installations



## Installations in Korea
Deung Ju Instrument Co., Ltd of Korea provides CEMS based on the MC3 multicomponent analyzer to customers in Korea. Attached please find a list of installationsEcoChem References and Installations



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# PERFORMANCE SPECIFICATION Z: SPECIFICATIONS AND TEST PROCEDURES FOR HCl CONTINUOUS EMISSION MONITORING SYSTEMS AT STATIONARY SOURCES

Revision 2.0 October, 2006i EXECUTIVE SUMMARY

This performance specification describes the crit eria that a hydrochloric acid (HCl) continuous emission monitoring system (CEMS) must meet to be considered valid for EPA compliance and/or other regulatory applications. Each HCl CEMS mu st meet the criteria for accuracy, stability, and instrumental response laid out in this docum ent. In addition, each HCl CEMS must meet the installation requirements in PS-Z.ii REVISION HISTORY

1.1 REVISION 1.0
This document was part of the T149 Alternative M onitoring Petition, and was approved by the Office of Air Quality and Standards in January of 2006

1.2 REVISION 2.0
This revision is an update of the original Proc edure Z document, October 2006. The following are key updates in revision 2.0:

1. Recommendation that all HCL QA gases be certified with a minimum tolerance of 5%

2. Recommendation that a site specific dynam ic spiking protocol be used and, the dynamic spiking protocol would contain the detailed test procedure(s).

3. Discussion for the use of quant itative introduction of the HCL calibration gas and subsequent total flow measurement as method for determining the reference HCL concentration during
each test run.

4. Updated the dynamic spiking overview section for easier flow of information

5. Updated the equations to include percent re lative standard deviation and the calculation for the reference HCL concentration when using q uantitative introduction of the HCL calibration gas with subsequent total flow measurement.iii TABLE OF CONTENTS

1.1 REVISION 1.0..................................................................................................................I I
1.2 REVISION 2.0..................................................................................................................I I

2.0 USING PERFORMANCE S PECIFICATIO N Z.......................................................................4

2.1 WHAT IS THE PURPOSE AND APPL ICABILITY OF PERFORMANCE SPECIFICATIO N Z?........................................................................................................4
2.2 WHAT WILL BE DISCUS SED IN PS-Z?.........................................................................4
2.3 WHAT ARE THE INSTALLATI ON AND PRE-PERFORMANCE SPECIFICATION TEST REQUIREMENTS?...................................................................5
2.4 WHAT SPECIAL DEFINITI ONS APPLY TO PS-Z?........................................................6

3.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQU IREMENTS ..................................9

3.1 WHAT DO I NEED TO KNOW TO ENSURE THE SAFETY OF PERSONS USING PS-Z? ..................................................................................................................9
3.2 WHAT EQUIPMENT AND SU PPLIES DO I NEED?.......................................................9
3.3 WHAT REGENTS AND STA NDARDS DO I NEED? ....................................................10

4.0 PERFORMANCE EVALUATION PROC EDURES AND R EPORTING................................11

4.1 WHAT IS THE PURPOSE OF TH E PERFORMANCE SPECIFICATION TESTS AND WHAT IS REQUIRED TO PERFORM THE TESTS? ..............................11
4.2 HOW DO I REPORT THE RESULTS OF THE INITIAL PERFORMANCE SPECIFICATION TEST?...............................................................................................15

5.0 PERFORMANCE CRITERIA AND CALCUL ATIONS..........................................................16

5.1 WHAT ARE THE PERFORMANCE CRI TERIA FOR MY HCL CEMS?........................16
5.2 WHAT CALCULATIONS, EQUATIONS, AND DATA ANALYSES ARE NEEDED?......................................................................................................................17
5.3 CRITERIA FOR AC CEPTANCE....................................................................................25
5.4 BIAS CORREC TION .....................................................................................................25

6.0 OTHER REQUIREMENTS AND INFORM ATION................................................................27

6.1 WHAT QUALITY CONTROL M EASURES ARE REQUIRED? .....................................27
6.2 WHAT CALIBRATION AND STANDA RDIZATION PROCEDURES MUST I PERFORM?...................................................................................................................27
6.3 WHAT POLLUTION PREVENTION PROCEDURES MUST I FOLLOW? [RESERVED ].................................................................................................................27

7.0 RELEVANT REFE RENCES.................................................................................................30

Table 1. Performance Specification Test Calibration Gas Ranges

Figure 1. Dynamic Spiking Overview4 2.0 USING PERFORMANCE SPECIFICATION Z

2.1 WHAT IS THE PURPOSE AND APPLICABI LITY OF PERFORMANCE SPECIFICATION Z?
The purpose of Performance Specification Z (PS-Z) is to establish the initial performance requirements for evaluating the acceptability of a HCl CEMS. Such app lications may include, (1) instrument, method or procedure calibration, and (2) evaluation or certification for in itial acceptance.

2.1.1 Application

This specification is for evaluating the acceptability of a HCl CEMS at t he time of installation and during periodic quality assurance checks. PS-Z applies to you if you will be using a HCl CEMS to demonstrate compliance with a regulatory HCl or HCl/Cl 2 emission standard.
2.1.2 Measurement Capabilities

The HCl CEMS must be capable of measuring HCl concen trations in the units of the applicable standard or in units that can be converted to units of the applicable standard.
2.1.3 Other Monitoring

If your HCl CEMS is capable of reporting the HCl concent ration in the units of the existing regulation, no additional monitoring is necessary. If your HCl CEMS does not report concentrations, in the units of the existing standard, then other monitoring (e.g., oxy gen, temperature, and pressure) are necessary to convert the units reported by your CEMS to the units of the standard.

2.2 WHAT WILL BE DISCUSSED IN PS-Z?

PS-Z covers two basic topics: (1) the instrument r equirements for an HCl CEMS and (2) the requirements that each HCl CEMS must meet during the performance specification test.

2.2.1 Instrument Requirements

The HCl CEMS must be able to accurately report conc entrations of HCl in stack effluent. It may do so by extracting a representative sample (path or point samp ling may be used if the samp le is representative) of stack effluent and analyzing the effluent to provide an output proportional to the HCl concentration. The CEMS operating range (zero to span) should encompas s the response of the HC l CEMS for all expected HCl concentrations, including the applicable emissi on limit. The CEMS must have a system response time that is less than or equal to two minutes. Fina lly, the instrument or operator must be able to perform daily calibration drift tests, quarterly calibrat ion error tests, and annual accuracy tests.5 2.2.2 Performance Specification Test

The purpose of the performance specification test is to establish the accuracy, precision, bias, and system response time of the HCl CEMS. Specifically , the following will be either tested or documented as part of the performance specification test requirements listed in Sections 3.0 and 4.0 of this document: (1) data recorder scale, (2) daily calibr ation drift, (3) installation and me asurement location, (4) calibration drift test, (5) calibration error te st, (6) system response time, (7) stratification test, (8) accuracy
determination.

2.3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE SPECIFICATION TEST REQUIREMENTS? 2.3.1 Installation Requirements

The sampling location of the HCl CEMS should be dow nstream of all pollution control equipment at a position where the HCl concentration is directly r epresentative or can be corrected so as to be representative of total emissions from the statio nary source. It is recommended that the sampling location be at least two equivalent diameters downstr eam of the nearest control devices, point of pollution generation, bend, or other point at which a change in pollutant concentration or flow disturbance may occur. The sampling location is also recommended to be at least a half equivalent diameter upstream from the exhaust or control device. The equivalent diameter is calculated according 40 CFR Part 60, Appendix A, Method 1, Section 2.1 I

.
Either point or path sampling may be used. For poi nt sampling the measurement point should be no less
than 1.0 meter from the stack or duct wall or located ov er the centroidal area of the stack or duct cross section. For a path sampling CEMS the effective measur ement path should be (1) totally within the inner area bounded by a line 1.0 meter from the stack or duc t wall, or (2) have at least 70 percent of the path within the inner 50 percent of the stac k diameter or duct cross section, or (3) be centrally located over any part of the centroidal area.

The sample collection and instrumental analyzer portio ns of your HCl CEMS may be located any distance from the sampling point provided the transmission efficiency from the sampling point to the sample collection point can be determined and meets the criteria outlined later in this performance specification. It is also recommended that the sampling probe for the HCl CEMS be located at point without stratification (section 3.1.5).6 2.3.2 Reference Method Measurement Location

You must select, as appropriate, an accessible refe rence method (RM) measurement point at least two equivalent diameters downstream from the nearest control device, the poi nt of pollutant generation, or other point at which a change in the pollutant concen tration or emission rate may occur, and at least a half equivalent diameter upstream from the efflue nt exhaust or control device. When pollutant concentration changes are due solely to diluent leakage ( e.g. , air heater leakages) and pollutants and diluents are simultaneously measured at the same loca tion, a half diameter may be used in lieu of two equivalent diameters. The CEMS and RM locations need not be the same. If dynamic spiking is employed to determine the system accuracy, bias, and pr ecision, the spiking of the calibration gas must encompass the sampling system of the HCL CEMS.

2.3.2.1 Reference Method Traverse Points
Select traverse points that assure acquisition of representative samples over the stack or duct crosssection. The minimum requirements are as follows: Establish a "meas urement line" that passes through
the centroidal area and in the directi on of any expected stratification. If this line interferes with the CEMS measurements, displace the line up to 30 cm (12 in.) (or 5 percent of the equivalent diameter of the cross section, whichever is less) from t he centroidal area. Locate three tr averse points at 16.7, 50.0, and 83.3 percent of the measurement line. If the measurement li ne is longer than 2.4 meters (7.8 ft) and pollutant stratification is not expected, the three traverse po ints may be located on the line at 0.4, 1.2, and 2.0 meters from the stack or duct wall. This option mu st not be used after wet scrubbers or at points where two streams with different pollutant concentrations are combined.

Other traverse points may be selected, provided t hat they can be shown to the satisfaction of the Administrator to provide a representative sample over the stack or duct cross section. Conduct all necessary RM tests within 3 cm (1.2 in.) of the traver se points, but no closer than 3 cm (1.2 in.) to the
stack or duct wall.

2.4 WHAT SPECIAL DEFINITIONS APPLY TO PS-Z?

Calibration Drift: The difference in the CEMS output readings from the established reference value after a stated period of operation during which no unsch eduled maintenance or adjustment took place.

Calibration Error: The mean difference between the concentration indicated by the CEMS and the known concentration generated by a calibration source at three levels when the entire CEMS, including the sampling interface is challenged. A CE test is performed to document the accuracy and linearity of
the CEMS over the ent ire measurement range.7 Centroidal Area: means a concentric area that is geometrically similar to the stack or duct cross section and is no greater than 1 percent of the stack or duct cross-sectional area.

Continuous Emission Monitoring System : means the total equipment required for the determination of a gas concentration or emission rate. The sample interface, pollutant analyzer, diluent analyzer, and data recorder are the major subsystems of the CEMS.

Correlation Coefficient: determines the extent of a linear rela tionship between two fields over a given period of time.

Data Recorder: The portion of the CEMS that provides a record of analyzer output, flags which indicate normal operation, and flags indicating abnormal operation. The data recorder may record other pertinent data such as effluent flow rates, and various instrument temperatures.

Diluent Analyzer: means that portion of the CEMS t hat senses the diluent gas (i.e. O 2 ) and generates an output proportional to the gas concentration.

Dynamic Spiking: a procedure used to document the accuracy, precision, and bias of the monitoring system by quantitatively sp iking a certified gas into the pollutant gas stream.

High-level drift: means the absolute difference between a high-level calibration gas and the monitor response, in units of the applicable standard.

Instrument Measurement Range : The range of HCl concentrations t he instrument can reliably measure from the lowest concentration to the highest.

Intercept: value of the Y variable when the X variable is equal to zero.

Linear Regression: a methodology used to find a formula that can be used to relate two variables that are linearly related.

Path Sampling CEMS : A CEMS that samples the source efflue nt along a path greater than 10 percent of the equivalent diameter of the stack or duct cross section.

Point Sampling CEMS : A CEMS that samples the source effluent at a single point.8 Pollutant Analyzer: means that portion of the CEMS that senses the pollutant gas and generates an output proportional to the gas concentration.

Relative Accuracy (RA): means the absolute mean difference between the gas concentration or emission rate determined by the CE MS and the value determined by t he Reference Method (RM), plus the 2.5 percent error confiden ce coefficient of a series of tests, divided by the m ean of the RM tests or the applicable emission limit.

Response Time: The time interval between the start of a step change in the system input and when the pollutant analyzer output reached 95% of the final value.

Sample Interface: The portion of the CEMS used for one or more of the following: sample acquisition, sample transport, sample conditioning, or protection of the monitor from the effects of stack gas.

Slope: The rate of change of Y relative to the change in X.

Stratification: means the change in effluent concentration in a duct, over time when comparing a reference measurement (centroid of duct ) to traversed sampling concentrations.

Zero drift: means the absolute difference between a high-level calibration gas and the monitor response, in units of the applicable standard.9 3.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQUIREMENTS

3.1 WHAT DO I NEED TO KNOW TO ENS URE THE SAFETY OF PERSONS USING PS-Z?

People using PS-Z may be exposed to hazardous material, operational hazards, and hazardous site conditions. PS-Z does not address all the safety issues associated with its use. It is your responsibility to ensure the safety of persons using PS-Z. Some he lpful references may include the CEMS manual, the CEMS manufacturer, other reference me thods, and on-site safety regulations.

3.2 WHAT EQUIPMENT AN D SUPPLIES DO I NEED? 3.2.1 Equipment for the CEMS

1. Sample Extraction System: This portion of the CEMS must present a sample of source effluent to the sampling module that is directly representative or can be corrected so as to be representative of source. The sample extraction system typically consists of a sample probe
and a heated umbilical line.

2. Pressure Regulation Module: The pressure regulation module is designed to remove both free particulates and water-soluble aerosols fr om the gas stream prior to analysis by the sampling module. This module also provides a sample gas to the analyzer at a constant pressure (optional).

3. Analysis module: The portion of the CEMS that quantita tes stack gas concentrations of HCl.

4. Diluent Module: This portion of the CEMS quantifies st ack gas concentrations of oxygen or
CO 2 . For systems with a multi-component analyzer, the same analyzer quantifies the concentration of all measured analytes.

5. System Controller: This portion of the CEMS provi des control of the analyzer, sample probe, pressure regulation module and the sample interface.

6. Data recorder : Your HCl CEMS must be able to record HCl concentrations and instrument status signals (flags).

3.2.2 Equipment Specifications

The CEMS data recorder output range must include zero and a high-level value. The range of the data recorder and the measurement range of the HCl CEMS will be documented. The high-level value is chosen by the source owner or operator and is defined as follows:10 For an HCl CEMS installed to measure controlled emi ssions or emissions that are in compliance with an applicable regulation, the high-level value should be at least 1.5 times the emission standard level and encompass the HCl concentration leve ls expected by the process.

The CEMS design should also allow the determinati on of calibration drift at the zero and high-level values. In special cases, the Administrator may approve a single-point calibr ation-drift determination.

3.3 WHAT REGENTS AND STANDARDS DO I NEED? 3.3.1 Reference Gases, Gas Cells, or Optical Filters

See Table 1 for reference gas concentration ranges.11 4.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING

4.1 WHAT IS THE PURPOSE OF THE PERFORM ANCE SPECIFICATION TESTS AND WHAT IS REQUIRED TO PERFORM THE TESTS?

The purpose of the performance specification tests is to determine the accuracy, precision, bias, and system response time of the HCl CEMS.

4.1.1 Pretest Preparation

Prior to the start of your initial performance specific ation tests, you must be sure that the HCl CEMS is installed according to the specificat ions laid out in this document. After installing the HCl CEMS, it is recommended you use the CEMS for a period of time to familiarize yourself with its ope ration. It is also recommend that you conduct daily chec ks of the zero and high-level drift, conduct a calibrati on error test, and conduct a calibration drift check to verify that th e instrument is functioning properly. When you are confident that the instrument is performing satisfac torily it is time to prepare for the performance specification tests.

4.1.2 Data Recorder Scale Check

The range of the data recorder a nd the measurement range of the HCl CEMS will be documented. The CEMS operating range (zero to span) and the range of the data recorder should encompass both the response of the HCl CEMS for all expected HCl co ncentrations and the applicable emission limit.

4.1.3 Calibration Drift Check

The HCL CEMS must perform a calibration check at leas t once per day. Certified gases must be used to perform the zero and high -level drift checks. All data will be recorded.

4.1.4 Installation and Measurement Location Check

The installation location of the HCL CEMS must adhere to section 1.3.1 of this document. In addition, the location of any reference method testing must adhere to section 1.3.2 of this document.

4.1.5 Stratification Test

The stratification test must be conducted when the facility is operating during normal operation. The purpose of this test is to verify that excess strati fication of the target pollutant does not exist at the sampling point of the monitoring system.

To determine whether effluent stratification exists, a dual probe system should be used to determine the average effluent concentration while measurements at each traverse point are being made. One probe,12 located at the stack or duct centroid, is used as a stationary reference point to indicate change in the effluent concentration over time. The second probe is used for sampling at the traverse points specified in Method 1. The traverse points are sampled for five minutes at each point. You may test for stratification at the HCl CEMS samp ling point by using either velocity tests as described in Method 2 II , HCl concentrations using Methods 26 or 26A, or an acceptable alternative (i.e. CO or Nox) A minimum of 12 sampling points will be used, with 6 sampling points along each of the two traverses.

4.1.6 Seven-day Calibration Drift Test

The seven-day calibration drift te st must be conducted when the fac ility is operating during normal operation. The purpose of this test is to verify that the instrument operat ion is stable. During thecalibration drift test period you must determine the magnitude of the zero calibration drift and the highlevel calibration drift at least once each day. During the stability tests no adjustments or calibrations may be made to the CEMS. If periodic automatic or ma nual adjustments are made to the CEMS zero and high-level calibration settings, conduct the CD test imm ediately before these adjustments, or conduct it in such a way that the CD may also be determined.

The calibration drift will be determined at the zero and high-level value of the HCl CEMS. Introduce to the CEMS the reference gases, gas cells, or optical filter s (these need not be certified) for the zero and high level values. Record the CEMS response and subtract this value from the reference value. The calibration gas concentrations are provided in Table 1.

4.1.7 Calibration Error

The HCL CEMS will be challenged three non-consecutive ti mes with zero, mid-level, and high-level certified HCL gases (Table 1). The cylinder gases need not be EPA Protocol 1 gases. The calibration gases will be injected into the sample system as clos e to the sampling probe outlet as practical and will pass through all CEMS components used during normal monitoring. The difference between the instrument response and t he reference value (certified gas) will be calculated after each injection and the resulting three differences will be averaged to determine the CE at each measurement point.
4.1.8 System Response Time

Introduce zero gas into the analyzer. When the system output has stabilized (no change greater than 1 percent of full scale for 30 sec), introduce an upscal e calibration gas and wait for a stable value. Record the time (upscale response time) required to reach 95 percent of the final stable value. Next, reintroduce the zero gas and wait for a stable reading before record ing the response time (downscale response time). Repeat the entire procedure three times and determine the mean upscale and downscale response times. The slower or longer of the two means is the system response time.13 Calibration gas ranges for the response time test are provided in Table 1. If using a multi-component analyzer, the response time can be bas ed on any analyte measured by the CEMS.
4.1.9 CEMS Accuracy

The accuracy of the HCl CEMS shall be determin ed by performing either a relative accuracy determination or by dynamic spiking.
4.1.9.1 Relative Accuracy (RA)

Conduct the RA test while the affect ed facility is operating during normal operation, or as specified in an applicable subpart. The RA test may be conducted during the CD test period.

Reference Methods (RM) . Unless otherwise specified in an applicable subpart of the regulations, Methods 26 or 26A, or their approved alternatives, ar e the reference methods for HCl. Other reference methods for moisture, oxygen, etc. may be necessary.

Sampling Strategy for RM Tests . Conduct the RM tests in such a way that they will yield results representative of the emissions from the source and c an be correlated to the CEMS data. It is preferable to conduct the diluent (if applicable), moisture (i f needed), and pollutant measurements simultaneously. However, diluent and moisture measurements t hat are taken within an hour of the pollutant measurements may be used to calculate dry pollutant concentration and emission rates. In order to correlate the CEMS and RM data prope rly, note the beginning and end of each RM test period of each run (including the exact time of day ) on the CEMS chart recordings or other permanent record of output. For integrated samples make a sample traverse of at least 21 minutes, sampling for an equal time at each traverse point.

Number of RM Tests . Conduct a minimum of nine sets of all necessary RM test runs.

NOTE: More than nine sets of RM tests may be performed. If this option is chosen, a maximum of three sets of the test results may be rejected so long as the total number of test results used to determine the RA is greater than or equal to nine. However, a ll data must be reported, incl uding the rejected data.

Correlation of RM and CEMS Data . Correlate the CEMS and the RM test data as to the time and duration by first determining from the CEMS final output (the one used for reporting) the integrated average pollutant concentration or emission rate for each pollutant RM test period. Consider system response time, if important, and confir m that the pair of results are on a consistent moisture, temperature, and diluent concentration basis. Then, compare eac h integrated CEMS value against the corresponding average RM value. If the RM has an integrated samp ling technique, make a direct comparison of the RM results and CEMS integrated average value.14 Calculate the mean difference between the RM and CEMS values in the units of the emission standard, the standard deviation, the confidence coefficient, and the relative accuracy according to the procedures
in Section 4.0.
4.1.9.2 Dynamic Spiking
Dynamic spiking can be used in lieu of the Relative Accuracy Determination as an alternative method for documenting the accuracy, precision, and bias of the HCl CEMS. This se ction provides an overview of a typical dynamic spiking procedure. A site specific dynamic spiking protocol, which provides detailed steps of the actual procedure, is required. Figure 1 provides an over view of a typical dynamic spiking arrangement.

While the HCl CEMS is sampling flue gas, HCl refe rence gas is introduced into the CEMS sample interface by using a mass flow controller (or equivalent ). The target ratio of actual flue gas to the HCl reference gas is 9:1, but must be kept at a minimum ratio of 1:1. The HCl conc entration is quantitated by
the HCl CEMS.

Certified HCL calibration gas is spiked at a minimum of three levels (low, mid, high) through the HCL CEMS measurement range. For each test level, a minimum of 30, one minute averaged HCL values are collected. The percent relative st andard deviation, for each data set, should not exceed 20%. Table 1 provides guidance on the HCL concentrations for the low, mid, and high test runs.

Several methods exist to calculate the dynamically spiked HCL concentration (represents the reference HCL concentration). Two common methods are: (1) Use of an element of opportunity and (2) Quantitative introduction of the HCL calibration gas with total flow measurement. Other methods may be used; however, a site specific protocol should document the procedure(s) used.

An element of opportunity can be used to calculate the dynamically spiked HCl concentration (represents the reference HCl concentration). The element of o pportunity can either be be an analyte, which would normally be present in the flue gas at steady concentrations, or total fl ow through the system. Examples of prospective analytes which could be used as elements of opportunity are O 2 , NOx, SO 2 , CO 2 , or moisture. The analyte(s) is measured using a cert ified reference CEMS, separate from the HCL CEMS.

Total flow through the system may also be used as an element of opportunity to calculate the dynamically spiked HCL concentration. Examples the total flow measurement are the use of a calibrated laminar flow element, or use of a tracer gas with subsequent downstream measurement (for example: hydrocarbon tracer gas with subsequent calibrated GC measurement downstream).

Regardless of the element of opportunity, It is re commended that the element of opportunity data set, for each test level (low, mid, high) have a relative pe rcent standard deviation less than or equal to 20%.15 Quantitatively introducing the HCL calibration gas, a nd, measuring the total flow is another method for documenting the dilution, and subsequent theoretical va lue of the HCL concentration spiked for each test run. Use of this method requires documenting the quantitative introduction of HCL gas into the system; such as a method 205 procedure or similar protocol.

It is important to compensate the HCl reference conc entration(s) for any background HCL present in the flue gas. The HCl concentration of the flue gas (bas eline HCL) shall be determined prior to each spiking trial. The baseline HCl concentration is based upon a series of at least 10, one-minute averaged data points. Baseline data must be collected immediately prio r to each test run. The data points must include the HCl concentration, element of opportunity concent ration(s) and/or the total flow. A site-specific standard operating procedure for the HCL dynamic spiking is required.

Linear regression is used to establis h the accuracy, precision, and bias of the HCl CEMS. The criteria for the HCl dynamic spiking are:

1. The correlation coefficient (r) mu st be greater than or equal to 0.90

2. The slope must be 1.0, +/- 0.15

3. The Intercept must be equal to or less than 15% of the instrument span

4.2 HOW DO I REPORT THE RESULTS OF TH E INITIAL PERFORMANCE SPECIFICATION TEST?

Summarize the results of the calibration drift, calibrati on error, response time, stratification, and accuracy tests in tabular form. Include all data sheets, calculations, and records of CEMS measurements necessary to substantiate the pe rformance of the CEMS and any other devices or methods (e.g., method 26A). The CEMS measurements shall be reported to the agency in units of ppmv, on a dry basis.16 5.0 PERFORMANCE CRITERIA AND CALCULATIONS

5.1 WHAT ARE THE PERFORMANCE CRITERIA FOR MY HCL CEMS?

You must demonstrate that your HCl CEMS has adequat e precision, accuracy, sy stem response time and data reporting capabilities to determi ne if your facility is in complianc e with HCl emission standards or operating permit limits as specifi ed in applicable regulations or permits. You will demonstrate this capacity by showing that your HCl CEMS meets the following performance criteria.

5.1.1 Data Recorder Scale

The measurement range of the HCL CEMS, and the data recorder scale, must encompass the expected HCL concentrations as well as the applicable emission limit.

5.1.2 Calibration Drift

The daily zero and high-level calibration drift is 5% of the instrument span. Zero and high-level calibration drifts shall be adjusted, at a minimum, whenever the 24-hour zero drift exceeds the limits of the calibration drift specification. The amount of exce ss zero and high-level drift measured at the 24-hour interval checks will be recorded. Section 4.2 prov ides the equations for calculating the zero and highlevel calibration drifts.

5.1.3 Installation and Measurement Location

The installation requirements and measurement locati on of the HCL CEMS will m eet the specifications
outlined in section 3.1.1 and 3.1.2 of this document.

5.1.4 Stratification Test

The stratification in the stack or duct, at the measur ement location, must be less than or equal to a 10 percent between the average concentrati on in the duct or stack and the concentration at any point more
than 1.0 meter form the duct or stack wall. Secti on 4.2.2 provides the equation for calculating the
stratification of the stack or duct.
5.1.5 Seven-day Calibration Drift Test Criteria

The daily zero and high-level drift each must be le ss than 5% of the instrument span for seven consecutive days. See Section 4.2.2 for the equations used to determine the zero and high-level drift.17 5.1.6 Calibration Error Test

The mean difference between the CEMS and the reference values, at all three test levels, must be no greater than 5% of span. See Section 4.2.3 for t he equation used to determine the calibration error.
5.1.7 Response Time Test

The CEMS response time shall not exceed 2.0 min to achieve 95 percent of the final stable value. If using a multi-component analyzer, the response time can be based on any analyte measured by the
CEMS.
5.1.8 Relative Accuracy

The RA of the CEMS must not be gr eater than 20% of the mean value of the reference method (RM) test data, or not greater than 10% in terms of the emission standard (ppmv, dry), or have an absolute difference of less than 5 ppmv between the mean reference value and the mean CEMS value. See Section 4.2.5 for the equations used to determi ne the relative accuracy of your CEMS.
5.1.9 Dynamic Spiking

Dynamically spiking may be used in lieu of a relative accuracy test as a means to document the accuracy, precision, and bias of the HCl CEMS.

The criteria for the HCl dynamic spiking is:

• The correlation coefficient, r, must be greater than or equal to 0.90

• The slope must be 1.0, +/- 0.15

• The Intercept must be equal to or less than 15% of the instrument span.

See Section 4.2.8 for equations to determine the linea r correlation coefficient, the slope and the intercept

.

At a minimum, the data set must meet the correlati on coefficient. If this is not met, the dynamic spiking procedure must be repeated until the co rrelation coefficient criteria is met. If the HCl CEMS has met the correlation coefficient requirement, but does not meet ei ther the slope, or intercept criteria, a bias exists and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine the corrected value are provided in Section 4.2.8.1. The correction factor must be applied to the HCl CEMS one-minute average data until a new dynamic spiking procedure indicates the specific bias no longer exists, or, a different correcti on factor (bias) is indicated.

5.2 WHAT CALCULATIONS, EQUATION S, AND DATA ANALYSES ARE NEEDED?18 5.2.1 Daily Upscale and Zero Drift

CD =( ⎪ R - A ⎪ / S ) * 100 (Equation 1)

where:

CD = Percent calibration drift (%),
R = Reference value of zero or high level calibration gas introduced into the monitoring system (ppmv),
A = Actual monitor response to calibration gas (ppmv),
S = Span of the instrument (ppmv).

5.2.2 Calibration Error

CE = ⎪ d avg / S ⎪ * 100 (Equation 2)

where:

CE = Percent calibrat ion error (%),

d avg = Mean difference between CEMS response and the known reference gas (ppmv),
S = Span of the monitor (ppmv).

5.2.3 Mean Difference

Calculate the arithmetic mean difference as follows:


# ∑ = i avg 

### d
n d 1 (Equation 3)

where :

d avg = Arithmetic mean of differences

n

= Number of data sets

di = difference of each data set19 And

i i i 

### y x d

− = (Equation 4)

where :

x i = Value at data set x

yi = Value at data set y

5.2.4 Relative Accuracy

The RA for the monitors will be calculated usin g the least restrictive of equation 6 or equation 7:

RA = ( ⎪ d avg ⎪ + ⎪ CC ⎪ ) (Equation 5)

or
RA = (( ⎪ d avg ⎪ + ⎪ CC ⎪ ) / TM avg ) * 100 (Equation 6)

where:

RA = Relative accuracy, either percent or ppmv or % absolute,

d avg = Arithmetic mean of differences between value measured by the installed CEMS and the reference method,

CC = Confidence coefficient,

TM avg = Average value measured by the reference test method monitors.

5.2.5 Confidence Coefficient

The confidence coefficient will be calculated using equation 8:

CC = t 0.975 * (S d / (n 1⁄2 )) (Equation 7)

where:

CC = Confidence coefficient,

t 0.975 = t-value obtained from Table 2.1 in Performance Specification 2, 40 CFR Part 60 Appendix B20 5.2.6 Standard Deviation (of Differences)

S d = Standard deviation of differences measured between the installed CEMS and the reference methods calculated using equation 8:

2 / 1 2

1

1 2

1 ⎥ ⎥ ⎥ ⎥ ⎥ ⎥

⎦ ⎤

⎢ ⎢ ⎢ ⎢ ⎢ ⎢

⎣ ⎡

− ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛

−

= 

## ∑ ∑
=

=

n n d

S n
i i n

i i

d 

## d (Equation 8)

where: n = Number of values in this data set.

5.2.7 Stratification

The value, at each traverse point, is compared to th e average value for all sampling points to determine the percent stratification us ing the following equation:



### % 100 *
ave i 

### C C S

−

= (Equation 9)

where:

S = percent stratification

C i = concentration or velocity at sampling point i

C ave = average concentration or velocity at all sampling points

5.2.8 Baseline data

5.2.8.1 HCL CEMS data
The baseline HCL concentration is measured prior to each dynamic spiking run. For each baseline HCL data set, calculate the average, in ppm, using equation 10.

Calculate the arithmetic mean of a data set as follows:


# ∑ = i 

### x n x 1 (Equation 10)

where :21 

### x = Arithmetic mean

n

= Number of data points

x

i = Value of each data point

5.2.8.2 Element of Opportunity Data
The element of opportunity data set is acquired prior to each dynamic spiking test run, simultaneous to
the baseline HCL concentration data set. For each el ement of opportunity, calculate the average value using equation 10.

5.2.8.3 Flow via dilution
When using dilution of a measured analyte (such as a hydrocarbon with s ubsequent GC measurement) as an indicator of total flow, calculate the total flow, in liters per minute using equation 11.

Calculate the total flow as follows:

Tflow = 

### ) ( * ) (
measured Analyte Tflow spike Analtye

− − (Equation 11)

Tflow = Total flow through the system in lpm

Analyte-Spike = Concentration of Spiked Analyte (ppm)

Analyte-measured = Measurement, downs tream, of spiked Analyte (ppm)

Calculate the average flow value, for the data set, using equation 10.

5.2.9 Dynamic Spiking Test run data

5.2.9.1 HCL CEMS data
For each dynamic spiking test run, calculate the av erage and percent relative standard deviation of the data set using equations 10 and 12, respectively.22 Calculate the percent standard deviation as follows:

2 / 1 2

1

1 2

1
⎥ ⎥ ⎥ ⎥ ⎥ ⎥ ⎥

⎦ ⎤

⎢ ⎢ ⎢ ⎢ ⎢ ⎢ ⎢

⎣ ⎡

− ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛

−

= 

## ∑ ∑ =

=

n n d

PRS n
i i n

i i

d 

## d (Equation 12)



### x

Where:



### = d 

### PRS Percent Relative Standard Deviation of the data set



### x = Arithmetic mean

5.2.9.2 Element of Opportunity data
For each dynamic spiking test run, calculate the av erage and percent relative standard deviation of the data set using equations 10 and 12, respectively. If using total flow as a means to determine the reference HCL calibration gas concentration, use equation 11 to calculate the total flow prior to determining the average and percent rela tive standard deviation of the data set.

5.2.10 Reference HCL concentration calculations 5.2.10.1 Element of opportunity to cal culate reference HCL concentration
Equation 13 is used to calculate the reference HCL co ncentration for a given dynamic spiking test run.23 HCl ref = 

### l BaselineHC CalGas pre Opp post Opp

avg avg 

### +

− −

− * 1 (Equation 13)

where:

Opp-post avg = average reference element of opportunity value during dynamic spiking test run

Opp-pre avg = average reference element of opport unity value during baseline test run

CalGas = HCl calibration gas concentration

Baseline HCl = CEMS HCl average baseline value

5.2.10.2 Quantitative HCL calibration gas introducti on and total flow to calculate reference HCL concentration
When using the quantitative introduction of calibrati on gas and total system flow to calculation the reference HCL concentration for a given dynamic spiki ng test run, use equation 14. Equation 11 is used to calculate the total system flow.

HCl ref = 

### l BaselineHC CalGas Tflow Cflow

avg avg 

### + * (Equation 14)

Where:

HCl ref = Reference HCl value for run “X”

Cflow = Average calibration HCL ga s flow rate into system (lpm)

Tflow = Average Total System Flow during run (lpm)

CalGas = HCl calibration gas concentration

Baseline HCl = CEMS HCl average baseline value24 5.2.11 Linear Regression Linear regression is used to calcul ate the accuracy, precision, and bias of the HCL CEMS. For each dynamic spiking test run, plot the HCL CEMS reference value, Xaxis, versus the HCL measured value, Y axis. Determine the correlation coefficient (r ), the slope, and the intercept using equations 15-18.



### x b b y o 1 

### ˆ +

= (Equation 15)

where:

b o = The y intercept

b 1 = The slope

The intercept is calculated according to the following equation:



### x b y b
o 1 

### − = (Equation 16)

where:


# ∑

= 

### = n

i i 

### x n x
1 

### 1



# ∑

= 

### = n

i i 

### y n y
1 

### 1

The slope of the line is calculated according to equation below:



# ∑ ∑

= =



### − − −

= n

1 i 2 i n

1 i i i

1 

### ) x x ( ) y y )( x x ( b (Equation 17)

The linear correlation coefficient is calc ulated according to the following equation.25 

# ∑ ∑

∑

= = =



### − − ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

− −

= n

i i n

i i n

i i i



### y y x x y y x x

r

1 2

1 2 2

1 2 

### ) ( ) ( ) )( ( (Equation 18)

5.3 CRITERIA FOR ACCEPTANCE The criteria for the HCl dynamic spiking is:

• The correlation coefficient, r, must be greater than or equal to 0.90

• The slope must be 1.0, +/- 0.15

• The Intercept must be equal to or less than 15% of the instrument span.

At a minimum, the data set must meet the correlati on coefficient. If this is not met, the dynamic spiking procedure must be repeated until the corr elation coefficient criteria are met. If the HCl CEMS has met the correlation coefficient requirement, but does not meet ei ther the slope, or intercept criteria, a bias exists and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine the corrected value are provided in Section 5.4. The correction factor must be applied to the HCl CEMS one-minute average data until a new dynamic spiking procedure indicates the specific bias no longer exists, or, a different correction factor (bias) is indicated.

5.4 BIAS CORRECTION If the HCl CEMS fails to meet both the slope and intercept criteria, the following correction factor must be applied to the one-minute average HCl data:

1 0 

### b b y C i

C 

### −

= (Equation 19)

Where:

C 

### C = corrected CEMS HCL concentration26 y

i = CEMS reported HCL concentration

b 0

= the intercept of the l east squares linear regression line

b 1 = the slope of the least squares linear regression line

b). If the HCl CEMS fails to meet the slope criter ia, but meets the intercept criteria, the following correction factor must be applied to the one-minute average HCl data:

1 

### b y C i

C 

### = (Equation 20)

c). If the HCl CEMS fails to meet the intercept criteria , but meets the slope criteria, the following correction factor must be applied to the one-minute average HCl data:

0 

### b y C i

C



### −

= (Equation 21)27 6.0 OTHER REQUIREMENTS AND INFORMATION

6.1 WHAT QUALITY CONTROL MEASURES ARE REQUIRED?
Ongoing quality control will include daily calibration drift tests, quarterly calibration error audits (absolute calibration audit), and annual accuracy test audits. Specific procedures and performance criteria are included in Procedure DD: Quality Control and Quality Assurance Requirements for Hydrochloric Acid Continuous Emission Monitoring Sy stems at Stationary Sources.

6.2 WHAT CALIBRATION AND STANDARDIZATION PROCEDURES MUST I PERFORM?
Refer to your CEMS owner’s manual and manufacture r to determine what calibration and standardization procedures are required for your HCl CEMS.

6.3 WHAT POLLUTION PREVENTION PROC EDURES MUST I FO LLOW? [RESERVED]28 Table 1. Performance Specification Test Calibration Gas Ranges

HCl Calibration Gas Concentrations a

Test Units Zero Mid-Level High-Level

Calibration Drift and Response Time Test b % of Span 0-30 NA 50-100

Calibration Error Test % of Span 0-30 30-50 50-100

Dynamic Spiking % of Span 0-50 25-75 50-100

a A copy of the supplier’s certificate of analysis mu st be provided for each gas cylinder. Calibration gases do not need to be Protocol 1 gases. It is recommended that the calibration gases, for all QA, have a
minimum tolerance of 5%.

b If conducting the response time using a multi-component analyzer, the response time test can be based on any measured analyte.29 Figure 1. Typical Dynamic Spiking Apparatus



### Typical Dynamic Spiking Apparatus

HCL CEMS 900-1000 ppm HCL in N2 Calibration Manifold (Mass flow meters) Sample Probe

• Heated Filter

• Pressure Control

• Laminar Flow Element Heated sample line

Flue Gas

Gas Conditioner Reference Measurement(s) Heated line inside sample umbillical30 7.0 RELEVANT REFERENCES

I. United States. Environmental Protection Agen cy [EPA]. Technology Tran sfer Network. Emission Measurement Center. Promulgated Methods. Me thod 1: Sample and Velocity Traverses for Stationary Sources. Washington, DC: EPA; 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-01.pdf via the Internet.

II. United States. Environmental Protection A gency [EPA}. Technology Transfer Network. Emission Measurement Center. Promulgated Method s. Method 2: Determination of Stack Gas Velocity and Volumetric Flow Rate. Wa shington, D.C: EPA; 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-02.pdf via the Internet.

III. United States. Environmental Protection Agenc y (EPA). Technology Transfer Network. Emission Measurement Center. Performance Specifications. Performance Specificat ion 2- Specifications and Test Procedures for SO2 and NOx Continuous Emission Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B, February 2000. Available: http://www.epa.gov/ttn/emc/perfspec.html via the Internet.

IV. United States. Environmental Protection Agency (EPA). Technol ogy Transfer Network. Emission Measurement Center. Performance Specificat ions. Performance Specification 4A - Specifications and Test Procedures for Carb on Monoxide Continuous Emission Monitoring Systems in Stationary Sour ces, 40 CFR 60 Appendix B, February 2000. Available: http://www.epa.gov/ttn/emc/perfspec.html via the Internet.

V. United States. Environmental Protection Agenc y (EPA). Technology Transfer Network. Emission Measurement Center. Performance Specificat ions. Performance Specification 4B - Specifications and Test Procedures for Carb on Monoxide and Oxygen Continuous Emission Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B, September 30, 1999.
Available: http://www.epa.gov/ttn/emc/perfspec.html via the Internet.

# HCL Dynamic Spiking Protocol

ELI LILLY AND COMPANY TIPPECANOE LABORATORIES LAFAYETTE, IN

August, 2006 Revision 2.0HCL Dynamic Spiking Protocol August, 2006

1 TABLE OF CONTENTS

1 REVISION HI STORY............................................................................................................. 2

1.1 REVISION 1.0 ................................................................................................................. 2
1.2 REVISION 2.0 ................................................................................................................. 2

2 OVERVIEW ....................................................................................................................... .... 3

3 DEFINITIONS .................................................................................................................... .... 5

4 EQUIPMENT ...................................................................................................................... ... 7

5 EQUIPMENT CALIBRATIO N AND STA NDARDS ................................................................ 8

5.1 HCL CEMS...................................................................................................................... 8
5.2 ELEMENT OF OPPO RTUNITY CEMS........................................................................... 8
5.3 FLOW MEASUREME NT SYSTEM................................................................................. 8 5.3.1 Laminar flow element ...................................................................................... 8 5.3.2 Flow by dilution................................................................................................ 9
5.4 GAS MANI FOLD ............................................................................................................. 9
5.5 HCL CALIBRATION GAS FO R DYNAMIC SPIKING ..................................................... 9

6 DYNAMIC SPIKIN G RANGE............................................................................................... 10

7 TYPICAL DYNAMIC SPI KING SET-UP .............................................................................. 10

8 DYNAMIC SPIKIN G PROCED URE .................................................................................... 11

8.1 COLLECTION OF BASELINE DA TA............................................................................ 11
8.2 COLLECTION OF TEST DATA .................................................................................... 11
8.3 DATA CALCUL ATIONS................................................................................................ 12 8.3.1 Baseline data................................................................................................. 12 8.3.2 Dynamic Spiking Te st run data ..................................................................... 14 8.3.3 Reference HCL concentra tion calculations ................................................... 15 8.3.4 Linear Regr ession ......................................................................................... 16
8.4 CRITERIA FOR AC CEPTANCE ................................................................................... 17
8.5 BIAS CORREC TION..................................................................................................... 18

9 TABLES ......................................................................................................................... ...... 19

10 REFERENC ES .................................................................................................................... 2 0

11 APPENDIXES..................................................................................................................... . 21HCL Dynamic Spiking Protocol August, 2006

2 

## 1 REVISION HISTORY

1.1 REVISION 1.0
Revision 1.0, Tippecanoe Laboratories NON-GMP Sta ndard Operating Procedure, Eli Lilly and Company, December 18, 2005.



### 1.2 REVISION 2.0
This revision is an update of the original Dynamic Spiking protocol, December 2005. The following are key updates in revision 2.0:

1. Recommendation that all HCL QA gases be certified with a minimum tolerance of 5%

2. Discussion for the use of quantit ative introduction of the HCL calibration gas and subsequent total flow measurement as method for determining the reference HCL concentration during each test

run.

3. Updated the dynamic spiking procedure des cription for easier flow of information

4. Updated the equations to include percent rela tive standard deviation and the calculation for the reference HCL concentration when using quantitativ e introduction of the HCL calibration gas with subsequent total flow measurement.HCL Dynamic Spiking Protocol August, 2006

3 

## 2 OVERVIEW

Dynamic Spiking is procedure to establish the accu racy, precision, and bias of a monitoring system. During the dynamic spiking procedure, a certified cali bration gas (+/- 5%) is spiked into the monitoring system while the system is sampling flue gas. It is important that the spiked calibration gas flow through the entire sampling system. The target ratio of flue gas to HCL calibration gas is 9:1, with a minimum requirement of 1:1. The HCL calibration gas is spik ed in three ranges (low, mid, high) through the range of HCL detector. A minimum of 30, one minute aver aged data points should be collected for each of the three test runs. It is recommended that the percent re lative standard deviation of the data set, for each test level, be less than or equal to 20%.
If the flue gas has significant amounts of HCL pres ent, the data may be corrected for the baseline HCL concentration. This is performed by collecting at least 10, one minute average HCL data points prior to each test run. The average of the ten baseline HCL values will be used to compensate the subsequent test run data for background HCL concentrations. It is important that the co ntrol device be running at steady state; alleviating la rge fluctuations in the background HCL concentrations.
The HCL CEMS will provide the measured HCL val ues. These values are compared, using linear regression, to the known or spiked HCL concentratio ns. There are two methods for calculating the known HCL concentrations: (1) Use of an element of opport unity and (2) Quantitative in troduction of the HCL calibration gas with total flow through the system.
An element of opportunity can be any element normally present, in steady concentrations, in the flue gas stream. Examples are O2, CO, NOx, SO2, CO2, and mo isture. Total flow through the system is also an example of an element of opportunity.
The element of opportunity is measured during the bas eline data collection, prior to the test run. The average value during this baseline collection period is used to establish the baseline concentration, or flow value, without any spiking of the calibration gas.
The element of opportunity is measured during eac h test run while the HCL calibration gas is being spiked. The elements of opportunity values, collected during each test run are averaged. Knowing the concentration of the HCL calibration gas, and the diluti on of the element of opport unity due to the spiking, the known value of the HCL calibration gas in the measurement stream can be calculated.
The known value of the spiked HCL calibration gas in the measurement stream can also be calculated by quantitatively introducing the HCL calibration gas, and, measuring the total flow through the system. In this case, the HCL calibration gas concentration, t he flow rate of spiked HCL calibration gas into the measurement stream, and the total flow through the system are used to calculate the known value of the spiked calibration gas.
As with the HCL CEMS data sets, it is recommended that the percent relative standard deviation for the element of opportunity data sets be less than or equal to 20%.
Once the data is collected, linear regression is performed using the known HCL spike values and the correlating HCL CEMS measured values. Cr iteria for the HCL dynamic spiking are:
1. The correlation coefficient ® must be greater than or equal to 0.90.
2. the slope of the regressi on line must be 1.0 +/- 0.15.HCL Dynamic Spiking Protocol August, 2006

4 3. The intercept, of the regression line, must be le ss than or equal to 15% of the instrument span.

The HCL CEMS must meet the correlation criteria. If ei ther the slope and/or intercept criteria are not met, a bias may be applied to the HCL CEMS one minute val ue. Performance Specification Z: Specifications and Test Procedures for the HCL Continuous Emission Monitoring Systems at Stationary Sources should be as a reference document for dynamic spiking requirements and calculations.HCL Dynamic Spiking Protocol August, 2006

5 

## 3 DEFINITIONS

Bias: The difference between the reference value and the measured value.

Calibration Drift: The difference in the CEMS output readings from the established reference value after a stated period of operation during which no unsch eduled maintenance or adjustment took place.

Continuous Emission Monitoring System : means the total equipment required for the determination of a gas concentration or emission rate. The sample interface, pollutant analyzer, diluent analyzer, and data recorder are the major subsystems of the CEMS.

Correlation Coefficient: determines the extent of a linear rela tionship between two fields over a given period of time.

Data Recorder: The portion of the CEMS that provides a record of analyzer output, flags which indicate normal operation, and flags indicating abnormal operation. The data recorder may record other pertinent data such as effluent flow rates, and various instrument temperatures.

Dynamic Spiking: a procedure used to document the accuracy, precision, and bias of the monitoring system by quantitatively sp iking a certified gas into the pollutant gas stream.

Element of Opportunity: Any element, present in the flue gas ma trix (or total flow) that has little
fluctuation and can be used to determine the refe rence HCL concentration during the dynamic spiking
test runs.

Gas Chromatograph: An analytical instrument which uses a carrier gas to transport gas/vapor phase samples to a solid matrix for separation, and subs equent detection by a analyte specific detector.

Gas manifold: Individual, or series of flow co ntrollers that allow controlled fl ow of a gas. Calibrated flow controllers can be used to quantitativ ely control the flow of gases.HCL Dynamic Spiking Protocol August, 2006

6 Instrument Measurement Range : The range of HCl concentrations the instrument can reliably measure from the lowest concentration to the highest.

Intercept: value of the Y variable when the X variable is equal to zero.

Laminar Flow Element: A device used to measure the flow gas through a system by measuring the pressure drop of the gas over a restrict ion (forces parallel, or laminar flow).

Linear Regression: a methodology used to find a formula that can be used to relate two variables that are linearly related.

Response Time: The time interval between the start of a step change in the system input and when the pollutant analyzer output reached 95% of the final value.

Sample Interface: The portion of the CEMS used for one or more of the following: sample acquisition, sample transport, sample conditioning, or protection of the monitor from the effects of stack gas.

Slope: The rate of change of Y relative to the change in X.

Upscale drift: means the absolute difference between a high-level calibration gas and the monitor response, in units of the applicable standard.

Zero drift: means the absolute difference between a high-level calibration gas and the monitor response, in units of the applicable standard.HCL Dynamic Spiking Protocol August, 2006

7 

## 4 EQUIPMENT

The following list contains typical equipment required to perform the HCL dynamic spiking.

1. HCL CEMS

2. Reference Analyzer(s) for the element of oppor tunity (examples are NOx, SO2, CO, CO2, O2)

3. Flow Measurement Systems

a. Laminar flow element

b. Gas chromatograph (for dilution flow with a hydrocarbon)

4. Calibration Equipment

a. Bubble Flow meter, manometer, or equivalent for primary flow calibration

b. Certified HCL Calibration gas for spiking

c. HCL calibration gases for zero and upscale drift check of the HCL CEMS

d. Calibration gas for the element(s) of opportunity CEMS calibration

e. Hydrocarbon gas for flow measurement via dilution sampling

5. Quantitative gas manifold, or equivalent, for introduction of the HCL calibration gas

6. Quantitative gas manifold, or equivalent, for the intr oduction of the hydrocarbon for dilution flow (if used)

7. Various fittings and tubingHCL Dynamic Spiking Protocol August, 2006

8 

## 5 EQUIPMENT CALIBRATION AND STANDARDS

Prior to performing the HCL dynamic spiking, it is important that all equipment and/or analyzers are calibrated. This section provides guidance on the calibration requirements for all equipment used during the HCL dynamic sp iking procedure.



### 5.1 HCL CEMS
Prior to performing the dynamic spiking procedur e, the HCL CEMS must pass the QA requirements specified in performance specification Z: Specifications and Test Procedures For HCL Continuous Emission Monitoring Systems at Stationary Sources . Typically, this would include passing the daily zero and upscale calibration drift check, and for annual audits passing both the zero and upscale drift check as well as a seven day drift test. All calibration ga ses must be certified gases, with a recommended
tolerance not to exceed +/- 5%.



### 5.2 ELEMENT OF OPPORTUNITY CEMS
The monitoring system used to measure the element(s) of opportunity, other than total flow, must pass a calibration directly prior to use. After dynamic sp iking run, the zero and upscale calibration drift are checked. The drift requirement, for both zero and upsc ale, is 3% of the reference value, unless stated otherwise in the applicable reference method. If either the zero or upscale calibration check fails the drift limit after a dynamic spiking run, the run must be repeated.



### 5.3 FLOW MEASUREMENT SYSTEM
Total flow may be used as an element of opport unity, or, as part of measuring the quantitative introduction of the HCL calibration gas for the dynamic spiking tests. There are several methods that can be used to provide a total flow measurement. Th is protocol outlines two approaches, laminar flow element and flow by dilution. Other total flow me asurement systems can be used; however, specific protocol describing the methodology must be used.



### 5.3.1 Laminar flow element
Prior to the dynamic spiking procedure, the laminar flow element is calibrated against a primary flow standard, such as a bubble flow meter. The calibra tion must include at least three points throughout the expected measurement range. After each dynamic spikin g test run, the calibration drift is checked at each of the three points. The laminar flow element mu st be re-calibrated if any of the drift check points exceed 10% of the expected value (estab lished during the pre-test calibration).HCL Dynamic Spiking Protocol August, 2006

9 

### 5.3.2 Flow by dilution
Flow by dilution is a method where a known concentra tion of gas is quantitatively introduced to the flue gas stream and measured downstream by a calibrate d instrument. For example, a known concentration of propane can be quantitatively introduced to the flue gas stream and the diluted propane measured
downstream.

Prior to the dynamic spiking procedure, the gas chro matograph is calibrated, using at least four points through the expected measurement range. After the dynamic spiking procedure is complete, the gas chromatograph is checked for bias at each of the four calibration levels. The bias should be less than 5% of the expected value for each point. Method 18 provides guidance for the calibration procedure and requirements.

Prior to the dynamic spiking proced ure, the gas manifold (used to qua ntitatively introduce propane, or similar hydrocarbon), which is typica lly a mass flow controller, is calib rated to a primary standard. After each test run, the gas manifold is checked for drift, and adjusted if t he drift exceeds 10% of the expected value (calibrated value prior to dynamic spiking pr ocedure). Method 205 provides guidance for this procedure.



### 5.4 GAS MANIFOLD
HCL may be quantitatively introduced into the flue gas st ream, and when used in conjunction with a total flow measurement, can provide the reference HCL spik ing concentrations for each dynamic spiking run.

Prior to the dynamic spiking procedure, the gas mani fold (used to quantitatively introduce HCL), which is typically a mass flow controller, is calibrated to a primary standard. After each test run, the gas manifold is checked for drift, and adjusted if the drift exceeds 10% of the expecte d value (calibrated value prior to dynamic spiking procedure). Method 205 provides guidance for this procedure.



### 5.5 HCL CALIBRATION GAS FOR DYNAMIC SPIKING
The HCL calibration gas used for dynamic spiking must be a certified gas with a tolerance less than or equal to 5%.HCL Dynamic Spiking Protocol August, 2006

10 

## 6 DYNAMIC SPIKING RANGE

The flue gas stream must be spiked at a minimum of th ree separate levels (low, mid, high) throughout the range of the HCL CEMS. The low level should be between 0 – 50%, the mid range should be between 25 – 75%, and the high range should be between 50 – 10 0% of the span of the instrument. The dynamic spiked HCL concentrations can only be used for one range (Table 1).



## 7 TYPICAL DYNAMIC SPIKING SET-UP

Figure 1. Typical Dynamic Spiking Apparatus



### Dynamic Spiking Apparatus

HCL CEMS 900-1200 ppm HCL in N2 Calibration Manifold (Mass flow meters) Sample Probe

• Heated Filter

• Pressure Control

• Laminar Flow Element Heated sample line

Flue Gas

Gas Conditioner Reference Measurement(s) Heated line inside sample umbillicalHCL Dynamic Spiking Protocol August, 2006

11 

## 8 DYNAMIC SPIKING PROCEDURE

This section describes the procedure used to perfor m HCL dynamic spiking. Prior to testing, it is important that all analyzers are calibrated according to section 6 of this document. In addition, the control device should be at a steady state (small fluct uations of HCL or elements of opportunity).



### 8.1 COLLECTION OF BASELINE DATA

The baseline data will be used to co mpensate the measured HCl, during the dynamic spiking run, for background concentrations of HCL which may be pres ent during normal operations. It is important to collect all element of opportunity data as well as HCL background data during the baseline collection period.

1. Collect a minimum of ten, 1 minute averaged HCL data points prior to each dynamic spiking
test run.

2. Collect ten, 1 minute averaged data points fo r the element(s) of opportunity to be used for calculating the reference HCL concentration. The element of opportunity data set is collected simultaneous to the HCL baseline data, and must be collected prior to each dynamic spiking
test run.

3. If using total flow, collect a minimum of one flow reading during the baseline data collection.

4. Prior to beginning the dynamic spike, ensure that all baseline data (HCL, element of opportunity, flow) does not exhibit large fluctuatio ns in concentration (steady state). If large fluctuations exist, the baseline data collection procedure must be repeated.



### 8.2 COLLECTION OF TEST DATA

The HCL CEMS must be tested at a minimum of th ree levels through the measurement range of the instrument (low, mid, high), Table 1. Prior to each dynamic spiking test run, it is important that the appropriate baseline data is collected (section 7.1) and that all equipment is calibrated and appropriate bias checks are performed (section 6).

1. Introduce the HCL calibration gas to the measurement system and allow the HCL CEMS values to reach a steady state. This may take up to 15 minutes.HCL Dynamic Spiking Protocol August, 2006

12 2. Collect a minimum of 30, one minute average HCL data points.

3. Collect a minimum of 30, one minute averag e element(s) of opportunity data points.

4. If using total flow through the system, collect at least five data points during the dynamic spiking test run.

5. If using quantitative introduction of the HCL calibr ation gas, collect at least five data points for the calibration gas flow rate into the system during the dynamic spiking test run.

6. Before stopping the dynamic spiking test run, en sure that the data sets are complete. It is recommended that the percent standard deviation, fo r all data sets, be less than or equal to
20%.

7. Stop the HCL calibration gas dynamic spiking and allow the system to return to baseline
conditions.

8. Perform a bias check for the element of oppo rtunity reference CEMS, the flow measurement system, and the gas manifold for the HCL calibration gas and hydrocarbon (if dilution flow is
used to calculate the reference HCL concentratio n). Section 6 provides guidance for the bias
checks.

9. Repeat the baseline data collection, and the dynamic spiking data collection, for subsequent
HCL test levels.

10. If dilution flow is used to calculate the HCl reference values, after the HCL dynamic spiking test runs are complete, perform a bias check of the dilution analyzer.



### 8.3 DATA CALCULATIONS
This section provides the calculations required to de termine the accuracy, precision, and bias of the HCL
CEMS.



### 8.3.1 Baseline data

8.3.1.1 HCL CEMS data
The baseline HCL concentration is measured prior to each dynamic spiking run. For each baseline HCL data set, calculate the average, in ppm, using equation 1.HCL Dynamic Spiking Protocol August, 2006

13 Calculate the arithmetic mean of a data set as follows:


# ∑ = i 

### x n x 1 (Equation 1)

where :



### x = Arithmetic mean

n

= Number of data points

x

i = Value of each data point

8.3.1.2 Element of Opportunity Data
The element of opportunity data set is acquired prior to each dynamic spiking test run, simultaneous to
the baseline HCL concentration data set. For each el ement of opportunity, calculate the average value using equation 1.

8.3.1.3 Flow via dilution
When using dilution of a measured analyte (such as a hydrocarbon with s ubsequent GC measurement) as an indicator of total flow, calculate the total flow, in liters per minute using equation 2.

Calculate the total flow as follows:

Tflow = 

### ) ( * ) (
measured Analyte Tflow spike Analtye

− − (Equation 2)

Tflow = Total flow through the system in lpm

Analyte-Spike = Concentration of Spiked Analyte (ppm)

Analyte-measured = Measurement, downs tream, of spiked Analyte (ppm)

Calculate the average flow value, for the data set, using equation 1.HCL Dynamic Spiking Protocol August, 2006

14 

### 8.3.2 Dynamic Spiking Test run data

8.3.2.1 HCL CEMS data
For each dynamic spiking test run, calculate the av erage and percent relative standard deviation of the data set using equations 1 and 3, respectively.

Calculate the percent standard deviation as follows:

2 / 1 2

1

1 2

1
⎥ ⎥ ⎥ ⎥ ⎥ ⎥ ⎥

⎦ ⎤

⎢ ⎢ ⎢ ⎢ ⎢ ⎢ ⎢

⎣ ⎡

− ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛

−

= 

## ∑ ∑ =

=

n n d

PRS n
i i n

i i

d 

## d (Equation 3)



### x

Where:



### = d 

### PRS Percent Relative Standard Deviation of the data set



### x = Arithmetic mean

8.3.2.2 Element of Opportunity data
For each dynamic spiking test run, calculate the av erage and percent relative standard deviation of the data set using equations 1 and 3, respectively. If usi ng total flow as a means to determine the reference HCL calibration gas concentration, use equation 2 to ca lculate the total flow prior to determining the average and percent relative standard deviation of the data set.HCL Dynamic Spiking Protocol August, 2006

15 

### 8.3.3 Reference HCL conc entration calculations
8.3.3.1 Element of opportunity to cal culate reference HCL concentration
Equation 4 is used to calculate the reference HCL concentration for a given dynamic spiking test run.

HCl ref = 

### l BaselineHC CalGas pre Opp post Opp

avg avg 

### +

− −

− * 1 (Equation 4)

where:

Opp-post avg = average reference element of opportunity value during dynamic spiking test run

Opp-pre avg = average reference element of opport unity value during baseline test run

CalGas = HCl calibration gas concentration

Baseline HCl = CEMS HCl average baseline value

8.3.3.2 Quantitative HCL calibration gas introducti on and total flow to calculate reference HCL concentration
When using the quantitative introduction of calibrati on gas and total system flow to calculation the reference HCL concentration for a given dynamic spiking test run, use equation 5. Equation 2 is used to calculate the total system flow.

HCl ref = 

### l BaselineHC CalGas Tflow Cflow

avg avg 

### + * (Equation 5)

Where:

HCl ref = Reference HCl value for run “X”

Cflow = Average calibration HCL ga s flow rate into system (lpm)HCL Dynamic Spiking Protocol August, 2006

16 Tflow = Average Total System Flow during run (lpm)

CalGas = HCl calibration gas concentration

Baseline HCl = CEMS HCl average baseline value



### 8.3.4 Linear Regression
Linear regression is used to calcul ate the accuracy, precision, and bias of the HCL CEMS. For each dynamic spiking test run, plot the HCL CEMS reference value, Xaxis, versus the HCL measured value, Y axis. Determine the correlation coefficient (r ), the slope, and the intercept using equations 6-9.



### x b b y o 1 

### ˆ +

= (Equation 6)

where:

b o = The y intercept

b 1 = The slope

The intercept is calculated according to the following equation:



### x b y b
o 1 

### − = (Equation 7)

where:


# ∑

= 

### = n

i i 

### x n x
1 

### 1



# ∑

= 

### = n

i i 

### y n y
1 

### 1

The slope of the line is calculated according to equation below:HCL Dynamic Spiking Protocol August, 2006

17 

# ∑ ∑

= =



### − − −

= n

1 i 2 i n

1 i i i

1 

### ) x x ( ) y y )( x x ( b (Equation 8)

The linear correlation coefficient is calc ulated according to the following equation.



# ∑ ∑

∑

= = =



### − − ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

− −

= n

i i n

i i n

i i i



### y y x x y y x x

r

1 2

1 2 2

1 2 

### ) ( ) ( ) )( ( (Equation 9)



### 8.4 CRITERIA FOR ACCEPTANCE
The criteria for the HCl dynamic spiking is:

• The correlation coefficient, r, must be greater than or equal to 0.90

• The slope must be 1.0, +/- 0.15

• The Intercept must be equal to or less than 15% of the instrument span.

At a minimum, the data set must meet the correlati on coefficient. If this is not met, the dynamic spiking procedure must be repeated until the corr elation coefficient criteria are met. If the HCl CEMS has met the correlation coefficient requirement, but does not meet ei ther the slope, or intercept criteria, a bias exists and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine the corrected value are provided in Section 8.5. The correction factor must be applied to the HCl CEMS one-minute average data until a new dynamic spiking procedure indicates the specific bias no longer exists, or, a different correction factor (bias) is indicated.HCL Dynamic Spiking Protocol August, 2006

18 

### 8.5 BIAS CORRECTION
If the HCl CEMS fails to meet both the slope and intercept criteria, the following correction factor must be applied to the one-minute average HCl data:

1 0 

### b b y C i

C 

### −

= (Equation 10)

Where:

C 

### C = corrected CEMS HCL concentration

y

i = CEMS reported HCL concentration

b 0

= the intercept of the l east squares linear regression line

b 1 = the slope of the least squares linear regression line

b). If the HCl CEMS fails to meet the slope criter ia, but meets the intercept criteria, the following correction factor must be applied to the one-minute average HCl data:

1 

### b y C i

C 

### = (Equation 11)

c). If the HCl CEMS fails to meet the intercept criteria , but meets the slope criteria, the following correction factor must be applied to the one-minute average HCl data:

0 

### b y C i

C



### −

= (Equation 12)HCL Dynamic Spiking Protocol August, 2006

19 

## 9 TABLES

Table 1. Ongoing Quality Assurance/Quality Control Calibration Gas Ranges

HCl Calibration Gas Concentrations a

Test Units Zero-level Mid-Level High-Level

Daily Calibration Drift % of Span 0-30 NA 50-100

Absolute Calibration
Audit % of Span 0-29 30-49 50-100

Dynamic Spiking % of Span 0-50 25-75 50-100

a A copy of the supplier’s certificate of analysis mu st be provided for each gas cylinder. Calibration gases do not need to be Protocol 1 gases. It is recommended that the calibration gases, for all QA, have a
minimum tolerance of 5%.HCL Dynamic Spiking Protocol August, 2006

20 

## 10 REFERENCES

1. United States Environmental Protection Agency (EPA). Technology Transfer Network, Emission Measurement Center, Promulgated Methods, Test Me thod 205: Verification of Gas Dilution Systems for Field Instrument Calibrations. Available: http://www.epa.gov/ttn/emc/promgate/m205.pdf via the internet.

2. United States Environmental Protection Agency (EPA). Technology Transfer Network, Emission Measurement Center, Promulgated Methods, Te st Method 18: Measurement of Gaseous Organic Compound Emissions by Gas Chromatography. Available: http://www.epa.gov/ttn/emc/promgate/m-18.pdf via the internet.

3. Performance Specification Z: Specifications and Test Procedures for Hydrochloric Acid Continuous Emission Monitoring Systems at Stat ionary Sources. Eli Lilly and Company, 2005.

4. Procedure DD: Quality Control and Quality Assurance Requirements for Hydrochloric Acid Continuous Emission Monitoring Systems at Stat ionary Sources. Eli Lilly and Company, 2005.

5. Dilution Flow Measurement Protocol: Measurement of Total flow using a tracer gas with subsequent down stream quantitat ion. Eli Lilly and Company, 2006.HCL Dynamic Spiking Protocol August, 2006

21 

## 11 APPENDICES

### (PROPOSED) TEST METHOD 322 - MEASUREMENT OF HYDROGEN CHLORIDE

EMISSIONS FROM PORTLAND CEMENT KILNS BY GFCIR 1.0 Applicability and Principle 1.1 Applicability. This method is applicable to the determination of hydrogen chloride (HCl) concentrations in emissions from portland cement kilns. This is an instrumental method for the measurement of HCl using an extractive sampling system and an infrared (IR) gas-filter correlation (GFC) analyzer. This method is intended to provide the cement industry with a direct interface instrumental method. A procedure for analyte spiking is included for quality assurance. This method is considered to be self-validating provided that the requirements in section 9 of this method are followed. 1.2 Principle. A gas sample is continuously extracted from a stack or duct over the test period using either a source-level hot/wet extractive subsystem or a dilution extractive subsystem. A nondispersive infrared gas filter correlation (NDIR-GFC) analyzer is specified for the measurement of HCl in the sample. The total measurement system is comprised of the extractive subsystem, the analyzer, and the data acquisition subsystem. Test system performance specifications are included in this method to provide for the collection of accurate, reproducible data.

1.3 Test System Operating Range. The measurement range (span) of the test system shall include the anticipated HCl concentrations of the effluent and spiked samples. The range should be selected so that the average of the effluent measurements is between 25 and 75 percent of span. If at any time during a test run, the effluent concentration exceeds the span value of the test system, the run shall be considered invalid. 2.0 Summary of Method 2.1 Sampling and Analysis. Kiln gas is continuously extracted from the stack or duct using either a source level, hot/wet extractive system, or an in-situ dilution probe or heated out-of-stack dilution system. The sample is then directed by a heated sample line maintained above 350 E F to a GFC analyzer having a range appropriate to the type of sampling system. The gas filter correlation analyzer incorporates a gas cell filled with HCl. This gas cell is periodically moved into the path of an infrared measurement beam of the instrument to filter out essentially all of the HCl absorption wavelengths. Spectral filtering provides a reference from which the HCl concentration of the sample can be determined. Interferences are minimized in the analyzer by choosing a spectral band over which compounds such as CO and H O either do not absorb significantly or do not

2 2 

### match the spectral pattern of the HCl infrared absorption.

### 2.2 Operator Requirements. The analyst must be familiar

with the specifications and test procedures of this method and follow them in order to obtain reproducible and accurate data. 3.0 Definitions 3.1 Measurement System. The total equipment required for the determination of gas concentration. The measurement system consists of the following major subsystems: 3.1.1 Sample Interface. That portion of a system used for one or more of the following: sample acquisition, sample transport, sample conditioning, or protection of the analyzers from the effects of the stack gas. 3.1.2 Gas Analyzer. That portion of the system that senses the gas to be measured and generates an output proportional to its concentration. 3.1.3 Data Recorder. A strip chart recorder, analog computer, or digital recorder for recording measurement data from the analyzer output. 3.2 Span. The upper limit of the gas concentration measurement range displayed on the data recorder. 3.3 Calibration Gas. A known concentration of a gas in an appropriate diluent gas (i.e., N ). 2 

### 3.4 Analyzer Calibration Error. The difference between the gas concentration exhibited by the gas analyzer and the known concentration of the calibration gas when the calibration gas is introduced directly to the analyzer. 3.5 Sampling System Bias. The sampling system bias is the difference between the gas concentrations exhibited by the measurement system when a known concentration gas is introduced at the outlet of the sampling probe and the known value of the calibration gas. 3.6 Response Time. The amount of time required for the measurement system to display 95 percent of a step change in gas concentration on the data recorder. 3.7 Calibration Curve. A graph or other systematic method of establishing the relationship between the analyzer response and the actual gas concentration introduced to the analyzer. 3.8 Linearity. The linear response of the analyzer or test system to known calibration inputs covering the concentration range of the system. 3.9 Interference Rejection. The ability of the system to reject the effect of interferences in the analytical measurement processes of the test system. 4.0 Interferences 4.1 Sampling System Interferences. An important consideration in measuring HCl using an extractive measurement system is to ensure that a representative kiln gas sample is delivered to the gas analyzer. A sampling system interferant is a factor that inhibits an analyte from reaching the analytical instrumentation. Condensed water vapor is a strong sampling system interferant for HCl and other water soluble compounds.

### "Cold spots" in the sampling system can allow water vapor in the

sample to condense resulting in removal of HCl from the sample stream. The extent of HCl sampling system bias depends on concentrations of potential interferants, moisture content of the gas stream, temperature of the gas stream, temperature of sampling system components, sample flow rate, and reactivity of HCl with other species in the gas stream. For measuring HCl in a wet gas stream, the temperatures of the gas stream and sampling system components and the sample flow rate are of primary importance. In order to prevent problems with condensation in the sampling system, these parameters must be closely monitored. 4.1.1 System Calibration Checks. Performing these calibration checks where HCl calibration gas is injected through the entire system both before and after each test run demonstrates the integrity of the sampling system and capability of the analyzer for measuring this water soluble and otherwise unstable compound under ideal conditions (i.e., HCl in N ). 2 

### 4.1.2 Analyte Spiking Checks. For analyte spiking checks, HCl calibration gas is quantitatively added to the sample stream at a point upstream of the particulate filter and all other sample handling components both before and after each test run. The volume of HCl spike gas should not exceed 10 percent of the total sample volume so that the sample matrix is relatively unaffected. Successfully performing these checks demonstrates the integrity of the sampling system for measuring this water soluble and reactive compound under actual sample matrix conditions. Successfully performing these checks also demonstrates the adequacy of the interference rejection capability of the analyzer. (See section 9.3 of this method.) 4.2 Analytical Interferences. Analytical interferences are reduced by the GFC spectroscopic technique required by the method. The accuracy of HCl measurements provided by some GFC analyzers is known to be sensitive to the moisture content of the sample. This must be taken into account in order to acquire accurate results. These analyzers must be calibrated for the specific moisture content of the samples. 5.0 Safety This method may involve sampling at locations having high positive or negative pressures, or high concentrations of hazardous or toxic pollutants, and cannot address all safety problems encountered under these diverse sampling conditions. It is the responsibility of the tester(s) to ensure proper safety and health practices, and to determine the applicability of regulatory limitations before performing this test method. Because HCl is a respiratory irritant, it is advisable to limit exposure to this compound. 6.0 Equipment and Supplies Note: Mention of company or product names does not constitute endorsement by the U. S. Environmental Protection Agency.

### 6.1 Measurement System. Use any GFC measurement system for

HCl that meets the specifications of this method. All sampling system components must be maintained above the kiln gas temperature, when possible, or at least 350 E F. The length of sample transport line should be minimized and sampling rate should be as high as possible to minimize adsorption of HCl. The essential components of the measurement system are described in sections 6.1.1 through 6.1.12. 6.1.1 Sample Probe. Glass, stainless steel, HastalloyTM, or equivalent, of sufficient length to traverse the sample points. The sampling probe shall be heated to a minimum of 350 E F to prevent condensation. Dilution extractive systems must use a dilution ratio such that the average diluted concentrations are between 25 to 75 percent of the selected measurement range of the analyzer. 6.1.2 Calibration Valve Assembly. Use a heated, three-way valve assembly, or equivalent, for selecting either sample gas or introducing calibration gases to the measurement system or introducing analyte spikes into the measurement system at the outlet of the sampling probe before the primary particulate filter. 6.1.3 Particulate Filter. A coarse filter or other device may be placed at the inlet of the probe for removal of large particulate (10 microns or greater). A heated (Balston® or equivalent) filter rated at 1 micron is necessary for primary particulate removal, and shall be placed immediately after the heated probe. The filter/filter holder shall be maintained at 350 E F or a higher temperature. Additional filters at the inlet of the gas analyzer may be used to prevent accumulation of particulate material in the measurement system and extend the useful life of components. All filters shall be fabricated of materials that are nonreactive with HCl. Some types of glass filters are known to react with HCl. 6.1.4 Sample Transport Lines. Stainless steel or polytetrafluoroethylene (PTFE) tubing shall be heated to a minimum temperature of 350 E F (sufficient to prevent condensation and to prevent HCl and NH from combining into ammonium chloride 3 

### in the sampling system) to transport the sample gas to the gas analyzer. 6.1.5 Sample Pump. Use a leak-free pump to pull the sample gas through the system at a flow rate sufficient to minimize the response time of the measurement system. The pump components that contact the sample must be heated to a temperature greater than 350 E F and must be constructed of a material that is nonreactive to HCl. 6.1.6 Sample Flow Rate Control. A sample flow rate control valve and rotameter, or equivalent, must be used to maintain a constant sampling rate within ±10 percent. These components must be heated to a temperature greater than 350 E F. ( Note : The tester may elect to install a back-pressure regulator to maintain

### the sample gas manifold at a constant pressure in order to

protect the analyzer(s) from over-pressurization, and to minimize the need for flow rate adjustments.) 6.1.7 Sample Gas Manifold. A sample gas manifold, heated to a minimum of 350 E F, is used to divert a portion of the sample gas stream to the analyzer and the remainder to the by-pass discharge vent. The sample gas manifold should also include provisions for introducing calibration gases directly to the analyzer. The manifold must be constructed of material that is nonreactive to the gas being sampled. 6.1.8 Gas Analyzer. Use a nondispersive infrared analyzer utilizing the gas filter correlation technique to determine HCl concentrations. The analyzer shall meet the applicable performance specifications of section 8.0 of this method. (Note: Housing the analyzer in a clean, thermally-stable, vibration free environment will minimize drift in the analyzer calibration.) The analyzer (system) shall be designed so that the response of a known calibration input shall not deviate by more than ±3 percent from the expected value. The analyzer or measurement system manufacturer may provide documentation that the instrument meets this design requirement. Alternatively, a known concentration gas standard and calibration dilution system meeting the requirements of Method 205 of appendix M to part 51 of this chapter, “Verification of Gas Dilution Systems for Field Calibrations” (or equivalent procedure), may be used to develop a multi-point calibration curve over the measurement range of the analyzer. 6.1.9 Gas Regulators. Single stage regulator with cross purge assembly that is used to purge the CGA fitting and regulator before and after use. (This purge is necessary to clear the calibration gas delivery system of ambient water vapor after the initial connection is made, or after cylinder changeover, and will extend the life of the regulator.) Wetted parts are 316 stainless steel to handle corrosive gases. 6.1.10 Data Recorder. A strip chart recorder, analog computer, or digital recorder, for recording measurement data. The data recorder resolution (i.e., readability) shall be 0.5 percent of span. Alternatively, a digital or analog meter having a resolution of 0.5 percent of span may be used to obtain the analyzer responses and the readings may be recorded manually. If this alternative is used, the readings shall be obtained at equally-spaced intervals over the duration of the sampling run. For sampling run durations of less than 1 hour, measurements at 1-minute intervals or a minimum of 30 measurements, whichever is less restrictive, shall be obtained. For sampling run durations greater than 1 hour, measurements at 2-minute intervals or a minimum of 96 measurements, whichever is less restrictive, shall be obtained. 6.1.11 Mass Flow Meters/Controllers. A mass flow meter having the appropriate calibrated range and a stated accuracy of

### ±2 percent of the measurement range is used to measure the HCl

spike flow rate. This device must be calibrated with the major component of the calibration spike gas (e.g., nitrogen) using an NIST traceable bubble meter or equivalent. When spiking HCl, the mass flow meter/controller should be thoroughly purged before and after introduction of the gas to prevent corrosion of the interior parts. 6.1.12 System Flow Measurement. A measurement device or procedure to determine the total flow rate of sample gas within the measurement system. A rotameter, or mass flow meter calibrated relative to a laboratory standard to within ±2 percent of the measurement value at the actual operating temperature, moisture content, and sample composition (molecular weight) is acceptable. A system which ensures that the total sample flow rate is constant within ±2 percent and which relies on an intermittent measurement of the actual flow rate (e.g., calibrated gas meter) is also acceptable. 6.2 HCl Calibration Gases. The calibration gases for the gas analyzer shall be HCl in N . Use at least three calibration 2 

### gases as specified below: 6.2.1 High-Range Gas. Concentration equivalent to 80 to 100 percent of the span. 6.2.2 Mid-Range Gas. Concentration equivalent to 40 to 60 percent of the span. 6.2.3 Zero Gas. Concentration of less than 0.25 percent of the span. Purified ambient air may be used for the zero gas by passing air through a charcoal filter or through one or more impingers containing a solution of 3 percent H O

. 2 2 

### 6.2.4 Spike Gas. A calibration gas of known concentration (typically 100 to 200 ppm) used for analyte spikes in accordance with the requirements of section 9.3 of this method. 7.0 Reagents and Standards 7.1 Hydrogen Chloride. Hydrogen Chloride is a reactive gas and is available in steel cylinders from various commercial gas vendors. The stability is such that it is not possible to purchase a cylinder mixture whose HCl concentration can be certified at better than ±5 percent. The stability of the cylinder may be monitored over time by periodically analyzing cylinder samples. The cylinder gas concentration must be verified within 1 month prior to the use of the calibration gas. Due to the relatively high uncertainty of HCl calibration gas values, difficulties may develop in meeting the performance specifications if the mid-range and high-range calibration gases are not consistent with each other. Where problems are encountered, the consistency of the test gas standards may be determined: (1) by comparing analyzer responses for the test gases with the responses to additional certified calibration gas standards, (2) by reanalysis of the calibration gases in accordance with sections 7.2.1 or 7.2.2 of this method, or (3) by other procedures subject to the approval of EPA.

### 7.2 Calibration Gas Concentration Verification. There are

two alternatives for establishing the concentrations of calibration gases. Alternative No. 1 is preferred. 7.2.1 Alternative No. 1. The value of the calibration gases may be obtained from the vendor's certified analysis within 1 month prior to the test. Obtain a certification from the gas manufacturer that identifies the analytical procedures and date of certification. 7.2.2 Alternative No. 2. Perform triplicate analyses of the gases using Method 26 of appendix A to part 60 of this chapter. Obtain gas mixtures with a manufacturer's tolerance not to exceed ±5 percent of the tag value. Within 1 month of the field test, analyze each of the calibration gases in triplicate using Method 26 of appendix A to part 60 of this chapter. The tester must follow all of the procedures in Method 26 (e.g., use midget impingers, heated Pallflex TX40H175 filter (TFE-glass mat), etc. if this analysis is performed. Citation 3 in section 13 of this method describes procedures and techniques that may be used for this analysis. Record the results on a data sheet. Each of the individual HCl analytical results for each calibration gas shall be within 5 percent (or 5 ppm, whichever is greater) of the triplicate set average; otherwise, discard the entire set and repeat the triplicate analyses. If the average of the triplicate analyses is within 5 percent of the calibration gas manufacturer's cylinder tag value, use the tag value; otherwise, conduct at least three additional analyses until the results of six consecutive runs agree within 5 percent (or 5 ppm, whichever is greater) of the average. Then use this average for the cylinder value. 7.3 Calibration Gas Dilution Systems. Sample flow rates of approximately 15 L/min are typical for extractive HCl measurement systems. These flow rates coupled with response times of 15 to 30 minutes will result in consumption of large quantities of calibration gases. The number of cylinders and amount of calibration gas can be reduced by the use of a calibration gas dilution system in accordance with Method 205 of appendix M to part 51 of this chapter, "Verification of Gas Dilution Systems for Field Instrument Calibrations." If this option is used, the tester shall also introduce an undiluted calibration gas approximating the effluent HCl concentration during the initial calibration error test of the measurement system as a quality assurance check. 8.0 Test System Performance Specifications 8.1 Analyzer Calibration Error. This error shall be less than ±5 percent of the emission standard concentration or ±1 ppm,(whichever is greater) for zero, mid-, and high-range gases. 8.2 Sampling System Bias. This bias shall be less than ±7.5 percent of the emission standard concentration or ±1.5 ppm (whichever is greater) for zero and mid-range gases. 8.3 Analyte Spike Recovery. This recovery shall be between

### 70 to 130 percent of the expected concentration of spiked samples

calculated with the average of the before and after run spikes. 9.0 Sample Collection, Preservation, and Storage 9.1 Pretest. Perform the procedures of sections 9.1.1 through 9.1.3.3 of this method before measurement of emissions (procedures in section 9.2 of this method). It is important to note that after a regulator is placed on an HCl gas cylinder valve, the regulator should be purged with dry N or dry 2 

### compressed air for approximately 10 minutes before initiating any HCl gas flow through the system. This purge is necessary to remove any ambient water vapor from within the regulator and calibration gas transport lines; the HCl in the calibration gas may react with this water vapor and increase system response time. A purge of the system should also be performed at the conclusion of a test day prior to removing the regulator from the gas cylinder. Although the regulator wetted parts are corrosion resistant, this will reduce the possibility of corrosion developing within the regulator and extend the life of the equipment. 9.1.1 Measurement System Preparation. Assemble the measurement system by following the manufacturer's written instructions for preparing and preconditioning the gas analyzer and, as applicable, the other system components. Introduce the calibration gases in any sequence, and make all necessary adjustments to calibrate the analyzer and the data recorder. If necessary, adjust the instrument for the specific moisture content of the samples. Adjust system components to achieve correct sampling rates. 9.1.2 Analyzer Calibration Error. Conduct the analyzer calibration error check in the field by introducing calibration gases to the measurement system at any point upstream of the gas analyzer in accordance with sections 9.1.2.1 and 9.1.2.2 of this method. 9.1.2.1 After the measurement system has been prepared for use, introduce the zero, mid-range, and high-range gases to the analyzer. During this check, make no adjustments to the system except those necessary to achieve the correct calibration gas flow rate at the analyzer. Record the analyzer responses to each calibration gas. Note : A calibration curve established prior to the analyzer calibration error check may be used to convert the analyzer response to the equivalent gas concentration introduced to the analyzer. However, the same correction procedure shall be used for all effluent and calibration measurements obtained during the test. 9.1.2.2 The analyzer calibration error check shall be considered invalid if the difference in gas concentration displayed by the analyzer and the concentration of the calibration gas exceeds ±5 percent of the emission standard concentration or ±1 ppm, (whichever is greater) for the zero, mid-, or high-range calibration gases. If an invalid calibration

### is exhibited, cross-check or recertify the calibration gases,

take corrective action, and repeat the analyzer calibration error check until acceptable performance is achieved. 9.1.3 Sampling System Bias Check. For nondilution extractive systems, perform the sampling system bias check by introducing calibration gases either at the probe inlet or at a calibration valve installed at the outlet of the sampling probe. For dilution systems, calibration gases for both the analyzer calibration error check and the sampling system bias check must be introduced prior to the point of sample dilution. Fordilution and nondilution systems, a zero gas and either a midrange or high-range gas (whichever more closely approximates the effluent concentration) shall be used for the sampling system bias check. 9.1.3.1 Introduce the upscale calibration gas, and record the gas concentration displayed by the analyzer. Then introduce zero gas, and record the gas concentration displayed by the analyzer. During the sampling system bias check, operate the system at the normal sampling rate, and make no adjustments to the measurement system other than those necessary to achieve proper calibration gas flow rates at the analyzer. Alternately introduce the zero and upscale gases until a stable response is achieved. The tester shall determine the measurement system response time by observing the times required to achieve a stable response for both the zero and upscale gases. Note the longer of the two times and note the time required for the measurement system to reach 95 percent of the step change in the effluent concentration as the response time. 9.1.3.2 For nondilution systems, where the analyzer calibration error test is performed by introducing gases directly to the analyzer, the sampling system bias check shall be considered invalid if the difference between the gas concentrations displayed by the measurement system for the sampling system bias check and the known gas concentration standard exceeds ±7.5 percent of the emission standard or ±1.5 ppm, (whichever is greater) for either the zero or the upscale calibration gases. If an invalid calibration is exhibited, take corrective action, and repeat the sampling system bias check until acceptable performance is achieved. If adjustment to the analyzer is required, first repeat the analyzer calibration error check, then repeat the sampling system bias check. 9.1.3.3 For dilution systems (and nondilution systems where all calibration gases are introduced at the probe), the comparison of the analyzer calibration error results and sampling system bias check results is not meaningful. For these systems, the sampling system bias check shall be considered invalid if the difference between the gas concentrations displayed by the analyzer and the actual gas concentrations exceed ±7.5 percent of the emission standard or ±1.5 ppm, (whichever is greater) for either the zero or the upscale calibration gases. If an invalid

### calibration is exhibited, take corrective action, and repeat the

sampling system bias check until acceptable performance is achieved. If adjustment to the analyzer is required, first repeat the analyzer calibration error check. 9.2 Emission Test Procedures 9.2.1 Selection of Sampling Site and Sampling Points. Select a measurement site and sampling points using the same criteria that are applicable to Method 26 of appendix A to part 60 of this chapter.
9.2.2 Sample Collection. Position the sampling probe at the first measurement point, and begin sampling at the same rate as used during the sampling system bias check. Maintain constant rate sampling (i.e., ±10 percent) during the entire run. Field test experience has shown that conditioning of the sample system is necessary for approximately 1-hour prior to conducting the first sample run. This conditioning period should be repeated after particulate filters are replaced and at the beginning of each new day or following any period when the sampling system is inoperative. Experience has also shown that prior to adequate conditioning of the system, the response to analyte spikes and/or the change from an upscale calibration gas to a representative effluent measurement may be delayed by more than twice the normal measurement system response time. It is recommended that the analyte spikes (see section 9.3 of this method) be performed to determine if the system is adequately conditioned. The sampling system is ready for use when the time required for the measurement system to equilibrate after a change from a representative effluent measurement to a representative spiked sample measurement approximates the calibration gas response time observed in section 9.1.3.1 of this method. 9.2.3 Sample Duration. After completing the sampling system bias checks and analyte spikes prior to a test run, constant rate sampling of the effluent should begin. For each run, use only those measurements obtained after all residual response to calibration standards or spikes are eliminated and representative effluent measurements are displayed to determine the average effluent concentration. At a minimum, this requires that the response time of the measurement system has elapsed before data are recorded for calculation of the average effluent concentration. Sampling should be continuous for the duration of the test run. The length of data collection should be at least as long as required for sample collection by Method 26 of part 60 of this chapter. One hour sampling runs using this method have provided reliable data for cement kilns. 9.2.4 Validation of Runs. Before and after each run, or if adjustments are necessary for the measurement system during the run, repeat the sampling system bias check procedure described in section 9.1.3 of this method. (Make no adjustments to the measurement system until after the drift checks are completed.)

### Record the analyzer's responses.

9.2.4.1 If the post-run sampling system bias for either the zero or upscale calibration gas exceeds the sampling system bias specification, then the run is considered invalid. Take corrective action, and repeat both the analyzer calibration error check procedure (section 9.1.2 of this method) and the sampling system bias check procedure (section 9.1.3 of this method) before repeating the run. 9.2.4.2 If the post-run sampling system bias for both the zero and upscale calibration gas are within the sampling system bias specification, then construct two 2-point straight lines, one using the pre-run zero and upscale check values and the other using the post-run zero and upscale check values. Use the slopes and y-intercepts of the two lines to calculate the gas concentration for the run in accordance with equation 1 of this method. 9.3 Analyte Spiking—Self-Validating Procedure. Use analyte spiking to verify the effectiveness of the sampling system for the target compounds in the actual kiln gas matrix. Quality assurance (QA) spiking should be performed before and after each sample run. The spikes may be performed following the sampling system bias checks (zero and mid-range system calibrations) before each run in a series and also after the last run. The HCl spike recovery should be within ±30 percent as calculated using equations 1 and 2 of this method. Two general approaches are applicable for the use of analyte spiking to validate a GFC HCl measurement system: (1) two independent measurement systems can be operated concurrently with analyte spikes introduced to one of the systems, or (2) a single measurement system can be used to analyze consecutively, spiked and unspiked samples in an alternating fashion. The two-system approach is similar to Method 301 of this appendix and the measurement bias is determined from the difference in the paired concurrent measurements relative to the amount of HCl spike added to the spiked system. The two-system approach must employ identical sampling systems and analyzers and both measurement systems should be calibrated using the same mid- and high-range calibration standards. The two-system approach should be largely unaffected by temporal variations in the effluent concentrations if both measurement systems achieve the same calibration responses and both systems have the same response times. (See Method 301 of this appendix for appropriate calculation procedures.) The single measurement system approach is applicable when the concentration of HCl in the source does not vary substantially during the period of the test. Since the approach depends on the comparison of consecutive spiked and unspiked samples, temporal variations in the effluent HCl concentrations will introduce errors in determining the expected concentration of the spiked samples. If the effluent HCl concentrations vary by more than ±10 percent (or ±5 ppm,

### whichever is greater) during the time required to obtain and

equilibrate a new sample (system response time), it may be necessary to: (1) use a dual sampling system approach, (2) postpone testing until stable emission concentrations are achieved, (3) switch to the two-system approach [if possible] or, (4) rely on alternative QA/QC procedures. The dual-sampling system alternative uses two sampling lines to convey sample to the gas distribution manifold. One of the sample lines is used to continuously extract unspiked kiln gas from the source. The other sample line serves as the analyte spike line. One GFC analyzer can be used to alternately measure the HCl concentration from the two sampling systems with the need to purge only the components between the common manifold and the analyzer. This minimizes the time required to acquire an equilibrated sample of spiked or unspiked kiln gas. If the source varies by more than ±10 percent or ±5 ppm, (whichever is greater) during the time it takes to switch from the unspiked sample line to the spiked sample line, then the dual-sampling system alternative approach is not applicable. As a last option, (where no other alternatives can be used) a humidified nitrogen stream may be generated in the field which approximates the moisture content of the kiln gas. Analyte spiking into this humidified stream can be employed to assure that the sampling system is adequate for transporting the HCl to the GFC analyzer and that the analyzer's water interference rejection is adequate. 9.3.1 Spike Gas Concentration and Spike Ratio. The volume of HCl spike gas should not exceed 10 percent of the total sample volume (i.e., spike to total sample ratio of 1:10) to ensure that the sample matrix is relatively unaffected. An ideal spike concentration should approximate the native effluent concentration, thus the spiked sample concentrations would represent approximately twice the native effluent concentrations. The ideal spike concentration may not be achieved because the native HCl concentration cannot be accurately predicted prior to the field test, and limited calibration gas standards will be available during the field test. Some flexibility is available by varying the spike ratio over the range from 1:10 to 1:20. Practical constraints must be applied to allow the tester to spike at an anticipated concentration. Thus, the tester may use a 100 ppm calibration gas and a spike ratio of 1:10 as default values where information regarding the expected HCl effluent concentration is not available prior to the tests. Alternatively, the tester may select another calibration gas standard and/or lower spike ratio (e.g., 1:20) to more closely approximate the effluent HCl concentration. 9.3.2 Spike Procedure. Introduce the HCl spike gas mixture at a constant flow rate (±2 percent) at less than 10 percent of the total sample flow rate. (For example, introduce the HCl spike gas at 1 L/min (±20 cc/min) into a total sample flow rate of 10 L/min). The spike gas must be preheated before

### introduction into the sample matrix to prevent a localized

condensation of the gas stream at the spike introduction point. A heated sample transport line(s) containing multiple transport tubes within the heated bundle may be used to spike gas up through the sampling system to the spike introduction point. Use a calibrated flow device (e.g., mass flow meter/controller) to monitor the spike flow rate. Use a calibrated flow device (e.g., rotameter, mass flow meter, orifice meter, or other method) to monitor the total sample flow rate. Calculate the spike ratio from the measurements of spike flow and total flow. (See equation 2 and 3 in section 10.2 of this method.) 9.3.3 Analyte Spiking. Determine the approximate effluent HCl concentrations by examination of preliminary samples. For single-system approaches, determine whether the HCl concentration varies significantly with time by comparing consecutive samples for the period of time corresponding to at least twice the system response time. (For analyzers without sample averaging, estimate average values for two to five minute periods by observing the instrument display or data recorder output.) If the concentration of the individual samples varies by more than ±10 percent relative to the mean value or ±5 ppm, (whichever is greater), an alternate approach may be needed. 9.3.3.1 Adjust the spike flow rate to the appropriate level relative to the total flow by metering spike gas through a calibrated mass flow meter or controller. Allow spike flow to equilibrate within the sampling system for at least the measurement system response time and a steady response to the spike gas is observed before recording response to the spiked gas sample. Next, terminate the spike gas flow and allow the measurement system to sample only the effluent. After the measurement system response time has elapsed and representative effluent measurements are obtained, record the effluent unspiked concentration. Immediately calculate the spike recovery. 9.3.3.2 If the spike recovery is not within acceptable limits and a change in the effluent concentration is suspected as the cause for exceeding the recovery limit, repeat the analyte spike procedure without making any adjustments to the analyzer or sampling system. If the second spike recovery falls within the recovery limits, disregard the first attempt and record the results of the second spike. 9.3.3.3 Analyte spikes must be performed before and after each test run. Sampling system bias checks must also be performed before and after each test run. Depending on the particular sampling strategy and other constraints, it may be necessary to compare effluent data either immediately before or immediately after the spike sample to determine the spike recovery. Either method is acceptable provided a consistent approach is used for the test program. The average spike recovery for the pre- and post-run spikes shall be used to determine if spike recovery is between 70 and 130 percent.

### C gas 

### ' ( m i 

### % m f 

### ) ( C avg 

### & b
c 

### )

m c 

### % ( b i 

### % b f 

### )

2 10.0 Data Analysis and Emission Calculations The average gas effluent concentration is determined from the average gas concentration displayed by the gas analyzer and is adjusted for the zero and upscale sampling system bias checks, as determined in accordance with section 9.2.3 of this method. The average gas concentration displayed by the analyzer may be determined by integration of the area under the curve for chart recorders, or by averaging all of the effluent measurements. Alternatively, the average may be calculated from measurements recorded at equally spaced intervals over the entire duration of the run. For sampling run durations of less than 1-hour, average measurements at 2-minute intervals or less, shall be used. For sampling run durations greater than 1-hour, measurements at 2- minute intervals or a minimum of 96 measurements, whichever is less restrictive, shall be used. Calculate the effluent gas concentration using equation 1.

(Eq. 1)

where: b = Yc 

### intercept of the calibrationleastsquares line. b = Y-intercept of the final bias check 2-point line. f 

### b = Y-intercept of the initial bias check 2-point i 

### line. C = Effluent gas concentration, as measured, ppm. gas 

### C = Average gas concentration indicated by gas avg 

### analyzer, as measured, ppm.

m = Slope of the calibration least-squares line. c 

### m = Slope of the final bias check 2-point line. f 

### m Slope of the initial bias check 2-point line. i = 

### The following equations are used to determine the percent recovery (%R) for analyte spiking:



## %R = (S /C ) x 100 (Eq. 2)

M E 

### where: S = Mean concentration of duplicate analyte spiked M 

### samples (observed). C = Expected concentration of analyte spiked samples E 

### (theoretical). 

## C = C (Q /Q ) + S (1-Q /Q ) (Eq. 3) E S S T U S T 

### where: C = Concentration of HCl spike gas (cylinder tag S 

### value). Q = Spike gas flow rate. S

### Q = Total sample flow rate (effluent sample flow plus T 

### spike flow). S = Native concentration of HCl in unspiked effluent U 

### samples. Acceptable recoveries for analyte spiking are ±30 percent. 11.0 Pollution Prevention Gas extracted from the source and analyzed or vented from the system manifold shall be either scrubbed, exhausted back into the stack, or discharged into the atmosphere where suitable dilution can occur to prevent harm to personnel health and welfare or plant or personal property. 12.0 Waste Management Gas standards of HCl are handled as according to the instructions enclosed with the materials safety data sheets. 13.0 References 1. Peeler, J.W., Summary Letter Report to Ann Dougherty, Portland Cement Association, June 20, 1996. 2. Test Protocol, Determination of Hydrogen Chloride Emissions from Cement Kilns (Instrumental Analyzer Procedure) Revision 4; June 20, 1996. 3. Westlin, Peter R. and John W. Brown. Methods for Collecting and Analyzing Gas Cylinder Samples. Source Evaluation Society Newsletter. 3 (3):5-15. September 1978.

# EcoChem

Meßtechnik GmbH

_____________ ________________________________ Geschäftsführer: Dr. Wolfgang Berkhahn Sitz der Gesellschaft: Überlingen/Bodensee Amtsgericht Überlingen HRB 1144 VAT-No. DE177730533 Sparkasse Bodensee Überlingen 1009182 (BLZ 690 500 01) IBAN DE83 6905 0001 0001 0091 82 EcoChem Meßtechnik Alte Nußdorfer Str. 27 88662 Überlingen

To whom it may concern

Überlingen, 24.04.2007 Telefon : 07551 915 838 Fax : 07551 915 839

MC3-Stack Monitoring System

Dear Sir or Madam, The MC3 has been approved by the German TÜV (TÜV Rheinland). The TÜV approval has been made in cooperation with the company Dr. Födisch Umweltmesstechnik AG and was financed 50% by EcoChem Meßtechnik GmbH. The sy stem is sold in Germany under the Födisch label MCA04. The analyzer in the system is the EcoChem MC3. The report has passed the responsible committee in Germany August 17 th

. The “Umweltbundesamt” (UBA) has released the system for publication mid of September. The system is published and recommmended now in the “Bundesanzeiger”.

Best regards

- Wolfgang Berkhahn -2005_936_328560_21203173A.doc

The duplicating of the report in an abridged way requires a written approval

. 

### TÜV Immissionsschutz und Energiesysteme GmbH TÜV Rheinland Group D–51105 Köln, Am Grauen Stein, Phone: +49-221/806-2756, Fax: +49-221/806-1349



### TÜV IMMISSIONSSCHUTZ UND ENERGIESYSTEME GmbH
Report about the performance test of the measuring equipment MCA 04 for the components CO, NO, SO 2 

### , HCl, NH 3 

### , H 2 

### O, CO 2 

### and O 2 

### of the Company Dr. Födisch Umweltmesstechnik AG

TÜV (MOT) report: 936/21203173/A Köln, 13.07.2005

The TÜV Immissionsschutz und Energiesysteme GmbH is the Department Pollution Protection for the field of works:

- Determination of the emissions and airborne substances of air po llution and odor nuisance; - Check of the regular installation and the function and calib ration of continuously worki ng emission measuring devices including systems for the data evaluation and emission remote monitoring; - Performance test of measuring equipment for the conti nuous monitoring of the emissi ons and airborne substances and of electronic systems for the data ev aluation and emission remote monitoring
accredited according to DIN EN ISO/IEC 17025 and DIN EN ISO 9002.
The accreditation will be valid up to 04-12-2005.

DAR Registration Number: DAP-PL-3856.99.

### 2 ABSTRACT On behalf of the Company Dr. Foedisch Umweltmesstechnik AG the TÜV Immissionsschutz und Energiesysteme GmbH carried out the performance test of the emission equipment MCA 04 fo r the components CO, NO, SO 2 

### , HCl, NH 3 

### , CO 2, 

### H 2 

### O and O 2 

### according to the guidelines for continuous emission measurings [1].

The measuring equipment is operating accordi ng to the principles of the gas filter correlation and of the bi-frequency measurem ent process for infrared-active gas molecules. The oxygen measurement is carried out according to the circonium dioxide measurement process.

The test was carried out within a laboratory test and a five-month field test with two measuring equipments in the waste gas of an industrial residual incineration. The smallest measurement ranges being tested were:

Carbon monoxide: 0 up to 75 mg/m 3 

### Hydrogen chloride: 0 up to 15 mg/m 3 

### Nitrogen monoxide: 0 up to 200 mg/m 3 

### Ammonia: 0 up to 30 mg/m 3 

### Sulphur dioxide: 0 up to 75 mg/m 3 

### Waste gas humidity: 0 up to 40 Vol.-% Carbon dioxide: 0 up to 20 Vol.-% Oxygen: 0 up to 25 Vol.-%

The conditions of the minimum requirem ents were met with the performance test. The TÜV Immissionsschutz und Energiesys teme GmbH will therefore suggest a publication as a performanc e-tested measuring equipment for the continuous recording of the emissions of CO, NO, SO 2 

### , HCl, NH 3 

### and CO 2 

### and of the reference measurands H 2 

### O and O 2 

### for systems according to TA Luft (Technical Instruction on Air), 13. BlmSchV and 17. BlmSchV and 30. BlmSchV.

### 3 Accredited Test Institute DAP-PL-3856.99

Report about the performance test of the measuring equipment MCA 04 for the components CO, NO, SO 2 

### , HCl, NH 3 

### , H 2 

### O, CO 2 

### and O 2 

### of the Company Dr. Födisch Umweltmesstechnik AG

Measuring equipment to be checked: MCA 04
Equipment manufacturer: Dr. Födisch Umweltmesstechnik AG Zwenkauer Straße 22

D-04420 Markranstädt
Check period: Oktober 2004 bis Juli 2005
Date of report: 13.07.2005
Number of report: 936/21203173/A
Size of report: 369 pages altogether Appendix as of page 186 Manual as of page 237 with 132 pages

### 4 

## 1 Summary and Suggestion of Announcement

1.1 Summarized representation of the test results

Minimum Requirement Requirement Test Result Assessment Page

2.1 Common requirements for measuring and eval uation equipment for the determination of dusty and gaseous emissions 2.1.1 General requirements 2.1.1.1 Normative conditions Compliance with the valid performance criteria The performance test has been carried out in compliance with the mentioned guidelines. fulfilled 39

2.1.1.2 Complete measuring equipment The test must cover the complete measuring equipment incl. operating instructions in German language. The performance-tested type covers the complete measuring equipment including sampling system, analyser cabinet and operating instructions in German language. fulfilled 40

2.1.1.3 Compliance with the minimum requirements Two pieces of measuring equipment identically constructed. Laboratory and three-month field test. The laboratory tests have been completed successfully. The endurance test has been carried out from 27.01. 2005 up to 06.07. 2005 with a single system. fulfilled 41

2.1.1.4 Analysis function Statistically proved connection between the display of the equipment and the reference method of measurement. A statistically proved connection between the standard reference method of measurement and the display of the equipment could be proved for each individual measuring component. fulfilled 44

2.1.1.5 Linearity Devi ation of the actual values from the target values of the characteristic curve of the equipment ≤ 2 % of the measuring range. The linearity has been tested with all measuring components. No deviations could be found being larger than ± 2 % each in relation to the measuring range respectively. fulfilled 105

2.1.1.6 Adjustment of the settings Protection against unauthorized or unintentional misadjustment of the measuring equipment. The adjustment of the measuring equipment is only possible with the knowledge of the appropriate passwords. fulfilled 111

2.1.1.7 Position of the zero point (living zero point) Position of the zero point at 10 % or 20 %, position of the reference point at 70 % of the full deflection. The position of the zero point had beenset to 4 mA. The position of the reference point may be adapted to the measuring range by the selection of the concentration of the test gas. fulfilled 112

### 5 Minimum requirement Requirement Test result Assessment Page

2.1.1.8

2.1.1.9 Zero point drift in the maintenance interval

Reference point drift in the maintenance interval Zero point drift in relation to the measuring range ≤ 3 %. Reference point drift in relation to the measuring range ≤ 3 %. The pieces of measuring equipment have been set for all measuring channels to be tested until 28.01.2005. From 28.01.2005 to 16.06.2005 no deviations of the measuring channels could be found larger than 2.9 % in relation to the final value of the measuring range. T herefore the maximum drift of the reference point display for all measuring channels has been below 3 % within t he complete test period in relation to the final value of the measuring range. fulfilled 113

2.1.1.10 Display range Displ ay range 1.5 times of the limiting value. As part of the performance test the measuring equipment has been set to the measuring ranges of the 17 th BlmSchV. Other measuring ranges may be set at the measuring equipment. fulfilled 119

2.1.1.11 Measured value output Connection options for recording unit. The connection of additional measuring instruments and peripheral devices is possible with appropriate connections. fulfilled 120

2.1.1.12 Status signals Message of the operating condition with the status signals operational readiness, maintenance, troubles. The measuring equipment is provided with the required status signals. fulfilled 121

2.1.1.13 Availability Av ailability during the performance test ≥ 95 %. The equipment has an availability of 98.1 or 98.7 %. Thus, as part of the performance test, they exceeded the required value of 95 % or 98 % for the oxygen measurement. The number of the invalid half-hour average values achieved at most due to the control and adjustment work required during normal operation is below the number of invalid half-hour average values permitted at most when dividing up the activities in two days according to the requirements for systems of the 13 th BlmSchV and also of the 17 th BlmSchV. fulfilled 122

2.1.1.14 Maintenance interval Maintenance interval must be determined and it must be > 8 days. The zero point alignment is done automatically every 24 hours. The results of the drift examinations can be found in this report under item 6 [2.1.1.8 Zero po int drift in the maintenance interval] or 6 [2.1.1.9 Reference point drift in the maintenance interval]. Therefore there was a maintenance interval of 2 months. fulfilled 124

### 6 Minimum requirement Requirement Test result Assessment Page

2.1.1.15 Repeatability T he repeatability from double-specifications must be determined. The repeatability has been determined during the field test and it is fulfilled for all components. fulfilled 125

2.1.1.16 Nominal utility conditions Requirements must be met with the nominal utility conditions according to DIN 43745 for
a) Power supply voltage b) Relative atmospheric humidity c) Content of the air of liquid water d) Oscillation. To a) No influence to the measurement signal could be found from 190 to 250 V.
To b) The influence of the atmospheric humidity has not been examined separately. But it has to be assumed due to the construction of the device that it is insensitive against atmospheric humidity, as long as the dewpoint is not reached.
To c) The analyser is splash-proof, it should not be used unprotectedly at places with liquid water in the air.
To d) During the endurance test the devices were exposed to the oscillations and vibrations occuring at the measuring position. No recognizable influences on the function of the devices could be found. For reason of precaution the site of installation or mounting place of the analyser should be possibly safe from vibrations.

The manufacturer does not mention the operat ing position of the analyser separately; it is predefined by the design. fulfilled 126

2.1.1.17 Automatic readjustment The corrective range permitted at most has to be determined. The measuring equipment carries out an automatic zero point alignment. If the control range of 6 or 10 % is exceede, the measuring equipment issues a status signal. fulfilled 127

### 7 Minimum requirement Requirement Test result Assessment Page

2.1.1.18 Ambient temperature range With installation in the open: -20 to 50 °C, with installation at temperature-controlled places: 5 to 40 °C. Two devices of the type MCA 04 have been exposed to temperature variations between +5 °C and +40 °C. Doing this, maximum deviations on the zero point of 3.7 % and of –4.1 % on the reference point have been determined in relation to the display range respectively, or 0.34 vol.-% with O 2

. fulfilled 128

2.1.1.19 Influence test gas flow Influence on the measurement signal < 1 % of the display range. It could be seen with the tested measurement equipment, that with a flow between 280 and 400 l/min the influence on the measurement signals is < 1 % in relation to the measurement range. If this range is exceeded, the measurement equipment issues a status signal. fulfilled 132

2.1.1.20 Drift of the measuring ray With optical methods, maximum influence of 2 % of the measurement range final value to the measurement signal at the angular range 0.3°. Not applicable, since the measurement equipment is operated extractively. Not applicable 134

2.1.1.21 Contamination monotoring Contamination monotoring during the operation with optical methods Not applicable, since the measurement equipment is operated extractively. Not applicable 135

2.1.1.22 Automatic recording of zero and reference point Measurement equipment must have a mechanism for the automatic recording of zero and reference point. Not applicable, since the measurement equipment has no possibility for the automatic recording of zero and reference points. Not applicable 136

2.1.1.23 Setting time The t 90 time must be ≤ 200 s. According to the measuring components there are t 90 times between 131 and 181 (O 2 80 s) for the tested measurement equipment. Therefore the required t 90 time has been met with all components. fulfiled 137

2.1.1.24 Multi component measurement equipment The requirements must be met for each individual component. The measurement results for all channels have been provided simultaneously with the assessment of the minimum requirements. fulfilled 140

2.1.1.25 Digital interface The digital interface must be completely described in the approriate standards and guidelines. Not applicable, since there is no authorized digital interface available. However, the measurement equipment MCA 04 is able to issue its measurement signals and its status of equipment. Not applicable 141

### 8 Minimum requirement Requirement Test result Assessment Page

2.1.1.26 Uncertainty of measurement Determination of extended uncertainty of measurement according to DIN EN ISO 14956, comparison with defined requirements. The uncertainties determined for all components are below the predefined values and therefore meet the requirements. fulfilled 142

2.2 Additional requirements of measurem ent equipment for the determi nation of gaseous emissions Not applicable here 2.3 Additional requirements of measurem ent equipment for the determi nation of gaseous emissions 2.3.1 General requirements 2.3.1.1 Detection limit Less than or equal to 5 % of the limit value of the daily average value. Detection limits between 0.49 and 4.85 % of the respective limit value of the daily average value have been found for the measuring components according to 17 th BlmSCHV, for NH 3 there has been a detection limit of 1.90 or 1.66 % of the measurement range. fulfilled 144

2.3.1.2 Temperature drift Change of zero point and reference point display ≤ 5 % of the measurement range starting out from 20 °C over the complete temperature range. For all tested devices the maximum temperature drift has been –3.7 % on the zero point and –3.5 % on the reference point for the components CO, NO, SO 2 , HCl, NH 3 and CO 2 of the measurement range respectively. fulfilled 147

2.3.1.3 Transverse sensitivity The sum of the transverse sensitivities shall be ≤ 5 % of the measurement range. The transverse sensitivities determined at most with both devices were 4.0 % on the zero point and on the reference point in relation to the appropriate measurement range. fulfilled 148

2.3.1.4 Sampling and preliminary processing Proper solid filtering,avoid crosscontamination effects as far as possible. The sampling systems used with the enduring prooftesting have been working properly in the more than tree-month field test even at higher waste gas humidities. Adsorption and desorption effects could not be observed during the test. fulfilled 155

2.3.1.5 Repeatab ility Repeatability ≥ 30. For the repeatability of the individual measuring components within the tested measurement ranges values between 30 and 183 have been determined. fulfilled 156

### 9 Minimum requirement Requirement Test result Assessment Page

2.3.2 Additional requirements of measurement equipment for the determination of organic compounds (total carbon) Not applicable here 2.4 Additional requirements of measurem ent equipment for the determinat ion of reference values 2.4.1 Measurement equipment fo r the determination of the oxygen content 2.4.1.1 Availability Av ailability during the performance test ≥ 98 % The devices have an availability of 98.1 % or 98.7 %. With that as part of the performance test they exceeded the required value of 98 % for oxygen. fulfilled 163

2.4.1.2 Detection limit ≤ 0.2 vol.-% O 2 Detection limits of 0.14 and 0.15 vol.-% O 2 have been determined for the measurement equipment. fulfilled 164

2.4.1.3 Repeatab ility Repeatability ≥ 70 The repeatability has been determined for the measurement range 0 to 25 vol.-% O 2 . The result was a value of 172. fulfilled 165

2.4.1.4 Temperature drift Change of zero point and reference point display ≤ 0.5 vol.-% O 2 , starting out from 20 °C over the complete temperature range. Two devices of the type MCA 04 have been exposed to temperatures between +5 °C and +40 °C in a climatic chamber. No deviations > 0.34 vol.-% O 2 have been determined. fulfilled 167

2.4.1.5 Transverse sensivity The sum of the transverse sensivities should be ≤ 0.2 vol.-% O 2

. For the measurement equipment MCA 04 no relevant transverse sensivities could be determined with the component O 2

. fulfilled 168

2.4.1.6 Sampling Proper solid filtering,avoid crosscontamination effects as far as possible. The sampling systems used with the enduring prooftesting have been working properly in the field test. Adsorption and desorption effects could not be observed during the test. Pay attention to a sufficient and complete heating of all components. The sampling systems may be adapted to the systems to be monitored according to the formulation. fulfilled 170

2.4.1.7 Drift in the maintenance intervall ≤ 0.2 vol.-% O 2 There were no drifts < 0.2 vol.-% O 2 to be determined during the field test. The maintenance interval for the test gas task correspondingly results according to item 6 [2.1.1.14 maintenance interval] of 2 months. fulfilled 171

### 10 Minimum requirement Requirement Test result Assessment Page

2.4.1.8 Linearity Devi ation of the actual values from the target values of the characteristic curve of the equipment ≤ 0.3 vol.-% O 2 The linearity has been tested for the measurement range 0 to 25 vol.-%. There has been no larger deviation determined than 0.17 vol.-%. fulfilled 172

2.4.2 Measurement equipment for the de termination of the waste gas volumetric flow Not applicable here 2.4.3 Measurement equipment for the determination of t he moisture content 2.4.3.1 Display range Measured values shall be in the upper third of the display range during normal operation. The important application cases may be covered with the measurement range 0 to 40 vol.-%. A reduction of the measurement range to smaller values is possible. fulfilled 173

2.4.3.2 Detection limit Smaller than 5 % of the measurement range. With values of < 0.4 % in relation to the measurement range the conditions of the minimum requirement were clearly reached. The measurement range 0 to 40 vol.-% meets the measuring range 0 to 321.4 g/m 3 as mass concentration. fulfilled 174

2.4.3.3 Repeatab ility Repeatability ≥ 30 The repeatability for water in the tested measurement ranges is 253. fulfilled 175
2.4.3.4 Temperature drift Change of zero point and reference point display ≤ 0.5 % of the measurement range, starting out from 20 °C over the complete temperature range. When testing the devices in a climatic chamber with a temperature range of +5 °C to +40 °C there was a maximum deviation at the zero point of –0.1 %, and at the reference point of –2.7 % in relation to the measurement range. fulfilled 177

2.4.3.5 Transverse sensitivities The sum of the transverse sensitivities shall be ≤ 4% of the measurement range. The maximum transverse sensitivity was 1 % and it is therefore < 4% of the display range with both devices. fulfilled 178

2.4.3.6 Calibration Gravim etric calibration The m easurement equipment has been adjusted, performance-tested and calibrated with gravimetric methods. fulfilled 180

Appendix E Requirements of m easurement and evaluation equipme nt in the sense of the 17 th BlmSchV E1 Requirements to measurement equipment of systems in the sense of the 17 th BlmSchV E 1.1 Measurement range requirements for the daily average value Proof of the minimum requirements in the range of the one and a half times limit value TMW. The display range of the tested measurement equipment had been set for the measuring component NO to 1.53 times of the limit value for the daily average value. fulfilled 181

E 1.2 Measurement range requirementsfor the halfhour average value Measurement range up to the one and a half times of the limit value HMW shall be covered. The display range of the tested measurement equipment may be adapted to the appropriate measurement task. fulfilled 182

### 11 1.2 Suggestion of Announcement
Due to the achieved positive results the followi ng recommendation is given for the announcement as a performance-tested measurement equipment:

1.2.1 Measurement task : Continuous monitoring of the emissions

1.2.2 Name of device : MCA 04

1.2.3 Measuring components : H 2 O, HCl, CO, NO, SO 2 , NH 3 , CO 2 , O 2

1.2.4 Manufacturer : Dr. Foedisch Umweltmesstechnik AG, D-04420 Markranstädt

1.2.5 Suitability : For systems requiring official approval and systems of the 27 th BlmSchV

1.2.6 Measurement ranges with the performance test : Component Measurement ranges

Waste gas humidity H 2 O 0 - 40 vol.-%
Hydrogen chloride HCl 0 – 15 0 - 90 mg/m 3 mg/m 3 Carbon monoxide CO 0 – 75 0 - 300 mg/m 3 mg/m 3 Nitrous oxide NO 0 – 200 0 - 395 mg/m 3 mg/m 3 Sulphur dioxide SO 2 0 – 75 0 - 300 mg/m 3 mg/m 3 Ammonia NH 3 0 – 30 0 - 75 mg/m 3 mg/m 3 Carbon dioxide CO 2 0 – 20 mg/m 3

Oxygen O 2 0 - 25 mg/m 3

1.2.7 Software version : MC3 Firmware V 1.83

1.2.8 Restrictions • For the component SO2 in the measurement range 0 to 75 mg/m 3 the minimum requirements for t he transverse sensitivity at concentrations of HCl > 50 mg/m 3 and N 2 O > 20 mg/m 3 are not met.

• For the component HCl in the measurement range 0 to 15 mg/m 3 the minimum requirements for the transverse sensitivity at concentrations of SO 2 > 200 mg/m 3 and N 2 O > 20 mg/m 3 are not met.

1.2.9 Notes : • The measurement equipment is operated with humid waste gas.

• The maintenance interval for the test gas task for the measurment equipment MCA 04 is two months.

1.2.10 Test institute : TÜV Immissionsschutz und Energiesysteme GmbH, Köln TÜV Rheinland Group

1.2.11 Test report : 936/21203173/A of 13.07. 2005T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 1 o f 7 

# PR O DUC T C O N F O R M I T Y CE R T I F I C A T E

T h i s i s t o c e r t i f y t h a t t he


# M C A 0 4 Mu l t i C o m p o n e nt An a l y s e r

m an u f a c t u r e d b y : 

# D r

. F ö d i sc h U m w e l t m esstec hn i

k A G Z w e n k a u e r S t r a ß e 1 59 D

- 04 4 20 M a r k r a n s t ä d t / O T K

u l w i tz G e rm a n y

ha s been a s s e s s ed b y S i r a Ce r t i f i c a t i on S e r v i c e and f o r t he c on d i t i on s s t a t ed on t h i s c e r t i f i c a t e c o m p li e s w i t h :



### M C E R T S P e r f o r m a n c e S t a nd a r d s f o r C on t i nuou s E m i s s i on M o n i t o r i ng S ys t e m s , V e r s i on 2 , R e v i s i on 1 ( A p r il 2003 )

C e r t i f i c a t i on R a n ge s :

SO 2 

### 0 t o 7 5 m g /m 3 

### 0 t o 3 0 0 m g /m 3 

### N O 0 t o 2 0 0 m g /m 3 

### 0 t o 3 9 5 m g /m 3 

### C O 0 t o 7 5 m g /m 3 

### 0 t o 3 0 0 m g /m 3 

### HCl 0 t o 1 5 m g /m 3 

### 0 t o 9 0 m g /m 3 

### NH 3 

### 0 t o 2 0 m g /m 3 

### 0 t o 7 5 m g /m 3 

### O 2 

### 0 t o 2 5 % v o l CO 2 

### 0 t o 2 0 % v o l H 2 

### O 0 t o 4 0 % v o l

P r o j e c t N o : 674 / 02 5 8 C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 I n i t i a l C e r t i f i c a t i o n : 02 J u l y 2007 T h i s C e r t i f i c a t e I s s u e d 02 J u l y 2007 R e n e w a l D a t e : 01 J u l y 2012 T e c hn i c a l D i r e c t o r

M C E R T S i s ope r a t ed on behal

f o f t he E n v i r on m en t A g

en cy b y 

# Si ra C e rt i f i c at i o n S e r v i c e
12 Ac o r n I ndu s t r i a l P a r k
, C r a y f o r d Road
, C r a y f o r d

Da r t f o r d
, K en t
, U K
, D A 1 4 A L T el : 01322 520500 F a x : 01322 520501T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 2 o f 7 

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An y p o t e n t i a l u s e r s h o u l d e n s u r e , i n c o n s u l t a t i o n w i t h t h e m a n u f

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s i o n m o n i t o r i n g s y s t e m is s u i t

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e r t o E n v ir o nm e n t A g e n c

y T ec h n i ca l Gu i d a n ce N o t

e M 2 : M o n i t o ri n g o f s t

ac k e m i s s i o n s t

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. T h is i s a v a il a b l e o n t h e A g e n c y ’ s we b si t e a t www

. m ce r t s

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O n t h e b a sis o f t h e a s s e s s m e n t a n d t h e r a n g e s r e q u ir e d f o r c o m p li a n ce w

i t h E U D i r ec

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T h i s c e r t i f i c a t i o n i s ba s ed on t he f o ll o wi n g T e s t R epo r t ( s ) a nd on S i r a ’ s a ss e ss m e n t a nd
o n go i n g s u r v e ill a n c e o f t h e p r o d u c t a nd t h e m a n u f a c t u r i n g p r o c e ss :

T Ü V R h e i n l a n d R epo r t N o : 9 36 / 2 1 2 0 3 1 7 3 / A d a t e d 13 / 0 7 / 0 5 T Ü V R h e i n l a n d R epo r t N o : 9 36 / 2 1 2 0 3 1 7 3 / B d a t e d 23 / 1 2 / 0 5 T Ü V R h e i n l a n d R epo r t N o : 9 36 / 2 1 2 0 4 2 3 1 / C da t e d 2 2 / 0 6 / 07

T Ü V r e p o r t s a r e a c c ep t e d o n t h e b a s i s o f t h e E n v i r on m en t A g e n cy ’ s do c u m e n t ‘ M C E R T S – G u i d an c e on t h e a cc e p t a n c e o f G e rm a n t y pe a p p r o v a l t e s t r e po r t s f o r C E M S ’ V e r s i o n 2 ( O c t o b e r 2 0 03 )

P r odu c t C e r t i f i e d

T h e M CA 04 m ea s u r i n g s

y s t e m c o n s i s t s o f t h e f o ll o w i n g p a r t s :

• H ea t ed s a m p l i ng p r o be T y p e S P 20 00 H

• H ea t ed l i ne ( l e n g t h d u r i ng Q A L 1 1 0 m)

• A na l y s e r u n i t M C A 0 4

T h i s ce r t i f

i ca t e a pp li e s t

o a l l i n s t r u m e n t

s f i tt e d w i t h s o f t wa r e v e r s i o n M

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. 83 o n w

a r d s ( s e r i a l n um b e r 05002 o n w a r d s )

.

C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h is C e r t i f i c a t e I s s u e d : 02 J u l y 2007T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 3 o f 7 

### C e r t i f i e d P e r f o r m a n ce

T h e i n s t r u m e n t

w a s e v a l u at

e d f o r u s e un d er t h e f

o l l o w i n g c o n d i t i o n s :

Amb i e n t T e mp er

at u re Ra n g e : +5 0 C t o + 40

0 C

U n l e ss o t h e r w i s e s t a t ed t h e e v a lu a t i on w a s c a rr i e d ou t on t h e c e r t i f i c a t i o n r an g e s SO 2 0 t o 7 5 m g /m 3

, N O 0 t o 2 0 0 m g /m 3

, C O 0 t o 75 m g /m 3

, HC l 0 t o 1 5 m g /m 3

, N H 3 0 t o 20 m g /m 3 , O 2 0 t o 2 5% v o l
, CO 2 0 t o 20% v o l & H 2 O 0 t o 4 0 % v ol

. T e s t R e s u l t s e x p r e s s e d a s % o f t h e c e r t i f i c a t i o n r ang e O t h e r r e s u l t s M C E R T S
s p e c i f i c a t i on <0

. 5 <1 <2 <4 L i n e a r i t y C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 17 - 0

. 7

- 0

. 9

- 0

. 9

- 0

. 8

- 0

. 7 2

. 0

2

. 0 <2 %

<2 %

<2 %

<2 %

<2 %

<2 %

<0

. 3 %

C r o s s
- s e n s i t i v i t y (O 2 , H 2 0
, CO 2 , CH 4 , N 2 O
, N O
, NO 2 , NH 3 , SO 2 , H C l )

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 <0

. 02 - 2

. 7

- 3

. 9

- 4

. 0

- 4

. 0

3

. 6

1

. 0

- 2

. 5 N o t e 1 <4 %

<4 %

<4 %

<4 %

<4 %

<4 %

<4 %

C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h is C e r t i f i c a t e I s s u e d : 02 J u l y 2007T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 4 o f 7 T e s t R e s u l t s e x p r e s s e d a s % o f t h e c e r t i f i c a t i o n r ang e O t h e r r e s u l t s M C E R T S
s p e c i f i c a t i on <0

. 5 <1 <2 <4 T e m p e r a t u r e d e p e nd e n t z e r o s h i f t

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 12

0

. 15

0

. 09

0

. 25

0

. 08

0

. 01

0

. 01

<0

. 01 <0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 5 %/ o C

T e m p e r a t u r e d e p e nd e n t upp e r r e f e r e n c e po i n t s h i f t

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 13

0

. 10

0

. 21

0

. 25

0

. 11

0

. 18

0

. 15

0

. 03 <0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 3 %/ o C

<0

. 5 %/ o C

R e s pon s e t i m e

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 144

151

162

181

176

151

131

85 <200 s

<200 s
<200 s
<600 s
<200 s
<200 s
<200 s
<200 s C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h is C e r t i f i c a t e I s s u e d : 02 J u l y 2007T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 5 o f 7 T e s t R e s u l t s e x p r e s s e d a s % o f t h e c e r t i f i c a t i o n r ang e O t h e r r e s u l t s M C E R T S
s p e c i f i c a t i on <0

. 5 <1 <2 <4 D e t e c t i on L i m i t

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 21

0

. 36

0

. 28

0

. 15 0

. 77

0

. 61

1

. 97

1

. 90 <2 %

<2 %

<2 %

<2 %

<2 %

<2 %

<2 %

<0

. 2 %

I n t e r f e r e n c e o f t e s t g a s f l o w o n t h e m e a s u r e m e n t s i g na l

O 2 - 0

. 7 N o t e 2 <1 %

V i b r a t i o n t e s t ( 10 t o 60 H z ( ± 0

. 3 mm )
, 6 0 t o 150 H z a t 19

. 6 m /s 2 ) N o t e 3 T o b e r e po r t e d

M a i n s v o l t a g e ( 190 V t o 2 5 0 V ) N o e ff e c t N o t s p e c i f i e d

S a m p l e ga s p r e ss u r e N o t e 3 T o b e r e po r t e d

S a m p l e ga s t e m p e r a t u r e N o t e 3 T o b e r e po r t e d

A na l y s i s f un c t i o n N o t e 4

C O

N O

SO 2
H 2 O

CO 2 O 2 99

. 5 %

96

. 2 %

98

. 9 %

99

. 8 %

99

. 8 %

99

. 9 % >95 %

>95 %

>95 %

>95 %

>95 %

>95 %

C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h is C e r t i f i c a t e I ss u e d : 02 J u l y 2007T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 6 o f 7 T e s t R e s u l t s e x p r e s s e d a s % o f t h e c e r t i f i c a t i o n r ang e O t h e r r e s u l t s M C E R T S
s p e c i f i c a t i on <0

. 5 <1 <2 <4 I n t e g r a l p e r f o r m a n c e N o t e 4

NH 3 HC l 5

. 0

9

. 6 <10 %

<10 %

A v a i l a b i li t y N o t e 4 98

. 1 % >95 %

Z e r o d r i ft d u r i n g f i e l d t r i a l N o t e 4

C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 20

0

. 15

0

. 43

<0

. 1

0

. 0

<0

. 1

<0

. 01 1

. 0 <2 % / w ee k

<2 % / w ee k

<2 % / w ee k

<2 % / w ee k

<2 % / w ee k

<2 % / w ee k

<0

. 2 % / w ee k

U pp e r r e f e r e n c e po i n t d r i f t d u r i ng f i e l d t r i a l N o t e 4 C O

N O

SO 2 HC l

NH 3
H 2 O

CO 2 O 2 0

. 30

0

. 35

0

. 06 0

. 52

1

. 10

0

. 60

1

. 00

- 0

. 8 <4 % / w ee k

<4 % / w ee k

<4 % / w ee k

<4 % / w ee k

<4 % / w ee k

<4 % / w ee k

<0

. 2 % / w ee k
M a i n t e nan c e I n t e r v a l N o t e 4 3 m on t h s T o b e r e po r t e d
N o t e 1 : F o r t h e c o m pon e n t SO 2 t h e r e qu i r e m e n t f o r c r o s s
- s e n s i t i v i t y w e r e no t m e t wi t h c o n c e n t r a t i on s o f HCl

4 0 m g /m 3 a nd N 2 O >2 0 m g /m 3

. F o r t h e c o m pon e n t HCl t h e r e qu i r e m e n t f o r c r o ss
- s e n s i t i v i t y w e r e no t m e t wi t h c on c e n t r a t i o n s o f SO 2 > 20 0 m g /m 3 a n d N 2 O > 20 m g /m 3

. N o t e 2 : T h e i n s t r u m en t m e t t h e r e qu i r e m e n t s wi t h a f l o w r a t e b e t w een 28 0

- 400 L / h

. I f t h e f l o w i s o u t s i d e t h i s r ang e t h e i n s t r u m e n t a l a r m s

. N o t e 3 : M C A 04 i s a n e x t r a c t i v e a n a l y s e r

. T e s t n o t ap p l i c a b l e

. N o t e 4 : F i e l d t e s t : T h e M C A 0 4 an a l ys e r w a s a ss e ss e d on t h e ba s i s o f a s i x m on t h f i e l d t r i a l m ou n t e d o n a

w a s t e i n c i n e r a t o r

. C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h i s C e r t i f i c a t e I s s u e d : 02 J u l y 2007T h i s c e r t i f i c a t e m a y o n l

y b e r ep r o d u c e d in i t

s e n t i r e t y a n d w i t

h o u t c ha n g e P ag e 7 o f 7 

### D e s c r i p t i on :

T he m u l t i

- c o m p o n e n t M C A 04 sys t e m i s an a b s o r p t i o n
- s p e c t r o m e t r i c m u l t i

- ga s s e n s o r f o r f l u e ga s m ea s u r e m e n t a nd c a n m e a s u r e u p t o 8 c o m p o n en t s

.
T he M C A 0 4 an a l ys e r e x t r a c t s s a m p l e g a s f r o m t he s t a c k v i a a h e a t e d p r o b e a n d h e a t e d li n e t o t h e a na l y s e r w h i c h i s a h ea t e d I R a n a l y s e r

. A ll c o m p o n e n t s o f t h e M C A 0 4 sys t e m a r e h e a t e d t o a t e m p e r a t u r e a b o v e t h e a c i d de w p o i n t t o a ll o w m o n i t o r i n g on v a r i o u s a p p li c a t i o n s

. T he M C A 04 a n a l ys e r u s e s g a s f il t e r c o rr e l a t i o n a n d a b i

- f r e q u e n cy m e a s u r i n g p r i n c i p l e d e p e nd i n g on t h e c o m p o n e n t s be i ng m ea s u r e d

. F o r t he o xy g e n m e a s u r e m en t a z i r c o n i a s en s o r i s u s e d

.

G e n e r a l N o t e s

1

. T h i s c e r t i f i c a t e i s b a s e d u p on t h e e qu i p m e n t t e s t e d

. T he M a nu f a c t u r e r i s r e s p o n s i b l e f o r en s u r i n g t h a t on
- go i n g p r o du c t i o n c o m p l i e s w i t h t h e s t a n da r d ( s ) a n d pe r f o rm an c e c r i t e r i a de f i n e d i n t h i s C e r t i f i c a t e

. T h e M an u f a c t u r e r i s r e qu i r e d t o m a i n t a i n a n a pp r o v e d q u a li t y m a n a g e m e n t sys t e m c o n t r o lli n g t h e m a nu f a c t u r e o f t h e c e r t i f i e d p r o d u c t. B o t h t he p r o du c t a nd t he q u a li t y m a n a ge m e n t sys t e m s ha ll b e s u b j e c t t o r e g u l a r s u r v e ill an c e a cc o r d i ng t o ‘R e gu l a t i o n s A p p li c a b l e t o t h e H o l de r s o f S i r a C e r t i f i c a t e s ’

. T he de s i gn o f t h e p r o d u c t c e r t i f i e d i s de f i n e d i n t h e S i r a D e s i g n S c h e d u l e f o r c e r t i f i c a t e N o

. S i r a M C 0 7 0 1 15 / 0 0

.
2

. I f c e r t i f i e d p r o du c t i s f o u nd n o t t o c o m p l y , S i r a C e r t i f i c a t i on S e r v i c e s h ou l d be n o t i f i e d i mm ed i a t e l y a t t he a d d r e s s s h o w n o n t h i s c e r t i f i c a t e

. 3

. T he C e r t i f i c a t i o n M a r ks t ha t c an be a pp l i ed t o t h e p r o du c t o r u s e d i n p ub li c i t y m a t e r i a l
a r e d e f i n e d i n ‘R e g u l a t i on s A pp li c a b l e t o t h e H o l d e r s o f S i r a C e r t i f i c a t e s ’

.
4

. T h i s do c u m e n t r e m a i n s t h e p r o pe r t y o f S i r a a n d s ha ll be r e t u r n ed w h en r e q u e s t ed b y t h e c o m p a n y

.

C e r t i f i c a t e N o : S i r a M C 0 7 011 5 / 0 0 T h i s C e r t i f i c a t e I s s u e d : 02 J u l y 200 7

# EcoChem Analytics Headquarters: 202 Reynolds, League City, TX 77573 Tel: 281-338-9888 Fax: 332-6152 Eastern USA : 8 Paret Lane, Hartsdale, NY 10530 Tel: 914-683-5920 Fax: 683-1029 Germany Alte Nussdorfer Str 27, D-88662 Uberlingen Tel:+49(7551)915838 Fax: 915-839 Email: sales@ecochem.biz Website: www.ecochem.biz


# BUDGETARY PROPOSAL Continuous Emissions Monitoring System (CEMS)

Quotation Number: XXXXXX

Quotation Date: XXXXX Customer: XXXXXXXXXX XXXXXXXXXX XXXXXXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 1 

# Table of Contents

1.0 BUDGETARY PRICING & SCHEDULE .........................................................................2
1.1 Budgetary Pricing ...........................................................................................................2 1.2 Project Schedule and Milestone Payments ................................................................4

2.0 CEMS DESCRIPTION .......................................................................................................5
2.1 MC3 Analyzer ..................................................................................................................5 2.2 MC3 System Cabinet .....................................................................................................7 2.3 MC3 System Controller ................................................................................................10 2.4 Sample Probe ................................................................................................................12 2.5 Sample Line ...................................................................................................................12 2.6 Data Acquisition System ..............................................................................................12 2.7 Building Shelter .............................................................................................................16 2.8 System Documentation ................................................................................................19 2.9 CEMS Drawings ............................................................................................................19

3.0 PROJECT ADMINISTRATION, TERMS AND CONDITIONS ...................................23
3.1 Warranty .........................................................................................................................23 3.2 Additional Insurance Coverage ..................................................................................23 3.3 Order Cancellation Policy ............................................................................................23 3.4 Terms and Conditions ..................................................................................................24 3.5 Payment Schedule .......................................................................................................24Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 2 

# 1.0 BUDGETARY PRICING & SCHEDULE

1.1 Budgetary Pricing

# Item Description Qty Unit Cost Ext Cost 1a Multicomponent Gas CEMS Each MC3 based system will include the capability tosimultaneously measure HCl, CO2, and H2O on a HOTWET basis. Each entire system is mounted inside a standalone cabinet, includes Operator Interface Color Touch Screen and sample system components (cell and pump filters, flow indication, sample pump) designed to operate in conjunction with a heated probe and sample line. 1 $51,500 $51,500

1b 

### OPTION – O2 Measurement The MC3 analyzer described in item 1a enhanced to include an oxygen measurement. 1 $1,890 $1,890

2 Heated Probe The probe will have initial filtr ation, probe isolation and injection ports for calibration gas (for sample system calibrations) and probe blow back. The probe will be controlled from temperature controllers in the analyzer cabinet. Probe length is one meter from flange to tip. Probe tube heaters are also provided. 1 $12,090 $12,090

3 Heated Sample Lines The heated sample line contains five tubes and 10 wires. The lines include a full redundant heaters and RTD

. The umbilical typically operates at 185 ° C or higher and is controlled by the system. --- $69/ft $69/ft

4 Factory Acceptance Test The FAT will be conducted in League City (Houston), TX and customer’s engineers will be able to test and verify system performance and functionality before it is shipped to customer’s plant site. Limited training is also conducted 1 $6,400 $6,400

5 QA/QC Manual EcoChem will assist in creating a custom QA/QC Plan for customer to ensure high system reliability, maximum online availability and meeting regulatory requirements. Weekly, monthly, quarterly and annual checklists are provided detailing proper maintenance intervals. 1 $3,400 $3,400Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 3 

### 6 Spare Parts -- Consumable (2 YEARS) Consumable parts like filters, sample pump rebuild kits for TWO-year operation 2 $1,440 $2,880

7 Spare Parts NON-Consumable Inventory Typical MC3 CEMS non-consumable spare parts kit 1 $7,800 $7,800

8 Calibration Gas Regulators Dual stage regulators for the gases to be measured – one Brass and one 316-Stainless Steel dual stage regulators will be provided. Provisions for use of instrument air as cal gas will be incorporated. Set of 2 $2,800 $2,800

9 Data Acquisition System

PART 60 Data acquisition system (software and hardware) configured for collecting data from MC3 analyzer and producing EXCEL reports. 1 $12,400 $12,400

10 Building Enclosure

8’ x 8’ x 9’ (internal height) building enclosure housing one CEMS. Dual 18,000 BTU A/C unit with 125 amp power panel. 1 $28,450 $28,450

11 Sensors for Building Enclosure

MSA Ultima X Series Gas Monitors for O2 and HCl detection within the Building Enclosure 1 $5,600 $5,600

12 Expedited Delivery Charge

System to be delivered in 60 days. An expedited fee of 10% on specific items from the original quote: items 1(CEMS), item 3 (sample line) and item 10 (Building Enclosure) is proposed. 1 $8,650 $8,650Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 4 

## 1.2 Project Schedule and Milestone Payments
Normal delivery schedule is 45 to 60 days delivery time after receipt of order (Without Building Enclosure)
Normal delivery schedule is 60 to 90 days delivery time after receipt of order (With Building Enclosure)

Milestone Payments (net 30 days)
Receipt of order 30% Factory Acceptance Test or System shipped from EcoChem 60% Final Acceptance or before system leaves US 10%
For international sales, complete payment before system leaves USBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 5 

# 2.0 CEMS DESCRIPTION

2.1 MC3 Analyzer The MC3 is a multicomponent IR gas analyzer that is specifically designed for continuous monitoring of a flue gas stream. The infrared optical bench, sample cell and control components are all integrated into one convenient, and easily serviced ventilated enclosure. Each enclosure cabinet is self-standing and weighs less than 500 lbs.
The MC3 has the following measurement range intervals:

Gas Range Interval** Measurement Technique*** Suggested Range****

CO2 0-10% to 0-50% SBDW To be decided HCl 0-20 PPM to 0-200 PPM GFC To be decided
H 2 

### O 0-10% to 0-50% SBDW To be decided * All components at 185 ° C or above; standard sample cell path 6 meters ** User can select appropriate range within the inte rval; two ranges (i.e.: dual ranging) are available but must be specified at time of order. *** GFC = Gas Filter Correlation, SBDW=Single B eam Dual Wavelength, ZRO=Zirconium Oxide **** Suggested range can be modified – final choice of range to be decided when system is ordered. For certain components, inlet and outlet ranges will be different.



### Weight 56 lb (25 kg) Dimensions Standard 19in rack m ount (Height x Depth x Width): 8.75in x 23in x 19in (22cm x 58 cm x 48cm) Flow Rate 2-7 liter per minute with 1⁄4” Swagelok connectors Display Menu-driven LCD Panel can be field-customized Power 115 volts AC / 60 Hz and 220 volts AC / 50 Hz Accuracy ± 2 % of full-scale value Lower Threshold 1 % of lowest range Response Time 10 sec Output Signals Analog: 8 signals of 0/4 – 20 mA; Digital: 2 ports RS 232-C, 1 port RS 422-A; Relays: Failure Indicator, Service and Maintenance Operating Temperature 0 – 105°F (0 – 40°C) Sample cell 185 oC or above with 6m path length Update Frequency Every 10 seconds

The infrared optical bench consists primarily of an infrared source with chopper, a sample cell that the infrared light pulses travel through, a motor driven filter disk with different optical filters or gas filled cells in the infrared light beam, and a solid state detector to measure energy of the infrared light pulses.Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 6 

### In order to understand the operation of the multi- component analyzer, we have summarized some of the important aspects of its functioning:


### Analysis Techniques The multi-component IR gas analyzer can m easure different gases using the Gas Filter Correlation (GFC) or the Single Beam Dual Wavelength (SBDW) techniques.

GFC is a well-established method to reduce cro ss sensitivities to gases th at cause interference in infrared measurements. In the technique an optical band pass filter is used to select an infrared band and then a cell filled with 100% concentration of the gas of interest is placed in the beam, effectively blocking the spectral lines that the gas absorbs at. It is important to note that variations in optical clarity like dirt on cell windows, source strength, and other causes not related to the spectral lines selected, will have no effect on the ratio of two pulses, making GFC an extremely sensitive and selective analytical technique. Typically CO, NO, NH 3 

### and HCl are measured using the GFC technique.
In the SBDW technique ultra narrow band optical filters are used to select infrared wavelengths. One wavelength is at a spectral line that the gas of interest absorbs (measuring) at, and the other is one at which it does not (reference). Typically SO 2 

### , NO 2 

### , CO 2 

### , H 2 

### O are measured using the SBDW technique.


### Folded Path Sample Cell The MC3 analyzer uses a folded path sample ce ll that is achieved by a specialized mirror configuration. These simple and robust sample ce lls have allowed IR photometers to routinely have extremely long path lengths (up to 20 me ters) yet occupy small volumes. The sample cell path length is fully adjustable for optim ization of each application and has reduced volume to save on maintenance and calibration gases.



### Construction The gas analyzer is specifically designed fo r Continuous Emission Monitoring service and the optical bench, sample cell and control components are all integrated into one convenient, and easily serviced enclosure. In particular, the integrated design allows the photometer source and detector to be housed in the same temperature controlled housing which significantly improves stability. A stepper motor controls the filter disk. The geometry and size of the filtersBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 7 

### is such that alignment of the filters is not criti cal. The solid-state detector is located on its own subassembly but in the temperature controlled housing.



### User Interface The MC3 analyzer has a very simple user interface with a digital alphanumeric keypad incorporated on the front panel.

The User Interface also allows complete access to system functionality and diagnostic information.


### Inputs and Outputs The IR analyzer communicates with the extern al devices (for example, PLC and/or plant control system) using a serial link and Modbus communications protocol. The analyzer also can be configured to provide 8 analog output signals (4-20 mamp).



## 2.2 MC3 System Cabinet The system cabinet houses the MC3 analyzer al ong with other necessary components. Interaction with the system is through a color touch screen display on the front panel. Components placement is optimized for easy access and there is ample sp ace available to house other equipment such as a datalogger, flow meter controller and/or other analyzers. On the following pages we show the system cabinet internals along with an overall system configuration. Digital keypad Escape (ESC) ke y

Enter key

Navigation keys (Up, Down, Left, Right) Online Help Measure Mode Display screenBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 8 

### MC3 System CabinetBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 9 

### MC3 System ConfigurationBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 10 

## 2.3 MC3 System Controller A Programmable Logic Controller (PLC) controls the entire system (sampling system and MC3 analyzer). A commonly used industry standard PLC is deployed. The PLC is flexible and has the capability to accommodate various configurations. Depending upon the customers needs separate modules can be added for input/output purposes, temperature controllers, Ethernet or serial communication etc. The PLC can be easily programmed in the field using a touch-screen display. Graphical illustrations (e.g. strip charts, bar charts etc) of gaseous concentr ation levels and various system conditions are also shown on the displa y screen. The touch-screen system provides over a dozen interactive screens. The MC3 analyzer co mmunicates with the PLC using a serial link and Modbus protocol. The PLC unit can be connected to the plant’s network and standard Ethernet TCP/IP can be used for communications. The PLC will include all hardware necessary to run the sample system along with analog inputs and outputs of measured parameters and digital signals.
The MC3 System Controller and Touch Screen capabilities are summarized below:

PLC/MC3 Interface Capabilities & Displays System Capabilities & Typical Base System Hardware Database Capabilities

 Concentration Values

 Absorbance Values

 Energies – IR Optics

 Span Factors - Range 1

 Span Factors - Range 2

 Cal Factors for Absorbance

 Pre-amp Gains

 RAMF Factors

 Signal Filtering times

 System Temperatures

 O2 mV and Offset

 Start Cal (Auto/Manual)

 Start single blend (Manual)

 Probe Purge (Auto/Manual)

 System into Maintenance

 System into Standby

 Run 9-15 point CGA (option)

 Reset Zero Point

 Reset Span Point

 Reset O2 Low

 Reset O2 20.9  Temperature Controllers (8)

 Control Sample System (16 Outputs)

 Analyzer Auto Correction

 Display Last Calibration

 2 Hours of Strip Chart Data

 O2 Wet & Dry Calculations

 Customer Analog Inputs (8)

 Customer Analog Outputs (8)

 Customer Digital Inputs (8)

 Customer Digital Outputs (8)

 Timeshare Capability

 Linearized O2 Capability

 O2 Slope and Intercept Capability

 Monitor Sample Flow from analyzer O2 sensor

 Direct PLC Access

 Modbus Port Available  All 1-minute averages for 16 channels (8 MC3 parameters and 8 analog inputs) written to SQL or to Excel CSV file (Daily File)

 System Status is written to database every minute

 Energies, Absorbance and Cal
Factors written to DB once per day for long term diagnostics

 10-second values for MC3
values written to Database during calibration

 Graphical interface to 10-
second calibration data

 Graphical interface to 1-
minute data

 Graphical interface to digital
status data.

 Historical calibrations – 30 daysBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 11 19. Passwords for different levels of user
access 20. Display of system flow rates and related variables
21. Advanced system settings
22. Settings related to time-sharing of analyzer between two sources

23. Access PLC internal settings
24. Analyzer setup connected to PLC 13. Graphical display of Calibration sequence
14. Defining the zero, span, calibration factor, range for calibration sequence 15. Tabular display results for all components during last calibration sequence

16. Calibration Gas Audit setup and sequencing

17. Flow monitor calibration setup 18. Initiating Flow Monitor and Opacity calibration sequences6. Name, unit and fullscale of components
7. PLC address locations for various tasks 8. Defining temperature settings for MC3 cell, detector, O2 sensor, sample line, sample pump, probe filter and probe tube 9. Analog input name, unit, full scale

12. Analog output reading, status and logic 10. Digital input name and status
11. Digital output status and logic 12 12 11 11

10 10

9 9 8 8 7 7 6 6

5 5 4 4 3 3

18 18

17 17

16 16

15 15

14 14

13 13

24 24

23 23

22 22

21 21

20 20

19 19 2 2 1 1

3. Operation mode (Normal, Standby, Maintenance) and Initiate Calibration Sequence

4. Status (Bad, Maintenance, Calibration and Online) for all components

5. Monitor energy levels for components and O2 sensor performance 1. Online screen-specific help and guidance

2. Real-Time stripchart for components being measured 19. Passwords for different levels of user
access 20. Display of system flow rates and related variables
21. Advanced system settings
22. Settings related to time-sharing of analyzer between two sources

23. Access PLC internal settings
24. Analyzer setup connected to PLC 19. Passwords for different levels of user
access 20. Display of system flow rates and related variables
21. Advanced system settings
22. Settings related to time-sharing of analyzer between two sources

23. Access PLC internal settings
24. Analyzer setup connected to PLC 13. Graphical display of Calibration sequence
14. Defining the zero, span, calibration factor, range for calibration sequence 15. Tabular display results for all components during last calibration sequence

16. Calibration Gas Audit setup and sequencing

17. Flow monitor calibration setup 18. Initiating Flow Monitor and Opacity calibration sequences 13. Graphical display of Calibration sequence
14. Defining the zero, span, calibration factor, range for calibration sequence 15. Tabular display results for all components during last calibration sequence

16. Calibration Gas Audit setup and sequencing

17. Flow monitor calibration setup 18. Initiating Flow Monitor and Opacity calibration sequences6. Name, unit and fullscale of components
7. PLC address locations for various tasks 8. Defining temperature settings for MC3 cell, detector, O2 sensor, sample line, sample pump, probe filter and probe tube 9. Analog input name, unit, full scale

12. Analog output reading, status and logic 10. Digital input name and status
11. Digital output status and logic6. Name, unit and fullscale of components
7. PLC address locations for various tasks 8. Defining temperature settings for MC3 cell, detector, O2 sensor, sample line, sample pump, probe filter and probe tube 9. Analog input name, unit, full scale

12. Analog output reading, status and logic 10. Digital input name and status
11. Digital output status and logic 12 12 11 11

10 10

9 9 8 8 7 7 6 6

5 5 4 4 3 3

18 18

17 17

16 16

15 15

14 14

13 13

24 24

23 23

22 22

21 21

20 20

19 19 2 2 1 1

3. Operation mode (Normal, Standby, Maintenance) and Initiate Calibration Sequence

4. Status (Bad, Maintenance, Calibration and Online) for all components

5. Monitor energy levels for components and O2 sensor performance 1. Online screen-specific help and guidance

2. Real-Time stripchart for components being measured
3. Operation mode (Normal, Standby, Maintenance) and Initiate Calibration Sequence

4. Status (Bad, Maintenance, Calibration and Online) for all components

5. Monitor energy levels for components and O2 sensor performance 1. Online screen-specific help and guidance

2. Real-Time stripchart for components being measured



### MC3 System Controller CapabilitiesBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 12 

## 2.4 Sample Probe The probe for the project is a one-meter heated pr obe with filter heater. This probe will include a stainless filter and a probe tip 316 stainless steel f ilter. The probe will ha ve probe isolation and injection ports for calibration gas and probe blow back. The probe will be controlled and powered from centralized temperature controllers in the CE MS enclosure. Probe tube heaters are also provided.



## 2.5 Sample Line The heated sample line contains five tubes and 10 wires. The lines include a fully redundant heater and RTD. The composition of the tubing and wiring is as follows: 2 – 3/8” Heated PFA tubes for sample gas (one is spare) 1 – 3/8” Non-heated Line for Blowback Air 1 – 1⁄4” Non-heated PFA line for Calibration Gas 1 – 1⁄4” Non-heated line for Probe Isolation 10 wires for heating the probe and probe tube 1 set heat trace 2 RTDs


## 2.6 Data Acquisition System

CEMTRAC II is a data acquisition and handling sy stem developed by EcoChem for facilities that need data logging for Process Performance Monitoring or Regulatory requirements like 40CFR Part 60. The system interfaces to the CEMS and Plant Parameters through Programmable Logic Controllers (PLC) using the industry standard MODBUS communications protocol. Utilizing the power of a PLC it is possible to control the analyzer s and also have a local repository of data. This eliminates the use of proprietary dataloggers leadi ng to very cost-effective, reliable and flexible system architecture.Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 13 Proposed system configuration for Agrifos facility



### The CEMTRAC II user interface can be integrated within a plant network or connected to the Internet. The system runs as an application in Windows XP / Vista thus making it simple to integrate into existing operations. CEMTRAC II supports multiple concurrent users and offers unlimited flexibility for future development. The database incorporates the power and reliability of Microsoft SQL Server 2005 (a widely-used industry standard program). It utilizes robust graphical database management tools native to SQL Server to automate backup and data integrity testing, schedule tasks and communicate events as they arise. CEMTRAC II incorporates powerful SQL transactions facilitating data import, export, tran sformation and analysis. It also provides easy access to program parameters (for customization) and the data itself (e.g. export of data to Microsoft EXCEL for analysis is easily accomplished.)
CEMTRAC II also creates regulatory reports that ar e linked to the database. The reporting interface is based around Microsoft EXCEL. Standard re ports include parameter values (one minute, 15- minute, hourly and daily averages), daily summary, calibration, downtime, and alarm reports. In addition, custom reports can be easily creat ed depending upon site-specific requirements.Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 14 Data flow for Cemtrac Data Acquisition System

Main Display Screen with Stripchart and System Status Realtime Display

Database Reportin PLC

MC3Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 15 Microsoft EXCEL Reporting Interface

Query ReportBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 16 

## 2.7 Building Shelter

The CEMS building is a fiberglass constructed me tal framed freestanding shelter with a rigid steel skid. The building is secure and is specifically designed to house one MC3-based CEMS along with necessary computer hardware (for combustion contro l, data acquisition and remote diagnostics). The housing shelter is assembled at the EcoChem facility in Houston and will be shipped to the customer plant site. The shelter is pre-wired to the lights, REDUNDANT air conditioners (18,000 BTU) with dual logic thermostat controller, room baseboard heaters (optional), wall outlets and CEMS. The overall dimensions of the shelter are approximately 8 feet long, 8 feet wide by 10 feet height. The shelter is insulated with 31⁄2" insulation in the walls and 6" in the ceiling. Also mounted is a panel containing the interface terminals for the customer's plant input and output signals. The shelter contains an entry plate for the sample line and dedi cated vent line exhausts for the analyzers. The floor in the shelter will be a diamond plate floor. An external grounding lug to the building frame for building grounding is provided. The building will also contain an air dryer for the incoming plant instrument air together with the appropria te plumbing for air and calibration gas distribution to the two systems. A calibration gas cylinder rack is included within the building enclosure. A counter desk is provided inside the housing shelte r where system documentation can be conveniently organized.

Recently EcoChem provided an almost identical build ing shelter to a coal-fired power plant. Below please find a collection of relevant photographs.



### Shelter Side View – Dual Air ConditionersBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 17 

### Shelter Front View

System cabinet within shelter MC3 analyzer within cabinetBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 18 

### Breaker Panel within Building HVAC Control within Building

Electrical bundle and Calibration Gas Tubing Entering Cabinet Fire Alarm & Internal Lighting

Desk within Building Crane loading Building shelter on TrailerBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 19 

## 2.8 System Documentation The delivered system includes documentation consis ting of the following master hard copy and 3 CDs: 1. System Drawings – layout, I/O, power distribution, interconnection 2. Operations Guide to MC3 – operation, calib ration, and preventive maintenance of MC3 3. Systems Guide – analyzer & system interface, measuring principle, troubleshooting 4. Parts List – detailed listing, recommended qua ntities, and description of consumable & spare parts 5. Auxiliary equipment manuals and/or website information on specific components (i.e. HVAC, pump, etc.)



## 2.9 CEMS Drawings

In this section we provide representative dr awings applicable for the installation. 1. A sample flow diagram showing the calibration gas and flue gas flow paths 2. A diagram showing the dimensions of a typical EcoChem CEMS cabinet 3. 

### A representative diagram showing the building shelterBudgetary Proposal No: XXXXXXQuote valid for 60 days from date of issue Budgetary Project Proposal Page 2025 PSI25 PSIHEATED PROBEBACK PURGECONTROL AIRCALIBRATION GASY1Y6Y7HEATEDINDETECTOROPTICAL FILTERSIR SOURCEMC3 HEATED CELL185°CCO, NOX, SO2, O2, H2O, CO2SPAN GAS 2SPAN GAS 1SAMPLECEMSENCLOSUREFTR1 - 10uY2Y3CONTROL AIRBACK PURGESAMPLE LINEHEATED SAMPLE LINESPAN GAS 3PETERSATxxx-031ZrO2OXYGENSENSOR1/4"3/8"Y5SAFETY AIRVENT1/4" TUBEFMINSTRUMENT AIR INPER PROBE/ EVERY FOUR HOURSPURGE FREQUENCY: 1 MINUTE -PROBE FILTER REQUIREMENTS:PRESSURE: 80 - 120 PSIGFLOWRATE: 14 SCFMDEWPOINT: -30°FDRY, CLEAN, OIL-FREE AIRINSTRUMENT AIR REQUIREMENTSZERO GASY4SPAN GAS 4Y10CGA MIDCGA LOWNOX, SO2CO, CO212% O2, BALANCE N21-5 LPMSPAN GAS 5Y11CGA HIGH202 REYNOLDS AVE., LEAGUE CITY, TX. 77573NO. REVISION APPR. DATE:DATE:DATE:DATE:SHEET:SCALE: NONEPROJECT:DWN.CKD.APPRD.05/09/01Sample Flow Diagram(Example schematic – final design dependent upon scope of project)Budgetary Proposal No: XXXXXXQuote valid for 60 days from date of issue Budgetary Project Proposal Page 21ECxxx-062PETERS2 4 VDC COIL264

L P M A I R81 0TOP VIEWBACK PANEL W/ RACK REMOVED SWING/SLIDE RACK FRONT DOORZERO GAS ENTRYSPAN 1 ENTRYSPAN 2 ENTRYSPAN 3 ENTRYINSTRUMENT AIRPOWER ENTERYSAMPLE LINE ENTRY2 4 VDC COILLEFT SIDE DOOR3/1/03241124326597810111815131416172119202223CABINET - 72" HIGH X 32" X 32"TOUCH SCREENMERCURY DISPLACEMENT RELAYSOLID STATE RELAYSOLENOID VALVES24 VDC POWER SUPPLY24 VAC POWER SUPPLYFILTER REGULATORCAL GAS FLOW METERSAMPLE PUMPMC3 ANALYZERPLUG STRIPPLC OUTPUT CARD - 8 RELAY OUTPUTSPLC OUTPUT CARD - TEMPERATURE CONTROLPLC WITH 450 CPUPLC ETHERNET CARD25202 REYNOLDS AVE., LEAGUE CITY, TX. 77573NO. REVISION APPR. DATE:DATE:DATE:DATE:SHEET:SCALE: NONEPROJECT:DWN.CKD.APPRD.MC3 CEMS Cabinet(Example schematic – final design dependent upon scope of project)Budgetary Proposal No: XXXXXXQuote valid for 60 days from date of issue Budgetary Project Proposal Page 22CEMS Shelter(Example schematic – final design dependent upon scope of project)Budgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 23 

# 3.0 Project Administration, Terms and Conditions

3.1 Warranty

Unless specified otherwise, all non-cons umable parts and operations have a wa rranty of 12 months from startup or 18 months from shipment whichever occurs earlier provided system is maintained and operated consistent with manufacturer’s guidelines. General conditions to be met by operator/owner for EcoChem Warranty and performance specifications to be valid: 1. Electrical power to instrumentation – is required to be 120VAC +/- 10 VAC with proper surge protection and conditioning. 2. Instrument Air – required quality is particulate and oil-free with a dew point of -20 ° F or better. 3. Ambient room conditions – proper dust control with temp eratures controlled between 50 ° F to 85 ° F. Humidity should be controlle d and vibrations minimized. 4. Calibration Gas – for certified systems, EPA Protocol #1 gas is required from a mutually approved supplier for certification testing. 5. Probe Access – proper safety and reasonable access is required for probe to be properly maintained.

For EcoChem to stand behind the CEMS of greater than 95%+ availability the following general guidelines are highly recommended: 1. Proper modem access by High speed VPN or dedicated telephone line 2. Proper inventory of consumable parts as detailed in EcoChem’s pre- delivery package available onsite prior to certification testing. 3. Proper inventory of Spare Parts (Level 1 and Level 2) as detailed in EcoChem’s pre-delivery package. 4. Technician training – minimum of 3 days during warranty period. Factory Acceptance testing and training is strongly recommended. Additional traini ng as staff turnover warrants or as or before maintenance contract expires. 5. First 12 months minimal maintenance contract – visits every 6 months by EcoChem. 6. Initial verification testing requires EcoChem’s onsite support to assi st plant staff or third party with Drift, Response, Linearity (Cal error), and RATA testing. 7. Timely notification to EcoChem of system problems related to wa rranty of CEM by competent project designee(s) with sufficient detail. Cell phone or land- line availability in the process monitoring or CEM building expedites troubleshooting and corrective action. 

## 3.2 Additional Insurance Coverage

Should customer’s insurance requirements exceed existing c overage carried by EcoChem Analytics, costs of any additional coverage's mutually agreed to will be invoiced on a prorated basis for the duration of the project and maintenance contract. 

## 3.3 Order Cancellation Policy

After receipt of Purchase Order (PO) the followi ng cancellation fee will apply to the project total:

• For orders cancelled after receipt of order the cancellation fee is 25% of PO

• For orders cancelled 15-30 days after receipt of order the cancellation fee is 50% of PO

• For orders cancelled greater than 30 days after receipt of order the cancellation fee will be 75% or more depending upon the amount of work performed on the projectBudgetary Propos al No: XXXXXX

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 24 

## 3.4 Terms and Conditions

1. LEGAL JURISDICTION: All questions concerning the validity a nd operation of this Agreement (Proposal, Contract, Quote, etc.) and the performance of the ob ligations imposed on both Pa rties under this Agreement (Proposal, Contract, Quote, etc.) will be governed and enforced by the laws of the State of Texas, U.S.A.

2. REPRESENTATION: EcoChem will not be bound by any promise or representation, written or oral, not made a part of the order and signed by an aut horized representative of EcoChem Analytics.

3. END-USE: The determination as to the adaptability of any of EcoChem’s products to the specific needs of the purchaser is solely the pur chaser’s prerogative and responsibility. EcoC hem is glad to offer suggestions on the use of its various products. Nevertheless, there ar e no warranties or product guarantees given except such expressed warranties offered in connection with the sale of a particular product.

4. ACCEPTANCE OF GOODS: All orders are subject to final accepta nce at our corporate facilities, League City, Texas, U.S.A.

5. FIRM PRICE PERIOD: Unless otherwise stated, all pricing is fi rm for (60 days) from date of quotation and is firm for goods released within (60 days) of order acceptance. Quoted price is valid only for the quantity indicated per item.

6. FREIGHT CHARGES: Collect to Customer or Direct Bill to Representative unless otherwise specified.

7. F.O.B. POINT: F.O.B. point is EcoChem’s factory in League City, Texas, USA. Our standard practice is to use F.O.B. SP PP & Add (Title of owne rship passes at EcoChem’s factory. Shipping charges are prepaid by EcoChem and added to invoice. Insurance liability is that of the buyer.) In addition, if you have a specific freight forwarder, please communicate this information to us. Feel free to contact your EcoChem representative who will assist you in making arra ngements regarding this item.

8. DELAYS: EcoChem Analytics Inc shall not be held re sponsible for delays or nonperformance by causes beyond EcoChem’s immediate control, including but not limited to delays of vendors or carriers, acts of God, fires, governmental actions and material shortages. Any such delays will automatically and without penalty affect a corresponding extension of scheduled shipping dates. In all cases, scheduled shipping dates are understood to be approximate and in no event will EcoChe m be liable for consequential or incidental damages due to delays or nonperformance.


## 3.5 Payment Schedule

Upon invoice net 30 days. Milestone payments specified in Section 1.2.

Delay of written purchase order receipt or milestone pa yments may result in a day-for-day delay in project schedule.


### Payments made to:

EcoChem Analytics 202 Reynolds Avenue League City, TX 77573, USA Attention: Accounting Tel: 281-338-9888 Fax: 281-332-6152