©3 am
\\
SC.
wltlfc
State Itoord of
U.S. Futile
-------
SAULS 0? COHTSS33S
PE080CTIOH Of XffiPUfORXBASiSD FBQSPSAXB SO® . ....... ?!
General Cometits .......... ........ g
l^roduetioa ............. 3.
of Superj>tiosphGt© .......... k
Flow JJiBgrEan ..................... 6
......... ..... 7
... ...... » T . . 6
of Superphosphate .<........ 9
. * . . ....... n
Velocity Traverse ....... ,,...„ ..... 15
Fluoride feinslons ................. 15
Sulfur QxldG Ekii.6f.dons . .......... ..... 1?
TOblo 1 - Stack Plow Coadltions . ........ ' « 19
Table 2 - Fluoride aalssioas ..* ..... ,.., 3D
fable 3 - Sulfur Oxide aaisslona » « , , , ..... gl
Table ^ - Sulfur ftloxide Bjalssioas ........ SR
Table 5 - Plsant Operating Bata ........... £13
Sfeble 6 > Msc«llafico«.ii
Fluoride Sampling and Analyzing
Sulfur Oxide Senplieg and,
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a Sfciosy&ates, Sae. o^mtes a glctfaS o&
;pmf&ie'©0 fltfiaorlBaifced Btajg&at© rods for ws©
S?tae!s esslssiosis frcsa tMo ^LaRt fco,-^
cc^loissta fsrara loml s^esic^siato. % eatesa
tl&a Jk>nt^to State &D&T& «%£ E@@3.t^ ?em>Gff;.
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Zft Jtoly of 1963, liiscusaloas be^eua betretea ctaff isQEfcere of the
Division of Air Pollution;, U.S. Public Health Service, and representatives
of Use Montana State Board of health coacesraiag the o>peyati0a of a phos-
phate <2efluori«atioB #laat at GsrrlBon, J&mtam. ^bies plaat, mscscd by
Rochy Mountain Phoephates, X®c., began operation In Garrlooa in July-
Auguat 1963* Eliortly thereErter, tbo f^ontaaa State Board of Health
received tnateroue cocsploiata about the opes-atton of this plaat.
At the request of the Moafcess State Board of Health, the Oalted
States Public fiealth Service agreed to sssiet ia perfonalag easlyses of
-.•^
the 0t«db effluents fw»a th@ plaat. %e agjpeeseat ie outllnsdi la a letter
'jfntod MovCTcb«r 27> 1963 by ». F. Ifeltea-a, Public Stealth Service, to
Er. John S. AB*ereoa, S^ecutlve Officer of the ftoatona State Board of
. Earlefly, the agreegteBt wao ae follows:
1. ^e U.S. Public Health Service will provide the equip-
Eeat euiteble for obtaining the Recessury stack series
*^-^
end vill loan this equipment to tho Moatofia State Board of
2. ffee Montana State Board of Health vill Bake an arrange-
ment for entering the plant and for providing tbo necessary
test boles and scaffolding.
3. The Technical Asslotaace Brench of the Mvlelon of Air
dilution, U.S. Public Health Service, will supply tw asen
. . , '
to assist in conducting the stack teats.
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2
k, Th« n«e«»swary laboratory analyses of the sawples will
b« ^ea* by the Montana nt$te Board of Health.
ToUotrifig court proceedings in June end July 19$», a forced. request
vas received by the Public Health Service to Initiate the stack test work
as outlined above. Stois re,
19&b, from ftp. John 0. Andereoa.
TJie etaeX test teea consisting of Richard W. Gerntle, ftogcr
Ghigdt»ra, John 8. HeMersoa, and Don R. Qoodvla (all of the Uoitea States
Public Health Service) arrived in Helena, ISoataaa, on August 17, 19^4.
Stack sffip^lipg at Bocky fountain Rioephatao, Inc. be®nn on August 1$, 196*1.
Kr» Ben tejke^ Induatrlal Hygiene Engineer, Jtontansi Btete Board of
Health, assisted la the stack testing. All analyses of samples were
performed at the Montana State Board of Health laboratory by Mr. Ludwig
Chemlct.
PKOBlJCriON OF DJil.l^ORISAl'ED PHCSFUATF. ROCK
Rocky Mountain Phosphates, Inc. IB engaged in &efl3iorlmting
phoe^heta rock to B«ke it ouitable for uoe in aninjal feed supple-
raent. As a fertiliser, it is not essential th*t fluorine be corapletely
ellalJmtedi however, for use as A mineral oupplessent in livestock and
poultry feeds, flworlne imat be almost ccsstpletely eHRilnated. ftontana
l^jos^bate rock as used in this plant contains on the order of 3. 5 percent
to 4.2 percent fluorine. 3fe© plant epecificaition oa the fluorine content
of fiefluorinatad roek product la O.lB percent fluoride.
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3
©re available for t&@ refiuction of fluoride
of p&oopliste rock, ftocky Mownteia SfeespltofceB libtratGo $&.vk of
the fljaari&e by islxing; pho&j?tet© rock, sulfw&e oejlfl, tsutar, aiad ]$W>G-
pltoric aei<& to foira triple sx^rptoeptefce. f&is radx, after agiR® a
hcnxrt'j i» calclmskl ia Q 3X>tajy Mia at tsa^znstusres MS t©
F; tMa siufest&Gtially volatisea all tbs fluoric®. Stilfate KSE}-
i« the auperphoBpfcafce rsaetiom 5le© deciTHpoae in t&e Jiilra,
guaatities of aulfur oaldee (solfur sail®© of the
siSttG^ ia sise, (65 perceal; tiuroa^ 300 isesia) it is
to f&e pi®iat ia txue&a. %r©e vertical 03JU>6 or® wood to etore the
rock. Seres? CGnvegrors r^sove the grouafl rock fros tlse storage silos
diE^zar®® It to a bslt fe®de,r. ?2ie belt feeder aieeteffgfia iato o
feed hopper afeoro the mixing den..
Sxilfuric aci<2 oa^t plioaphorie acifl tuna received la railroaS
cars apaS are stored in horizontal Btoraga tasfee. 33)3 afalfurie aciti ie
t ^ percent sulfuric scifi eade fsoa s^sltesr eff-gas in
, Ibntatm, Kje 52 percent phot^ioric acid is jstircfoaoed froa
J. S., Slmplot of Pocetello, IdaSjo. In tfee f orssatiOQ ef the
the nulfuric aci
-------
k
through rotanteterB. Flow IB Initiated by air pressure cm the acid
storage tanks. Hbospbate rock IG fed at a rate of 16 tons/hr by a screw
conveyor. Ihe resulting slurry falls Into the 20 ft jj 1*0 ft x 20 ft high
concrete structure called a den. 2he reaction continues In the den for
6 to 12 hours. After this tine, the material Is removed by a rubber-
tired, front-bucket truck loader and is transferred by a belt conveyor
to the storage abed. If the superphosphate la not removed within 13 hours,
it "sets up" and becomes very difficult to remove.
Vent gases (containing fluorides) are removed from the den by a
blower and are passed through a vertical open-tower t&ter scrubber to the
atmosphere. flhe scrubber is a 10 ft diaraeter tower about 1? ft high with
a 5-1/2 ft diameter by 15 ft hi$i stack, tfeter is pvmrped from a small
pond (80 ft x 50 ft x 3 ft deep) to the scrubber sprays. The water returns
to the pond by gravity. Occasionally, lime 3.0 added to the pond to neutra-
11 ae the pond vater. In the top of the scrubber, above the sprays, a steel
grating supports a k to 6 inch layer of stone and llree. Fluorides are
removed from the vent gases by reacting them with this line.
DEFttTORIWION OF SUPERPHOSPHAOS
The superphosphate is allowed to age a minimum of 2*t hours before
being introduced into the rotary kiln. Depending on the age of the super*
phosphate produced, the fluorine content will average between 1.5 to
2 percent fluoride* 2fce feed to the kiln Is on a seolcontlnuoua basis.
Actually, charging is accojoplished by a front-bucket truck loader at the
rate of one load every 15 oimites. Each load waighs about 1 ton, and
the plant assumes, therefore, a feed rate of *t tons/hr. 3he crude
-------
: $
1© «&©watet aty a tetot a&ew&or to e fctfeafesr in
we rexJusro»3 to &iz*3 33& eas*© sastmisS. ^®5v«> a Jclla f®3«3 belt
%8&roa jPeoiter. 15® IteS mt& ^ t^o i^lt i^ ujKUfem Imt wot
has elopsei* USsfi &Usi io ilrad witlii u&t'aml @p& v&& lias a
f . The
io e£K»t 4 Jxr^ra. Bt^& smso^ ^ras t5^j J.^iin aa^j (Maj^m-gffifl Sato -
ft 41«»e^«p * 23^ ^fe k$^ etaefe* AM*
as it passstc to ^tara^a. %€> p*o^aatt le ecM 5a imlk cr
iste«X sijjos ^re p^y^idol; f «^ toajfc
fear
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ROCKY [.iOUNTAIWPHOSPHATES, IMC.
GARRISON, MONTANA
FLOW DIAGRAM
•TO ATMOSPHERE
VI C. \ 1 UH
m'lJIVtf • , , . ,
i\um
1
| - I FEED HOPPER , .
V 1 — *— .- •• -
ii UJ
11 SULFUR 1C. AC ID: PHOSPHORIC:
Sg . WATER\T AC'D '
YTVA MIXING \\/
- CO'flE "TP^ r— 1
>—J U
DB L>-Q
TO ATMOSPHERE /~^^
'•"A SUPERPHOSPHATE VEHT GAS
•r-'
- TO STORAGE;
. '-
SUPERPHOSPHATE-
CAMPLING^ . FROM STORAGE , . |
l_ .POINT r* *"/ " _ — ^l
!~l 1 — "JiH ROTARY KILH' pi?nni!rT
t riwUUOl
/ \ ' U 1 — -— - COOLER'
/ \ --^
i \ /•
/
KILN CYCLONE/ LI ML A
•SAMPLING-ATI
• POINT —A
/ \SCRUBBER.
1
MAKE-UP . ^pPUMP
WATER
7 1
^ -—^.^.^.^.-^yS
BLOV/ER PUSTIC LINc° POND
~1
i / \
to GRINDING, SCREENING
gg 1 BAGGING i
gg- STORAGE BUILDING
v
1
1
STACK
NATURAL GAS
Sketch
CT\
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ROCKY MOUNTAIN PHOSPHATES, INC.
GARRISON, MONT.
PLANT LAYOUT
.7
!RAW ROCK
I
RAW ROCK STORAGE -.
PLASTIC!
: LINED !
: i POND
TRAILER COURT;
(i.ML) i
MIXING i
HOUSE 4!
DEN '
o
UJ
J—
oo
' LU
O
5i !
o
o!
OS :
STACK
CYCLONE
DIGESTED ROCK
STORAGE- .
SHOP;
ife
COOLER
NOTE:. Drawing not to scale.
BAGGING &
STORAGE
OFFICE'
LAB";
as
o
ce
cc. •
CM
o
Oi
TO DEER LODGE & BUTTE
ROUTE #10
Sketch 2 ,
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8
la tbt datflttorinatloa of phospMte roc* as eoadueted by Becky
j> Inc., 0vqperpbos^iatQ jarcxSiictioa ie t&e Initial et«p.
Salfwric acid, jdx>8£&oric aeld, wter, and jbosjtjate rode are nixed and
ag«d. {tonally Aa Bajxrphoaphate pro&ietica, 15 $o *»0 percent of tbe
Input fjaorias la eaittad froa tho alxer afi4 aea. 2t»9 nuorln« Is
in thfi $tm» of sUlcoa tetvefl^oriae (SiF^)* Other consUtu^nts erf the
cfflswat fitareea would tee eezlaon (Uojcide, &teR»« and eoao emlfwr dioxl^«
A cosseao393y uaed abatessesrt device to rcsaove tfea fluorlno f rcs» the
n&xl^s 4te* effluent @&« ie » high inteasity scrw!bl>er ttttiag copious
quantities of voter oar fluoalllcic acid up to about £0 pereest by vei^b
Iteddqr Mouatads Phosphates utilizes SB opefc-towa? »cnft>ber oo a eoatrol
devlee. %c ecrubbar is a 10 ft di^xeteer vertical toner divided iato
four qpta
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the uoodea toffies is pro's £&aeetioa of one jsa®a of the acrutelior ^howfl
three of the ei^t aoaalas to be eocspletcly covered with a
eryet&lMnQ depoeit, iaai eating that the«« eproy
-WKTC aot fttnctloslPg.
3, Total wat^r fl«m rate to tlie scrubber tma
50 gpm.
to the ^sflu^rifiatiag kiln uauelly &verag«tj
1.5 to 2 percent fluorine. Practically all of this fluorine, down to
«t least O.lB percent, e-Aist fee rtssoved bsfors the product is suitable
for animal feed suppleKsent, Thie is oeeoe^li^te^ tor subject iag the;
eupea-phofipfcate to t«mpemt»re@ up to ebcait 2,^00° P. 'Kiero is also GO
apparent. ifiecesa|>oeiticm of calcius eulfatc, resulting la «»© foraatioa
of cmlfta- oxiSes.
^te actfeo4 of efcis-ilcn control applied by Boc&y Mountain Phos-
phates is Iliac Injection into the exhsuwt g&a BtJNasaa frcns the kiln.
Subsequently , the exhaust gas 0tr«ata is passed through a cyclone sepa-
rator. Ihe theory le that the line will react with the pollutcnte end
fora eolid particulate oesuoounds, ^tich can be r®ooved in the eyclcms-
^
t^pe espaintore. Veriations of this technique are need la eimHar eitu-
ationc. Some 4efieieficlcB were ooted la tola
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10
1. Considerable fiaounte of the Una du»t settle out in
the
-------
u
Evrary effort wao Em4e to ©osutact easjplli^i when the plant
operating eoaUauously &&£ at a ussdfona feed rat®. Stis^ It
was practically iisposaifolQ. a® feeS rat<5 is ttasefi u$oa batc&
of taiper$bo8pfeat<9 to the kils. 3bi& is aceospllfl&eft tuy usiag a
tireO tractoar vltfe a front- eml lea<2er. ISte plant BBasgesKWJft cssraseo
tfela vchiele^ idasn Ioe404 rwHrslly, to hold 2,000 I£JB. One ioad free
this tntek 10 placea into tfeo Itils fee^ hopp«3r *rvery 15 lalmites, result-
log in a feed rate of obmrfe % tono/hr» la scttial practice, t&e capacity
' of tisle l&a&exf cam vasy greet ly, Uurlog the csas^liag, ex tjpical trucli-
Ioa4 of kiln feed was wi^ed cM fouofi to cosstaln ©aljr 1,250 pcuads.
later ^rlcg the week, tw» other trucklo»^e of f«G^l viex-e wslghe«2. &e@e
two locuto vel^ied 1,T50 peruads and 2,WtO 5oaaecti¥ely. Frcra
the kiln f e«d bogper, the eroerj^osifeite paeeod tferowgh a bucket elevator,
breaker* bojrper, SymtroH feeder to a belt feeder. Ifee capacity of this
vsus greatei1 tten tliat provided t«y the eoiml four loads per
result was ttet smterlal ^BB as»t fed to the feiln
»1£ jslnutea ^RiM ^>e requires to feeS oae tntchloart
thie equl|sneiBt« fetll the o@st load «as placsd in tb« feed hopper, BO
laaterlal «SMEI adfie^ to the kiln.
Peecl rat« to the kila wno alK) affected fey frequent e^uipracnt
feilxxres. &urlng the weele of 8enplla@f there «ere ueuaUy several brs
(towns per dj^r. On zaoat occasion*, repairs were Instituted quickly 00
that the feed could be started in t&oxtt an hour. If repairs vere not
too <31f fi
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failures, easg&lng was eoatimiod. For najer fepais'8 requiring
1 hour to complete, it wao usual practice to etop the hiln assd
tfee fuel feed rate to the feilra. At these ttesa, 8enpH»3 me
operating conditions returned to BOBBS!.
It wao also eorsal piaat practice to ecaso operati% the Kiln if
teoxolo^iesl coMltioss %r@r@ such that tfeet kiln etoch ptose wes
toward e aearty imller eoyurt or t»«&rS Ossrisoa. For the first
of the cteck esr^iliEis, the westher was eool^timd the wind
ftroa the noythwaot. During tbie tiao, ao «^ut
-------
13
addition vmrle* considerably, ana, during the veek of the sampling, it
«aa higher than for any week of the month of Auguot. Those data are
tabulated in table 5-
Initial aasqpUog was conducted on the rotary kiln stack gases.
A sampling holt was provided 11 ft above the stuck inlet st en elevation
of bctwwn 30 and 35 ft above the base of the static. During the initial
test, line wa» added continuously to the static gaoetf leaving the kiln)
this ia norml operating procedure. «t® saapling was conaucted on
Auguvt 18^ 19, and 20* Velocity traverses were saxd« oa the 18th and 30th.
2%ree caeaiplee were collected for flworide and three, for sulfur oxideo.
The •asplea vere collected in the sequences fluoride, sulfur oxides,
fluoride, «alfur oxides, etc. ftii« resulted in « 0et (fluoride aad
sulfur oxide) of samples being taken oa each of three successive liag, the flcv through
the «eaple trai» ba
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tsottwa of tho 0tac&. Bccauea of this esaditiea
ttee stack fces& with t&0 plaat opes-atis® eorEally ao
attempt «a» ffiafie to fietewsioe t&© offcctl^eaoso e£ llzoa
«4«sout His® Q<^ltion. fcmr cs^lea wspa fe&«
aErales of fluoride BE^ too oiK^les ©f owlfui' osifeo.
All ef tJteeo cssaaaleo wss-o ts&ea Oa the fjsfterjaaon of Auguo^ 21.
GA Augrast 23, ttse plaat ©porct^ tfee Gt^ej^os^ate ps^sacing
fedLlitiea* ^e Gajmcit^ of these facilities is eotaoidoysbl^ greater
than tStQ ^Clnaf4j3atlon kils capacity eo that t&^ ex© onl^ qparateS
evaiy other ^r ^r a period &£ 6 hots'o. Fo&t etm^itioao durieg th©
edsting ore uaif&am* ISie s^s& is ?€& ot a csdfoj^s rat@ &$• © screw feafier
acid., ^to0p$iorl€ aoidj, as^ va&cr feed rates are
ia&icatieg flow ssters aM ore coatsrolled ^r fen4 valves.
Gases ©volved frosa t&@ ouiKsi^ossis&atc Sen are esb@ast$d fey
end dio^oarged iEto &a opio- tower liqoia seryMt^r* The
coansetien TJOO l®cat«gd ia tk@ tipper part of tfes serulibor above the epsraye*
S5i© jBO^or isoHutoatefixsa tfeo ^im «ye fMorlas eos^oun^s*
tfee nising Sea fe&<3 bssa operatic about cma-teilf bousr, a settle
eolleetcd for fluoride aaa^rsio. Pollcwing tMo, © GS55ple was collected.
eM aaslyscfi for sulfur Slcmige end eulfor tri®ni«3B. Sigaificeiit ©slsaions
of sulfur oatifiea wsrc? not esicoaot^aped. Bollorsdi^ tho etalfur sosids
tea eass^les wea« taken for fluoride eaalyMo.
velcsity tresverc® tsea raa<3« oa tbe corufefesr eteck.
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VELOCITY
Data oa the reloeity travorsoa arc given la table 1. Three
Telocity treversee were aad® oa the kilo stack} the first two were
the ptant was operatiag rarmlly vlth Mas eMltioa. Tbeoe
collected on August 18 ©ad August 20* ®w results were 2^,800 ecfa
and 25>600 «efbi» IhcrLog the cluecU of the effoetlvaaeafl of lisas addition,
1±c vvloetty travearse gave e @tack velocity of oaly l^itOO oofm. The
reaooao for thle lover valwe era i^ot dicer. Sose reduction In gas flow
Is Sue to the fact that the Ilao-aadltloa blover «ee not operatlag.
It is doubtful if ttile can explata co^letely ti» lower atack velocity.
It 10 ware likely tfeat the resSuctloa le caused \y variation in plaat
operating coatttlona: I.e., fuel @a@ rate to kiln.
FLUORIDE B-HSSIONS
All fluorlae eatasloa data tbrou^bout this report includes both
psrtlculftte and gaseous fluorine enleeions, uhlch Are expressed as
fluoride ioa (?"). The results of the fluorine easplios ore gives on
table £. Hifiheet concentaratlons were fouoa la tbe efflAieat gas from
the euper^u>sphate den* Ihrce sas&les were analyxed* Kve first, efter
only o«e-half hour of operation, indicated a fluoride stack gas concen-
tration of 12,000 jpa. fhe eecondi end third sassplee were takes after
2-1/2 and 6 hours of operation. By tbia t>l&at the concentration of
fluoride la Use scrubber stack had reached 18,1*30 ppni and 19,320 ppa,
respectively.
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16
Becattse of the physical arrangement of th« piping, it was
iapoesihl* to ataple upvtrcaa of the scrubber aad thereby check the
effleieaoy of the fluoride rosoval In the «crubber. For tbia reason,
a fluoride balance KB* made around the superphosphate dea.
Fluoride la feed Material:
1. Bocks 16 toas/hr x 2,000 li/ton x V.2^ fluoride « l,3i# Ib/hr
2. Phosphoric acid:
i» toas/hr x 2,000 Ib/toa at 1^ fl»orld» « 80 Ib/hr
Total Input fluoride l,teO lbA»r
'*,».•'
FlMorl4« la dea pro<2uct;
3D toaa/hr x 2,000 Ib/toa x 1*9^ fluoride « 1,1^ lb fluoridte/hr
Calculated fluoride evolved in the den would tet
1,1*20 Ib/hr . 1,1^0 Ib/hr - 260 Ib/far
S» at&ck aoalysis (table 2) ehova that «» average exslealoa rate
of fluoride «ou» 234 Ib/hr. This rate ladieate* little, if aty, fluoride
ie yeaoved ia the scrubber. 13i« fluoride balance id only an
but it does iadieate relatively lov effieieaxqr for the dea scrubber*
Sable 2 indicates fluoride ooocentratioaa in the kiln atack
hovever, it nuet be reseajbered that the kila stack eaiaeioaa are on a
2%~br/dey baeie vhlle the superphosphate dea eadB&ioae are for only tbe
Halted tlree vhich tbe dea operates—tusually 6 hrAwtch. When operatiog
with line additioa in wfcat ia considered aonxal operation, the kiln
atack panglee analysed 2,070; 1,500; aad 2,330 ppa fluoride* fhe overage
of the three oengplefi resulted la aa emisaloa of 1^2 Ib/hr fluoride* An
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17
effideaoy .eSiock ..0*3 tho Ilmr;e4<3itte3 e«3 oyeleaa a© a
eoatral device ma eaa^s nai^g- a material balaoee.
nuerlAft in kiln feeds
3.6 tcas/hr (row rock) » 2,000 It/to© g 1.9$ flnorlte » 13?
Fluoride in fclln proflactj
1*6 toaa/W (pitM^i^t;; 2; 3,000 ib/tm % Q.l££ flycrlcfe e 6 Ib/hr
FltK>ria« 1m esAauet @ase3: .\3T 12?/h.r - 6
to control dgvie**
Slaea the tto@@ stack SSE^I@
ezaitted, littJUi e^vastaso eaa tee creSltoS to t-tto emtroi device.
01 s of tfeo partlculat® collact-ed IB the ^cloae «ci3 efemst X
flsjaaelde. Eotli the SJoatasa State Board of ieeCLth la^Gratos
ISsaatat« SfeMg^stes, Sac. Istbosmtoz^- e^ree on thla comectteation.
low casweetyzstlon of .flwcrida ia the eyoXao® po^oot ts«iM lodieoto low
fluoride collection efficieeey*
Unite erodlsMe f?Ga a siMIar plant in Florida ekowo
effici@!sey of t?isir ccuatrol device feo fe© oUlg^tly eves*
mam @Ksm e^ssx©^
ialfur dlo%iS@ a&ti j^alfur trlosld« cs&lesloes aare gives is
to&lo 3 eM table fe, respectively, gi^if leant esjisEiiosa of eolfur
cKi<3es taere jn©t es^eotus^. ia the Sea scrubber. This ae@tn^tloi» v&s
et£tatiated toy oss scc^le, cM oo addltloaal sac^lea wsra to&en.
«feen operating norKslly, wltb llsse a<^Utio9^ ttec klla steck
casiplea a?mlyaed ^,JSX>; 2,S85{ sad 2,480 55® sulfur Oioxi^o. Ube
average of the three eas$»l@fi gives aa appxe«i&i&t« ealsaion of 7^1
-------
as
&UadS@. Tm> ozsqpli&a VSSTQ ossuS^rssiS v&t&Q3t Utos
s- OB
With JUtoo Ra^lfeioa, i5ie ttoea eulftas- triositile
. Kltli
ioto t!» «tae& gaocs, t^o s-oculto war® ^T eM 1»OSO ^a @u&ft&-
«ou34 lie a&out 1^3 Ib/^ of oulfur tr4essi«!te. /^ftffCEt^, the
ccae ©f tlss calfur oxides.
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i, B^QC no'? ©
, XBC. OABKISGB
I>la8t Volusa at Nolans, efts et
operating Bteck eo^dl- Velocity Steck std eondltioao
^figt^ •-..^Ca^?^-.:..1?M^^^--M.^^^*L--5Sil^u-. .j--.^/?80-^--.^1^^^^^^1^- ,. IP^** g9>gS"J^
8-18-6^ Kila st®dc ^oaxml f}6,600 15.5 3^5° F £*»,800
6-80-64 Kiln etBCk SarJsaX ^5,500 2j6»7 ^2B9 F 25,^00
Kiln stack
Scrubber £loa^&l 7»£Q& * 112 F . 5>05O
-------
H». Bate
Iceaticn
Sslcslon,
ittie otcck
2,0^0 0.202 X ID*3 1,630
0.07% * a*f3 i,iso
0.1S0 x 3D"3 1,730
153
110
l£g
UitfcGUt 11528
stack
Serufefeor staels
staek
3,150
£,680 0*223
2,050
s 20
-3
132
.in
31T
ia Ella stsw^i
oa aRgiaitu^*
-------
Tebla 3. SUITUB SKSXHS EM53IOS3
ROCKS MOIfflTAXH JS06JHA3EBS, IBC. - GAKBIS08, MDSEAHft
Sample
So. Bate £«uapliag location Operating cooditioaa
19-2 d-19-64 Kiln stack
20*6 8-20-64 Kila stack
21-2 6-21-6^ KUa stack
2L-5 &-21-64 Kiln stack
21^8 8ȣl-64 Kila stack
22*2 &-22-6> Scrubber etack
ter^a
Sorscal
Without Use addition
Without Itee addition
Sfemal
»t\nnmit
*•*•»** *M 9*
r* ?<£tJK
2 ^iQP
6,070
2,600
380
0.6^5 x ID*3
0.378 x 10"3
o.Uio x 10" 3
1.004 x ID"3
0.430 x 10"3
0.063 » 10"3
rlaalnn
Jb/hr '
566
615
852
365
£2
* Tea pereoat moisture aosuoed ia kila stock g&sae. eonaal varisticno in aoieture coateat will not
have aa appreciebl® effect on nogaitudtt of the eiieaioas.
Scrubber otack gaeea are assuaed to eootain 5 poreeat aolsture (saturated coaditioas at 110° ?
stack taKperature).
All conceatretioas are on a vet fcasis aad at standard coaditioas of 70° F &ad 29.92 inches of
Bttrcury.
-------
geqple
I Jo.
19-3
21-3
21-6
* ftea pareeo
not have aa
Table 4, Bl
f^CSCIf S&USEEAIJf ¥5061
^3at0 Bi-ffifplifss lo^ati©*
S- 19-64 &lla stack
8-20-61* Kila stack
Q-2b.6k KUa stack
8»21-6^- fills stack
8-2I-& Kila stack
&-Z2-6k Scrubbsr etecSc.
W(}t( irUUimJK JSHH)&.K?!SS
FEAIBSj BfC. * GAEKISOU, MOU2AHA,
^fHsg^afcyftf^ ft MI *
i C^eratiag eoRdltioas ppa Ib/s
^or^al 1S5
Uorsal ^73
Hitbout liaa a^fiitlos ^7
tiltbeot liae addititm 1,O20
POn^l 1^9
t ffioioture assumed ia klla stack ^s«s. JJoneal variatioas la
OppTPtXisbl^ O^OCt Oa Ea^JltUC1** n' i-.Vi** *»a4ir,»:ift!»n-
4>mnV MM&n^ca AI«M> flb mEWevwMh^t •••ink ^wmeH
^•«k 4 1* fi <^jMn^MM>4» v^n.4 ^h^«««Mh f es^t^nvm^^
Ealaalca,
ef IbA*
0*026 a 2C"3
0.098 x ID*3
0.123 2 Hf 3
0.1^ x Kf 3
o.gn x io"3
0.027 x ID*3
Eoistupe
kV> «y\«^4-H
eoatsBt
A9A r>+ 1
39
1T9
«iii
nfj° is
etadi
JuU.
osremy
coaecatraticms are oa a -set "basis aad at otosdarfi coediticsas of 70° F ana 29.
-------
Table 5
Ifo. of 50 Ib
of titses plant cfewt
Kp&raaaaBxc
0-1
6-2
8-3
6-5
8-6 '
8-7
8-8
8-9
6-10
8-11
8- 12
6-13
S»l4
6-15
6-15
6-17
8- .13
8-19
8-30
3-21
8-22
8-23
17.5
12.0
3/6.5
6.0
•
s»o
22.0
18.0
21.5
6.5
17.5
15.0
19.0
8.0 '
19.0
17.0
i4.o
21*0
17.0
ss.o
SD.5
3A.O
18.5
or Jtaxa® QGCsew
&9 feilsa stack j
£0
3Js
• ' g?
15
.
«,
30
10
30
5
15
£0
29
12
BO
22
2S
3?
33
6l
13
32
eccauao or p©juw
p® Jailer eooyt
1
g
1
1
».
.
1
1
«.
.
»
1
a
«
2
1
~
-
•
•
«.
1
1
^irrso oiGiaing a,Q
1
«,
1 .
1
.
«
„
„
„
«
-
1
-
1
1
1
1
-
.
.
1
1
s
Graad total
15.7
-------
max
6, MISCELLANEOUS
HJOSPKASB, IHC, -
feunsple rozs&er
of
{&multa of
£0-1
£0-2
3>3
30*4
Mia stack alutSg*
(5-<3ay~e>ld)
ftirticulate eollecteS in
Kiln
0.175$
Iff $
• y f3
1.96 f£ fluoric
0.95 ^ flusarlde
fiav
acid
22-8
1,^5 ^ fluori£o
i».e 5
sludge
9-9T
-------
OF SUIJFUR UZOXZUB fSD SUtfTB 2RIOXIDB
soam
When ftantpling 6tacit gaaes Tor various concentrations of sulfur
dioxide and aulfur trioxide, thie raothod la used.
APPARATUS
tubing (preferably Vycor or quarts, Pyrex) of suitable size
with A ball .Joint at one end and a removable filter at the other. (One-
half Inch OD x 6 ft. long Pyrcx tubing has taea uaed,)
mter
A Buchner filtering funnel with a ooareo fritted glass to support
a resnonretole filter la recfulred to remove any partlcaLate or acid mist.
Kaolin vool (resin-free), fritted quartz t or gl&as wool (fyrex brand
Ho- 3950) are suitable filters.
Adapter
Six plug-type connecting tubes, ^/UO, one with a 90° bend with
a socket Joint*
A beavy insulated heating tape wltii a vswrlable voltage supply
is needed to prevent condensation in exposed portion© of the probe and
adapter. Alternatively, glass wool or other cui table insulator* may be
used if temperature extremes are aot too great.
Calibrated
evacttated tanks are required to provide aa accurate sample
volume measurement. Qoo cubic foot tanks have been used satisfactorily*
-------
A flood vacmsa source la needed to evacuate the calibrated tanks.
An obooluta pressure of about 5 laches o£ Ecreury should be
Msyoogetgr
A 3
leap Sulfur Aboorlaer
Ihree ASIS4 D1S66 larap sulfur abasTfeos-s witSi emrse eintercd
Filter ty&e with a ^0-aaa diameter Corning eieSiim ©iatered
Teflem fofelns
tw8>l»g, caae-qmrt®p inch ID, for esms^ctiag se
Alternatively, 8 rm %reK tubiag idtJti 1%3tll aad eocl^at eo^mections nay
be used.
Eatia
§Q-*al aM 10-^al burettes
Dainiaed
Deionized ^ater should be i\@ed instead of distilled water.
Alcool
Iso^rcyl
Dilute isopropyl alcohol vith HJ> at a ^:1 ratio.
-------
3 acrcent Efrdroipta I^eyoxlde
Dilute 30 percent Bg02 with HgO at a U10 ratio, Prepare fresh
dally.
Barl«a Chloride (BaiClg-aH 0, Reagent CfcaAe)
(X 0100 H Barium Chloride
Dlaaolve l.gaOjS BaClg'ailgO in tal «20 oad dilute to 1 liter with
isopxropjrl alcohol .
Tborin Indicator
Benaanearoonle acid disodiua salt
O.g Peyogitt flaorl ,
0,2 ©a %<9rin indicator in 100 al HO,
SAMPUHO
Set up the apparatus as efoty.m in figure 1* Md 30 ml 80 percent
ieojnropiyl alcohol in the first scrubber and 10 ol la the filter tube.
Add 50 ml 3 percent HO to the third scrufcber. A little sillconft grease
on the iipper parts of the joints nay be need to prevent Im&age. Heat
4
the probe so that ao condensation accure vhlle eaittplliig. Sample at &
rate of about 2 cu ft per 30 minutes while sampling. Becord the tank
vaauua and temperature initially end at 10 minute latervala. Note the
boroaetric pressure.
SAMPLE
Disconnect the probe, heating tape, and Adapter and allow to oool.
Oonoect the spare absorber and add 50 ml 3 percent BL0. to act as an &lr
c «c
filter, Beplace the vater in the ice-water bath with tap water. Draw
-------
Draw air through the system for V) minute* and remove the spare absorber.
v
th* third scrubber and transfer its contents and lt§
vater MU&inga to a 250nnl -volumetric flask, dilute with vater to the
mark. Aa&lyza thla for SO .
&
Stopper th* first scrubber and apply auction to the filter end.
Reoore the suction line and allow the partial vaeuun in the first ecrubfcer
to draw the solution from the filter. Rinse the filter tube with 80
percent leopropyl alaohol Mforc the suction i« lost. Transfer the
contents of the first smrubbcr and its vashings to a 250-ml volu&etrie
flaslt and dilute to mark with 80 percent iaopropyl oloobol* Analyze this
for SO,.
3
8ulfur Trioxide
Plpet a suitable aliquot to a flask and dilute to 100 ml with £0
percent leopropyl alcohol. Add a few drops of Iborin indicator (enough
to give a yellow color). Titrate with 0.01 H BaCl to the pink end
point. £&ke a blank determination in parallel.
Sulfur Sioxlde
Stanafer a suitable aliquot to a flaak and add k times this voluftae
of icopropyl alcohol. Dilute to 100 ml with 30 percent iaopropyl alcohol,
add enough ^btorin indioator to give a yellow color, and titrate with
Btandard 0.01 K BaCl to the pink end point. H«n a Dl&nk determination
2
in parallel.
-------
CAWUU2IQS3
ppa 00. or SO toy volrai© » £^ j
2 j
p p
(toy teuda) Vt •/• - ^
i «
where A a al 0.01 S3 Bad used for titration of
» sal 0,01 II faCl^ uae<| i'or titmtiOQ of blank
normality of BaCl
_
&
F «» dilution
',.,=3 final tank t^apezvatwe,
iaitial tank
V. a TOiiffije of tank, liters
1Q
P. o flcal absolute tarik jEreseiBrei ia
(JP^ o (F . flual vacuum)
r D
P. m initial aboolute tank pj?o8Emre> in
3.
(P » (P . initial
X V
Devttlapaent Company Analytical Jtepartcient, "
of Sulfur Dioxide and Sulfur ajpioxide in Stack Qaswso," ©neryvllle Metliod
-------
i Figure'' 1." SAMPLING TRAIN FOR SULFUR OXIDES
iGLASS WOOL FILTER!
COARSE ;
FRITTED'
DISK i
J
i PROBE;
FILTER
TUBE
BALL& SOCKET
JOINT
ASTM DI266 LAMP SULFUR
ABSORBERS
CONTROL VALVE
MANOMETER
-THERMOMETER
0*3
EVACUATED
TAliK
-------
OF SOLUBLE
LAKE KE7THOD
soon
lhi» »ethod 10 uaed for the determination of soluble fluoridee la
stack 0u*s. Accuracy within 0.02 »g/litar In the concentration range
of 0*00 to Z.to ag/liter Is obtainable. I&« l«t«rfer*aces fron »t*ck
0UMM nttcttMlt«t« distillation of the aanplea.
AFPAEA3US
!Wb
-------
KEAOBJUS
1 H (&pptaiiayte) j^tpaJBydriaglda: Dissolve JJ0 g?a KaOJi pallets la
as* fiilut* to I liter.
Solfuric Acid,
Silvgr
Sgadaat 4,5-dihydjro3^y-3 (p- eulf ©|tiQc^laao)« 2, T-
salt.
Solution; Dissolve 0.959 $a %aei5o la I$gO R^S dilate to 500 aL
Ct>aceatangt«d gydrochloric Aeld
gj,yeoflypL CSilortdc Oct^^tote ^lutioa; Dleeolve 0.133 gp toOClg'S BLO
In 25 til BgO. Adl4 350 ial co^aeatreted RCL and dilate to 500 al with
Sefgreaee Eolutioat Dilute T tal cosccRtrat^d SCL to 10 oL with H^O.
10 «1 Spa^aa eolutioa to 200 ial BJ) and add the HC1 colwtiQft* Mix well.
fe
nol^tioa is used to set t&e ssero point aai iff stable
Beaff«at ; MX well equal perto of tho Spadas eolation and
8 HQ eolutloa. This reagent is ctable for at least 3
Stcuafera< mssolvo 3*09^7 go, dacy MP aad dilute to 1 liter*
©ilute 1 si of this sototion to I liter. 2Ms f irsal ^lutlon coataioa
0.0, 10.0, 20.0, 30.0, to.O, and 50.0 al stazadard KiP colutioa
into separate UO-al beeitera. Add 50.0r 1^0.0, 30.0, 20.0, 10,0, and
0.0 ml HgQ, respectively* to the toeokera. Shea* add 10 al of alxod
-------
to «e!i fecato, £Us tfearougfrly §£*£ ffeafl tfeo afeaoyteaise© ot
570 «*»• Htot eoJBceatratioa vs abaorbaaee oa a *e$ta»gnlffir gnspSi paper.
At leMfc eat poissifc gfoouM be res t$t& mxfa car^lc? ood eacft tiase tb&t
R aav batch of &dxed r^aaseat io .^a,<§9. It 10
cazgdas tie at tfes ©aag t^K^eyat^ye as caeSi ^grcet ^dff csreaco
0.01
6AKP1IBG
Sot i® ttoe £$puratu0 a@ s^owa to figure 1« Mi 100 ml 0.1
to ee^ of th« first t^o i£^iog@r@» leave tlse tMrS fisy to catcfii or^r
«jv?sr. Silica gel ncy b« places Is tha fourth Ir^iogor to oSscorfe
addltloQ^L aolotwre (tM& kolps to protect tfee JEeter ce4 FSSJ?}.
ease lee la t&e fesfcfe. BEW? the ecs^plo tfepma^i t^e train at 1 cfe for
3D BdJaarteo or as miitable. B@oor€ K^er fcessperatures and jtraseareo at
10 fflSLmite lwt«rvala teiog sKs^Hag oad obtoia en svoroge. Seeorfl
tba eoiuti-ca ©ad Its H^O \waMsjga from tfea t^rce
ct
to & ^X>-ml volsEaetric flask o«d $llut0 to tfee ESjsli. Flpet a suitable
(25 to 50 sal haa Hreen found sotegtiflt© fcsp 25 cu ft stack saspleo
power plant e) a^d «2il«to to 300 ol «ltlj BLO. 'Qile is uae3 for
^5
dlstllletion.
Uso th® aatbod of ^lllayfl and dieter as described; in "Standard
for tbo E^otEatioa of %!ot«r anS t^a0te«ater,0 llth
-------
A*erlo«a Wblio Health Association, Inc., Haw York City, I960, p*gc*
to 125*
The ftaarlde vac distilled vlth atesa using •ulfuric Mid distilling
over *t 155° C. EM* dlstllUftg fletak ia hnowm n» the Aleoe flack, which
ie «M<| «t«wlvclir by the nlujslaiffl ccwpa»lo« for fluorinn
This i* actmlly a dsieon f laak with tlie nsck to vhlch the dellTtry
is «ttaebe4 seeled off vStb
Rljmt * »idt*tao nllqwt etia dilute to 50-nl, Add 10 nl of «lxed
'reogemt ««a rtad th« abaofbanec at *>10 MM. If the •bsoiftanc* falln
e«libratloa curve raage, repeat ttoe proeedwre u&lag a eaaaller
CALCWATIOSB
Cto«centratio)Q -tig
Ulstillatlon dllutioa factor
Fg «> Saaffidc dillutioa factca?
7 • San^le te»s>erettire
V <* Voltaws of oejffiolft (at supllug
P_ « Pr«ss«xe «st tura$ile meter
^ Krvl» »»<3 Scho^boe, P. J», "tepid fhotOMetric Detwnaiiiotloii of
Fluoride la Water." Analytical Cbwdetry, 30 » S032-3^ (D*c««bea:, 1958).
Bcllack, B.t ^ab^Hfled riucsrlda DlstUlatloa Method.1* Jasfltt 50
(April, 1SJ58).
-------
THERMOMETER
ICE-WATER
BATH
. \
f
i
V
6
s
(
N__
)
/•*
(
\ /
1
)
p
MANOMETER
t
GREENBURG-SMITH
IMPINGERS
DRY GAS METER
SAMPLING APPARATUS
FIGURE I
-------
DIFFUSION ESTIMATES FOR GARRISON, MONTANA
UNSTABLE TO NEUTRAL CONDITIONS
Ground-level concentrations beneath the plume axis were computed
for various distances under the assumption that a plume traveling along
the valley would spread (diffuse) in a manner subject to usual diffusion
calculations for a distance up to 5 ton (3.! miles). These concentrations
are tabulated for the kiln and scrubber separately, and a graph is prepared
showing a distribution of concentration down wind, assuming the two
sources to be immediately adjacent. Maximum values may not appear since
computations were for specific distances only. The summed values reflect
in nearly every case the contribution from one or the other source, and
in no case are they significantly greater than from the greater source
alone.
Plume center-line concentrations only were computed for stability
class F since under stable conditions the plume may not lower to the
valley floor but may impinge on valley sides with maximum concentrations
approaching those within the plume itself. These concentrations are also
tabulated.
/
All computations are based on the following emission rates:
Kiln 141 Ib F'/hr 738 lb S0p/hr
Scrubber 286 lb F"/hr 22 lb
EFFECTIVE STACK HEIGHT
The Holland equation was used to estimate effective stack heights
based on the following data:
Kiln stack Scrubber stack
Diameter 8' 0" 5' 6"
Height 210' 35'
Stack velocity 900 ^/rain 600' /mln
Stack temperature 1*00° F at 30' 112 F
Air temperature: 60 F, Pressure: 900 mb
Effective stack heights were found to be:
Wind speed 22 1/2 mph 11 mph 7 «ph
Kiln stack 233 ft 256 ft 286 ft
Scrubber stack 39 ft 46 ft 49 ft
The Holland equation is considered relatively good for neutral
atmospheric stability. Even under unstable conditions it appears that
effluents from the scrubber stack will remain within the valley since
the stack velocity and temperature are both very low.
-------
GROUND LEVEL CONCENTRATIONS (gm/nr)
Stability j2? b&ta g* ^ • <•
class and -^^
vind speed Source Pollutant 1/16 mi 1/8 mi 1/6 mi 1/3 mi
A Kiln Fl
*f mph, S00
— £.
^^Jf^Yi
P/y\ , cv- .v.. ,,-- Scrubber Fl
... •— ^
Kiln Fl
'" "' T4 ^ft
cxi-/ £/X) ^ 2
9 mph Scrubber Fl
\ ^ QfN
'^r,-?^ /^sf^ ' • ^2
. Kiln Fl
V* "•';""'• "D ' so2
11 mph . Scrubber Fl
\/^^c/T/^Xu- S02
PLUME
'Vf/Ztfs,^ j. Kiln Fl
__^ ^"jph S°2
U&*-'/' • '' Scrubber Fl
'a3xlo-19
.2x10"
.5x10"?
.9xK>
.0x10"??
.7x10"^
.2x10"^
CENTER- LINE
5
2
1
8
.IxlO"1
• 7
1x10" 2
5x10"! 1
2.6x10" 5
8.9x10:^ 2
9
4
3
2
3
1
4
3
.5x30-;
.9x10" '
.6x10
:&SS"^
:^:^ '
CONCENTRATIONS
1
6
2
2
.2x10"?'
.4xUO"
~1
.oxio"2
.8xio:^
1
7
2
2
.6 mi
.4x10
.1x10
.8x10
.3x10
9-5xio"r 5.4xio
4
6
5
l
9
2
2
(gm/m3)
2
1
3
.9x10
.4x10"^
.3x10 5
.8xlo-f
.5xlo"6
.4x10"?
.0x10"
.OxlO~2
.0x10"
.Oxio:2
2
1;
-1
2
9
7
5
3
1
9
.8x10
.1x10
.7x10
.4x10
.4x10
.8x10
.7x10
.0x10
.1x10
.4x10
1.25 mi
-5
-5
-5
-6
"j! 1.3xlo"ij
6.8xlo"p
\ 2.7xlo"|
5 2.3x10
-5
-4
-4
-5
-3
-2
-2
-4
3
3
1
7
6
5
2
1
8
.1 mi
.OxlO'ji
.5x10
.9xlO"|
.6x10" b
.1x10"^
.7x10"^
.OxlO"3
.6x10"''
-------
FUMIGATION CONDITIONS THAT MAY BE EXPECTED:
Clark Fork valley, downstream (to northwest)
Valley volume was estimated by measurements of contour spacing
at various points along the valley. The measurements were continued
down-valley for a distance of about k miles (measured along the valley,
not a straight- line distance), to the point where Warm Springs Creek
enters Clark Fork. The effective top of the valley was estimated at
4,6bO ft msl for these computations, and it is assumed for these purposes
that the plumes would remain within this volume.
Assuming a drift of the plumes of 2 mph along the valley and emis-
sion rates (total from the two stacks) of 1*27 Ib/hr of fluorine and
760 Ib/hr of SOg fumigation conditions would produce a concentration with-
in this valley area of VfO |igm/nr of fluorine and 820 ngm/m3 Of SOg.
Little Slackfoot valley, upstream (eastward)
A similar estimate of the valley volume was made, but it was
limited to a distance of 2 1/2 miles upstream.
With the same assumptions, a fumigation concentration within
this valley of 600 ngm/m^ of fluorine and 1050 kigm/nr of SO is obtained.
Clark Fork valley, upstream (southeastward)
Map data is insufficient to provide a satisfactory estimate of
valley volume for a significant distance upstream. However, the cross
section of the valley within the first 1/2 mile or so suggests that
similar concentrations would be found within this valley also.
The figures given above are rough estimates only and assume a
uniform mixing within the entire portion of the valley used in the volume
estimate. However, the valleys are of variable cross section and the
concentrations under fumigation conditions will vary inversely as the
cross section of the valley.
Under Inversion conditions accompanied by light winds, it is
possible that the plume from the kiln stack will not be .trapped in the
valley. If this plume escapes, the concentrations estimated for fumi-
gations will be reduced for fluorine by about one-third; and for SO-,
by over 95 percent. It is likely that this plume will be trapped or
partially trapped most of the time, but meteorological data available is
not sufficient to estimate the effective inversion heights with confidence.
-------
>p
9
B
7
i
b
4
2
10
9
8
7
6
b
4
3
2
10
9
H
7
6
5
4
3
2
1
-
r"tjitidittitMitFi i n 1 1 1 1 ititfiimti i ii i ttt
M-!E^|^:|-|l:]}|l^i|^^
~
-
Hr--:i±-.:3J.:±: :::::::::- ::: --:::::: :
' ^1 i i « - - . , n - , — — r -TT-
— j "j"" " T "
1
^^jj|^ij j^lj^^P^)^:^^
.1.
— H- t •
-t 4 - -
.
i n
— \ l. •*•*'
--I-1 Hi+H-H
r
"
i - -+-- i
t = r = i:jg|:' = = = ::::;:; ;{•=====:=:— =
— t— t-F - - 31 - £ ft ff - --
— t) i I • t i
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• . ' ' •. ' ' -Ground-Level Concentration of Fluorides , :
-,.' :• •"• ' '•'••; (Total frdhi both sources) gm/nP ,. '
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II
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m
+ 10*
A = Unstable
.B = Moderately unstable
D = Neutral stability
,
Ground-Level Concentration of Sulfur Dioxide
(Total from both sources) gm/m? '.
-------
GROU»0) LEVEL GQS3C8RBAXIOBS (ppa)
Stability
class an4 %
vind speed Source
Pollutant 1/16
1/8 ai 1/6 ni 1/3 ai
.6 ml
1.25 ai 3.1 mi
A Kiln
7 fflpb
Scrubber
Fl
Fl
6.75
1.53X10*1 J
1.10x10" 3 2.35X1D"1 3.02X30"2
-2
1.
2».02zlO
9.83x10
"*
Kila
scrnbl>er
Fl
Fl
5.02
1.37x10"
e.olkio"
1.10x10
-1
2.08x10"* 1.19x10"
9.13XU
1
9.83x10
D
U aph
Kiln
Scrubber
Fl
Fl
" 5^Sxlo""
T rf!ft»1ft<"
6.^5
2.6I010*1 Lfiaao"1
2.58x!0"3 6.
^.05x!0"3 1.
1.35
3
k.
6.38x10'
"2
l-_
2.80zlO"3
AjO
«.
.^Scrubber
Fl
Fl
PU&-3S CS2ITEB-LISS
o p
1.72x10
2.27xl02
3
8.51
2.37x10
*K£JxlQ
5.7^x10
8.19
1.27x10
1.58x10
k.00x10
*"1
7.31x10
1.19
l.kk
3-
"1
-------
BUOOSSTBD CFUXDB8 FOR EMISSION STANDARDS AND AMBIENT AIR QUWUMl CRITERIA
. FOX WCKl MOUNTAIN PHOSPHATES, INC. AMD GARRISON, MONTANA.
EMI68IGBS
Fluorides In general and gaeeous fluorides in particular are
important as air pollutants, first because hydrogen fluoride (HP)
and silicon t«trafluorlde (SiP. ) are toxic to some plant e in concen-
trations as low as 0.1 part per billion and secondly; because fluorides,
both gaseous and particulate, may be accumulated by vegetation.
Animals which consume vegetation containing in excess of 30-50 ppm
fluoride can develop fluorosis.
There are no regulations applicable specifically to stack emis-
sion rates for fluorides in the United States. One such regulation,
however, has been proposed for Folk-Hillsborough Counties in Florida.
This regulation Bight not be directly applicable to the plant under
study as it could be unnecessarily restrictive. The Florida proposed
regulation is designed for use in an area where there is a large
number of fluoride emitting plants. The proposal, however, is of
interest as a reference point and as an Indication of performance vhich
can be achieved. The proposed Florida regulation would limit emissions
of fluorides to 0.6 pounds per ton of P~0~ produced in the manufacture
of phosphoric acid and calcined or defluorlnated phosphate rock. In
the manufacture of normal phosphate, superphosphate or noroal super-
phosphate, the proposed emission limit for gaseous and/or water soluble
* ' •
fluorides (F~) is 30 pounds per operating day per plant. Applying these
standards to the Rocky Mountain Ifeoephatc plant, gives the following
-------
2.
approxtBate results:
Rocky Mountain Plant
Average emission at Allowable emissions
time of stack analyses, per Florida proposal,
Operation pounds (p"]>/hour Lrm pounds (F~)/hour
Mixer and Den £'94 1.25*
Kiln l*»g 0.6
Total k26 1.85
£4-hour/doy operation
From the foregoing, it is obvious that a substantial reduction
of emissions would be required at the Garrison plant, if the proposed
Florida regulatione were applied.
In view of the lack of fluoride emission standards, a store
simplified approach mast be taken to arrive at an allowable fluoride
emission rate for this plant. (tee euch approach vould be the require-
ment that fluoride emissions be controlled to a degree that is usually-
attainable in similar processes. The emission from the mixer and
den is the larger source of fluorides, and its effluent is discharged
•
from a relatively low stack. Methodo now in use to control similar
emissions and processes Include simple spray tovers, packed towers,
and various high energy devices, such as jet scrubbers and venturl
scrubbers. Published data indicate that even multiple pass spray tovers
achieve fluoride removal efficiencies well above 90 percent—often as
high'as 99 percent. In Great Britain where industrial operations are
generally controlled by the "chemical efficiency11 that can be attained,
the emission limitation for this same type of process is 0.1^3 grains
F- per cubic ft. Applying this criteria to the plant under study,
2 .
results in the following:
-------
7,600 cfca a 0.1% grains x Ib n &)> P* » ^.a
cf 7>000 gr fey
percent ratactlom 28U - t*g! a 98.5 percent
la view of the practical possibilltico lloted above, it ID cug-
gested that aa Gverege efficiency of 93 percent be specified ana
maintained for emissions from the miner and &ezt operation.
Aooumlng that toe total fluoride csaieolons from the mixer end
den operation were 95 percent controlled, tfeo coatroi of fluorifiee
from tbe klla would probably not have to exceed 90 percent beccuso
of the tall stack.
Applying 93 percent control to the mixer and den and 90 percent
control to t&e kiln stack, the total fluoride emieoioas Kould be as
follows:
Kilns 1U2 lb/hr x 0.10 » 1^ lb/ar
Ben: a8^ Ib/hr x 0.0§ • lU lb/ar
28 Ib/hr
•2ho 28 pounds per hour vould be the total oHotmble emisnlon
regardleoe of production rates, control equipaont efficiency, or specif le
source.
An Indication of the toprovement la air quality that might be
*
achieved if fluoride emissions are reduced to £3 Ibe/howr can be
-------
• fc.
Jteosa Deteos-elogical dioperoion eoiralati©ao. While thooe
osc not esaet, they o refiuco^ to eteout .3 pp
if tfa© fi©a ©aissioas vere reduced 95 pcscoat.
g) Kiln emisBions
ThQ estimates Eaxisruai gr@\md level of F from tho kiln
is espeetefl to occur ialth an u&atablo ate©sph0r@ (looping plume) and
ar-9 E3S*i ^?iad. ®ie concentration vtsuM approxiraata .14 ppa ©t a Si stone©
of about 1300 feet frosa the kiln st&ek. la&ieiog kiltt (aiseioas by
90 fe?e@fit, i$ouM reduce this eoacestration to approximatea .03
*
For tfe® aaraing inverelon fer^toip (fxmi®atioa) eaoe,
appears to be important in Garrison, tho fluaria© levels ore
-------
et" .06 £
level©
ppj if th® p-opocea
2bsr
inverGicao
owtest
ecMovotU
vedlejr location with Its Buroerous
eteorologieaX fists, iffi^eo 4t
the fiogree of control ecseeeasy to oliaiiaatcs
eati prevent GSCGGDIVO ceeisiailBtlo-a of fluorifio ia
It \iill, therefor©; l>o nocosoctry after a period of
at th® refluec^ ©aiesica yat© to e©tomioe if
has "bo^n reallcofl or better furthor roiuetioa io
for such aotQjmlnatioao usuM bo t&o eaa3^rceo ©2"
vegetatiosi to determine i^ ttea f iKdPiSo eoateat
to ^0 ppa or lees.
A csssbor of cosssrunitiea
of saifm1 fllosi&o in easdesloas t© 80^3
emits ^30d<4200> ppm la the kiln s%ac& QQOOO
-------
6.
referring to the attached calculated ground level concen-
trations, it ia estimated that the S02 concentration (from tho den
eerubber) reaches a maximum of 0,26 ppm at about 330 feet from the
sourc*, tdth ft near neutral atmospheric stability and a wind speed
of 11 mph.
The fumigation level IB estimated at oA? ppm to which the kiln
emission is the major contributor. Since thle concentration IB very
close to the suggested level of 0.5 ppm for 1 hour, It is felt that
the sulfur dioxide concentrations in the kiln effluent gases should be
United to 2000 ppm at stack conditions»
BDXJDR THXOOTi: EMISSIONS
Regulations applicable to emission of sulfur trloxlde and
sulfurlc acid nist have been ueed by only a few agencies. The oxtiy
one reasonably applicable is 0.3 grains per scf expressed as 100 percent
suLfurie acid, a regulation of the San Francisco Bay Area Air Pollution
Control District. The kiln stack of the plant in question vae emitting
gases containing 0.2 to 1.1 grains per standard cubic foot (an average
of 0.7 grains per scf) vhen lime vaa being added to the kiln effluent
Another vay to view the emissions of sulfur trioxide is to
estimate ground concentrations on the basis of emissions, stack height
and meteorological dispersion formulas. Xn this Banner, we estimate
*
that ground concentrations of sulfur trioxide, calculated as 100 percent
-------
7.
sulTuric acid, could on occasion reseh or exoeeH 0.2 eg/a . \5hile
there are no ambient air quality/ aton^ardo for culferie acid mict
in tho Xted ted States, there Io eonoidorablo expert opinion that if a
peak co¢rotion of 0.3 iag/Kr is not excec&eft, no detrimental
effects on health will bo observed. For thlo Beacon, it ic
that 80. caacentrationa in the kiln etack fee Halted to .3 grnlao/otonfiarfl
cubic foot.
VISIBLE B-SSS1QH3
Tbe stack earapling team >mo unefelo, tseeauso of procosn conditions
in the etack, to measure total particulate esniBQionc from the plnnt.
Hovever, it vas obvious that there vas eonoidcr&ble particulate matter
in the pltaae. These emissions could \>Q regulated on the bo sis of
visual observations of the plume. Such a regulation would limit the
discharge of any contaminant for o period of throe minutes in any one
hour, vhich nould obscure an observer's view by greater than k) percent.
This type of measurement is baaed upon the Ringlemann chart vhich is
also applied to black or gray emoke. A ^0 percent equivalent opacity,
•which we are Buggeoting, for the Qarrison otandard io equivalent to •
Mo. 2 on the fUngelraann chart. Thin type of regulation is enforced in
many areas of the United States.
Control devices applied to reduce other emissions may reduce the
partieulate emissions. Therefore, if the plant could demonstrate a solid
particulate oaioeion of 0.1 grain per standard cubic foot or leas, the
visible emission opacity regulation could be -waived,
------- |