Chapter 8- Paim, Ink . and Other C.cutling Manufac:r uring 02!01105 

### The t erm**N"'~** 

### m ay be calcula ted us i ng equat i on 8.4-16:

where 

## = = 

### ( 8.4 - 1 6}

to ta l moles of gas in the vessel headspace at the initial temperature total mo le s of 

### gas in the vessel h eadspace at the final t emperature. The total number of mo l es (n , and n,) may be calculated using the ideal 

### gas law 

### as shown i n equat ion 8.4 - 17 and 8 . 4-18 .

where 

## P , = 

### P, 

## = v R 

## = T, ; 

## T, 

## = P, V 

# n, = RT I 

### P,V 

### n z = 

# RT l 

### total system pre ssure at 

### initial tem perature to tal system pres s u re at 

### final temp erature volume of gas space in the vessel gas constant initial temperature of vessel contents final temperature of vessel contents. (8. 4-17) (8 . 4- I 8)

The total number of moles o f volatile component x in the vessel headspace at th e initial and final temperatures (n, , , 

### and 

## n. , 2 ) 

### are also calculated using equations 8.4 - 17 and 8.4 -1 8, except d1e partial p ressu res ofthe volatile co mponent are 

### used instead of the to tal system pressure .

Ex amp le 8 .4-3 

### For the same 

### d isperser described 

### in exampl e 8 .4 - 2, 

### what beat-up emiss i ons wou ld b e estimated using option 2?

8 . 4-16 EIIP Volume II 

## VES015900Chapter 8 - Paint. Ink . and Other Coating A1amifat.:tun·ng 01101105 Step 1 : Appl y Equations 8.4-17 and 8.4-18, Determine Tollll M o le s In the Vessel Headspace at Initial and Final Temperatur es 

### = 

### P , V 

### n, RT, 

## = (14 .7 psia)(I33.68 ft 3 ) ( 10.73 ft 3 psia ) 

# (sJr R) lbmole 0 

### R = 0.34 1 lbmole P

, V n 2=- - -= RT, {14.7 ps ia)(\33.68 ft 3 ) ( I 0.73 

### ft 3 psia) { • ) lbmole • R 565 R 

# = 0.324 Lbmole Step 2 : Apply Equation 8.4-16, Dete rmine N,,. N,,.. 

## =

## ~(n**,** + n 2 ) 

# =**~(0.341 +**  0.324) 

## = 0.333 l bmole S tep 3: A pply Equations 8.4-12 a nd 8.4 - 13 , Calculation ofNonconden sab le Partial Pressures a nd Initial a nd Flna l Temperatu r es T hese c.alcul ations are shown in St ep 4 of example 8 .4- 2. Pa , = 13.5psia Pa 2 = 12.34 psia S te p 4 : Determine Partial Pressures of Volati l e Com pon ent s These values were detennined in Step s 2 and 3 of example 8 . 4-2: Component x (P ,}r 1 • psi 

### a To l uene 0.313 

### MEK 0.888 Elll' Volume ll (P,)n, p sia 0.626

1.73 8.4-17 

## VESOJ5901Chapr.r 8 - Paim.Ink . a>rd Other Coating Man11 fiJ<turi11g 01/0IIf)J Ste p 5: A p p l y Equa tions 8.4 - 1 7 and 8.4 - 18 , D etermine Moles of Co n de n sa b l e Co mpounds lo tb e Ve ss el Headspa ce at I nitial n od n nal T e mperatu r es



# "x.• = (I:(P ,h.)(V} = (o . 3t3 +o. ssspsiaxm . 6s tt 3 ) RT 1 ( 10.73 ft 3 psia ) ( 537 . R) l bmole ' R = 0 .02791bmol e**"~** ; 

## (r<P . >TlXv) "' (0.626+ 

### 1.73 psia }( 133.68 A ') RT 2 ( 10 . 73 f\ 1 psia ) 

# (s 6 S ' R) l bmole · R = 0.0520 lbmo l c S t e p 

### 6: App l y Equation 8 . 4-15, C a l cu l ate Total Mol es ofVOC E mi ss ion s 

## n,.,,, = 

## N ,, I n (

# ~::)**(n A.2**  n ,,,),_,

= {0.333)

# In**(.~~~~** { 0.0520- 0.027 9 ) 

## = 0.00582 lbmole VOC / batch Using the average vapor molec ular weight from e x ample 8.4-2, the tota l ma ss of VOC e mitted per batch is : Evoc = (o . 00582 lbmole)( 77 lb ) 

# = 0.448 lb/ba tc h batch lb mole For 25 batches per year, the annual em i ss i ons are: Evoc = (0 .448lb / batcb)(25 batcbes/yr ) = 11. 2 lb /y r This e:,'li.mate 

### is essentially the same 

### as th e emissions estimated using option I in example 8.4-2.

8.4 - 18 

### EllP Volume ll 

## VESOI5902Chapter 8- Pa;m . lnk . ond Othe.r Coating**Mot~ufl" tu.ring**  0110/105 

### S t ep 7: De ter mine the Amo un t of Eac h Vo l atile S p ec ie s i n the Total VOC E m . lsslons Anr age Mass E mi ss ion P art ia l Ave ro ge Vapor Nu mber o f 

### Pre ssure , Ph ase M o l e lbmol e Mo l ecular 1- Co mpound ps;. Fradlon Emitted**eig ~t**  l blb atcb lblyr Toluene 

### 0.47 

### 0.26 l 0.0015 

### 92 0. 1 38 3 .4 5 MEK 1.31 0.74 0.0043 72 0 .3 1 7.7 4 Totals 1.78 0.0058 0.448 11.2 

### 4. 3 E mi ssio n Model f or S piU s The 

### eva poralion rate a n d VOC emiss i ons t h at resu lt fro m a 

### liquid c h emical s p ill can be 

### estimated using a sim ple model if the size (area) of t h e spill is known or can be estima t ed. Other more complex spill models are al so a vaila bl e, but they ma y require more inp u t data (E PA , 1987). Equation 8.4- 1 9, used for the sim ple mode l, is us lbllows:

where 

## E. M

, = 

### K, = A = 

### P

, = 

### 3600 

## = HR 

## = R 

## = T 

## = M X ll' X 

### A X p X 

### 3600 X 

### HR. E = • • .,. X X 

### R xT emissions of VOC species x from the spill Ob / event) molecular weight of VOC specie.s x Obllb -mole) gas -p hase ma ss transfer coefficient for VOC species x (ft/sec) surface a rea of spill 

### (fl') (8 .4-19 }



### vapor p ressure o f VOC spec i es x (if a pure chemical is sp illed) or the partial pre ssure ofchemica l x ( if a mixrure ofVOCs i s sp illed) at temperature T (ps in ) ' 3600 sec/ hr d u rat i o n of s pill**(hr/cv~ t)**  

### uni v ersal gas co n stant at I atmosphere of pres sure, 10 .73 p s ia-ll 3 / 0 R-Ib - mo l e 

### t emperature of t he liquid sp ill ed, • R ("F 

### + 4 60).

1 The vapor pressures ofVOC spccico ore li"ed in AP-42 o n Tab le 7.1-3 (EPA , 1997b) Tho portilll prcsoure of VOC species x (Pj ma y be ca l cul oted using Equation 8.4 - 3 or Equ ati on 8 .4-4. 

### EIIP Volume II 8 .4-19 

### VES015903Chapter 8- Paint, Ink . lind Other C()(lh·ng Manufo,·trJrlng 

### The gas- ph ase mass transfer coefficient(!<,.) may be calculat ed using Equation 8. 4- 20 :

where 

## K , 

## u D, 

# - K, : 0.()()438 X uO. ?I X ( 

### 0 • ) "JJl 

### 3.lxl0 " 4 

### gas-phase mas s tran s fer co efficient for 

### VOC specie s 

### x ( ft /sec) wind speed ( mile / hr } diffusion coeffic i e n t f

or 

### VO C species 

### x in 

### aii (ft' /sec). 0110/IOS

(8. 4-20)



### Diffilsion coefficients 

### (OJ can be 

### fo und in chemica l handbooks and are 

### usua ll y expressed in units of 

### square centimeters per 

### second (Cil1 1 

### / sec). If a diffusion coefficient is not available for 

### a particular chemica l , the gas -phase mass trllnsfcr coe ffi cient ( J<.. ) 

### may be estimated using Equation 8.4-2 1:

where 

## K. 

## u M, 

# - 

# - K, = 

### 0.00438 >< U O . ?S X (

# ~) 1/3



### gas- phase mass llllnsfer coefficient for VOC species x (Illsec) wind speed ( mile/hr) molecular wei gh t orvoc spec ies l( 

### (l b!lb-m o l e). (8.4 - 21 )



### Equations 8.4-20 and 8.4-21 and other similar correla t ions th at are used in more complex models were developed to est imate evaporation from liquid surfaces exposed to natural w i nd effects. The standard p ractice when using these equations is that the w i nd speed i s th e valu e at a height I0 me ters above th e surface (EPA, 1994a) . Thus , t he equations shoul d b e acceptable for estimating mass transfer coefficie nts for spi ll s that are outdoors. lf the spill is indoors, however , the equation should be used with caution. The wind profile i nside a building likely differs from the profile outside, so tbe velocity at a height of 10 meter s (ev en if 

### that mucb open space exists above the spi ll } w i ll no t ha ve the same meaning as it would outdoors . At a minimum, wben app l ying the equation to a sp ill indoors, the u ser s hould d eve lop sit e-speci fic est imat es of the air vel ocity above th e spill and recognize the potential that us ing this approach may underesti mate the emis sio n s . An alternative approach for es tima ting gas-phase mas s trllnsfcr coefficients is discussed i n Section 4. 5 of this chapter. The a lternative replaces the wi ndsp eed variable with a constant referen ce mass transfer coeffici ent. This a pproach likel y overstat es tbe emissions, particularl y i n a room with lit tle a ir movement , because it a ssumes the gas above tb e liquid i s well mixed. Thus, equation 8.4 -21 generally is preferable t o lhe alternati ve for estimating emissions from spills and other surface evaporation scenarios. 8.4-20 EIIP Volume ll 

## VES0 15904Chapt<r 8 - Paint , ln k, end Other Couring Manufu<1urlng 01/0JAJJ Example 8 . 4-4 illustrate s the us e of equations 8.4-19 and 8. 4 -2 1. Examp l e X.4 - 4 Methyl ethyl ketone (MBK) i s spi lled 0 111 0 the gro und outside of a build ing. The fo ll owing data are given: • The spill is no t d e te cted for I hour; it t akes an add itio nal 2 hours to recover the re ma ining MEK; the dUJ3 ti o n ofth e sp ill (H R), therefore. is 3 hours. • The a'oerage wind speed (U) is 8 milelbr. • The amb i ent t omptrarure (T) is 77 ° F or 537" R (" R 

### = • f +460 ). • Thesurfaceareao f the s piii(A )is lOO ft'. • The molecular weight o f MEK ( M ,) is 72 . 1 0 l b/l b-mole. • The vapor pressure ofMEK (P ,) at 77"F is approximately 1. 93 psi a. Step 

### 1: Usi ng Equation 8.4-21 , calculate the Gas-phase 

### Mass Transfer Coefnclent 

### (KJ 

## K. = 0.00438 X 

### U O.?l X (

# ~) Ill 

## = 0.00438 X g 0.7 1 X ( 

# ..2!.) 113 

### 72.1 

## = 0.01397 ftlsec Ste p 2: Us in g Equation 8.4-19, Calculate Emissions (E,) 1\A X J( X 

### A X p X 

### 3600 X 

### HR 

### E 

## =**·~ ·~**  

## •

• R x T**72=·~J_x_O~·~O~l3~9~7 IOO** **~. 3~** **~-"~ 3**  

### 10.73 X 

### S37 = 

### 364 lb 

### MEK/spill EllP Volume ll 

### 8 . 4-2 1 

## VES015905Chapter 8- Paim , Ink , am/ Other C.()(ltiug Mamifat:furing 0210//()J 

### 4.4 E miss i o n Model for S ur face Evaporation Emissions from surface evaporation of VOCs from open or partially covered mixing tanks during coating mixing operations can be estimated using E quation 8 .4 -22, which is also based on the simple vaporization model for s pill s.

where E, 

### M, 

## = 1<,. 

## = A 

## P

, 

## = 3600 

## = H R 

## = T = 

### B = 

### E : M,.x K,.x Ax P , x 3600 x 

### H 

### x R x T x B
emissions o f VOC species x (lblyr) m

olecular weight of VOC species x (lb/lb-mole) gas-phase mass transfer coe fficient for VOC species x (ft/sec) s urface area of exposure or opening of tank (tr) 

### (8.4 -22 )

true 

### vapor pressure o f VOC x (if a 

### pure chemical is 

### used) or the partial p res sure of chemi ca l x (if a mixture ofVOC s is used) at tempe r ature T 

### (psi 

### a) ' 3600 sec/hr batch time (hr1batch ) universal gas constant at I atmosphere of pressure, 10.73 p s ia- ft 3

### ? R- lb mole; temperatme of the l iquid, 0 

### R (°F+460) num ber of batch es per year (batche sl yr). Equations 8 . 4 - 20 o r 8 . 4-21 

### can be used to e s timate K, . Total VO C emissions wou l d equal t he sum of all VOC species emissions. Note that usi ng these equa t ions t o est imat e mass transfer coefficients for VOC in a tank inside a building is s ubj ect to the same u ncertainty d i scussed in Section 4.3 for spills inside a building becau s e such applications differ from the sit u

ation for which the equatio n was developed.

' The parti al pressure o f VOC spec i e s x ( P 

### J may be ca l cu lated using E q uation 8.4 - 3 or Equ at i

on 8 .4- 4 . 

### 8.4-22 EliP 

### Volume IT 

## VES015906Chapter 8 - Paint, Jnk, and Other Coating**Mtmrifa~:tun·ng** Exam ples 8.4 · 5 and 8.4-6 illustrate tbe use of Equation 8.4-22. Examp l e 8.4 -5 A covered tank is used to m i x to l uene and various insoluble materials. What are the toluene emissions due to surface evaporation? Th e following data are given: • Toluene is the only compound that is a liqui d • The batch time (1-1) is 4 hours. • The number of batches per year (B) is 550. • The average air v eloci ty through the building above the tank (U) is 0.1 miles/hr. • The 3Illbient te mperature (T) i s 77•p or 537•R ( 0 R = •p + 460). • Tbe opening in the cover ofthe m ix ing tank (A) for the agitator shaft is 4 ft: . • T11e molecu l ar weight of to luen e (MJ is 92 l bll b-mo l e. • The partial vapor pressure oftol uene (P 

## J at ?7°F is approximate l y 0.55 ps i a. 01/0liOS



### S t ep 1 : Us in g E quation 

### 8.4 ·2 1 , cal cul a t e the G a s- pha se 

### Mass Tra n sf e r C oeffici e nt 

### (K,) 

## K,. 

## = 0. 0043 8 X 

### U 0
· 78 X (

# ~) l/3 

## = 0 . 00438 X Q.] O.?S X (

# ~~) 1J3

= 

### 0.000422 ftlsec

BliP Volume ll 8 . 4-23 

## VESOJ5907**Cliapt~r** 8- Paint, Ink. and**Orh~r** Cooting Manufo<·ruring 01101/0J Step 2: U sl o g E<jualio n 8.4 -22, c al c ulat e ann ual emiss ions 

### (EJ M xK,.xA>< P ><3600xH

X K X 

## B E =



## • R><T



## = 92 X 

### 0.000422 )( 4 X 

### 0 . 55 X 

### 360 0 X 

### 4 X 

### 550 1 0.73 )( 537 

## = 117 lb toluene/yr Example 8.4-6 An ink manufac c urer u,;es a**lhr ~**  r oll mill to ensure that the fmi.s hed ink produce 

### meec. particle size and unifonnity standards. Macerial is fed to the rollers betw een the feed and cente r r

olls . Material is then t ransferred fro m the cente r ro ll co the apron roll where it is removed by a Stali onary kni (e blade. Wh at a re the em i ssion s due t o surface evaporntion ? The following dat a are given: • T he ro ller elemenl.'l are 1 4 i nche s in**dia~n r**  and 30 incheo long ; • The printing ink being processed con tui ns a l i ght petroleum d is tillate oil wit h a molecular weight of254 ; • The 

### rollers operate at ambient l emperature of77°F; • The MSDS shows tha1 the vapor pressure for the ligh t perroleum distillate oil at 

## n•F is 0.097 psia; • The mo l e fraction of petroleum d i • • ill•le oi l in the ink mixture is estimaled to be 0.3; • Each batch takes 1. 5 h o urs; an d • 400 b a tches are processed annua ll y.



### 8.4-24 EllP Volume II 

### VE$015908Chapter 8 - Pcrim. Ink . and Odr'r Couri11g J Wam if ocruring 01/01105 Ste p 1 : D etermine Li quid S urfa ce Area on t he R oll ers F

or tbis illustration, i t is assumed that liquid covers 

### the entire 

### surface area of each ro ller . A = tr X 

### d x Lx N., 11 .,.



### = trX 14 x 

### 30x 3 

### = 3,956 in 2 

### (27. 5 ft 2 ) S tep 

### 2: Apply Equation 

### 8.4-3 , Determ in e P artla l Pressure of Ugb t Pet r oleu m D is tilla te 

### O il



### = 0.3x0 .097 

### = 0 . 0291 ps ia Step 3: Apply Equation 8.4-29, D ete rmin e Mass Tran sfer Coefficient 

### N

ote that 

### this example illusrrntes use of tb e alternativ e procedure 

### des cribed in Section 

### 4.5. Equa t ion 8.4-21 

### may be 

### used i f a site -specific estima te of a ir velocity over the ro llers C'dO be 

### es t imated . 

## K , = ( 18 t 

### 0.83 X M ,


### = 

# (**8r ~**  0.83 X 

### 254 

### = 0 .3 43 cmjs(O .Oll3 ft /s)

EIIP Volume II 

### 8.4-25 

## VES015909Clrapter 8- Pu;111 , Int. and Other Ctmting Ma,nifU ,·n;riug 01/0f/()j Step 4 : A pply Equation 8.4-22, Calc ula te Annua l Emi ss ions M , x K, x Ax P, x36 00xH 

### E, 

### = Rx T x B 254 X 0.01 13 X 7 . 5 X 0.029) X 3600 X 1.5 ()() 

# = x4 l 0.73x 537 

### = 861 lb / yr 

### 4.5 Gas Sweep o r Pu rge This section preswts two models for estimating emissions from a gas sweep or purge through a partially filled process vessel. The first model (option l) is from 

### Comrol of Volatile Organic Emissions from Batch Processes (EPA, 1994c) . The second model (option 2) is a modified versio n of the first model in that it**includ~** a procedure based on**~ite specific**  conditions for estimating the degree to which the ex.haust gas is sat urated with o r ganic compounds (Hatfield, 2003 ). Note that option 2 is recommended on ly for applications where the head space e x. change ra t e is Je ss 

### tl1ru1 5 per minute beca u se available data s uggest it may underestimate em issions at higher exchange rates (Watson, 2004). Applying the surface evaporation mode l to est imate e m issio ns from a gas sweep or purge i s inappropriate. As noted in section 4.3 , the wind speed correla tion for estimating the mass transfer coefficient was developed for scenarios where the flow is uniform across a relatively quiescent li qui d surface, and the wind 

### speed is taken at I 0 meters above the surface . Flow inside a tank is not unifonn, sweep air may be impinging on the liquid surfac . e. the liquid surface is likely turbulent from agitation, material added while loading the vessel may be dropped on the liquid surface causing splashes, and the wind speed cannot be detennined at I 0 meters above the surface. Furthermore, even ift he general corre l ation is still vali d under these conditions, the gas velocity is no t uniform across the surface of t he liquid, and there is no consensus regarding the value to u se o r the point at which the ve l ocity s houl d be determined for use i n the correlation. 4.S . J O ption 1 The eq u ation for calcu l ating gas sweep or purge em i ss ions t hat is in 

### Control of Volatile Organic Compound Emission from Botch Pro ce s.<es is shown i n Equation 8.4 · 23 (BPA, 1 994c). 

## B 

# =

• P ,xF,..x M, x6 0xOH P r X R X T Pr - I:P, (H.4-23)

8.4-26 EUP Volume II 

## VES 0 1591 0Chopltr 8 - Paint, I nk, anti Other 

## c ...m.g Monufocrurltrg 01/0f/()j where 

### E, = 

### emissions of VOC 

### species x, lb/yr 

### P, 

## = partial pressure of VOC 

### species 

### x, psia 

### F., flow rate into the vessel, II' 

### linin 

### M

, 

## = molecul ar weight of VOC 

### species x , lb/lbmole 

### 60 

## = 60 min/hr 

## OH = 

### h ours that the 

### gas sweep or purge operates, hr /yr 

### R 

## = universal gas 

### constant 

### (10.73 ps ia fi'llbmo le 

### • R ) T temperature of the exhaust gas, "R 

### Pr 

## = total system pressure, psia. 

### Note that to use th . is model. the exhaU>t gas stream is assumed to be 

### in equilibrium with the 

### liquid if the flow rate into the vessel is 

### l ess than 100 

### ft'hnin (i.e., 

### the partial pressure 

### is equal 

### to t h

e vapor pressure for a tank with o n e compound in 

### the liqui d phase). The 

### exhaus t stream 

### is assumed 

### to be 

### 25 percent satura t ed if the tlow is greater than 100 fil i min. Example 8.4 -7 illustrates th e u se of Equation 8.4 -23. Examp l e 8.4-7 A gas sweep is operated while material is added to a high - speed disperser. What 

### nrc the un n lllll VOC emissions during purges? The follow ing data rue provided: • The average composition oftl 1e material in the high-speed disperser while the sweep operates is 30"/o by we1gbttoluene. 20"k by weight MEK, and 50"/o by weight insolubl e pigments and nonvolatile resins: • The temperature ofthe ma terial i n 

### the VC$.•tl and the 

### exhau.>t gas is 

## n·F (537°R): • The partial pressures oftoluene nnd MEK at77°F are 0.313 psia a nd 0 . 888 psia, respectively (see Example 8.4 -2, S tep 2) : 

### • n. e inlet purge t l ow ra t e is 

### 5 ll'Jmin; • The molecular weig ht of tolu e ne is 92.1 l b/l bmole; • The molecula r weight ofMEK i s 72. 1 lbllbmole ; and • The purge operates for 1,000 

### hr / yr.

EUP Volume II 

### 8.4 - 27 

## VES015911Chapter8 - Palnt , Jnl:, and Oth.r Coat i ng Manu fimuring 0] 1()/ /()

j Ste p 1: Apply E quation 8.4-23 t o C alculate T oluene E oli ssio u s Note that since te purge flow is 

### < I 00 ft 3 /mi n, the exbaust gas stream i s ass um ed to 

### be sa turated with toluene and MEK. 

### E 

# = P,xF"'x M ,x6 0xOH x 

### P r ' R xT Pr - !P, 

## = 0.313x5 x92 . 1 x60 x i,OOO 14. 7


# ------ -- ....:....-x -- -,-- ----,- 1 0.73 x537 14.7 - (0.313+0 . 888) 

## = 1 , 6341b/ yr Ste p 

### 2: Apply Equation 8.4-23 to colculate 

### MEK Emission s E ), 

### = 0.888 x5 x72. 1 x60 x 1.000 14.7 X 

### 1 0.73 x537 14.7- (0. 313 + 0.888) = 

### 3,630 lb/ 

### yr S tep 3: S um t he Emiss ion s fr o m Stci >S 1 uod 2

4 . 5.2 Option 2 

### E voc z 

### 1 ,63 4+ 3,630 

### = 5,264 lb I 

### yr
This model is the same as the model in Option I except tbar it adds a site-specific saturation factor for each VOC species in the exit 

### gas stream . Equation 8.4-24 is used to calculate the sa turation factor. 

### P , K,A K,A 

## s), : ---s;;-: D · S :d 

### P

, F 

### + K , A K , A t 

### F., t 

### S,F, (8. 4-24) where



### 8.4-28 

## S, K,. 

### A = FOC" = 

### F ..,

A saturation factor for 

### VOC species 

### x mass transfer coefficient for VOC species x surface area ofthe liquid volumetric flow rate oftbe noncondensab1e purge {e . g. , air , nilrogco) volumetric flow rate of 

### VOC species x at the saturated partia l pressure . 

### EIIP Volume II 

### VES015912Chapt<r B- Paint , ink, 01rd Other Coortng M a

nrifac• trtrlng (}2/Qf/QJ 

### Equation 8 . 4-24 was deve l oped bosed o n th e fo llowing relationships and assumption s. Equat i on 8.4-25 relat es the evaporatio n rate fo r a VOC species x withi n a vessel t o its molecu l a r w e i ght. mass transfer coefficien t, su rf ace 

### are a , and ot her known variables [ Crowl 

### & Louvar, 2002]. (8 . 4 - 25) where 

### E ., 

### M

, 

### K

, A 

### R T 

### ps.u



## ' P

, = = = = 

## = = 

### evaporation rate (lblmin) molecular weight of VOC species 

### x mass transfer coe ffi cient (ft./ min ) surface 

### area ( fl ") 

### ideal gas con sta nt tem peratu re o f li q u id partia l p ress ure of VOC specie s x in 

### a s atura t ed gas 

### stream (t ru e 

### vapor p

ressure if the liqu i d i s pure s pecies x) 

### actual partial pre ssu re of VOC species x 

### next to the liq u id surface. Equation 8 . 4-26 is the basic eq ua tion for calcul ati ng the emission rate for VOC s pecies x 

### f rom a 

### gas sweep or purge opera t ion based o n th e exi t gas flow rate , partia l pressure of VOC spec ies 

### x , mo lecular weigh t, and other kno wn variab les. 

### E 

### = FP T**M** 

### = 

### M , PP , y 

### RT p X 

### RT ( 8 . 4-26) 

### whe r e = = 

## = = = = T



### e miss i ons from 

### vesse l vent ( lbhnin) exit gas fl ow r ate ( I f/ min) overa ll sys tem press ure ideal gus con sta nt temperatur e o f li qui d actual pa rti a l pre ssure ofVOC specie s x mo l ec u l

ar we i g

ht of VOC species x . F

o

r a vessel at stead y sta te condi ti ons , the emission rat e from the gas 

### sweep activity i s equal to t he e\• aporation rate ofVOC species x from 

### the liquid within the vessel [Hatfield , 2003 ]. These two equations can be se1 

### equal and solved for the saturat i on level S , (i.e., P, IP,**s.~.** 

### res u lting in Equation 8. 4- 2 4 . Eli!' Volume II 8.4-29 

## VESOI5913ChapterS - Painr , Ink , and Other Caallng Manufu<totrlng 01f(JJJ(JJ 

### Cnlculation o f VOC emissions usin g E qu a tion 8.4-24 is based on t he followin g ass u m pt

ions: • The vessel is at steady s t a te so t h at the evaporation reate equal s the discharge rate 

### in the exi t gas str eam . • The vapor s pace**~** 

### perfectly mixed 

### so that once the V OC evaporate s there is no additio nal resistence 1(1 

### m ass t ransfer to the exit gas s t ream (t his means th e reference mas s transf e r coeffic ien t. as discussed be lo w , is a lso assumed 10 

### be f or 

### a perfectly mixed system). • The equation is recommended only fo r headspace exchange rates up to 

### 5 per minute. The 

### ratio of the mass transfe.- coefficients between the 

### compoun d of**intere.~** 

### (KJ 

### and the 

### reference compound 

## (KJ i s expressed u sing 

### Equati on 8.4-27 (Crowl and Louv ar , 2002):

where mass tran sf er coefficient for VOC species x mass tran sfe r coefficient fo r a reference compound diffus i on coeffic i ent for VOC species x 

### in air diffusion coefficient for a reference compound in 

### air. ( 8 .4 - 27)

The gas-phase diffusion coefficient D for a compound is estimated from the rati o of the mo l ecu l ar weigh t o f the 

### compound of in teres t and a known compo und (no nn ally water) using Eq uati on 8.4 -2 !\:

where molecular w e i gh t of a reference compound mo l ecular weight ofVOC s p ecies x. ( 8 . 4-28)

Combining Equations 8.4 - 27 and 8.4-28 results in a relationship that cao be used to estimate the mass transfer coefficient of a given volatile compound:

8.4-30 

### EIIP Volume IT 

### VES0 15 914CAopltr 8 - Pailfl , Int. and Oth'" Coating Muno l[act11ring 01101/0J 

# K = 

# K (M . ·)}:;
, • M 

## • (8.4 - 29) Water i s commonly used as a base reference for estimating the mass transfer coefficient for many compounds of interest. The mass transfer coetllcient of water at 

## n•r and 14. 7 psia i s 0.83 cm/s (0.0272 ftls) (Matthiesen, 1986) . The saturated partial vo lumetric now rate of VOC species x can be est imated from the saturated partial pressure of the VOC species x , dte inlet gas purge rate, and the part ial pressure of the noncondensable gas at saturated conditions using Equation 8 . 4-30:

where F**S~ !**  = 

### ' fw: 

### p s. • =



## • P

r = 

### F"' - F X 

### P , ... • - "' p - 1:P s.. T • (8.4-30)

volumeui c flow rate ofVOC species x at the saturated part i al pre ss ure volumetric now ra te of the noncondensable gas (i.e . , air , nitrog e n) partia l p ressure of VOC species x in a saturated gas stream (true vapor pre ss ure i f the liqui d is pure species x) total system pressure . The saturation fuctOr (S,) may be solved using the standard quadratic soluti on. A lthough the standard quadratic equation contains two roots. only the one solution shown in Equation 8.4 -31 produces a realistic value since S, must be a positive number between 0 and 1 .0. 

### S _ - ( K, A + 

### F .., ) + 

## J(K , A+ F,,J + 4F ,s. K , A ' 2F "' 

## • (8.4-3 1) Fim1lly, the em ission rate for VOC s p ec i es x may be calculated us i ng Equation 8.4 - 32, which i s s im i lar to Equation 8 . 4 -2 3 , except that th e sanuuted partial pressure is mu ltipl ied by the saturation factor. 

### E 

# = X 

### M ,x S ,x P, ... x F., x60xOH P T X s.t R X 

### T PT - 

### l:P, (8.4-32) For multi-component liquid mixture s, Equation 8.4-24 may be expanded to inc lude partial volumetric flow rates for each VOC species in the liquid, as shown in Equation 8.4-33 :

EUP Volume II 8.4 - 31

## VES015915Clwpter 8- Point, l11k. and Other CtNirlng**Mm;ufaL'turit~g** 01/V/IQJ 

### (8.4-33)

ln equation 8.4-33, the subsctipt x identifies the VOC species for w h ich the saturation level is being calculated, and 

### terms j 

### through n represent 

### the ot h e r VOC species in the liquid . Eq uation 8.4-33 is solved in 

### an iterative trial and error 

### manner wit h 

### the initial value ofS for each 

### VOC s pecies assigned to 1.0. The value ofS t hat is calculated for each VOC species is then used as the s tarting point for the next iteration. Finally, when the saturation level 

### S of

### each VOC species remains the 

### same for subsequent iterations, the calculation process is stopped . .Examples 8.4-8 and 8 .4-9 illusrrate the use of Equations 8.4-29 through 8.4-33 to estimate emissions from purging a partia ll y filled vessel.

Exnrople 8.4- 8 A 

### high-speed d i sperser operotes with a @llS sweep 

### while mater i a l i s added 1 0 

### the ves s el. What are the annual VOC 

### emis s ions? The 

### fo llowing data are 

### given: • Mineral spirits are 

### tbe only material in the liquid phase; 

### • The molecula r weight of mineral sp iri ts is 145 

### lb/lbmole; • The contents ofthe 

### vessel and the purge are at a temperature of77"F (537"R); 

### • Vapor pressure of 

### ruineral gpirits a t 77"F 

### is 0.0032 psia; 

### • The gas 

### sweep is 5 

### acfm; • The diameter of

### the tank 

### is 5 

### R; and • The gas sweep operates for I ,000 hr lyr. S t e p 1: App l y 

### Eq uation 

### 8.4 - 29, Es flmalc Mas s Tra n sfer Coefficient Us i ng water as the reference compou nd resu lts i n t h

e foll o wi ng eq uation: 

## ( 18) 1. = 0.83x 145 

## = 0.414 cm / s(0 . 815ft / min ) 8.4-32 EfiP 

### Vo lume II 

### VES0 1 5 9 1 6Chapin- 8- PainJ , I

nk

, and Other C<x•lf•g M an llfo <turing 01/0JJf)j St

ep 

### 2: D et ermine Sur f a ce Ar ea o f Liqu i d in th e 

### Tank 

### A 

# = JrX 

### d 2 4 

### = 19 . 6 

### ft 2 S t. e p 3: App l y E qu a ti on 8 . 4-30 , De t e rm i ne S a t urat ed P a r tial Vo lumelri c Flow R ate o f l\1 i n c ral Sp iri ts in Exit Ga s Strea m 

### F "' :



## • = 

### 5 X 

### 14 .7- 0 . 0032 

### = 0. 00109 

### ftl / m in S t e p 4: Ap p l y Equation 8 . 4 - 3 1 , C al c ulat e S uttuatlon Factor For Min e r al S pirit s 

### in tb e Exi t Go s S tream 

# s . =



## = -( }(.A + F .,. ) + 

## J ( (K , A+ F ., ) '+ 4F , 

## s.. K,A ) 2 F Sm 

## •

- ((0. 815)(1 9.6 ) 

### + 5) 

### + J((! 0 . 8 1 5 )( 19.6) 

### + 5 )' 

### +( 4 }(o.oo 109 }( 0.8 1 5 )(1 9.6 }) ( 2 }( 0 . 00 1 09 )

- 20 . 97 4 

### + .J4 39 . 909 

### + 0 . 06965 0. 00 2 1 8 

### = 0. 76 St ep 

### 5 : Ajlply Equatio n 

### 8 . 4 -32 , C nl c ul o te An n ual Emiss i o n s 

### E 

# =

' = M , xS,x P ,"'x F x 60 x OH x Pr 

### R x T 

### Pr - l:P ,"' 145x 0 .76 x 0 . 003 2x Sx 

### 60x 1 ,000 14 .7 X 

### 1 0.73x 537 14.7-0.0032 

## = 1 8 lb / yr 

### E

IIP Volume 

### U 8.4 - 33 

### V E S 01 59 17Cltapttr 8 - Paint.lnk . and Other Coorfng Ma nufilct uring Example 8.4 -9 Determine the annu al emi ss i ons fr o n1 purging the high - speed dispers er in**exan~p c**  8 .4-7 us ing Option 2. The fo llo wing addirion • l in forma ti on is pi'Ovided : The d i ameter of the tank i s 5 II . 01JfJIIOJ

S t ep I. Ap pl y Equation 8.4-29 , Estima te 1\fa ss Transfer Coefficien t s for T o luen e and MEK For toluene: 

### ( 18 ) y, K , .,0 . 83x - = 0.482cm/s(0 . 948ft / min ) 92.1 Fo rMEK : 

### ( 18 

# ) y, K , 

### = 0.83 x - = 0 . 52 3 crnfs(L.029 ft/min) 72. 1 S t ep 2: D eter mine Surface Area of Liquid in t he Tank 

### ;rx d 1 

### nx ( 5 ) 2 

### ft ' A 

# = = = 19 6 - 

### 4 4 . Step 3: Det e rmin e Sat u r ated Partia l Press u r es of VOC Species 

### See E xample 

### 8. 4- 2 , Step 2 fo r the calcu l a t ions of the f o llowing : VOC V P at 77 ° F , p si a Liquid Mole Fractions P .•', psi a Toluene 0 .58 0.54 0. 313 M E K 1. 93 0.46 0.88& S t ep 4 : App l y Equation 8.4 -30, D e termine Saturated Partial Volumetric Flowrate of Each VOC S pecies

8.4-34 

### EliP Volume II 

### VES015918Chapter 8 - Painr ,**Ink ~**  tmd Other UH.lf ing J \Jarm fiu. : turln g 0110//()5 

# ""

...

## -~**.!.' ,-,-** **=** F

, = 

### P ,. 

### x p _ 

### tP"' T > 

### S. ( ) 0.313 F

, 

### for toluene 

### = Sx 14 . 7 _ (0 .3!3 + O. SSS ) 

### = O.IJ60ft 3 

### / min 

### S•( K) 0 . 888 F, 

### for ME 

### = Sx 14.7 - (0.313 + 0.888) 

### = 0.3288 

### ft 

### '/ min Step 5. A ppl y Equation 8.4-33, Calculate the Sa turation Factors fo r Each YOC S p«ies 

### Using t rial and error, the following result s arc ob tained :**.\:~,** 

## s, s, s ' 

## s , voc K,A ft' /min (Ite r ation 0) 

### (Iteration 1 ) (iteration 2) (lteralioa 3) 

### Toluene 18.6 1 7 0 . 116 1 0.77372 0 . 77682 0 . 77678 

### MEK 20 .200 0 . 3288 1 0 . 78 769 0 . 7906 5 0. 7 9061 

### For example , t he S, (iteration 1 ) for toluene is calculated as follows: 

### K,A S' 

## =**::K A-+-=F** **-+-: :"-:** **;:: =-::** **F:< .**  

### ,. ::-, .X I'IC! A X I J 18.6 1 7 

# = 18 . 617 + 5+ ( 1 )( 0.116 ) + ( 1 ){ 0.3288 ) 

## = 0.773 72



### EITP 

### Volum e II 8.4-35 

## VESOI59 19C hapt e r 8 - Pa;,ll , Ink. and Ocher C oo tin g Mam ifac: rur ; ng 01/Q / /Q

J 

### Step 6: Apply Equation 8.4-32 , Calcu l ate Annual Emissions 

### M , x S, x P, 5 " 

### x f ., 

### x 60x OH R xT X 

### p - :l:P S. o T ' 

### 92.1x 0 . 777x 0 . 313x 5x 60x 1000 14.7 

### E, (toluene)= 

### J0.73x 537 x 14.7 - (0.3 13+ 0.888) 

# = 1,270 lb / yr 

### 72. lx 0.791 x 0.888x 5x 60x 1000 14 . 7 E , (ME K ) = 

### 10.73 x 537 x 14.7 - (0.313+0.888 ) 

# = 2,87 1 lb / yr Step 

### 7: S um Emissio n s !<'rom Step 

### 6



### 4 . 6 Solvent Reclamation Ev oc 

### = 1 ,270+ 2,871 

### = 4 ,1 41 lb/y r After being collected from coating manufacruring operations, waste cleani ng solvents may be purified and 

### reused. DiStillation is one of the 

### most common methods of purifying o 

### s olvent. Many forms of distillation are used including batch, sim ple continuous, o r steam disti ll ation. A batch distillation proces s co nsi sts of at least four separate activities including: (I) charging waste solvent into t he still . (2) heating the batch to its boiling point, (3) collecting the distillate in a rece iver, and ( 4) filling a container or vessel with the collected distillate for storage. Steps I, 3 and 4 can be modeled using the fillin g model described earlier in t his section (Equation 8.4-1). Emissions from beating to boiling (Step 2) catmot be modeled u si ng either of the equa t ions for heatup described in Section 

### 4.2 of this chapter because the equations a re m athema ti cally invalid when the partial pressure ofair is zero . However , the emissions can be es6mated using Equation 8 . 4-34. 

## (Px ) E .. 

# oc = --•**x&~xM** 

### • Pa 1 • 

### (8.4 - 34) 

### 8. 4- 36 El[ l' Volume IT 

## VES015920Chapter 8 - Point, ink , ond Othrr Coating Manl ifcl<1 uring 01/0 i/0 5 

### where (Px). 

### - partial pressure ofVOC species x at the condenser outlet temperature (also the vapor pressure of the pure compound because only one compou nd is condens ing) 

### t:.n 

### M. Pa, 

## =**~** 

### moles of air in tl1e 

### vessel headspace at the initial temperature molecular weight of VOC species x partial pre ss ure of air at 

### the condenser outlet temperature . Calculation ofVOC emissions using Equation 8.4-34 is based on the following assump ti ons: • all of the air in the vessel headspace at the initial temperature has been expelled wben the l iquid in the ve.'>Sel begins to 

### bo il • t h e heated vapors l eaving t he sti ll pass through a condenser • air leaving the condenser is saturated with VOC vapors at 

### the exit gas temperature of t h

e condenser. Furthermore, while the liqui d in the vessel i s boiling, emissions are assumed to be zero because only VOC vapor is expelled from the vessel and it all condenses in the condenser. Examp le 8.4 -10 illust rates the use of the filling and beating equations to estimate VOC emiss ions ft-om solvent reclamation.

EliP Volume II 8.4 - 37 

## VES01592 1Ch a p ter 8 - Pu i m, I nk, n nr l O t her C.{)a ting Ma u ufilt · ruring 01101/0S E

xam p l e 8 ,4 - JQ The Bright Blue Paint Company i n Case Smdy 

### 8 . 3·1 recovers toluene from 300 tonslyr of waste cleaning solvent using a batch distillation unit. What are the estimated annual VOC emissions? The following data are given: • Th e still is half fi lled fo r each d istillation opera tion (i.e.,**lh ~**  ve ssel vapor space equals !he vo l u me of was te so l vent f or 

### each b atch); • T h e expelled a i r a nd VOC v apors a r e r

· o uted to a condenser t hat ope ra t es with a n o utl et temperature of20°C (68° F); • The still bo r r oms at the end of the disti ll ation contain 3 percent of the initia l waste solvem; • Analysis shows the waste solvent is about 

### 99 percent toluene (on 

### a mo lar ba>is), and the remaining I pen;<:nl is dissolved solids and nonvolatile liquids ; • Typ i ca l ini ti a l temperature of the waste so l vent i s 25°C ( 7 7 ° F); • To l uene dens i t y i s 7 .2 1 l b/ g al ; • Fina l t em perat ure ( to l uene b oil ing poi nt) is Ill °C (232°F); a nd • Displ aced air from all ft.lling steps is assum<."<l to be sarurated with toluene vapors (i.e., the saturation fa ctor is 1.0).


### S tep 

### 1 : De t e r mi ne Vo lum e of Wa s t e Solve nt C h a r ged t o the 

### S till Q 

## =

# 00**onsso ve** **)x(2 000l** **)** yr to n 

### 7.2 1 lb = 

### 83,2 18galfyr S t e p 2: Deter mi n e the T o lu en e V ap or Pr ess u r e a t 

### t b e lll ltial T e mp e ra ture Numero u s 

### r esou rces are available 

### f or e s tim a tin g v apor press u re s . Thi s exam p l e u ses 

### the Antoine 

### equat ion (De a n , 1 992).

where 8. 4- 38 

### B l og(VP 

## ) = A- -- • T+C (8 .4- 35)


### E

ITP Vo lume II 

### V ES0 \ 592 2Chaptn- 8**-Pain~** Ink , and Othu C<Hiring M anoifacoorlng 01/0/IOJ 

### VP , T 

### A , B , C 

## = = ; 

### vapor pres su re of 

### VOC species x. mm 

### Hg temperature, 

## •c Antoine Cons tan ts . For toluene at 

### 1he initial temperat u

re of1he 

### st ill (25°C), 

### the Antoine eq uation give s the f ollowing resullS: log (VP , ) 

### VP. 1,344.8 

### = 6 ' 

### 95 4

- 25 + 2 1 9.48 

## = 28 .4 

### mm Hg ( 0.549 psia) S t e p 3: Ap ply**E~uation** 8.4-3 , 

### Det e rm ine Toluene Partial Pressure a ttb e Initia l Temper atu re 

### P, 

### = M , X 

### VP, 

### = (0 . 99)x ( 0. 549 ) 

### = 0 .544 psia S t ep 4: Apply Equation 8.4-1 , C al c ulate To l uene Emissions From C hu glng Waste Solvent to the Still 

### E ")(" 1 2 .46 X 

### S X 

### P , X 

### M , X 

### Q = 

### T 12.46 X I x 

### 0.5 44 X 

### 9.21 X 

### 83.2 

### = 537 

### = 97 

### lb / yr S t e p 

### 5: Ap ply E q uations 

### 8.4-1 1 and 

### 8 . 4 - 12 , Determine Amount ofNoncon deo sab l c 

### Gas in tb c Ves s el Bead s pace Wh en 

### Heatin g Begins. Although 1he de scription of the problem doesn't specif)' tbe s i ze of each batch or t h

e size of th e s till , it says 1he headspace vol ume fo r 

### eac h batch i s equal to 1he volume of wa s te 

### solv ent Thus , t he total volume of free s pace in t h

e st ill a t the s tart of h eatup forall of the ba t ches during the year eq uals 1he total volume ofwaste solvent processed (i . e., 

### 83,218 gal ).

EIIP 

### Volume 11 

### 8. 4-39 

### VES015923**Chc1.pt~r** 8- Paint . h:k.. end Othe-r Cootfng Monufacn,ring 0110/IOJ 

### Pa, = 14.7 - l:(P,) 71 

### = 1 4.7 - 0.544 

### = 14 . 1 6psin 6n 

### =

= 

## ( P a,) x ( V ) 

### (R)x 

# m ( 14 . 1 6)x (83.218)x( ft /? .48 ga J ( 10.73 )x ( 53 7)) 

### = 27.3lbmoleof airexpelled / yr S tep 6: Apply Equ ation 8.4-35, De termi ne Vapor Pr essure and Partial Pres s ure of Tolu en e at 

### 20 °C (Condenser Outlet Temperatur e) 

### log( VI' ) = A - _ B_ X 

### T+C 

### = 6.954- 1,344 . 8 20 + 219.48 VP, 

### = P , 

### = 2 1. 80 mmH g(0. 422 psia ) S te p 7: A pp ly E quation 8.4-34 , Determi ne Amount o f Toluene Emitted With the E xp elled A ir During fJ eatup 

## ( r .) = - p " x6nx M , 

### a , (0.422) 

### = (14 .7- 0 . 4 22) x (27.3) x (92 . 1 ) 

### = 7 41b /yr Step 

### 8: A p ply Equation 8.4-1, Ca l c u la te Emis s ion s From Filling th e R eceiver with D istilled T olue11e at 

### 2o•c (68°F} Note that since 3 percent oftbe initial waste solvent remains in tbe stilL the total volume of recovered 

### toluene is 97 percent oflhe 

### total waste solven t processed.

8.4-40 

### EDP Volume 

## n VES015924Chapter 8- Pu;nt, In* . ttnd Other Coati1tg Mamift u:tun'ng ()2/0 J /05

= 

### 1 2.46x Sx 

### P , x 

### M, x 

### Q x 0 . 97

T 12. 46x 

### I x 0.422x 92. 1 x 

### 832 x0.97 

### = 

### 528 = 

### 74 l b / yr S tep 9 : Appl y Equalion 8.4-l , Calculate E m iss ion s From Fillin g a Sto ra ge Vessel or Dru ms With Di stilled 

### Tol uene F r om the Recei ve r 

### A s sume the distilled t ol u ene is still at 

## 2o •c (68 ° F) 

# = 12.46 X S X P, X M , X 

### Q X 0.9 7 

### T 12.46 X I X 

### 0.422 X 

### 92.1 X 83.2 X 0 .97 

### =**~~ --** **~~ 52** **~-- ~~** **--** = 

### 74lbf yr Step 1 0 : S um th e Emiss ion s from Ste p s 4 , 7 , 8 , and 9 E voc 

### = 97 

### + 7 4 

### + 7 4 

### + 7 4
= 3191b / yr 

### 4.7 E mi ss ion Mode l for Liquid Matc rlaJ S torag e The preferred metJ t od for calculat ing em iss i on s from**~1 01uge**  

### t anks is the usc of equat ion s presented in AP - 42. I !!' A 

### h as developed 

### a softwure pa ckage (TANKS) f o r ca l cu l ating these types of em iss io ns. Th e reader i s referred to C h apter I o f thi s vo lume , Jnrrodu c ti on to Stationary Poim Source Emis sions Inventory Developm ent, for more inf ormation on using t h e TANKS 

### program . Additionally , the reader should consult t heir state agency 

### andlor !he EPA's Clearinghouse for Inventories and Emission Factors (CHIEF) 

### W ebsite for the most recent version ofT ANKS. 

### 4.8 Emission Mode l for Wastewate r Treatme nt VOC emiss i on s from a 

### wastewater tre a tment s ystem may be estimated using equat ions present e

d in Ai r Emissions M o dels for Waste and Wo. N

e water (EPA, 1994a) , 

### and Chup ter 5, Prefen·ed and A lternati ve Metho dsfor Es timating Air EmissimLvji·om Was te wmer Colle c tion and Treatment Facilities, of this vo l ume. These d ocuments, a s well as models s u ch as WA TER9 are availab l e on the EPA's CH I EF Web site. BliP Volum e li 8.4-4 1 

### VE SOI5925Chapter 8 - Pu;m, In k, and Other Coaling Manu}Q, ·ru rl

ng 0 1 /() / /()5 

# 5.0 Oth e r Method s for Es timatin g E mi ss ion s Section 4 presented m ode l s for estimat in g emissions from spec ific coating man u factu ring ac tivitie s . Thi s 

### section presents o t her types of m c lhods for calcula ti n g emissions from manu facturin g facil iti es. The ot h er melhods de s cribed in this 

### section inc lude emission factors, material balances, and t est ing. 

### 5 . 1 E mi ss i o n Ca l c ulati on s Us i ng E mi ss ion Fact o r s Emission factors ha,• e l ong been 

### used to ca lculate emissions from coating manufacturing facilities. EPA maintains 

### a compilation ofapproved emissio n factors in AP-42 

### for criteria po llu tantS and h azardous air pollutants (HAPs). Available e missio n fac t ors for paint manufac turin g can be fo und in Section 6. 4 of AP-42 

### and in a t echni ca l memorandum from EPA to the 

### National P aint and Coatings A ssoc i ation (E PA , 19951) . Emission fa c tors for ink 

### manu facturi n g can be found in Section 6.7 o f AP - 42. 

### TI 1 e National As sociation of Print ing Ink 

### Manufacturers, In c. (NAPIM) , has also de veloped 

### ink manufacturing cmi ss ioo factors (NAPIM , 1996 ). The mos t comprehensive so u rce for tox ic air pollutan t emission factors is the Factor lnfonnation and REtrieval (FIRE) 

### data system , which also cont ain s criteria pollutant emissio n fac t ors (EPA, 1999 ). 

### VOC emission factors are a vail able in AP-42 

### for calculating tolal p lant emissions and mixing operation emissions from 

### a pain t manu facturing facility and for vehic l e cooking and pigment mixing emission s from an ink man uf.1 cturing fac ility . In a d dition, emi ss i o n factors 

### are availab le for est i mating VOC e mission s from th e 

### following types of sources found in a coating manu facturing f.1cility: • Solvent reclamatio n systems ; • Pans wa s hing equip ment; and • Process piping (i.e., equipment l eaks) . Emiss io n factors arc a l so availab le fo r es ti ma tin g PMIPM 10 

### emissions from coating manufacturing facilities. S. l . J 

### Total VO C E mi ss ion s fr om P aint M a n uf ac tu rin g F a c

iU t les A VOC emi ssion factor can be used for calculat i n g total VOC emissions from paint manufacturi n g facilities. The emi ssion factor presented in AP - 42 

### is essen ti ally a 

### loss factor that represen ts an emission rate to be applied t o a production rate (NPCA, 1995) . Tbe VOC emission factor presen ted in AP-42 

### for paint manufacturing is 30 lb 

### total VOCslton product (E PA , 1995 b) . To calculate total VOCs using this emission factor, see 

### Equation 8.5 - 1: E

llP Vol u me 

### n 8.5- 1 

### VES0l5926Chapter 8- Paim . l11k, and Other Cooliug Mo1wfm : fllrl11g



### where E VIJC 

### EFvoc = 

## Q. total em i ssions ofVOCs from the facility (lb / yr) VOC e mis sion f.1ctor (lb VOCs/ton produc t) amount of product produced (ton/yr) . Table 8.5-1. Li st o f Variables an d Symbol s Variable Symbol To t al VOC emissions Evuc VOC emission facto r 

### Efvoc Amount of product produced Q, ..

, Emissions ofVOC or PM species x B, Amount ofVOC species 

### x used by the fac i l ity 

### Q. Total amount of solvent s use d Q , Amount of VOC in spent solvent pr ocessed 

## Ovoc Concentration of VOC or PM/PM •• spect es x in solvent or pigment 

# c. x, rtliJ>ectivcly Mass percent of species x in total mixture 

### X. Vo l ume perc-ent of species x in total mixrurc 

### Y, Number of species in tota l mixmre n Flow rote through exhaust vent 

### FR Molecular weight of total mixture M Molecular weight of VOC or PM**~pccics** x M, Operating hours 

### OH Surface area of solvent exposed ro the atntosphere A Number ofcleaning units i n use NU PMIPM ,. emis;ions E ,.. PMIPM ,. emission factor 

## EF,.. , Amount of pij!jllent containing species x used by the facility Q , Quont i ty ofVOC or PM species x that is received as a raw material 

### Q.. 8.5 -2 01101105 (11 .5 -1)

Units lb/yt various



## -- toni)'l ' lb/yr lb/yr lb

/ yr tonlyr mass % 

### mass % vo lum e% number tl 'l min lb!lb -molc lb/lb -molc br/yr ft ' c le aning units l blyr lblton lblyt, tonlyr lblyr 

### EJIP Volume ll 

### VES015927Clwptvr 8 - Paim , Ink. and Other CC<> t i ng M amifiJ<turing 0110 1105 Tob i e 8 .5-l. (co ntin ue d ) Variab l e Symb ol Units Quantity ofVOC or PM sp ecies 

### x**~h ipp** **d** out in final product Q. l b/y r Quan t ity of VOC o r PM spec ies 

### x reoovered by all me thods Q. , J b/yr Quantity of VOC o r P M sp eci es x co nta i ned i n all waste gentrated Q . l blyr Quantity of VOC o r P M species x remain i ng i o rnw material Q ., J blyr inventory Concentration ofVOC or PM species x 

# eM Pi!!!!' ' or 

### fl'I MM W Because the 

### VOC' emissions calculated in Equation 

### 8.5-1 are plant wide emissions , speciated emissions can 

### be estima ted based on total so l vent used . Specia t ed VOC emis sio ns arc calcula ted u sing Equat i on 8. 5 - 2 :

w here 

### E,. = 

## Evoc = 

### Q. = 

### Q, = 

### E, = Evoc >< 

### Q ,I

Q

, (8.5 - 2)

E mi ss i ons ofVO C species 

### x from the facili ty ( l b/ yr); VOC emissions from t he facility , ca l culated using Equation 8 . 5- 1 (lblyr); Amount ofVOC species x used by the facility ( l blyr); and Total amount of solvent s 

### used by the facility (lblyr). With no other infonnation available , one i mponant assumptio n made 

### in Equation 8 .5 -2 is that all sol vents ev aporate at the same rate . The amount of VOC species x used by a facility (Q,)**c~n** 

### be ob tai ned by r eviewing purch ase and i nventory records and appropriate techn i ca l da ta**heet ~.**  Purchase and inventory records can 

### be u s ed to es timate the amount o f a particu lar ma te rial cons umed. T he s um of spec i ated emissions for a ll VO C com ponents calc ul ate d u sing Eq u atio n 8.5-2 cannot exceed the to t a l VOC emissions ca l cu l ated i n E quation 

### 8.5- 1. The use o f Equat i ons 

### l! . S-1 and 8 . 5-2 is demonstrated in Example 8.5- I.

EUP Vo lwne 11 

### 8.5 -3 

## VES015928C hapt er 8- Paint , Ink. a11d Other C ou ting M a 11u [ o ct 1Lring 0 1 /() / /0J
This example s hows bow tota l 

### a nd sp ccintcd VOC emissions 

### may be ca lcu l ated fo r 

### a puint 

### manufactur i ng f acility using th e produ cti o n -bused 

### VOC emil;s i o n 

### f ac tor fr om AP- 42 , Tab l e 

### 6.4 - 1, and Equat i ons 

### 8 .5·1 and 8 . 5-2 . Given: 

### EF,, oc 30 lb VOCfton product 

### Q

,.... 1,250 ton o f p a in tf yr 

### Q,.... 250 , 000 lb used b y the facilit y/yr Q, 

### 1, 500,000 lb sol v ent s used b y the faci lity/yr Total VOC emissions would be calculated 

### using Equation 8.5 - 1 : Evoc Efvoc x 

### Q ,... 3

0 X 

### (,250 37,500 l b VOCs/yr T he amo unt of xylen es u sed b y the facility (Q , ,...,) was e stimated b y conduct i ng a 

### review of purchase 

### and i nYeotory r e<:or ds and t echnica l dnto s b eels. Xylenes emissions would be ca l culated u s ing E quation 8 .5 -2 : 37,500 lb VOCs emilled/yr 

### 250,000 lb xyl en es used by th e facility /yr 1.500,000 lb soh'elllS 

### us ed b y the facility /yr 

## Evoc X Q/Q. 

### 3 7, 500 X 

### 250,000/1.500 , 000 6 ,250 lb xyl enesl yr 

### ln addition to the 30 lb V OCs/to n prod uct emissio n facto r , EPA has recent l y res tat ed the e mi ssion fa ctor for total VOC emissio ns for overall operations from a pa i nt manuf acturin g faci lity based o n the a m oum of s olv e nt used (E PA, 

### l99 5 f). Developme n t of the new proposed facto r , 0 .03 4 lb VOCs emitted / lb s o l vent used, i s bas ed on the follow ing infonnati o n and assump ti ons: • The emission estimates us ed to develop th e 30 lb VOC sl ton coating emi ss ion factor appear to be based on the formu l ation of conventio nal coatings that were 

### preva l ent i n the l ate 1 950s and eany 1 960 s. • Densities for conventional coatings were typically 10 to 15 lbll!ill ( an average density of 1 2.5 lbl gal was used) during the late 1950s and early 1960s . 

### 8.5 - 4 EIJP Vol ume II 

## VES015929C hopter 8- Paint , l11k , ond Other Cooti ng J 't-lanu fat:t uring 01/ 0/

IO S • An 

### avemge so l ven t co nte nt of 

### 5.5 lb VOCs/gal coating was assumed for conven ti ona l coatings ( EPA , ! 995f). Use of the proposed factor by facilities th a t primarily manu facture water-based , low -solvent, or high -so lids coatings should resu lt in 

### more acc urate emissio n s than use of the 

### 30 l b VOC sl to n coating factor. To calc ulate total VOCs using th i s proposed emission facto r, use Equation 

### 85-3:

where 

## = = 

## = Evoc; e 

### EF VOC X 

### Q , total VOC em i ssions from a facility ( lb/yr) VOC em i ssion foetor (lb VOCsllb solvent used) total nmount of solvents used (lb/yr). Spcciated emis sions a re then calcula t ed u sing Equation 8.5-4:

where 

### E , EFvoc Q. 

## = = 

### emissions of VOC species 

### x from 

### a facility 

### (J blyr) VOC emission factor (lb VOCsflb solvent used ) amount of VOC species x used by the facility ( lblyr) . ( 8 .5 - 3 )

(8.5-4)



### T h e sum of spccia ted emissions for all VOC**component~** 

### calculated i n Equation 8 . 5-4 cannot exceed the tota l VOC emissions calculated i n Equation 8.5-3 . The use of Equat i o n s 8 . 5 - 3 and 8.5-4 is demonstmted in Examp l e 8.5-2. 

### 5. 1. 2 VOC Emissio n s from Pai n t 

### .M1xi ng Operations VOC emissions from paint mixing equ ip ment may 

### be cal culated using emission factors. AP - 42 

### s uggests that "about I 

### or 2 

### p ercent of so l vent is l ost even under very weU 

### controlled condit i ons " (EPA , 199Sb). This percentage 

### range can be translated into 

### an emi ss ion factor 

### range ofO.O I 

### to 0 . 02 lb solvent lostllb sol vent used . 

### Review ofbackground information i ndicates that this emission factor range applies specifically to paint mi x ing operations ( i. e ., operations where solventS are added as raw materials) (EPA , 1995f) . AP-42 

### states that the consumption-based emission factor ofO.Ol to 0 . 02lb VOCs l ostllb solvent 

### used appl ie s even to fac ilities that have emission sources tha t are we ll controlled. 

### If a facility E I!P 

### Volume U 

### 8. 5-5 

### VES015930Chapter 8- Po im, Jni:, ond OrJr.r Coating M onufoctoring 01/0/IOJ 

### contains mixers or other proce ss vess el s th a t are u n covered or otherwise poorly conrrolled , an emission factor greater tban 

### 0.02 lb solvc ntlostllb solven t use d may need to be applied (NPCA, 

### 1995). Example 8.5-2 

### This example shows how t ol al a nd specia te< l VOC 

### emiss i o ns may be 

### calculated f or a 

### pa int manufucturing f acility using 

### the proposed sol> · ent-bosed VOC 

### emission fuctor , as shown in 

### Equation 8 .5 - 3.

E

voc 0.034 

### lb VOC$11b 

### solve nt used 350,000 

### lb**sol~l<** 

### used by the 

### facilitylyr 

### EF,'OC X 

### Q, 0.034 X 350 , 000 11 , 900 

### lb VOCstyr 

### Xy l ene emissions wou l d be ca l cu l ated using Equation 8.5-4 : El'voc •**Q~** -= 

### E, 0 . 034 

### l b VOCs/lb 

### so l v ent 15,000 

### lb xylene s cont ai n ed in sol vents used by the faci li tyfyr EFvoc" Q , 0.034 X 15 , 000 510 

### lb xylenesfyr Total VOC em iss ion s can also be 

### calculated by summ i ng the speci a ted VOC emissions . Use Equation 8.5-5 for calcularing spccinted VO C emiss ions from mixers u si ng the consump t i on- based emission factor .

where 

### emissions ofVOC spec i es x from mixing equ ipment (lb iyr) VO C emission factor ( lb VOCsflb solvent used) ( 8 .5 -5)



### E " = 

### EF,'OC = 

## Q

. 

## = amount o f VOC species x added to mixing equipment as a raw m a terial (lblyr).



### 8.5·6 Ell!' Volum e II 

## VES015931Clrcptor 8 - Paint , JnJ; and Othor Coating Manll focturln g 01/01105 The amount ofVOC species x used i n mi xi ng equipment 

### (Qj refers to the tota l amount ofVOC s pecies x that is added to mixing equipment 

### as a row material. Once the so l vent is miKed with other materials, it is no longer considered a raw ma terial. The u se of Eq u ati on 8 .5-5 i s also demo ns trated in Exam ple 8.5 - 3 . Ex amp l e 8.5-3 This example shows ho w speciated VOC omissions from mixing equipment may be calculated using Equatio n 8 . 5 - S and tho o mission factor from Section 6 . 4 . 1 of AP-41. This example 

### assumes an a,..,,..SC l evel of VOC control on process equipment. Consequently , the averuge oftbe r.mgo (I to 2 percent) reported in AP-41 is used. 0.015 lb xyl enes emin ed'lb xylen es used 15,000 lb xylenes added to mixing equipment /yr Efvoc x Q , 0.0J5 X 15,000 225 l b xylenes/yr
5 . 1. 3 V O C Emi s sions f r o m I n k M a n u facturing F a ciliti es Emission factors are also available for VOC sources from ink manufacturing faciliti es. Section 6 . 7 of AP-41 ptesentS VOC emission factors for vehicle cooking. NA PIM has also developed VOC emission factors for m ix ing, milli ng , a nd tub wash processes for both paste a . nd liquid inks (NAP LM, 1996). Emission factors 

### ore availab l e for sheetfed three-roll mill and hcatset paste inks , and for low- VOC and high-VO C liq ui d inks. Equation 

### 8.5-6 can be used to cst i mute emis$ions using emiss i o n factors. 

### (8.5-6) where 

## Evoc: EFvoc = 

### Q,. VOC emissions ( l b/yr) VOC emission factor (lb VOC/ton product) am01mt ofproduct produc ed (tonlyr). Speciored emissions can be calculated nsing Equation 8.5 -7 :
EIIP Volume IT 8.5 - 7 

### VES015932Chaptu 8- Paim , Ink. ami Orlr.r Coating Ma11ufnt. 111ri "B 

### wbere 

### E, Evoc 

### Q

, Q , 

## = = 

## = = E, = 

### Evoc X 

## Q .J Q , emissions of VO C species x (lblyr) V

OC em i ssions ca l cula t ed u sin g Equation R .5 - 6 (lb/yr) amo un t ofVOC species x 

### used (lb/yr) total amount of so lvent use d ( lb / yr) . 01/Q/IOJ 

### (8.5-7)

With n o other infonnation availab l e, one important assumption made in Equat i on 8 .5-7 

### is that 

### all solvents eva porate at the Satne rate. The 

### amoum of VOC speci es x 

### used by a 

### facility 

### (QJ can 

### be obtained b y reviewing p urchase and 

### inven tory records and 

### appropriate techni cal 

### data sheets . Purchase and 

### inventOry records can 

### be 

### used to 

### estimate the 

### amount ofa 

### particular material consumed. Example 8.5-4 illustrates t he**u.~e** 

### of th ese equations . 

### Bx nmple 8. 5-4 T h is 

### ex amp l e sho ws how VOC 

### and spc ciatcd VO C 

### em i ssions may be 

### calcu l a

te d for ge n eral vehicle coo king at 

### an inlc manufactur i ng facilit y using the producti on -b ased VOC emis si on factor li·om AP42, 

### Tab l e 6.7 - 1 , and 

### E q

uati ons 8 .5 -6 and 

### 8.5 -7 . G i ven: 

### EF,.oc = 

### Q. 

### Q

...... 

## Q

. 

# -

- 120 lb VOC / ton produ c t 500 tons of inklyr 100,000 lb usedlyr 1, 000,000 lb soh'r nt s 

### usedlyr VOC emiss i ons woul d be calcula ted using Equation 

### 8. 5-6: 

### Evoe = 

### Ef voc x Q , = 120 X 500 60,000 lb VOCs/yr The amou nt of toluene u sed**(Q ~,.,.,.)**  wa s es t ima t ed b y con duc ting a review o f purcha se a nd i nventory records, batch reco rd \, 

### a n

d t echni ca l data sheets . Toluene emissions wou ld be ca lculatetl u sing Eq111ltion 

### 8 .5 -7 : 60,000 lb VOCs 

### eminedlyr I 00,000 lb toluene usedlyr 1, 000,000 lb solvents usedlyr E.. oc x 

### 0 / Q , 60,000 X I 00 , 00011,000,000 6,000 l b to l uenelyr 8.5-8 E IIP Volume IT 

### VE S0l 5 933Chtlpter 8 - Ptrint, 111/c, mrd Olhvr Co ati11g Mmmflu:turlng 01 /0 l i05 5.1.4 T otal and S pcciated VOC Emi ssio n s fr o m Solv ent Reclamation V OC emissions from th e loading and operation ofa distillatio n de vi ce may 

### be calcu l ate d using emission factors (EPA , 1995d). To calculate total VOC s from loading or o p eration of the disti ll ation devi ce , use Equ a ti o n 8 . 5 - 8 : 

### Evoc = 

### EFv oc x Qvoc where (8.5 · 8) E,.

'OC - 

### EF\'OC - 

## O

voc a VOC emissions from loading or operation of the di s tillation device 0blyr ) VOC emission fucto r for loading ofthe distillation devi c e or for the dis til l ation co l umn condenser ven t 

## O b VOCs emitted/ ton VOCs processed} a mount ofVOC in spent so l ve nt p r ocessed throug h the dis tillat ion devic e ( tonlyr). Speciated VO C emissions are then c a l culat ed u sing Equ ation 

### 8 .5-9:
where 

## E , 

## = Evoc 

# - c , 

# - E , = 

### E voc x C.flOO (8 . 5 -9)

e mi ssio ns ofVOC spec i es x from loading or operati on of the disti llation device (l blyr) VOC em i ssions fr om l oad ing or operation of t he di s tillation d evi ce , c a lc ulated using E qua tio n 

### 8.5 · 9 (lb /yr) co nce n tration o fV O C speci es x in the sol vent p r ocessed throug b the di s tillation system ( m as s %). Example 8.4 - 5 ill us trates the use of Equations 8 . 5-8 and 8.5 - 9. 

### If

the speci es x concentra ti on i s pro vi ded on a vo l ume basis, the vo l ume percent wi ll need to 

### be co nverted to mass percent. Ifmo lecular weight of the to t a l mixture is lcnown , the vo lume per cent of species x i o th e tota l mixture can b e co nv erted to mass percent using E qu at ion 8.5·10:

EllP Vol ume IT 

### M 

### Y X - • X 

### 100



## • M (8.5 ·10 )

8 . 5- 9 

### VES0 15934Chapter 8 -**Pt~int ln** **.** om! Oth" Coat i ng**Monllfocturir~g** 

### where 

## X, Y

, M, 

### M 

## = 

## = = 

### mass percent of spec i es 

### x in total mixture volume percent of spec i es x in to ta l mixture molecul ar weight of 

### species x mol ecular weight of to tal mixture. 0 1/0//()j



### If molecular weight of the tota l mixture i s not known. the vo lume percent can b e co n verted to mass percent using Equation 8.5 -11 :

where M n 

## Y

, M

, = 

## = = = 

### mol ecu lar weight of total mixtu re number of species in to tal mixture vol ume percent of s pecies x in total mixture m

ole cula r weight of species x . Exa mple 8 5 .. 5 First . tota l VOC emissions from**op..~tion** ofa disti llati on device may be calculated using an emission factor from AP -42, Table 4 . 7-1 ond Equatio n 8.5-8. EFvoc 3.30 l b 

### VOCslton solven t 

### proc:es:.ed Qvcx: 5 tons 

### spen t solvent proces.sed /yr Bvoc EFv oc x Qvoc = 3.30 X 5 

### • 16.5 lb VOCs em ine<J /yr (8 . 5-11)

Next . t otal VOC emissi ons are s pec i at cd u siog tbe conc entration ofVOC 

### s pecies x**(m~ ss**  % ) and Equatio n 8.5-9. 

## Evoc I 6.5 l b VOCs!yr (calc . ulate d 

### above); 

### C. 

## = 99"1. toluene in spent solvent 

### E. 

### Evoc X C / 100 16 .5 X 99 / 1

()() 16 .3 lb to l uene emittedlyr 

### 8.5 -10 ELIP Volume ll 

### VES015935Chapter 8 - Paint , ink, a nd Oth er Cooling Ma•ufucturing 0110/105 5.1.5 

### VOC E missions 

### from P arts 

### C leaning VOC emission factors for parts cleaning 

### in cold cleaners, open- t op vapor degreMcrs, or conveyorized degrcascrs are presented in AP-42. 

### Emiss io n factors for cold c l eaners and vapor degreMers are in units of ton s VOC / yr / unit or Jb 

### VOC/hrfftl . Emission factors for vapor and 

### nonboiling conveyorized degreasers are presented only in units of ton VOC/yr/ unit. lf 

### using emission factors based on the surface area of the exposed solvent, use 

### Equation 8 .5- 1 2.

where

A 

## = OH 

## = fvoc = 

### BFvoc x A 

### x OH (8.5-12) 

### VOC emiss ions from a cold cleaner or open- top 111tpor degreaser ( lbl yr) VOC emission factor for cold cleaners or open-top vapor dcgreJsers (lblhr / ft') 

### surface 

### area of so lvent exposed to the atmosphere (ftl) 

### hours per year that the col d c leaner or vapor degreaser i s in 

### operation (hr/yr). If

### using emission fac t ors based on the number of cleaning units, use Equation 8.5- 1 3.

where 

### Evoc = 

### EFvoc = 

### NU 

## = 2000 = 

### Evoc = 

### BFvoc x 

### NU x 

### 2000 (8.5 -1 3)

VOC emi ss ions from a cold cleaner, an open- top v apor degn:aser , or a conveyorized degreaser ( lblyr) VOC em iss ion fac tor for cold cleaners, open - to p vapor degre osers . or conveyorized dcgreasers (ton!yr / unit) number ofcleaning units in 

### use (units) 2,000 lb/ ton. Spocia ted VOC emissions from parts cleaning may be ca lcul a t ed using Equation 8 .5- 14: 

### E, • EFvoc x C,/100 (8.5- 14)

' Certain halogenated solvenu thot are widely used for solvent cleaning (e . g.. t,l , 1 -trichloro<thAoc) have b<>:n categorized as 'VOC..-xempt " by vari ous Stat< and federa l rcgulolioD$. H owever, the emiJsion faetoo reported in AP-42 nre still app licable for t hese sol vents (EPA. L**99~e).** 

### E

lll' Volume II 8.5 - 1 1 

## VES015936Chapter 8 - Poi11t, 11!1: ., and**Oth~r** Coariug Mtmu[U<"Iilring where 

### E" 

## = Evoc ; 

# c, emissions of VO C species x from parts cleaning (lb/ yr) 

### VOC emissions ca l cu luted usi n g Equation 8.5 - 11 or 8.5- 1 2 (lb/yr) 

### concentration o fVO C 

### species x in 

### cleaning solvent (mass%). E

xamples 8 .5 -6 and 

### 8.5 · 7 show the 

### application of Equations 

### 8.5 - 12, 8.5·13, and 

### 8.5-14. Example 8.5-6 01101 /0 J

'J"his e.ample shows how t04al and speciated VOC emissions from a cold cleaner may be colculated using Equations 8.5-12 and 8.5- 14 and an emission factor (from AP-42, Tab l e 4 .6-2) that 

### is boscd on the surface area of the exposed sol vent . First, total VOC emissions arc cnlculated mung Equation 

### 8.5 ·1 2. EFvoc ; 

### A**~** O H Evoc 0 . 0 8 

### lblbr ift' 5.25 

### 11' 3,000 

### hr /yr EFvoc x A x OH 0 .

08 " 5.25 " 3 , 000 1.260 I b VOCJyr Next. total VOC emissions are speciated using the concentr.ltion of VOC species x (mass%) and Equation 8.5 -1 4 . Evoc 1,260 lb VOCslyr (calcul.1led above) 

### C. 990 /o trichl oroethylene i n c l ean ing solvent 

### E., 

## = EFv oc x C/ 100 

## = 1,260 X 99 / 100 

## = I ,24 7 

### l b tricbloroethylenc/yr



### 8.5-12 

### Elll' Volume ll 

## VES015937Chapte r 8 - Palm , Ink , and Othf?r Coming Manufa c turing 0210 /IOJ 

### Example 8. 5 - 7 This example s hows h ow total VOC 

### emissions are calculated from several cold c l eaners us ing Equ ati on 8.5-13 

### and an emis sion factor from Tab le 4 - 6.2 

### ofAP - 42 . 

### EFvoc 

### 0.33 t onlyr / unit NU 5 

### units E

voc**~** 

### Ef voc x NU x 

### 2 , 000 

## = 0 . 33 X 

### 5 X 

### 2 , 000 

### 3, 300 l b VOCiyr 5 . 1.6 V O C Emi ssio n s from Eq ui p me nt Leaks Emiss i ons factors for equipment lea ks from pwnps , va lves, and connectors i n the coating manufacturing industry were developed from a bagging study conducted to develop equations con-el a tin g to tal organic carbon re a d ings as methane (obtained using Method 2 I ) to VOC emission rate. Using these equations and method 21 screeni ng data for facilities in tbe ind ustry, average uncontrolled VOC emission factors, on a per component basis, were developed and are p

resented in the following tab le (Shine, 2003 ): T abl e 8.5-2. E m iss i on Factors for Eq uipme nt Co mpon e n ts at C o atings Man u fact u ri n g Facilities Average Emiss ion Factor Componwt k glb rlc ornpon• nt lb/ hr / compon e nt Pumps 0.0042 1 9 0 . 00930 1 Valves 0.000412 0.000908 Connectors 0.000015 0 . 000033 Additi onal information regarding various techniques for estimating equ ipment leak emissions is provided in Chapter 4 of this volume. Exam pl e 8.5-8 shows appl i cation of the em ission fac tors in T ab le 8.5-2 to the equipmen t components for the Bright B l u e Paint Company described in Case Study 8.3-1 of thi s chapter.

EIIP Vo l ume II 8.5 -13 

### VES0!5938Chapr.,.8-**Pabt~** Int. and Orh.r Cooling Mun11[u<rwri11g 0110//0J Example 8**~8** The Brigbl B l ue Paint Com p any in Case Smdy 8.3·1 uses 1 5 valve s, 10 p umps, and 50 coooeclors in p aint maoulacturing operatioM . A ss umi n 11 1h ese equi pmenl componenl s a re i n serv i ce 8,760 br /yr , what are lhe e stima te d annu a l VO C emi ssions from equipment leaks? Evoc = ( 1 5 values x 0.0009081blhr / va l ve+ 10 pumps x 0 . 00930Jlblhr /pump + 50 co nnecl ors x 0 . 000033 Jb lhr/con neclo r) x 8, 760 hr fyr 949lblyr
5 .1.7 PMIPM 10 E m l.ssions fr o m a Pai n t o r In k Man ufactu ring FacJUty AP-42 also presents PM emission factors fro m pai nt and ink manufacturing, which are based on th e amowlt of pigment us ed by a fa c ilit y. T h e AP-4 2 factor fo r paint manu facturing is 20 lb PM/t on pigment. The AP-42 factor for pi gment mhdng at an i nk manufacturing facility is 2 l b P M / to n pigment. T o calculate 

### PM emiss i ons us i ng these em iss ion factors. usc Equation 8 . 5- 15 .

where E,.., 

# = EF,., EQ , 

## = total PM emissions ( lb l yr) 

### PM emission factor (lb PMiton pigment) total pigment (lon/}'1'). (8.5-15)



### PM ,0 can conserv atively be es tim ated by assuming that 

### all of the 

### PM emitted i s 

### PM 1 0 • Spec iated PM emissions 

### arc calcu l accd u si n g Equ a tion 8.5- 1 6:

where 

## E, = 

### EF .,.. = 

## Q, 

# c. = (8 . 5 - 16)

total emissions of PM species 

### x (lblyr) 

### PM emission factor from AP-42, Table 

### 6. 4- 1 or Table 6.7-1 (lb PM/ton pigment} amount of pigment conlaining species 

### x use d by the facility (tonlyr) Concentralion of 

### PM species x in pigment 

### x (mass%). 8.5 - 14 E UPVo1umell 

## VES015939Cloaptu 8 -Paint , Jnt, and Oth" C<Jaring Manu fi

wurlng 0 210/ /Q

j 

### Use of Equation 8.5 - 16 is demonstroted i n Example 8.5-9 . Example 8 5.9 This 

### example demonstn1tes how spe<:iateu PM emissions 

### from pi gment mixing at an in k manufacruring f acility may be ca l culated usiJtg tbe consumption-based PM emission factoo· from Table 

### 6 . 7 -1 ofAP -42 

### and Equation 

### 8.5-16 : El',,. llb 

### PM/ton pigment Q. 5 tons 

### ZnO/yr C,. 800A. Zn 

### in ZnO 

### E. El'rv. X Q. X C / 100 : 2x5 x 801!00 • 81b Zn!yr 

### 5 . 2 VO C a nd P M E mis s i o n C al c ul ati on s Us in g Mat e ri a l B al an c e The material bal ance method requires the totaling of all materials received at t h

e plant and tl ten s ubtracting out all of the known l osses or transfers of the material off-sit e (i nclud i ng finished product a nd waste material). TI1e 

### difference is assumed to h ave been emitted to the atmo sphere. 

### The quantity received and 

### the quantity lost or 

### used should be for the 

### same time period, typically January I to December 31 

### for the year ofthe inventory (NPCA, 1995). Use Equation 8.5-17 for calculating emissions using the material balance approach . 

### E

, 

### = Q,- Q,- Q," •**~** 

### • 

## O .u (8.5-17) 

### where 

### E, Q , ; 

## Q. Q

,.. = 

### Q

. Q ,. 

## = EllP 

### Volume IT emissions of VOC or 

### PM species x (lb/ yr) quantity ofVOC or 

### PM species x 

### that 

### is received as a 

### raw material (lb/yr) quantity of VOC or 

### PM species x that is 

### shipped out in the final product (Jb/ yr) 

### quantity ofVOC or 

### PM species 

### x that 

### is recovered by 

### all method s 

### (e.g., solvent recovery) (lb!yr) quantity ofVOC or 

### PM species 

### x that is 

### comained in 

### all waste generated during the evaluation period (e.g., wastewater, sludge , drum residue) (lb!yr) 

### quanti ty of VOC or 

### PM species x that 

### remains in 

### the raw material inventory (lb!)T). 

### 8.5-15 

## VES01 5940Chapr.r 8- Puim, InC, and Other C0<1ring Manllfo<turlng 01/()1/05 

### The use of Equation 8.5-17 is 

### demons1111tcd in Example 8.5-10. Exnmple 8.5 - 10 ·ntis example shows 

### how t ota l e O oylc nc glycol emissioots for a paint manufacruoing fac il ity may be cal cula ted using Equat io n 8.5-17. Ouw are us follows: • In a given year, a paint facility rece ive s 100, 000 lb ofethy l ene g l ycol (Q , ) . • Based 

### on tbe total amount ofproduct shipped 

### otT -site and 

### records ofproduCt 

### composi ti on, the facility 

### rstimates that th e amoWlt ofethylene glycol sbipped 

### out in 

### final product ( Q ,) 

### is 69,000 lb; • Based 

### on waste compos ition analyse s, the amount of 

### waste sent off-site , and 

### wasteWilter discharge rates, the facility es ti mates 

### th at the amount of

### ethylene glycol that was 

### found in 

### all wastes 

### generated during the year (Q.) is 5 , 000 

### l b; and • The amou nt ofethy l ene glyco l that was l bund t o be in the facility 's i nven t ory at t he end of the evaluation peoind (Q") is 15,000 lb. Emission ofed1ylene glycol 

### are ca l cu l atod 

### os follows: 

### E, Q, - Q, - 

### Q .,.- 

### Q.,**~** 100.000 - 69 , 000- 10 , 000- 5,000 - 15.000 I , 000 lb ethylene glyco Vyr 

### 5.3 Emission Calculatio n s U s ing Test Data**B~cause** 

### vent or stack testing is 

### rel a tively uncommon for paint and ink 

### manufacturing facil i ties . emissions tes t data for these pla . n

ts are typicaUy in the form of exposure monitoring results. Industrial hygiene data may be 

### used in conjunction wi th exhaust system tlow rates to calculate f ugitive emissio ns from 

### a room, noor , 

### or b uildi ng ( NP CA, 1995). Use Equation l!.5- 18 1br calculating these emissions.

wbc:re 

### E = X 

### FR X 

### 60 X 

### OH X 

# c, X 

### 0.0026 X 

### M, I >< 

### IW 

### E,. = 

### emissions of VOC or PM species x (lblyr) FR flow ra t e through e xhaust vent ilation sys tem (ft'lmin) (8 . 5-18)



### 8.5- 1 6 EllP Volume II 

## VES015941Chapter 8 - Paint . l n k

. and Other Coating Monufi · tcwring 0 110/ IYJS 

### 60 = 

### OH 

## = C

.:u = 

### 0.0026 

# M. = 1 x 

## to• 

## = 60 m inlhr hours per year t hat the exhaust sys te m i s o pera t ional (hr / yr) 

### c on cen tration ofVOC o r PM species x (ppmv or ftl!MMft') 

### mola r volume o f gas a t 6 8°F (mo le / it') molecular weight ofVOC or PM s pec ies x (lb/lb - mole) I " I 

# o• ft' IMMft3 • 

### Example 8.5-11 illustrates the use of Equation 8 .5-18. VO C losses from certain operations (e . g . , filling ofcontai n ers) may also be measured by petfonn ing a stud y usi n g a gravimet ric analysis s u ch as American Society For Testi ng and Materials (AS T M) Standard 

### 02369, Test Method for Vola tile Content ojCoati11gs. The operatio n u n

der evaluation could be si m ulated on a small scale , and VOC ana ly sis would be conduc ted on sampl es taken before and after the simu lated activity (EPA, 1992b) . Example 8.5- 11 

### This ex amp l e shows how E quati on S. S-1 8 is u s ed to 

### calculate f ugit i ve emiss i ons of xylenes from a building where several mixi ng vesse l s are located. The fo ll owing data are given: • The bui l ding exhaust 11ow rat e (F R ) i

s 20,000 ft 3 

### 1

min; • The exhaust s ys t em operat es for 7, 920 hr / y

r (OH) ; • Indus t rial hygiene data ind i cate that t he concentra tio n of m ixed xylenes in the b uilding (C, ) 

### i s 0. 1 ppmv; a nd • Th e mo l ecula r w e

ight of mixed xylenes ( M ,) 

### is I06 l b!lb-mo l e. Xyl enes emissions are calcul ated a s follows: 

### E, FR X 60 X OH X 

## c . X 

### 0.0026 X M, I X IO ' 2 Q . QO() X 60 X 

### 7.920 X 

### 0 .J X 

### 0 . 0026 X 

### 106 1 x 1o• 

### 26

2 lb x ylen e sl yr

EIIP Volume II 8 .5 - 17 

### VES015942Chapte r 8 - Ptlinr. Ink, and Other Coating Mamifitcrlfrlng 02 1 01/05

[This page imentionally**1~(1** blank.]

8 . 5 -18 

### EIIP Volume II 

## VES015943**Chopt~r** 8- Paint. J d, and Othrr Coating Monufa, · rurlng 01101/0J 

# 6.0 References Bureau oftbe Cens us. 1997 . 

### Th e C urr e

ntllldllstrial Reponfor Paint, Vamis h. and Lacq uer {MA28F)- 1996. Uni ted States D epartment of Commerce. Pages 2 and3. C r owl, Danie l and 

### Lou var, Joseph. 2002. C hemical Process Safery, Fundamental s W ith Applications. Second Editio n . Practice H a UPTR , Upper Saddle River , NJ 07458 . www.pbplr.com. ISBN: 0- 13 -018 1 76-5. 

### Dean. John, Editor . 1992. Lange' s H andbook of Chemistry. Founeenth Ed i t ion . McGraw-Hill. EIIP. 19% . 

### Preferred and Altemative M e th o d

s fo r Estimating Air Emissions from H a t-Mix Asphalt Plants, Final Report. 

### Prepared for t h

e Point Sources Comm i ttee , Emis sion In ventory Improvement Program under BPA Co n tmc t No. 68 - 02-0160 , Work Assignment No. 82. 

### U . S. Enviro n mental Protecti o n Ag ency, Office of Air Qua lity Planning and Standards. Researc h Triangle Park, Nm th Carolina. 

### EIIP. 2000 . 

### How to In c01porate The Effec t s of Air Po/111tion Control Device Efficiencies and Ma /fimc tions lmo Emission llll'ent ory Estimates. Chapter I 2 in 

### EIIP Volume 

# n. Paint Sources Preferred and Altemati••e M et

h

ods. U.S. Enviro nmental Protection A gen cy, Office of Air Qualiry P l anning and Stllndards. Research Triangle 

### Park, Nonh Carolina. (Er iP 

### Int erne t address http :// www.epa.govlttn/chief/eiip ) . EPA . 1987. 

### Estimating Releases und Waste T reum 1 e111 Efficie ncies for the Toxic Che m ical R elease inv e ntory Form . 

### U.S. Environmenta l Protection Agency, 

### Office of Pes ti ci d es and Toxic Substances . EPA-560/ 4 - 88-002 . Washington, D .C . EPA. 1991. 

### Contro l T ec/mologiesfor Ha za rdous Air Pollutants Handbook . U.S . E nvironmenta l Protection Agency, Air ond En e rgy Engi n eering Research Laboratory, EPA-625 /6-9 1 / 014. Researc h Triang l e Purk, North Carolina. E PA. l9 92a . 

### Control ofVOC Emi ssio n s from ink alld Paint Manufacturing Pro cesses . 

### U.S. Enviromnental P roteCtion Agency , Office of A ir Quality Planning and Standa rds, EPA-450/3-92-013 . Res earch Triangl e Park., North Carolina . EPA. 1992b. 

### Protocol for Detem•ining Emissions from Paint and Coating Mixing Processes. U.S. Environmen tal Protection Ab>ency, Office of Air Quality P lanning and Standards ,**R~arch** 

### Triangle Park, North Carolina . 

### EIIP Vo lume II 8.6- 1 

### VES015944Chapter 8- PuiiTI , Ink, and Other Coating Mamifu c- nm·ng 01101/05 

### EPA. 1 994a. Air Emissions Modelsfor Waste and Wastewater. U.S. Environmental Protection Agency, Office of Air 

### Quality Planning and Standards, EPA-453 / R-94 - 0803. Research Triang l e Park, North Caro lin a. EPA. 1994b. Quality Assurance Handbook for Air Pollution Measurements Systems: Volume III, Stationary Source Specific Methods. U.S. Environmenta l Protection Agency , Office of Research and Development, EPA-600/R-94 -038c . Was hi ngton, D.C. EPA. 1994c. Co!llrol of Volatile Organic Compound Emissionsfrom Bat ch ProcessesAlternate Control Techniques. U . S . Environme nta l Pr o te ction Agency, Office of Air Quality Planning and Standards, EPA-453 / R-93-0 17. Research Triangle Park, North Carolina. EPA. 1995a. Compilatimr of Air Polhtfgllt Emission Factm-s. Volume I: Stationa1y Point and Area Sources. Fifth Edition, AP - 42 . Section 

### 7.1 . Organic Liquid Storage Tanks. U.S. Environmental Protection Agency , Office o f Air Qua lity Planning an d Standards. Research Triangle Park, Nort h Carolin a. EPA. 1995b . Compilation of Air Pollutam Emission Factors. Volume 

### 1: Stationary Point and Area Sources, Fifth Edition, AP-42. Section 6.4. Paint and Varnish. U.S . Environmental Protection Agency, O ffice of Air Quality P lanning and Standar ds. Research Triangle Park, No rth Carolina . EPA. 1995c . Compilation o(Air Pollutant Emission Factors. Volume 

### 1: Stationary Poim and Area Sources , Fifth Edition, AP-42 . Section 5.2, Transpo rt ation and Marketing of Petroleum Liquids. 

### U.S . Environmental Prot ection Agency, Office ofAir Quality P l anning and Standards . Research Triangle Park, North Caroli n a. EPA. 1995d. Compilation of Air Pollutant Emi<simr Factors. Volume 1: 

### Stationmy Point and Area Sources , Fifth Edition, AP- 42 . Section 4. 7 , 

### Wast e Solvent Reclamation. U.S. Environmenta l Protection Agency, Office of Air Qua li ty Plan ni n g a n d Standards . Research Triangle Park, North Carolina. E

PA . 1995e. Compilation of Air Pollwam Emission Factors. Volume 

### 1: Stationary Point and Area Sources, Fifth Edition, AP-42. Section 4.6. Solvent Degreasing. U.S. Environmenta l Protection Agency , Office of Air Quality Planni ng and Standards . Research Triangle Par k , North Carolina. E

PA . 199 5f . Memorandum on AP-42 Emission Factors for t he Paint and Varnis h In d ustry fro m Dennis Beauregard, U.S. Environmental Prot ect ion Agency, Office of Air Quality Plann ing an d Standards, Researc h T r i angle Park, N orth Carol ina, to Robert J. 

### Nels on, National Paint a n d Coatings Asso c iation. Washington, D . C.



### 8.6-2 EIIP Vo lume II 

### VES015945Chapter 8 - Point, Ink , and Other Coating Monufac:tunirg 0110 1 /0

5 

### EPA. 1995g. 

### Protocol for Equipme/11 Leak Emission Estimates. U.S . Environmentlll Protection Agency, Office of Air Qu a lity Planning and Standards, EPA-453/R-95-017. Re sea rch Triangle Park, North Carolin a. EPA. 1995h. 

### Survey of Control Tec hn ologies for Low Concentration Organi c Vapor Gas Streams. U.S . Environmental Protect io n Agency , Office ofResearcb and 

### Development, EPA-456/R- 95 - 003. Research Triangle Park, North Carolina . (Internet address, hnp : l/ www.epa.gov / ttn/catc/dirl / low _ vo.pd.(l EPA. 1997a. Toxic Release Inventory System. EPA. 1997b. 

### Compilarion of Air Pol/ulan/ Emission Factors. Volume 1: Starionory Point and Area Sources, Fifth Edition , AP-42 . Section 7.1, Organic Liquid Stomge Tank s. U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards. Research Triangle Park, North Carolina. EPA. 1999 . 

### Factor Information and Rerrieva l (FIRE) Database System. Vers ion 6. 22. Updated annually. U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, Research Triangle Park, Nottb Caro li na . (Internet address, http: / /www .epa.gov/ttn/chief/fire.html) EPA . 2000. Source Classification Codes for Point and Area Sources. Updated April6 , 2000 . USEPA Technology Tmnsfer 

### Network. hup: l/ www.epa.gov/ ttn!chieflscccode s. html F is her , Perry W. , Steven A- 

### Frey , and Kaushik Deb . 1993. 

### Emission Estimation Methodologies

- Paittt Manufacturing Industry , Paper 93 - TP-57.07, Air and Waste Management Association , presented at the 86th Aonual Meeting a nd Exl>ibitioo, Denver, Colorado , June 13-18, 1993 . Hatfield. Allen. 

### Improved Algorilhumfor Estimating Process Emissions From Bat c h Heating, Environmental Progress . Vol. 1 7, No .3 , pp . 190-194. (FaU 1 998) Hatfield , Allen. 

### A Mode/for Estfmati11g Process Emissions from Purge Opet·ation s in Bar c

h and Cominuous Chemical Operations, Environmenta l Progress. March 2003. Mathiessen, R.C. 

### Estimating Chemical Exposure Levels in. 

### the Workplace, Chemical Engineering Progress. April 1986. 

### p. 30. 

### NAI'IM. 19%. 

### N ational Associatio n of Printing Ink M011ujacrurers Guid e to E.<timating VOC Emissio n s .from Prinling Ink Mamifa c lurin g. National Association of Printing Ink M

anufacturers, Inc. Hasbrouk Heights , New 

### Jersey. NPCA . 1995. 

### Emission Estimatinn Guidance Manual for the Paint and Cooting,t ln duvrry (Second Edition). National Paint and Coatings Association, Inc ., Washington, D. C. E UP 

### Vo lume U 

### 8.6-3 

## VES015946Chaptrr 8 - Pafnt , Ink , and Other Cooling Mnnufo<mrlng 01/01/05 

### Noyes, Robert , Editor. 1993. Poll11tio n Pr evention Tedrnology Handbook. 

### Noy es Publications, Park Ridge, New Jersey. 

### Shine, Brenda. Development 

### of Equipment 

### Leak Emissi on 

### FactOrs at Coatings Mnnu lllcturing Facilities. Memorandum to MO N Coati n gs Pruject Fiel in 

### E P

A Docket No . OAR-2003 - 0178. Docket Item No. IV-B - 03 . Apri130. 2003 . Watson, 

### Douglas . G r eenfield E nvironm e ntal , Inc. Letter toR. McDonald , EPA. 

### R esponse to 

### l'roposed Venting Emission Methodo logy . September 29, 2004.

8.6-4 

### 'BliP Volume ll 

## VES015947UN IT ED STATES ENVIRONM E N TA L PROTECTION AG E N CY RESE-AR C H T R I AN GLE PARK . NC 2 ?11 1 

# o

cr , 9 1996**'-~ OE**  Of 

### Mr . Robert 

### J . Nelson Director 4 1A OUA.LITY ' I..Ah.NtHG A ND $lAHOARDS 

### National Paint and C oatings Association 1500 Rhode Is l and Avenue, Northwest Washington , D . C . 20005-5597 Dear Mr . Ne l son: This is in response to our meetings on June 9 and August 29, 1 995 and your letter of June 14, 1995, regarding Section 6 . 4 of AP-42 for Paint and V arni sh Manufacturing . Based 

### upon information presented at the June 9 meeting by 

### Mr . Frederick Ullrich of Benjamin Moore and 

### Co . and 

### Mr . Robert R iple y of Guardsman Products, Inc . , NPCA believe s th e 30 lbs of volatile organic compound (VOC )/

ton ofcoat ing emission factor for paint manufacturing in Table 6.4-1 is inco rrect and shoul d be expressed in terms of solv ent used 

### to formulate coatings . As I discussed during our meeting on August . 29 , I 995 , 

### l hav e reviewed the backgroun d [jles for Section 6 . 4 t o docun1ent the derivation of the e mission factor in Table 6.4· I and the es t ima te of solvent lo sses in the t ext. The following summarizes t he results of my findings :

The 

### 30 lbs ofVOC/ton ofcoating emission factor in Table 6 . 4·1 ofAP-42 is discussed in Reference I to the Section. Pages 4-45 and 

### 4-46 of Reference I indicate that the factor is 

### based 

### upon material balance s and 

### represents " all :1tmospheric losses . " Allhough the em i ssion factor in Table 6.4-1 i s ident i fied a s " uncontrolled ", it apparently reflects tbe use of " good housekeeping " practices s u c h as k eeping lids clo sed during mixing. This is supported by Reference 2 to tbe 

### Sect ion which sta t e s o n Page 13 that "Alt h o u gh some plants use open vat mixing w ith certain sol v ents , the volatilil it y of most thinners require s that mixing be done in totall y e n c losed tanks 

### t o prevent appreciable lo sses o f these e xpensive products." Another estimate of VOC emissions from paint manufacturing is found in the text of Section 6 . 4 . The estimate i s from Reference 2 on Page 13 which state s that " In g eneral, the 

### lo s s o f solvents to atmo s phere !Torn such mixing amounts to no more than I or 2% ofthe solvent used ." 

### Thi s s tatement indicates that the I t o 2% lo ss es timate applie s only to m ixin g at paint man ufac turing and do es not i nclu de other operation s . The emis s ion es t ima t es used to d evel op th e emission factor in Tabl e 6.4 - 1 appear to be based upon forrnu l atton of"co n ventiona l" coatings that were p r evalent durin g the l ate 1950's and early 1960 ' s . At that time, coating d ens ities were typ i cal l y 10 to IS l b s/ gallon ( Refere n ce 2 , Page 4-47) . Assuming an average co ating density of 12.5 lbslgall on , a ton of coa t ings would yield 1 60 gallon s . A ss uming an average solve nt co ntent for • conventional " coatings of 5.5 

### lbs of VOC/gallon of coating (" Control of Volatile Organi c Compound Em i ssion s fTom Existing 

# -

V

ES 0l5948

### 2 Stationary Sources • Volume VI : Surfa ce Coating of Miscellaneous M etal Parts and Products," EPA-450·2-78-015, Page 1·10), 880 lbs o f !he 

### coatings wo u ld be solvent. The 

### 30 lbs of VOC/ton of coating emission fac tor would therefore 

### be equivalent to 

### a loss rate of 30 lbs 

## of VOC/880 lbs of VOC or 3 .4 % on the basis of solvent used. This seems to compare favorably with the 1 

### to 2% loss estimale in the tex1 

### which only accounts for losses 

### from mixing. In SUmm.81)', 

### it appears that 

### the 30 lb s of VOC/ton of coating emission fa ctor in Section 6.4 is expressed 

### as the author intended. It 

### was likely developed based 

### upon the form ul ation of co nven tio n al coatings and 

### represents us e of good housekeeping practices . 

### An alternative to using this factor for the formulation of waterborne or high soli ds coat ings would be use of t he equivalent solvent lo ss rate of3.4% for the overall operation. As 

### we discussed during o ur meeting on August29, 1995, I 

### have · enc losed the August 1992 redraft of the AP-42 section fo r paint and varnish manufacturing . At t hat time, we were not able to identify any 

### new emissions infom1at . ion to update the emission factors in 

### AP-42 . Although the namtive portion ofthe section was 

### updated and expanded, NPCA comment ed that additional efforts were n eeded to adequately address newer coating technologies . Any comments that NPCA and its members may be able to provide 

### reg a rding the technical adequacy of the inf ormation and spec ific 

### areas needing improvement would be appreciated . Finally, as w e discussed, the Point Sources Committee of the Emission Inventory Improvement Program (EilP) 

### is developing a document fo r esti mating emissions from paint manufacturing operations. I 

### will forward a copy of the 

### draft document for your review and comment 

### upon its availability . The EUP 

### guidance document will establish a 

### hierarchy of emission estimation techniques based 

### primarily upon the accuracy ofthe methods and will allow users to select a method 

### best suited to their needs . Please contact me (9 19) 541 -5512 with any questions or comments regarding this matter .

En closur e Sincerely ,
Dennis Beauregard E

nvironmental Engineer Em i s s ion Factor and Inventory Group



## VE S015949

# VES015950 . pdf

# I VOLUME II : CHAPTER 8 

# Preferred and Alternative Methods for Estimating Air Emissions from Paint and Ink Manufacturing Facilities

M a r c h 1 998

Prepared by: Eastern R esea r c h Group, Inc . Prepared for. Poi nt Sources Commlttee Emission I nventory**~rove ent**  Program



## VES015950

### DISCLAIMER This document was furnished 10 the Emission inventory Improvement Program and the U.S . Enviro nmental Prot ectio n Agency by 

### Eastern Research Group, Jnc ., Monisvi ll c . North Carolina. Thi s repon is 

### inten ded to be a final d ocument a n d has been review e\1 and approved for publication . The opinions , find i n

gs, n nd conclus i ons express e\1 represent a consensu s of the members of the Emission Inventory Improvement Program.

V(lfllmc II,**r~r ~.**  PalM -.1 IIlk M .Uu

Jf.acRI!iqJ.. noti ,( lfl**ta..r:~ 'Rtii~Mrdl**  (Woup. ((1(. Pnil 

### orr ..**~** fk)); :! UIO 

### .,,,..,m...**~~: .**  Nt1n& r __ , _**1j(,()** 

## VES015951ACKNOWLEDGEMENT This document was prepared by Eastern Research Group, Inc. for the Point Sources Co mmittee o f t he Emiss i o n Inventory Improvement Program an d for Dennis Beauregard ofrhe Emi ss ion Factor and I nventory Group, U.S . E nvir onmental Protect ion Agency. Member.; of the Point Sources Co m mittee contributing to th e preparation of this document are: Dennis Beauregard:**~Ch air.**  E m

ission Foe tor and l nvenl o 1

y Group , U.S. Environmenta l**Pr~cc ion**  A ge ncy Bill Gill, Co-Chair, Texas Natural Resource Conservati on Conunission**Den~><:** Als t on · Gui den. Gal son Consulting Bob BettertOn, South Carol i na Depanment of**~U~ t**  ond Environmental Control Paul Brochi. Tex.as Natural Resource: Conservat ion Conunh. s i o

u A l

ice Fredl und , Louisiana Del"'nment o f En , •iro nmcnlal Quality Gary lielm, Alr Quality Management , Inc . Martin Hochha us e r, Allegheny County Health Department Toch**Manga~.** Bay Area Air Quality Management Dis trict Ralph Patt c...on,**\\ r~S<X>** **nsin** Oe!"'nment of Naturnl Rtoouroc:s Jim Southerland, Nonh Carolina Oe!"'mnmr of Envirocwent and Natunl Resources Eillln T sabari . Omaba Air Quality C0111rol Divuion Bob W ooten. Nonh Carolina Depanment of Envil"'Mlent 8lld Natural Resources

EIIP Volume II 

### iii


### VES015952CHAPTER 8 • PAINT AND INK MANUFACTURING 3t.li98



### Th is page is inte ntionally le ft blank .

i v EIIP Volume II 

## VES015953

# CONTENTS Secti on Pa ge l 

### Introduc t ion 0 0 0 0 0 .. 0 0 0 0.. 0 0 00 

### 0 0 00 

### 0 00 

### 0 0 0 0 0 0 00 

### 0 0 0 00 

### 0 00 

### 0 0 0 0 0 00 

### 0 0 00 

### 0 0 0 80 1-1 2 

### Source Ca t egory Description 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0 0 .. 0 0 0 0 0 0 0 0 0 0. . 0 . . 0 0 0. 8.2-1 2.1 Process Descript ion . . .. 0. . . 0 0 . 0 0 0 0 0 0 0 • . 0 . 0 0 0 0 • 0 0 0 0 0 0 0 0 0 0 0 0 0. . 8.2 - 1 2 olol Preassembly and Prem ix 0 .. o o o 0 o o o 0 0 0 0 0 0 o o 0 0 0 0 0 0 0 . 0 . .... 0 802-2 201.2 P i gment Grinding or Milling ... . .. 0 • .. 0 0. . • . 0 0 0 0 0 0 0 0 0 . 0 • 0 • 8 02-2 20 1 03 Product Finishing 0 0 0 0 0 0 0 0 0 0 0 0 0 0 • 0 ... 0 0 ••• 0 0 0 0 0 , 0 0 0 0.•. 0 8 0 2- 3 2.1.4 Product Filling .. 0 0 0 . 0 0 . 0 . 0. .. .. . .. . 0 .. .. 0 . 0 0 0 . 0 . . . . • . . 802-3 2o2 Emission Sources 0 o o o o o o o o 0 0 0 . . 0 0 • o • •• 0 0 0 0 • •• o 0 0 0 • 0 0 • . 0 . 0 • .. 0 802 -4 2020 1 Process Operations 0 0 0 0 o 0 00 

### 0 •.. 0 0 •. 0 .• 0 . 0 0 . 0 0 0 0 00 

### 0 0 0 0 0 0 . 802-4 2o2.2 Miscellaneous Openuions 0 0 0 0 0 0 0 . 0 0 ...• 0 . 0 0 0 0 0 0 0 . 0 0 0 0 0 0. . 8.2 - 5 2.2.3 Material Storage 0 0 0 0 0 0 0 0 . . . .. • ....... . • ... . 0 0 0 . 0 0 . . • . . . 8 . 2-6 202.4 Equipment Leaks 0 .. 0 0 . 0 0 0 . 0 0 •• 0 0 0 0 0 0 0

• 0 0 0 0 0 0 0 . 0 0 0 • 0 0 0 0 8 o 2 -6 2o2 o 5 Spills 0.. o 0 . o o .. o . 0 0 0 . . 0 o . o o ... 0 ... 0 . 0 0 0 0 0 0 0 0 . 0 .. . • . 0 0 8 . 2-7 2 03 P rocess 

### Design a nd O perat ing Factors Influencing Em i ssio ns 0 0 . 0 0 0 0 0 . . . 8.2-7 2030 1 VOC 

### Control System s 0 0 0 0 0 .. .. • . . . 0 0 • ... ....• 0 0 . 0 . . . . • . . 8 . 2- 7 2.3 o2 P MJPM 10 

### Control System s o .• 0 0 ..• 0 . ... 0 . 0 0 0 0 0 0 0. 0 . • . . . . . 802 - 8 20303 Equipment or Pro cess M odifications ... .• 0 . • 0 . 0 . 0 0 0 • 0 0 0 0 0 0 0 0 8.2-8 

### 3 Overvi ew of Ava ilable Methods 0 0 0 0 0 00 

### 0. ...... 00 • ••••••• • 

### 0 0 0 0 0 0 0 0 00.. • 

### 8 .3 - 1 30 1 Emission Estimation Methodolog ies o 0 o o 0 0 0 0 0 0 0 0 . 0 0 0 0 0 0

• • 0 .. .. • . . 0 8.3 -1 3o l.l Emiss io n Facrors .. . 0 0 . 0 0 0 0 0 0 . 0 . 0 .... 0 • 0 0 .. 0 0 ••• 0 0 0 0 0 0 0 0 803- 1 3. 1 02 Source-specific Mo de l s 0 o 0 o o 0 o o 0 . 0 •. 0 0 . • 0 0 0 . 0 0

• •• . .. . • 0 0 0 803 -2 3. 10 3 Material (Mass) Balnncc Ca lculations •. . . . 0 . 0 .. 0. 0 •• 0 0 . 0. 0 . . 8 03-2 3. 1 0 4 Test Data . 0 0 0 0 0 0 . 0 0 0 0 0 0 0 0 0 0 0 . 0 . 0 . 0 0 . 0 0 0 . 0 0 .. 0. 0 0 0

0 . . . 8.3- 2 3.2 Comparison of Availab l e Em i ssion Estit n atio n Methodologies 0 0 0 • 0 • 0 . . . 803 -3 3 . 2 0 1 Emission Factors 0 0 •• 0 0 0 0 0.. . . . 0 .. . ...... 0 0 •. 0.. . . . . . . . . 8.3-3 3.2o2 Emission Models 0 . 0 0 .. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 • 0 8.3 -3 3o2o3 Material Ba lance Calculations o o . 0 .. 0 0 .... 0 0 0 0 0 0 0 0.. . 0 ... .. 8.3 - 10 3.204 Test Data . ... .. . . 0 .. o 0. 0 . . 0 .... 0 0 0 .. 0 .. 0 00. 

### 0.. 0 0 .. 0 0 . 8 03- 10

EIIP Volu""' II v 

## VESOI5954

# CONTENTS {CONTINUED) Section Page 8.4 -1 4 Preferred Methods for Estimati ng E mi ssions 4 . 1 Emiss i on Ca l cu lati ons Usi ng Source-s pecific E mission M odelsfEquat i ons . . 8.4-1 4. 1.1 Emi ssio n M ode l for Material Lo adi ng . . . . . . . . . . . . . . . . . . . . . . . 8.4-4 4 .1 .2 Heat-up Losses ............ . ... ....... ....... . ......... 8.4- 1 2 4. 1.3 E m ission Model for Spill s ...... ..... ... .. .......... .. .. .. 8.4- 18 4. 1.4 Emi ss i ons Model for Surface Evaporation . . .. .. .... . ........ . 8.4-21 4. 1. 5 Emission Model for Liquid Mat erial Storage . ................. 8 . 4-23 4.1.6 Emission Model for Wastewater Treannent ... . .............. 8.4-23 4.2 Emission Calculations Us ing Emission Factors ............ ......... . 8.4 - 24 4.2 . I T otal and Spec i oted VOC Emissions from Solvent Reclamation . ... ................ . ..... . ..... .. • •. ..... 8 .4- 24 4.2 . 2 VOC Emission s !Tom P arts C leaning . . . .. . ..... ....... . ... . . 8 .4- 27 4. 2.3 VOC E mi ssio ns from Equipment Leaks .... ................. 8.4-29 4 . 2 .4 PMIP.M 10 Emissio ns fi·om a P a int o r Ink Manufdc turin g Fa c ility . .. 8.4 -29 

### 5 Altemative Methods for E stimating E missions . . . . . . . . . . . . • . . . . . . . . . . . . . . . 8.5-1 5 .1 Emiss i on Calcul a ti ons Usi ng Emissio n Fac tors . . . . . . . . . . . . . . . . . . . . . 8.5 - 1 5.LI T otal VOC Emissions from P aint Manufactnring Faci li ti es. .... . . 8.5 -1 5.1.2 VOC Emissions from Paint Mixing Operations . . . . . . . . . . . . . . . 8.5 - 6 5 . 1.3 VOC Emissions from Ink Manufactnring Facilities . . . . . . . . . . . . 8.5 - 8 5.2 Emissions from M iscellaneous Process Equipment with Exhaust Systems . 8 . 5 - 10 5.3 VOC and PM Emission Calculations Using Material Balance .......... 8.5 - 11 5.4 Emission C<l l culati ons Using Tes t Data .... . ...... .. ..... .. . . ..... 8 .5 -12 6 Quality Ass urdOc e/Qua lity Co ntro l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.6-1



### vi 6.1 General Factor s Invo lved in E mi ss ion Estima tion Techniqu es . . . . . . . . . . 8.6-1 6.1.1 Emission**cto s**  ... . . ..... . .. . ..... . . .. . . .. . ........ .. 8.6 -l 6.1.2 Emissio n M odels . . . . . . . • • • . . . . . . . . . . . . . . . . . . . . • . . . . . . . 8.6-3 6. 1.3 M a terial Balance. . . . . . . . . . . . . . .. .. . . . . .. . . . . . . . . . . . . . . . 8.6 - 3 6. 1. 4 T esting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . 8.6 -3

EIIP Volumo II 

## VES015955

# CONTENTS {CONTINUED) Section Page 6.2 Data Attribute Rating System (OARS) Scores. . . . . . . . . . . . . . . . . . . . . . 8.6-4 7 Data Coding Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • • . . . . . . . . . . . . 8.7- 1 7. 1 Souree Classification Codes .............................. . . ... . !!.7-1 7 .1 .1 Paint and Ink Manufacturing Emiss ions ..... ..• •. .... . • .... . 8.7 -1 7.1.2 Cold Solvent C leaning 

### and Degreasing. . . . . . . . • . . . . . . . . . . . . . 8.7-1 7. 1.3 Solvent Reclamation ... .... ...... ...... ... .. ...... . ..... !!.7-1 7. 1.4 Material Storoge ................. ..... ... ......... ..... 8.7 - 1 7.2 AIRS Control Device Codes . . . .. . .. . . .. .. .. .. .. • . .. . . . . . . .. . . . 8.7 -2 8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . • . . . . . . 8.8 - 1 Appendix A: Example Data Collection Fonns aod Instructions

E

IIP Volumo II 

## VES015956

# FIGURES AND TABLES Figure Page 8.6-1 E x a mp l e Emissio n Inventory Checklist for Paint and I nk Manufacturing Facilities 8.6-2 Ta b les P age 8.2 - 1 Typical Paint and Ink Man u facturi n g P l ant Control Techniques 8 .2 -7 8.3 - 1 SIIDll11ary of Pref erred and Al t ernative Emissio n Estimation Methods for Pai nt a n d Ink Manufacruring Opera t ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.3-4 8.3 - 2 

### Case Study 8.3-1: The Bright B l ue P aint Company Emissions Surrunary . ...... 8.3-6 8.3 - 3 Case Study 8.3- 2 : The Hot Pink Pa i nt Company E missions Summary . . . . . . . . . 8.3-9 R.4 - l L ist of Variables and Symbol s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.4-2 8.5- 1 L ist of Variables and Symbols . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . . 8.5- 2 8.6- 1 

### OARS Scores: AP - 42 Emission Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 .6-5 8.6 -2 O ARS Scores: Emission Mode l s 8 . 6-6 

### 8 . 6-3 OARS Scores: Material Balance 8.6 -7 8.6-4 

### OARS Scores: Testing Da ta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.6 - 8 8.7 - 1 Source Classification Codes for Paint and 

### Ink Manufacruring Operatio n s (SIC Code 2851) .. . ............ . ................. ... .............. 8.7-3 8 . 7-2 AIRS Control Device Co d es . ... .•. .. . . •. ..... •. . . . . . .• .. ...... . .. . .. 8.7- 21



### viii EII P Volume II 

## VES015957

# 1 INTRODUCTION The purposes of the preferred methods guidelines are to describe emission estimation techniques for point sources in a clear and unambiguo us mallller and to provide concise example calcul ations to aid in the preparation of emission inventories. While emissions estimates are not provided, the information presented in this document may be used to select an emission estimation technique best suited to a particular app lication. This chapter describes the procedures and reconunended approaches for estimating emissions from pa i nt and ink manufacturing operations and is intended to assist industry as well as regulatory agency personnel. Thus, some partS of the document may be more relevant to one group than to the other. Section 2 of this chapter conta i ns a general description of the paint and i nk m anufacturing source category, common emission sources, and an overview of available control technologies. Sect i on 3 of this chapter provides an overview of avai lable emission estimation methods. It should be noted that the use of site-specific emiss ions data is always preferred over the use of default values developed through use of industry-averaged data . However, depending upon available resources, obtaining site-sp«ific data may not be cost effective. Section 4 presents the preferred methods for estimating emissions from paint and ink manufacturing operations , whil e Section 

### 5 presents the alternative emission estimation techniques. Quality assurance (QA) and quality contro l (QC) procedures are described in Section 6. Coding procedures used for data i nput an d storage are discussed in Section 7. Some states use their own unique identification codes, so individual state agencies should be contacted to determine the appropriate coding scheme to use. References are cited in Section 8. Appendix A provides example data collection fon n s to assist in information gathering prior to emissions calcu l ations .

EIIP Volume II 8.1 - 1


### VES015958CHAPTER 8 • PAIN T AND INK MANU F

A C TURING 313198

This page is i ntentionall y left blank.



### 8.1 - 2 EI/P Volume II 

## VE S015959

# 2 SOURCE CATEGORY DESCRIPTION 2 . 1 PROCESS DESCRIPTION This section provides a brief overview of paint and ink manufucturing operations. The re.ader is referred to 

### Control of VOC Emissions from Ink and Paint Manufacturing Processes, April 1992, for more detail (EPA, 1992a). Paint 

### and ink are suspensions of finely separated pigment particles in a li quid that when spread over a surfuce in a thin layer 

### will fonn a solid, cohesive , and adherent film. Types of paints that are current ly manufactured include architectural coatings, product finishes (e.g. , finishes for automobiles, machinery , m etal and wood furniture, and appliances) , and special -purpose coating s (e . g ., industrial new construction and main tenance pa in ts , traffic marking paints, and marine paints) (EPA, 1992a). More than 70 percent of architec tu . ral coatings are water-based. However, sol vent-based paint is still predominantly used for product finishes and special-purpose coating s (Noyes, 1993). 

### Inks that are currently manufactured include l etterpress , lithographic and offset, gravure , and flexographic inks (EPA, 1992a). Letterpress and lithographic inks are rypicall)' cl assified as paste inks. Gravure and flexogmpbic inks are typically water- or sol vent-based and are classified as liquid inks (NAPIM , 1996). Speci alty ink products inc l ude textile and silk screen ink, invisible inks, powder 

### inks , carbon paper, typewr iter, and duplicating i nks (EPA, 1992a). Paint and ink rnanufucturing can be classified as a batch process a nd generally involves the blending/mixing of resiJ1s, pigmen ts, solvent s, and addi tives . Traditional pa i nt and ink manufacturing cons i sts of four major steps: • Preassembly and prem i x; Pigment grinding/milling/dispersing; Product fmish i ng/blending; and Product filling/pac kaging (Fisher et al., 1993) . These steps are described in more detail in the s ections below.

EIIP Volume II 8.2- 1 

## VES015960CHAPTER 8- PAINT AND INK MANUFACTURING 

### 2 .1 . 1 PREA SS EMBL Y AN D PR E MI X 

### In the preassembly and premix step, liquid row materials are assembled and then mixed in containers to form a viscou s material to 

### which pigments are added (EPA, 1992a). For so lvent-based paints, the raw ingredients include re1;ins, organic solvents, plasticizers, dry pigment, and pigment extenders. Raw materials used 

### in the preassembly and p remix step for water-based paints include water, ammonia, dispersant, pigmen t, and pigment ex t endet 'S (Noyes, 1993). Raw materials for i n

k manufacturing include pigments, oils, resins, so l vents, and driers (EPA, 1992a). The premix stage results in the fonnntion of an imcnnediate product that is referred to as the base or mill base (EPA. 1992a). The type 

### of equipment used 

### in the premix 

### Step depends on the batch size and the type of paint and ink 

### being produced. 

### Dnnns equipped with a portable mixer may be used for drum-sized batches. These mixers nonnally have an impeller with three or four blades. Other materials made 

### in ponab le mix 

### tanks may be blended using larger, permanent**high~o;peed** 

### dispersers or v1oriable-speed mixers fitted with paddle, propeller, turbine, or dise-cype agitators (EPA. 1992a). Paint 1u1d 

### ink manufuc turing facilities may use typical grinding equipm en t to accomplish the premix operations ( EPA , 1992a ) . This approach, common with water-based paints and inks, eliminates the need to transfer t h e mate ri a l to anoU1er type of equipment for the grinding/milling step d escribed below. 

### 2 . 1.2 P I GM E NT G RI ND I N G OR M ILLI N G 

### Pigment grinding or milling 

### entails the incorporation of the pigment into the paint 

### and 

### ink vehicle to 

### yield a fine particle dispersion . The three Stages of this 

### proce.o;s include welling, grinding, and 

### dispersion, which may overlap in any grinding operation. The welling agent, oonnally a surfactant, wets the pigment particles by displacing air , 

### moisture, and gases that are adsorbed on the surface of the pigment panicles. Grinding is the mechanical breakup and separation of pigment clusters into iso l ated particles and may be facilitated by the use of grinding media su ch as pebbles, ball.s, or beads. Finally, dispersion is the movement of welled panicles i nto the body of t he liqu id vehi c l e to produce a particle suspension. (EI'A , 1992a). The re is a wide array of m i lling equipment TI1e type of equ ipment used depend s o o the types of pigments bei ng handled (Noyes. 199 3). More com m only used equipment includ e the following: roller 

### mills , ball and pebble mills, allritors, sand mills, bead and shot miUs, high-speed stone and colloid mills. high-speed dispersers, high-speed impingement mills, nnd horizo ntal medi a m ills (EPA, 1 992a). However, it should be noted that roller a n d ball mi ll s are somewha t outda ted methods in cu!TCnt pigment base manufacturing technol ogy . Additionally , these types of equipment are usually associated with elevated levels of volatile organic compound (VOC) emissions due lo their more open design. Roller m i lls may have from one to five rolls that grind pigmeots into vehicles. Most paint and ink facilities that use rollennills operate with conventional three-roll mill s. Roller mills are 8 . 2 -2 EIIP Volume II 

## VES015961313198 CHAPTER 8 • PAI/IfT AND INK MANUFACTURING labor intellllive, requiring highly sk illed operators. Their lack of speed and high opera ting cost make them unsuitable for larg e-vo l ume production. The use of roller mills is confmed to the manufacture of very hi gh quality paint and i nks a n d viscous pigmented product s thai require fine d is persion and clean color (EPA, 

### 1 992a). H igh-speed dispersers are 

### the**mo~t** universally used method of dispersion in the paint and ink indusb)'. Some paint an d ink blends are manufactured ent i rely in one piece of equipment using high-speed, disk-type impellers. Because no grinding media are present in the mixing vat, pigment disperses on itself and against the surfaces of the rotor. While high -s peed disk dispersion may work well for some products such as undercoats and primers, i t may not 

### be appropriate for high-quality paints and inks . It can, however, be used for prem ix operations of high-quality paints and inks,**thtL~** reducing the number of passes in a media mill or reducing the amount of time spen t in a ball mill (EPA, 

### 1992a ) . 2. 1 .3 P RODUCT F INISHING Final product specifica tions for col or, viscosity, and other coating characterist ic s are achieved in the product finishing step. This process generally consists of thinning, tinti n g, a nd blending. Most of the solvents, tints, and shades arc added during this operation (Fisher et ul., 

### 1993). Product finishing activities for solvenl-based paints and i nks involve adding variou s combinat i ons of pigments, organic solvents, and res in s. For water - based paints and inks , u preservative, an antifoami ng agent , a polyvinyl acet ate em ul sion, and water arc a dded at this step of the manufacturing process (Noyes, 

### 1 993). Blending is the process of mixing the added ingredients to meet product speeificatio!lll. Blending may consist of additional milling in a ball mill or 

### added mixing and dispersing in a ponable mix tank/high-speed disperser setup (EPA, 1992a). 2. 1 . 4 P RODUCT F ILLI N G The fina l step in the paint and ink manufacturing process is the product filling operat ion. During the filling step, filtration is performed to remove impurities and to catch sma ll particles of grinding media (Fis her et al., 

### 1993) . Paints and inks may be filtered in a variety of ways and the end use of the product detenn i n es !he type of filtration required. Some products require on.ly a clort1 bag filter ; other products require filtering equipment such as stra iners or sieves (Fisher et al. , 

### 1993). Once the material has bee n fi l ter ed, it can 

### be transferred into pa ils, drums, totes , lank wagons, or other containers for shipment. F i lling may be accomplished either manually or mechanically depending on 

### the number and size of the containers to 

### be filled (EPA, 

### 1992a ).

EIIP Volume II 8.2-3 

## VES 015962CHAPT ER 8 • PAINT AND IN K MANUFACTURING 

## 2.2 EMISSION SOURCE S Several air emission sources have bee n ide ntified for paint and ink manuf acturing operations; t hey are as follows: Process operations ; Miscellaneous operations; 

### Material storage ; • Equipment leaks; and Spills. Eac h of the a bove emissioo sourc es is d esc n'bed in mon: detail in 

### the followin g sec ti ons. 2 .2 . 1 P ROCESS OPERAnO N S Pro cess operations cover emiss i o n s fi'Om mix.ing , grinding , blending, a nd filling activities. Em issions fi-om these opera tio n s can generally be classit l ed i n one of the following four c ategori es. 

### Ma te ri al Loading Em issions VOC emissions may occur during material loading of mixing and grinding equ ipment due to displacement of organic vapors. VOCs may be emitted from a mixing tanl.: when 

### the device is uncoven:d o r when a lid is open . For cenain 

### grinding equi pment, VOCs may 

### be released fro m the chute thro ugh wbicb ingiedient s are added. Paniculate matter ( PM ) and PM l ess than or equ al to 10 lilll in diameter (PM 10 ) emiss i ons may also occur during !he material l oading process from handling of p igments and o tl1 er so li ds. VOC aod PM em i ssions duri ng material l oa ding emissions may occur as point sourc e or fugit ive , depending on whether a PM emissions collection system is in place . 

### Heat-up Losses He a t-up lo s ses occur during operation of higb-speed dispersers, ball and pebble m ills , a nd similar 

### types of dispersing equipment . Owing tb e grinding/dispersing pro cess , !he re is a ri se in temperature as some of th e kinetic e nergy o f mi xing is converted to th erma l energy. 

# n us rise in temperature i s controlled through the use of cold water jackets . As the VOCs i n the mixers beat 

### up, !he vapor in !he headspace expands , forcing emiss io n s from the equipment . Heat -up losses are classified as fugitive (Fisher et 

### a!. , 1 993}. 

### 8.2-4 EIIP Volume II 

### VES0159633/3198 C HAPTER 8 - PAINT AND INK MANUFACTURING 

### Surface Evapor ati on Smface evaporation may occur during mixing, dispersing, and blendin g operations if the vess el co ntents are exposed to the atmosphere. For certain types of mixing and gri nding equipment, VOCs may be em i tted through agitator shaft openings or a ro und the edges of a vessel l id. VOC em issions from older vertical media miUs**{i ~**  saud mills , bead mills, and s h ot mills) may occur fTom th e exposed filtering screen. Surface evaporation emissions are generally fugitive in nature (EPA, 1992a). 

### Fill ing Losses Emissions during product filling occur during transfer and free-fall into the receiving container. Re sultant losses duri ng the filling operations are classified as fugitive. 2 . 2.2 MISCELLANEOUS OPERA TIO NS In addi tion to typical process operations associated with pa i nt and ink manufacturi n g, miscellaneous operations can generate emis sio ns (primarily in the form of VOCs). These o pe rations are discussed below: 

### Solve n t Reclamation Solvent reclamation refers to the purification ofdhty or spen t solvent through use of a distillation device. VOC em i ssions occur from loading solvent into the distillation equipment, operation of the distillation equipment, and spillage. Emi s sions fr om load ing and spilli ng are classified as fugitive , while emissions from operation of the equipment are generally discharged through a condenser vent and are thus classified as point source. 

### Cleaning C le aning is an important ancillary part of the pa i nt and ink manufacturing process. Process equipment may be cleaned w i th solvent as often as after each batch . VOC emissions resu lt from charging the mixer or disperser with solvent and can be characterized as fugitive. In addition to this type of clean i ng, small items used in tbe paint an d ink manufitcturing process may be cleaned by washing with solvents in a cold cleaner or open-top vapor degreaser (F isher et al. , 1993). Of the two technologies, the use of a cold cleaner is more common. V OC emissions !Tom this type of cleaning are classified as fugitive. 

### Wastewater Treatment A pa int and ink manufacturing faci l ity may us e a wastewater treatment system to treat contamina ted water generated during the 

### paint and ink manufac lll ring process (e.g., water that has been use d to clean equipment used i n the production of water-based paint and hlk). W as tewater treatment systems generally consist of a series of surf ace impoundments that are used for equalization , neutralization, aeration, and clarification of the waste stream. Fug i ti ve IE

liP Volume II 

### 8.2 - 5 

## VES0159 64CHAPTER 8 · PAINT AND INK MANUF A C TUR ING 313198 VOC emissions may occur from each type of basin. Procedures used to est i mate e missions from wastewater treatment fac i l i ties are d escribed in d et ail i n Volume 

### II, Chapter 

### 5 , Preferred and Alternative Methods 

## for Estimating Air Emissions from Wastewater Collection and Treatment. 

### 2 . 2 . 3 M ATER I AL 

### STORAGE Various types and sizes of s torage tanks are used to store solvents and r esins used i n the paint and ink manufacturing process. Most of these tanks have a fixed-roof desib'll (Fisher et at. , 1993). T h e two significant types o f emissions from fixed-roof 

### tanks are breathin g and working losses. Brea thing loss is the expulsio n of vapor from a tank through vapor expansion and contraction that result from c h anges in ambien t temperature and barometr i c pressure. This loss occurs with out any liquid level change i n the t ank (EPA , 1 995a). T he combined loss from filling and emptying tanks is called working lo ss . Evaporation during filling operations results fr om an increase in the liq uid level in the tank . As the liquid l evel increases, t11e pressure ins i de the 

### tank exceeds the relief pressure and vapors are expelled from the tank. Evaporative em i ssions during e mptying occur when 

### air drawn into the tank during l iquid removal becomes saturated w i th organic vapor and expan ds, expelling vapor through the vapor relief valve (EPA, 1995a). Emissions from tanks 

### are characterized a s 

### a point sou rce because VOCs are released through a ven t. 

### 2 . 2.4 E Q U I PMENT L E AKS In order t o transport stored materials (i.e. , orga nic solvents and res i ns) from s torage t anks to the p aint and ink manufacturi ng operation, a network of pipes , pumps, va l ves, and flanges is employed. As liquid material is p umped from the storage tanks to the particular process are a, the pipes and s upporting hardware (process line compo nents) m ay deve l op leaks over time. When l eaks occur, volati l e components i n the transported material 

### are released to the atmosphere. Thi s generally occurs from the following process li ne components: • Pump seals ; 

### • V alves; Compre s sor seals; • Safety reli ef valves; Flanges;

8.2-6 EIIP Volume II 

## VES015965313198 CHAP71ER 8 • PAINT AN D INK MANUFACTURING 

### • Ope n-ended lines; and 

### Sampling connect i ons (Fisher et 

### a l. , 1993). E

m iss i ons from equi pment lea ks can be characterized 

### as fugitive and are described in d eta il i n Vol ume 

### II, Chapter 

### 4, P referred and Alternazive Methods for ES1imating Fugitive Emissions from Equipment Leaks . 2.2.5 S P IU S 

### So l vents, resins , or product may be acc i de n tally spilled during manufacturing or cleani ng activities . Materi als that are spilled on t o the ground may s pread over a n area, vaporize , and t h

us result in an a ir emission (EPA, 1 98 7 ). Such an e miss ion wo uld be 

### characterized as fugitive. 

## 2.3 PROCESS DESIGN AND OPERATING fACTORS INFLUENCING EMISSIONS VOC and PM emi ssions from paint and ink manufacturing m ay be reduced through use of add-on cont rol systems or through equipment and process modificatio n s. Co nt rol dev i ces and te chni ques connuonly us ed at 

### pain t a nd ink 

### manu facturing f&cilities are presented in Ta ble 

### 8.2 - 1. TABLE 8 . 2-1 TYP I CAL PAINT AND INK M A NUFACTURING PLAN T CONTROL TE C HNIQU ES' 

### Emissio n Source 

### PoUutant ro n tro l**T~hnlque** !r ypical 

### Efficiency (%) 

### Material L oading Operat ions PM and PM 1 

### Fabr i c F ilter 95 . 99 

### Mixing Operations VOCs Tank 

### Lid 4 0 . 

### 96 • Source: EPA, 1992a. 2 . 3.1 VOC CONTROL SYSTEMS 

### A VOC control system consists of a cap ture devi ce and a removal device. The ca pture device (such 

### as a h ood or enclos u re) captures the VOC-laden air from the emissio n area and d ucts the emissio n stream to removal equ ipme nt such as a recovery device (e.g. , an adsorber) or a combustion d e vice (e . g., an incinerator) th a t remov es the VOCs from the air . The overall efficiency of a control system is calcul a ted by multiplying the capture system efficiency by tl1e removal d evice efficiency (EPA, 1 99 2a).

EIIP Volume II 

### 8 .2- 7 

## VES015966CHAPTER 8 ·P AINT AND INK MANUFACTURING 3/3198 Removal equipment available for treating VOC-co ntaining air streams includes recovery devices (i.e., carbon adsorption, absorption, and condensation) and combw.1ion devices(i.e . , therma l i n cinerators, catalytic i n cinerators, and i ndustrial boilers and process heaters). Con t rol efficiencies for thi s eq u i

p ment can range fro m 50 to 

### 99 percent. Carbon adsorbers, absorbers (scrubbers), condensers, and cata lytic incinerators are generally not appropriate for paint and ink ma nufacturing facili ties becaus e these devices are no t designed to treat low VOC i nlet concentrations that are typical for the paint and i nk industry. In addi t ion, the wide mixture of organics that may be em i tted at a paint and 

### ink facility 

### will tend to reduce the efficiency of these types of control devices. Industrial and process heate rs are capable of effect ively treating the types and levels of VOCs generated by the paint and ink i ndustry but are found in few, if any , paint and ink manufacturing £,cilities (EPA, 

### 1992a). Tbennal incineration is a n applicable control technique for the paint and ink industry but is used b y a limited number of facilities. Tbennal incinerators pass the em i ssion stream through a combustion chamber where tbe VOC .s are burned at temperatures ranging from 

### 700 to 

### 1,300' C . VOC removal efficiencies of 98 percent or greater may be achieved depending on the design of the equipment The majority of paint and ink facilities u se equipment and process modifications to reduce VOC emiss i ons . These are d iscussed in more detail later in Section 2 .3.3. 

### 2 . 3.2 PM / PM 10 CONT R O L S YS T E M S PM/PM 10 control systems for the paint and ink industry consist of a caprure device paired with a conttol device 

### that is typically a fabric filter (baghouse). These systems are typically empl oyed to red uce PM emissions from charging pigments and other solids into mixing and grinding devices . With fabric filter systems, particles are ca ught on the surface of the bags while the cleaned gaseous stteam passes tlrrough. To minimize pressure drop, the bags must be cleaned periodically as tlte dust layer builds up (EIIP, 

### 1996). The captured dust may be recycled or sent for off-site disposal or treatment. Fabric 

### filters are least efficient with particles 0.1 to 0.3 , m in diameter and with emission streams of high moisture content. When operated under optimum conditions, they can achiev e control efficiencies of up to 99 + percent (EPA, 

### 199 1 ). However, typical control efficiencies range from 95 to 99 percent . 

### 2. 3 . 3 EQUIPMENT OR PRO C E SS M O DIFICAT I O N S Mos t paint and ink manufacturing fucilities reduce VOC emissions through equipment or process modifications. Some of these techniques will also reduce PM emissions. Modifications include those discussed bel ow.

8.2-8 cliP Volume II 

## VES015967313198 CHAPTER 8 • PAINT AND INK MANUFACTURING Tank Lids Tank lids are the most common equipment modification used during paint and ink manufacturing activities to control VOC emissions. Lids reduce the amount of VOCs emitted during mix ing operatio n s and range in control e fficien c y from 40 to 96 percent (EPA, 1992a). Modified Milling Equipment VOC and 

### PM emissio ns may be reduced by converting older milling equipment to newer, more efficient closed sys tems such as horizontal media mills. Typically, horizontal media mills are charged by pumping material 1Tom containers or prem ix equipment thro u gh an enclosed piping system. Material discharg e i s also through enclosed pipes or hoses. VOC l osses during operation of the hor i zontal media mill are controlled becau se the filtering screen is enclosed by 

### a sheet metal cover (EPA, 1992a) . Equipment Cleaning Devices Several types of equipment can be used to re duce amounts of sol vents used during vessel cleaning and thus decrease VOC emissions. These include the following: R ub ber wipers (used to 

### scrape the clinging paint and ink 

### from the sides of the tank); High - pressure spray heads (used to clean proce ss tanks); Tanks lined with TeflonThf (Teflonn• reduces the ability of paint and in k to cling to the sides of the tank); Plastic (or foam) "pigs " (a "pig" is moved through the pipes and pushes leftover paint and ink [ from previous batches ] throug h the pipe fi·om the pipe walls); and • Automatic tub washers . The degree to which VOC emissions from cleaning activities are reduced will depend on the frequency of using one or more of tbe al ternative cleaning techniques li sted above. It has been reported that high-pressure spray heads can reduce cleaning material use by 80 to 90 percen t (EPA , 1992a). Use of Pigments In Pa ste Form PM emissions may be reduced by us i ng pigments that have been wetted or mixed with resins. Since these pigments are wet, less or no dust is generated when the package is opened and as pigment is dumped i nto mixing vessels (Noyes , 

### 1 993) .

EIIP Volume II 8.2 -9 

## VESOJ5968CHAPTER 8- PAINT AND INK MANUFACTURING Product Reformulation Produc tion of paints and inks th a t contain reduced or no VOCs will reduce VOC emissions from paint and ink manufacturing facilities. High - solids and water-based paints and inks contain less VOCs than traditional so lv ent - based paints and i n ks. Powder coatings and the majority of radiation-{:urable paints a nd inks contain no VOCs (EPA, 1992a). 3/3198



### 8.2 - 10 EII P Volume II 

## VES015969

# 3 OVERVIEW OF AVAILABLE METHODS 3.1 EMISSION ESTIMATION METHODS Several methods are availab l e fur calculating emissions from paint a n d ink manufacturing operations. The best 

### method to use depends upon the emission source being evaluated, available data, available resources, and the degree o f accuracy required in the estima te. Although preferred methods are identified, this document does not manda te any emission estimation metho d . Industry personnel using dtis m anual should contact the appropriate state or local air pollution control agency regarding suggested met hods prior to t he i r use. This section discusses the methods a vailab le for calc u lating emissions from paint and ink manufacturin g operations and identifies the preferred method of calculation. A discussion of the sampling and analytical methods available for monitoring each po ll utant is provided in Chapter I of thi s volume, Introduction to Point Source Emission Invemory Dew/opment . 

### Estimation techniques for storage tank emi ssions are d iscussed i n Chapter 1 of this volume. Equations and filctors for calcu l ating emissions from equipmen t leaks are discussed in Chapter 4 , and procedures for estimating emissions from was tewater are described in Chapter 5. Tims, this chapter will addre ss only process operations, miscellaneous operations, and spills. 3 . 1.1 EMI SS I O N FA CTORS 

### An emiss i on factor can be defmed as a pollutant emission rate relative to a l evel of source activity. Emission factors are typ i cally based on the results of source tests performed at an iodividual plant or at one or more fllcilities within an industry. Chapter I of this volume contains a d eta iled discussion of the reliability/ quality of available emission factors. Emission factors may be used to ca lculate total VOC and PM emissions from a paint and ink manufacturing facility, as well as emissions from specific types of equipment typically found at such a filcility. These types o f equipment include the following: Process equipment; • Solvent reclamation systems; • Parts washing equipment; and • Process piping.

EIIP Volume II 

### 8.3 - 1 

## VES015970CHAPTER 8 - PAINT AND INK MANUFACTURING 3/3198 EPA-approved em i ssion fuc tors for these sources may be found i n 

### AP - 42 , the 

### Lo c ating and 

### Estimating series of doc uments, the Factor Infonnation and Retrieval (FIRE) System, and/or 

### Protocol for 

### Equipment Leak Emission Estimates (EPA, 1995g). Emission factors may also be available through trade associations such as the National Associat i o n of Printing 

### Ink Manufacturers, Inc . (NAPIM). 

### 3.1.2 SOU RCE -sP EC IFI C MOD E LS Theoretical, more complex "models" or equatio n s can be used for estimating em i ssions. Emission est i mating models/equations are available for the foUowing types of emissions found at a paint or ink maoufuctur ing fucility: • Mater i al loading; Heat-up losses from di spersion/grinding activities ; • S u rface evaporation during mixing/b len ding operations; Filling; • Cleaning solvent loading ; Mater i al storage; • Spi l ls; and • Wastewater treatment. Inputs for theoretical models/equ ations generaUy faU into the foUowing categories: chemica l/

physical properties of the material(s) i nvolved (e.g., vapor pressure, vapor molecu l ar weight) , operating data (e.g., amount of material processed, operating hours) and physical characteristics/properties of the source (e.g., tank color, tank diameter). 

### 3 .1. 3 MAT ER I A L ( M ASS ) BALAN C E CAL C U LATION S The material balance approach to emissions estimation considers the given facility as a sort of "black box," where one compares the total quant ity of raw materials co ns umed versus amounts of m aterials leaving the fac i lity as pro duct or waste. Waste can cons i st o f used filt er bags or cartridges , spent solvent or still bottoms, dust coUector ma terial, pigment bags and/or dnnn residue , and wastewater (NPCA, 1995) . 

### 3.1.4 T EST D A T A Testing can be performed to quantify point source or fugitive emiss i ons. ln point source testing , effluent gas samp l es are usually collected from a s tack using probes inserted thro ugh a port 

### in the stack wal l. Pollutants in d1e gas sample are collected in or on various media that 8.3-2 Eii/P Volume II 

### VES015971313198 CHAPTER 8 - PAINT AN D INK MANUFACTURING are subsequently sent to a laboratory for a n alysis. Pollutant concentrations are obtained by di vi ding the amou nt of pollutant collected du ri ng the test by the volume of gas sampled. Emission rates are then determined by multiplyi ng the pollutant concentration by the volumetric stack gas flow rate. Because there are many steps in the stack sampl ing procedures where errors can occur, only experienced stack testers should perform such tests. Industrial hygiene data (concentrations) can be used in conjunction with exhaust system flow rates to calcula te fugitive emissions from a room, floor , or building. Direct-reading instruments that may be used to obtain an instantaneous reading of vapor concentrations include photoioniza t ion detectors , portabl e infrared spectrophotometers, and portable gas chromatographs (NPCA , 

### 1995) . VOC l osses from certain operations ( e .g., filli ng of conta i ners) may also be measured by performing a study using a gravimetric anal ysis such as American Society for Testi ng and Materials (ASTM) Standard 02369: 

### Test Merlwdfor Volatile Conte111 of CoMings . Section 6 of this document, Quality Assurance/Q uality Contro l , and Chapter I of Volume TI in this series provi de information regarding test data quality. 

## 3.2 COMPARISON OF AVAILABLE EMISSION ESTIMATION METHODOLOGIES Table 8.3 - l identifies the preferred and alternative emission**~1ima ion**  approaches for selected poll utants and sources of emissions. The best method to use depends upon the emission so

urce being evaluated, available data, available resources, and the degree of accuracy required in the estimate. 

### Io general, a more accurate method 

### will require greater resources tha n a less accu rate me thod. Case studies 

### 8.3-1 and 8.3-2 present examples of two facilities with varying levels of resources. The emission estimation methods selected for each are driven by availab le resources a n d need for accuracy . 

### 3 . 2.1 EMIS SION FA CTORS Use of paint manufacturing emission factors fro m Section 6.4 of 

### AP - 4 2 and ink manufacturing emission factors from Section 6. 7 of 

### AP- 42 i s generally accep ted by regulatory agencies, and the ir**IL~e** in c.al culating total facility or process-specific emissio ns i s more cost-effective than collection and analysis of air sampl es or use of emission models. Additionally , there are potentially significant linu t ations 

### with the material balance approach. 

### 3.2.2 EMI SSION MODELS Use of emission models/equations to estimate emiss i ons from paint and ink manufactur i ng facilities is a more complex and time-consuming p rocess t han 

### the use of em i ssion factors. Enuss i on models/equat i o n s require more detailed inputs th an use of emission fac tors; how ever, they provide an emission estimate based on site-specific condi ti ons.
EIIP Volume II 8.3 - 3 

## VES015972CHAPTER 8- PAINT AN D INK MANUFACTURING 313!98 

### TABLE 8 . 3·1 SUMMARY OF PR EFERRED AND AI.TERN.ATIVE EM ISSION E STIMATION METHODS FOR PAINT AND INK MANUFACTURING OPERATIONS Pref erred Emission Alternative Emi ss ion Poll utant Emb si o n Sour ce Estl mati on Approach Esdm ati on Approach**PM/PI\'~•** (Total and To t a l Facility Emissions Emission Fact or Material Balance Speciated ) Test ing" Proce$$ Equ ip menf E mission Facto r" Materia l Balance Testin g" VOC ( To t al and**Mi~ing:** Emission Model" Emi5:sion Factor' Speciated} Mate . ria l Loading Material Bal ance He at- up l osses T esting' S urfucc Evaporation Product Filli n g E mission Modef M aterial B a la nce Test i ng

., Solvent Reclamation E mission Factort Materia l B a la nce**Test ng** **~** Cle anin g; Solvent Load ing Emission Modef M ate<ial Balance Test i ng' Cleanin g; Parts E mission F'actcW Mate<ia l B a la nce Washing Test i ngtWa s t

ewater Treatment E m

i ssion**Mode ~**  M ateria l Ba l a nce Test i ng ' Mat erial S t orage E m ission**Mode~** Material B a lan c e Testing' Equi pment Leaks E mission Fact ot***Mat~~** B a la n ce Tcst i n Spi lls E m

i ssion**Mode~** Mate:t B alan ce Tcst i n ' EPA , 1995b ; in d1 is chapter , see Sections 5.1.1 and 5.1.2 (VOC} and 42.4 (PM / PM,.,)for more detail. • Refers to point source (stack } testing and/or fug itive te sting (i.e., collec ti o n of iodustrial hygiene data) . ' Refers to an y equipment where pigments are handled. ' Fisher et a l., 1993 ; EPA, 1 995c; NPCA. 1995; EPA , 1 993. Models are also avail a bl e for grinding equipment. ' EPA, 1995 c; see**Sec~ on**  4 .1.1 of t his document for more detail. 1 EPA, t9 95 d: see Section 4 2. 1 of this document for more detai l. ' EPA, J9 95e; see Section 4 .2.2 of this document f o r more detail. ' EPA, 1 994a;""" Sect ion 4. 1.6 of this document for more detail. ' EPA, 1 995a; sec Section 4 .1.5 of t hi s document for more det ail. ' EPA, 1 995g; see Section 4 .2 .3 of t his document for more detai l. k EPAl 1 987; 

### see $ecl ion 4. 1.3 o f t his docwne nt for more de-tail.



### 8.3-4 EIIP Volume II 

## V E SOI5973313198 CHAPTER 8 - P AIN T AND INK MANUFACTURING Case Srudy 8.3- l: The Bright B l ue Pajnt Company Description The B ri ght B l ue P a

i nt Company produces both water - and solvent-based in dustri a

l and consumer pa

i nts a t a total rate of about 2 , 200, 000 gallons annually. The water-based pa i nts account f or 65% of tota l production, with 

### 55% being consumer products and I 0"/o being industria l products. Sol vent-based paints account for the remaining 3 5 % of the paints manufacrured of which 17% is consmner paint s and o f which 18% is i ndustria l pa i nts. The ma j ority · of the consumer products contain l ess than 1. 5 poun d s per gallon VOCs , wh il e the industria l coat i ngs may be 

### as hi g h 

### as 3 pounds per gallon VOCs. The four main ma nufacturing operations at the Bright Blue Pain t Company are: P

reassembl y and premix; Pigment grinding/milling ; P

r oduct fmis binglblendi ng; and Product filling/pac k aging . The company manufacrures seven different paint products t hat can vary in any given year. B atch sizes range fi·om 300 to I ,600 gallo ns. Liqui d storage of pa i nt ingredients and cl eaning compoun ds is in bulk t anks ranging ftom 2 , 500 to I 0 , 000 gallons and i n 55 - gallon drums. Powder ingredient s are •tored in paper sacks or fiber drums ranging from 10 t o 200 pounds. Equipment is cleaned after each batch . Approximately 72,000 gallons of cl emtiog sol vents are used for equipment cleani ng each year. Small parts are also cleaned as necessary using an open-top vapor degreaser . Emjs: ion Sources Em i ss i on sources for thi s tacil i ty inc l ude:

Emissions M i xing (mater i a l loadi ng, heat-up, surface evaporati on) ; Filling l osses; Cleaning (parts, mi xers/ tanks); Solvent reclamati on; Material s torage; Equipment leaks; aod Spills. Emissions, the emission es timation method selected, and supporting data for this fac i lity are summarized in Table 8.3-2.

EIIP Volume II 8.3-5


### VE $01597400


### ..... 

# ""**~** 

# f "' T ABLE 

## 8.3-2 CASE STUDY 

## 8.3- 1 : T HE B RIGHT BL UE P AI N T C O M PA NY E MISSIONS SUMMARY [mlssio• VOC P.:\liPM• £m inion Souru: £s-tlmatio• Me1bod" Embsions EmWioou S uooo rUo . • Olio ' 

### Mlliatc**ltf'itl l.oadl** **l1 ~**  

# ... 

# - 26.5 toof)T T •77 • F : S -1. ,. 5.; to1tteot • 1 .00&.000 VOC: loodln& log modtl ( Equodon 3 . 4-1);**~T** &al: Metbyl <lb)'l "" ••• • S64,too**go~ r.t.~** **'M** .,. . : Al'-41 tmlsilon ractor total soticb =**~92;00t** lb •atloa 8.4-14) l ltat.,up lo Qn: "nt.,up IOSi model ( Eqoaolon 8..4 - 1 6) 1 7 1 11>/)T 0 

### n -n• F: Tl - 

### •os •P; tnoi«uh.r ""tffhl ( M\V) ofp1lnt mlltW"e • 8S IW lb-mole ;**ue~t** MW •77 1 bllb-molc: 8: 1600-lb**batt r~t**  350; lOOO· I b batc.bes, 700: CitO- I b bo«• <S. 1 315: JOO.Ib batc:loes . 500**Surr~** tn pCi r aUn n : Otmr. nt s 15 to afyr 0 U = O . . lS mill'fl r ; T • 77 ' F : vaporiuckltt modrl (f...q u 1tio• 8.4-18) Blitc h Jlt.C AI'U 8att. hclmt ( lbJbat c. h**~** 

### l!tl .....iliiL 1 600 41.8 6 1000 26.8 8 600 20 6 300 13.4 8 Product F i lli n g Load i ng l onmo d c:J (Rqu • tJon 8.4-1) l?Jiblyr 0 Total prod••d • 2,200 . 0 00 gal; T • 77 " P ; M W o t p 11ln t :1 n d t n k m bt• rl! • KS l bllb · mo l\' -**lng** ltqu i 1 Jm e n 1 cle a n l na: l o a dlne l olls m ode l ll? lb/yr 0 T o t al cl u. nin . &

to l ve nt • 72, 000 gaVyr; ( E<I•••Ion8 . 4 - 1 ) dtoa nln g sol vttll , ,.Mpor IJrtuurt • 0 . 9 psi • ; M W of v•pon • J 00 lb llb - mole; T - 1s• p S•1a ll punt tleanln(:: AP -42 e1illfssion 0 . 33 0 O n e optn•top vapo r d ce•·eaJel' b u'td factor (Ec ( U II I

IO. 8.4 · 24) tonlyr for**p~t.rts** dean ha

st: t mlulon fattor 111 hued 0 1\ nu mber or clunf n st**unit~** Sol vent R edam11tlon I 

# tl;;t · z

emls!llon factor uorlon S.A-19) 99t l blyr 0 300 ton s of sotve.ot are prO«Sttd IDDillll V Materi al S toraat TANKS 3toolyr 0 EquJpment Lnks**SOC~ fl** **"** ll\ trl&t tmlnlon futon 13 tonfyr 0 IS rthtt. Jt pttmp stl l "- 111d 

### s toU« t l)t1 ; """ "o f -rotlott • II. 760 h r/fr C')

### ~ 'll 

## rn :., Q>

### ~

## ~

# ~**~ ~** **~ ~**  C') 

# j

i

V E SOI5975

### ~ TABLE 

## 8.3-2 ,;::

## ~ CASE STUDY 

## 8.3-1: THE BRIGHT BLUE PA INT COMPANY EM ISSION SUMMARY (CONTINUED) 

## "'

00 

## w .:., £ , miu.ioa Sou ru**m~~Son** Eidmatloa M etltod" Spills Clctne<lts VllpCINOOOO model (Equatioo 8.4-15) Total • £quariOD oumbcn reftt to those used m Seccion 4 ofthlt chapler. '**S~1nbo l•**  used aroddin<d in Table 8 . 4·1 .**t~** SOCMI • Synthelx orpnic d•cnueAI rn.1.nufac1urinj: industry. VOC PM/PM• £m.iuiou £missions S.p p ortloa l> ota' 7lblyt 0 One spill ofbepcme: 

### ':"j"!' pressure • 0 . 9 psio: MW•IOOibllb-mole: •?j ' f:oreaof<pill• 1511': el«nuo**tone~** I bour: U • S trulellu 36.4 ton/yT 26.5 toni\T

# ~ "'

(')

### ~ "'0 

# § "' '

### ~**~** 

## ....**~** 0**~** :>:

### ~**~** 

### c:**~** (')

# ~**~**
VESOI5976CHAPTER 8 • PAINT AND INK MANUFACTURING 313198 Case Srudy 8.3 - 2: The Hot Pink Paint Company Description The Hot Pink Paint Company produces specia l ty coa ti ngs fo r a variety of surface coating industries. The faci l ity produces 500 , 000 gallons solvent - based coat ings annually. Tbe facility operates 8, 760 hours per year. The four main manufaciUring operations are: Preassembly and premix; Pigment grind i ng/mi lling; Product fin i sh i ng'b l endi ng; and Product filling/packaging. The company manufaciUres 5, 000 di fferent pa i nt products that can vary i n any gi ven year. Ba tch sizes r•nge from I00 to 2,000 gallons. Liqui d storage of paint i ngredient s and cleaning compound s is in bulk tanks ranging from 2,500 to 1 0,000 gallons and in 55-gallon drums. Powder ingredients 

### are stored in paper sacks or fiber drums ranging fro m 10 to 200 pounds. Equipment is cl eaned after each batch . Approximatel y 50 , 000 g a llons ofcleaning sol vents are use d for equi pment cleaning each year. Small parts 

### are also cleaned as necessary us i ng 

### an open -top vapor de greaser . Emission Sources Emission sources for thi s facility incl ude: Mixing (mater i al loading, beat - up sUiface evapo,..tion); Filli nJ! losses; Cleanmg (pam, mixen; / tanks ); Sol ven t reclamati on; Mater i al storage; Equipment leaks; and Spills. Emi ssions Calculated emissions, the emission estima ti on method selected, aod support i ng data fo r th i s &cility are summar i zed in Tab l e 8 . 3- 3 .



### 8.3-8 EIIP Volume II 

## VES015977

## ~**~** i "'

9" 

# "" • 

# ..., TA B LE 8 .3 · 3 CASE STUDY 

### 8.3 ·2 : T HE H OT P I NK P AINT COMPANY EMI SSIONS S UMMARY**WHJt~~** Enlma . l io ft .Hmi n io. Soa r e r M t t b od'" Mixllll! VOC : E.PA restattd**m~ission** factor 

# ( =on A**-3 ~** **~** ,.; AP-42 emissioo factor

ualion**ll ~24** **)** Prod\K'I Filling Load in& loss model (Equation 8.4- I ) Cleaning Equt:J)menl ete&ning : IOidiDg loss modo! (Cquat ion 8 . 4-l) S •

n a

ll**a1t~** c: le:tning; AP.ot2 emission f'b,c t or (Equ atio n 8 .4 -24) Sol vent R e cl a m ati o n AP -42**emi~s on**  ::t.1or (Eou • t

i on 8 .4 -19 M

a teri a l Storugc TANKS E

qui11 ment Lc a b S O C M f avcra&c cm i !!ltiOH futrors S

p iJi s Mh t cr

iu

l bll) o rK.-e (Eq u at ion 8 . 5 · 6) I o t a.1 Equat io n " 'tm ben; ref\'r to chose u sed in Soc:t i o n 4 o f thi" cba ptec . " Sy m bo l s us e d :Itt' defi ned io Tab 'c**.4-1 .**  • S OCMI .., Syn theti c**Ort~ltn c**  c h cmieltl m H n Ufltt l u ring ind u :s-t

ry . 

### v oc E.- 5.6 tonlyr 34lblyr 151 lb lyr CU3 ' ''nf y

r J961 b lyr I t

on/

VI ' 6 tonl y t

' 400 lb lyr I L4 too/ y r**~VP •**  E mlsslo .. SuDU ortl • a D ata • 6.6 1 oofyr SOO.OOO**;** solvmt used • 7;0 ,000 • -1 <oi;.J.• • l ,lU ,OOO 1b 0 SOO,OOO 

# rs 

# = ; molcculu ,..eight (MW)= S I b-mok; npor PftS""" = 0.34 ps'"; T = 77 ' F ; S • 1.45 0 T oW ct .. l\ing ooh·ent - 50.000**~r. c:** **~ning** solvent V'apOI' rcresrure - 0 . psia; MW 

### or va. p ora e 00 l bllb -'I T'IOh' : T=77 ° F 0 0.\t tlpel l .CO(l vapor d egi'CL"iel' i! u . oocd f o r pa rts cl camng.; cm iS"Sioo factors based on n umber ofclcanin a unifll 0 1 2 0 to n s o f so h •e.u M.re prottiS0\ 1 an n ua lly 0 0 S**'' aJ** **~** 5 p u m1'**~tllt,** and 2 (()lU\CCtOts : h o u n; or o p c: ntti o n .e 8 76 0 hr / y l' 0 S Og al los t. dc: n sJt

y o f$ pl 1 Jed lnliiC i i:. l • 8**lbl IJ** **: ss** **um .**  wors t**ca.~ :**  1111 !lpiltC!d mat er

ial eNaporate s 6. 6 to n/yr

# ~ "'

(') 

## $: 

# ,**~** 

# "'**~ ~**  "'i

# ~**~ ~** **~ ~**  (')

# ~**~** VES0 159 7 8CHAPTER 8 • PAINT AND INK MANUFACTURING 313198 3.2.3 MATERIAL BALANCE CAL C ULATIONS 

### Calculating emissions from a paint or ink manufacturing fac i lity using m aterial balance appears to represent a straightforward approach to emissions estimations. However, few fac ilit i es track material u sage and waste generatio n with the overall accuracy needed for application of t h

is met hod , and inaccuracies associated with individual material tracking or o t her activities inherent to each material h andling step often accumu late into large deviations. Because emi ssions from specific materials are typically below 1.5 percent of gross consumpt ion , an error of only ± 5.0 percent in any one step of the operation can s i gnificantly skew emissions calculations. Pote n tial sources of error i n the material balance calculation method include th e following: The delivery o f bulk raw material s at a paint or ink m anufacturing facility is often tracked by volume, not by weight Since density will 

### vaty with temperatures, the actual mass per un . it volume of materials del ivered in tl1e swn mer may be 

### less than that received in the winter. • Raw mate rials received by paint or ink manuf actu ring facilities may potent ially be 

### used in h undreds or d10usands of finis h ed products . In order to complete the material balance. it is crucial th at the exact quantity and speciation ofeach material shipped off-site in the produ c t be known. F

or many fac ilities , it is extremely difficu l t, or currently impossible, to accurately track the distribution of specific raw materials acro ss their entire produ c

t lin e. The amount of raw m ateria l contain ed i n was t e must also he 

### considered. Thi s may involve precise analys is of t he concentration of the material of interest in each waste stream. Batch product ion of paint or ink ofte n requires the man ual addition of raw ma t erials. Sometim es these ad d itions are no t accurately meas u red or recorded (NPCA, 1995). 3.2 . 4 T E ST DATA 

### Use of stack and/or indus trial hygiene test data is likely to be 

### the most accurate method o f quantify i ng air emiss i on s rrom paint and ink**man f.~ctu** **ing** 

### operation s . H owever, collection and analysis of air samples from manufacturing faciliti es can be very expensive and especi ally complicated for paint and ink 

### manufacturing faci lit ies where a variety of VOCs are emitted and 

### where most of t he emissions may be fugitive in 

### nature. Test data from one specific process may n

ot be 

### representative of the entire m anufacturing operation and may provide onl y one example (a snapshot) of the facility's emiss i ons . To be re pres e n tat ive, t est data wo u ld n e ed to be 

### c ollected over a period of ti m e that covers production of multi p le paint and ink 

### formulations. It 

### may be necessary to sample multiple
8.3-10 EIIP Volume II 

### V ES 0 15979313198 CHAPTER 8 - PAJNT AND INK MANU F

ACTURING production areas. I n ad dition, the se methods do not address fi1gitive emissions that occur outside of a building. If testing i s performed, care should be taken to ensnre that a representative operational cycle has been selected. Ifpossible, full cycles should be monitored as opposed to portions of cycles.

EIIP Volume II 8.3-11 

## VES015980CHAPTER 8 - PAINT AND INK MANUFACTURING 313198



### This page is 

### intentionaUy left blank.

8.3-12 EIIP Volume If 

### VES01598l

# 4 PREFERRED METHODS FOR ESTIMATING EMISSIONS The preferred methods for es t imat i ng VOC and PM emissions from pa i nt and 

### ink m anufacturi ng operations are presented i n this section. Titis section describes these methodologies and provides examples to illus tJ: ate the use of each calculation t echn i que. Although the methods identified in 

### this section 

### are the preferred methods and the methods in Section 5 are alternat i ve methods , the inventory preparer should determine which method is the most appropriat e for each situation . For certain sou rce types 

### (e.g. , material storage or storage tank 

### emissions), the reader is 

### referred to other chapters in 

### Volume 

### II for details on using the suggested methodo logy . Tab l e 8.4-1 lists tbe variables used in Equat i ons 8.4-1 through 8 . 4-27. 

### 4.1 EMIS S ION CALCULATION USING SOUR C E-SPECIFIC EMI SSI ON MODELS/EQUATIONS Use of source - specific emissio n models/ equations i s the preferred technique for estimati n g VOC emissions from: • Mix ing operations (material loading , beat- u p losses, and surface evaporation); • Product fi lli ng ; • Vessel cleanin g operat i ons; Wastewater treatment processes; Mat erial storage; and • Spills.

EIIP Volume II 

### 8.4 - 1


### V E S015982CHAPTER 8 • PAINT AND IN K MANUFACTURING 313198 

### T

A

BLE 8 . 4-1 LI ST OF VA RI A B LES AND S YM B OLS 

### Va riable Sym bol 

### U11its Total VOC Emissions Evoc lblvr Saturation Fac10r 

# s dimensionless Vapor Press u re of the Material Loaded p 

### pounds per square inch absolu te (psia) Vapor Mo l ecular Weight M lb/lb-mole Vo l ume ofM aterial Loaded Q 

### 1 ,000 gallyr Temperature T 

### •R Part i al Vapor Pressure ofVOC Species x P , ps i a L

iquid Mo l e Fraction of VOC Species x Ill, 

### mole/mole True Vapor Pressure of VOC Species x 

### VP . , psi a Henry's 

### Law Constant for VOC Species x H, 

### ps i a Liquid Mass Fraction ofVOC Species x 

### Zx Jbllb Mo l ecular Weight ofVOC Species x 

## M, Jbllb-mole Vapor Mo l e Fraction ofVOC Species x y, mole / mo l e Loading Emissions of VOC or PMIPM 1 0 

### E , lb/yr Species x Vapor Mass Frac t ion of VOC S pecies x X. 

### lbllb Initial Partial Pressure ofV O C Species x (P,)., , psi a Fioal Partial Pressure ofVOC Species x (P,}n 

### psi a Nu mber of Pouod- Moles of Gas Dis p laced 

## a n Jb - moles/cycle Vapor Molecular Weight, average 

### M lbllb-mole Nu mber ofCycles/Year CYC cycleslyr

8.4-2 EIIP V ol

ume II


### V E S0159833/3198 CHAPTER 8- PAINT AND INK MANUF ACTURING 

### TABL£ 8.4·1 (CONTINUED ) 

### Va ri able Symbol Units 

### Volume of Free Space in Vessel 

## v ft3 U

niversal Gas Constant at I Annosphere o f R 10. 7 3 

### psia · W/lb - mole · Pressure 

## • R Initial Gas Pressure i n Vessel Pa, psia Final Gas Press ure in Vessel Pa 2 psi a Ini t ial Temperarure of Vessel 

### Tl • R Final Temperature of Vessel T2 • R 

### Molecular Weight of Liquid Mixture M , lbllb-mole Gas-phase Mass Transfer Coefficient for VOC 

### K, ftlsec Species x Surf.1ce Area (of Spill or Tank) A tr Duration of Spill 

### HR he/e v ent Wind Speed 

## u milelhr Diffusion Coefficient for VOC Species x in Air 

## D, tr / sec Batch Time H hr / batch Number of B atches per Ye a r 

### B batcheslyr VOC Emission Factor EFvoc various Amou nt of VOC in 

### Spen t Solvent Processed Q v o c 

### tonlyr Concentration ofVOC or PMIPM 10 

### Species x in 

# c, mass**~0** 

### Solv ent or Pigment 

### x, Respectively Mass Percent o f S pecies x in Total Mixture 

## Xx mass%

EIIP Volume II 8.4-3 

## VESOI5984CHAP TER 8 • PAINT AND INK MANUF ACTURING 313198 TA BLE 8 . 4-1 ( CONT I N U ED) 

### Va ri a bl e Sym bol Un ils Vo lume Percent of Species x i n Total Mixture y**volume% ~**  

### Nwnber of Species in Total Mixture n number Operating Hours 

### OH hr / yr Number of Cleaning Units in 

### Use NU cleaning uni ts PM/PM 10 

### Emissions E • ., 

### lb ryr .PM/PM , 0 

### Emi ssion Factor EF ,.., lb/ ton Amount of Pigment Containing Species x Used Q, 

### lb/ yr , ton/ yr by the Facility These models are 

### disc ussed with examp l es given below . For additional g ui dance on estimating emission s from wastewater collection and treatmen t, see Chapter 

### 5 of this volume. See 

### also Chapter l of this volume for additional gu i dance on material storage. It is not recommended that paint and ink manufacturing facilities apply these models to each of the hundreds or even thousands of different formulation s. Rather, formulations should be grouped based on composition and production rate, and 

### a representative re c ipe and composi ti on s hould be defined for each group. TI1e emission calculations are d1en performed for each of the group representatives. In 

### general, there are no specific guidelines for defining product groups except tbat the number o f product groups chos en should be manageab le (o n the order of 15 

### to 20), 

### and each product grou p composition should be fairly characteristic of its components (Fisher et 

### al., 1993) . 

### 4. 1.1 EMI SS ION MOD EL FOR MATERIAL LOADIN G 

### VOC emissions resulting from the addition of mat erial s to mixers, grinding equ ipment, and thindown tanks may be calcul a t ed using 

### a l oading loss equation (wh ich is presented in Section 5.2 

### of

### AP- 42; EPA, 1995c) . T h is equat io n, shown below as Equation8.4 - l, is related to tank car or tank truck loading , but can be applied to any tank or vessel loading (NPCA, 1995). This equation may also be applied t o estimate product filling losses.

8.4-4 IEIIP Volume II 

## VESOl5985313198



### where: 

### Evoc 

## s p M Q 

### T 

## = = = = = CHAPTER 8 • PAINT AND IN K MANUFAC TURING 

## = 12.46 • S • p • 

### M • Q T 

### Total VOC loading emissions (lb/}1-); (8 .4 - 1)



### Saturation factor (dimensionless; see Table 5.2- 1 

### in AP - 42); 

### Vapor pre ss ure of the mat erial loaded at temperature T (psia); Vapor molecular weight (lbllb-mole); Volume of material loaded (1,000 gall yr); and Temperature (•R). Calcu l ation ofVOC em is sions using Equation 8.4-1 

### is based on the following assumptions: • The vapors displaced from the process vessel are identical to the vapors from t he materials being loaded; • The volwne o f vapor dis plac ed is equal to 

### the volume of mat erial l oaded into the vessel ; 

### The vapor wi thin tbe headspace of the vessel is sanuated a t roo m temperature and remains at room temperature during loading; and All 

### solvent additions are coincident at a constant temperature (in 

### reality, solven t additions m ay be p has ed) (Fisher et at., 1993). 

### If m u ltiple solvents are 

### used , the vapor pressure (P) 

### wiU need to 

### be calculated using Equation 8.4· 

### 2:
where: p 

## P

, 

## = Vapor pressure o f mat erial loaded (ps i a); Partial pressure ofVOC s pecies x 

### (psia ) . (8 . 4-2)



### P, may be calcul ated using Rao ult's Law (for ideal solutions) o r usi ng Henry's Law constants (when gases are dissolved a t low concentrations in water).**Raoul~s** 

### Law is given in Equation 8 . 4 · 3: 

### P = tn • 

### VP X "'""'x X 

### (8.4 -3)

EIIP Volume II 

### 8.4 - 5 

## VES015986CHAPTER 8 • PAINT AND INK MANUFACTURING 

### where: 

## P, fl1x 

### VP,**~ ~**  = 

### Partia l vapor pressure of VOC spec ies x (psia); Liquid mole fraction ofVOC species x 

### (mole/mole); and Tr ue vapor pressure ofVOC species 

### x (ps i a). P, 

### may be c alculat ed usi n g Henry's Law constants and Equation 8.4 - 4:



### where:
= = = 

### P = m • 

### H l X X 

### Partial vapor pressure ofVOC species x 

### (psia); Liquid mole f raction ofVOC species x 

### (moleimole); and Henry ' s Law constant for VOC species 

### x . 3/3198

(8 .4-4)



### The liquid mo le fract ion ofVOC spec ies x (m,.) may be 

### calculated if the liquid weig ht fractions of all species are known. Equation 8.4 · 5 

### is us ed :

where:

8.4 - 6 

## = = Liquid mole fraction of VOC species x (mole/mole); Liquid mass fraction ofVOC species x (lbllb); and Molecular weight of VOC species x (lbllb-mole). (8.4-5)

EIIP Volume II


### V E SOI5987313198 CHAPT E R 8- PAINT AND INK MANU F

ACTURING 

### T h e vapor molecular weigh t (M) 

### will also need to be 

### calculated ifmultiple solvents are used for a single cleaning event. Equation**8.~** 

### may be 

### used:
where: 

### M y

, 

### M, = = 

### M =**~(y,** 

### * M,) Vapor mo lecul ar weight (lb/lb-mole) ; Vapor mole fraction ofVOC species 

### x (mole/mole) ; and Mo l ecular weight ofVOC species x 

### (lb / lb-mo l e). (8.4 - 6)

The 

### vapor mole fraction (y,) 

### is calculated using Equation 8.4-7:



### where: = = p = 

### P, Y, : - 

### p Vapor mole fraction ofVOC species x 

### ( m ole / mo le); (8. 4-7)



### Partial pre ssure ofVOC species x 

### (calculated using Equat ion 8.4-3 

### or 8.4- 4) 

### (psia); and Vapor pressure oftbe material lo aded (calculated using Equation 8.4-2). Speciated VOC emissions are calculated using Equation 8.4 - 8:
where:

=

EIIP Volume II 

### (8.4 - 8) Loading em iss ions of VOC speci es x (lb/yr) ; Total VOC loading emissions, calculated using Equation 8.4 - 1 (lb/ yr) ; and Vapor mass fraction ofVOC species x (lbllb) .

8.4-7 

## VESOI5988CHAPTER 8 - PAINT AND INK MANUFACTURING The 

### vapor mass fract i on ofVOC spec ies x (x ,) is calculated using Equation 8.4-9:

where: = X : 

## ' y • 

### M 

## ' '

M Vapor mass fraction ofVOC species x (Jb/lb); (8.4-9)

X, 

### y, Vapor mole fraction of VOC s pecies x, calculated using Equation 8.4-7 (mole/mole); M, M = 

### Mo lecul ar weight ofVOC species x (Jb/lb-mole) ; and Vapor molecular weigh t, calculated using Equation 8.4 -6 (lbllb - mo l e). Example 8.4-1 illustrates the us e of the loading equation (Equation 8.4 - 1) and the supplemental equatio ns (Equat ion s &.4-2 through 8.4-9). Example 8.4- 1 A mixing vessel is cleaned widt a solvent mixture a t the end of each day . The following data are given : • The yearly consumption of the solvent mixture ( Q) 

### is 

### 600,000 gal; • The cleaning solvent is a 50/50 mixtu re (by weig ht) of toluene a n

d heptane ; • The solvent mixture is splash loaded into the vessel (S = 

### 1 . 45); and • The temperature of the solvent is 77 " f or 537•R ( • R = 

### • f + 460).



### 8.4-8 EII P Volume II 

## VES015989313198 CHAPTER 8 ·P A INT AND INK MANU FACTURING Emissions are calculated 

### b y following Steps 1 through 8 below . S tep 1: A pp ly E qu atio n 8.4 -S- C a l cul a tion o f Liquid M o l e Frac t i on (m J Liqu i d M a ss Molec ul a r F r actio n , 

### z, Wel g b t , M , (lb of xllb of (lb o f xll b-mole Liquld Mole Fr ac tion , m , Compo n e n t liquid) ofx ) (mol e o f xl m o l e of liq u id ) Toluene 0.50 92 

### UM,._ - (0.5 I 92) 

### E(zjM,) ((0 . 5 / 92) + (0.5/100) ] =0.52 Heptane 0.50 1 00**z.LM~** = (0.51100} 

### E(

z/MJ [(0.5192) 

### + (0.5/100)]

= 0.48 S tep 2 : Ap p ly Eq u at i o n 8 . 4 -3 - C a l c u l ati on of P a rti al Vapor Pr ess u r e (P ,) Uquid Mo l e Fr acti on, m , Va por ( mo l e of xl m o l e P r ess ure, VP , Partial Vap or Com p o n e nt o fllqu l d) 

### ( p s i a ) Pr ess ure, P , ( p sla) Toluene 0.52 0.58 

### m, • VP, 

## =0.52 

## * 0.58 =0.30 

### Heptane 0.48 0.90 

### m, • VP, = 0.48 

## * 0.90 = 0.43

£1/P Volume II 

### 8.4 -9 

## VES015990CHAPTER 8- PAINT AND INK MANUFACTURING S tep 3 : A pply Equation 8.4-2 - C alcula ti on of V apor Pr ess ure (P) p = 

## = = 

### :EP, 0 .3 0 

### + 0 . 43 0.73 

### psia S tep 

### 4 : App l y Equatlo u8 .4-7- Calculation of Vap or Mole Fraction (y,) Vapor Mole Partial Vap or Total Vapor Fraction , y ,

Pr ess ur e, 

### P , Pressur e, P ( mole ofx/ mole Co mpon e nt ( p s i a) ( p s la) of v apor) T o l uene 0 . 30 0 . 73**~'** 

### = 0.30 

### p 0 .7 3 

## = 0.4 1 Hepta ne 0 .4 3 0 . 73 

## f , = !ill. p 0 . 73 

### =0 . 59 S tep 

### 5: Apply E quati o n 

### 8 . 4-6- Ca l culation of Vapor Molecular Welgbt 

### (M) M 

## = = :E(y , 

### * M, ) ( 0.41. 92) 

### + (0 . 59. 1 00 ) 97 lbllb - mo l e 313198

8.4-10 c liP V olume II 

### VES01599l3/3198 C HAPTER 8 • PAINT AND INK MANU F

A C T URING Ste p 6 : Apply E qu atio n 8 . 4-9 - Ca l c ul ation of Vapor Ma ss Fra c tion ( I , ) V apor Mole Mo l e c ul ar W e ight, Vapor Mo l ecul a r Vapor 

### Mas s Frac tion, 

### y, 

### M, Weig ht, 

### M Fracti o n , :1: , (mole ofx / mole 

### (lb of x/lb -mole 

### (lb of \ ' apor / l b- (Jb of x/lb of Compon e n t o f vapor) of x ) mole of v apor) v apor) Tol uen e 0 .4 1 92 9 7 y,. • M = 0 .41* 92 M 9 7 = 0 .3 9 He p tan e· 0 .59 1 0 0 97**59*****00** M 9 7 = 0 .6 1 St

e p 7 : Ap pl y E quati on 8.4 - 1 - Calc ul ate Total VOC Emi ssio n s (E,. 0 

### c) 

### S•P • M • Q E \'OC = 12.46 •**-=--=--=.:..:.. ~**  

### T 

## = 12 . 46 ... 1 .45 • 0 .7 3 

## * 97 

## * 600 

### 5 3 7 

## = 1 ,4 29 lb VOC s f yr S tep 8: A pp ly Equation 8. 4 - 8 - Ca l cul ate Speciated VOC Emi s sio n s (E ,) VO C Vapor M ass F ractio n , Eml ss lon s ,E , .oc X, S p ecta ted VOC Co mp o n e n t ( lb VOC s ) ( lb ofx/lb ofVO Cs ) Emi ss ions , E , ( lb x ) T o l uene 1 ,4 29 0.39 Ev oc 

## * x, = 1 ,429 • 0 . 39 = 557 H ep tan e 1,429 0 . 61 E voc 

### * x, = 1,4 29 • 0 . 61 = 872

E

IIP V ol

ume II 8 . 4-11 

## VE S015 99 2CHAPTE R 8 • PAINT AND INK MANUFACTURING 313198 4 . 1.2 H EA T-tiP L O S SE S 

### Heat-up losses that occur during the operation of high -speed dispersers, bead and ball miUs, and 

### similar types ofdispersing equipmen t may be estimated by application of the Id eal Gas Law 

### and vapor-liquid equilibr i a principles. Emissions are calculated using the following assumptions: Covers are closed duri ng operation, but it is possible for vapors to 

### be vented during operation; • No material is added during heat-up; The di sp l aced gas is always saturated with VOC vapor in equili brium with the liquid mixture; • The moles of gas displaced from the vessel result from the expansion ofgases during heat- u p and an increase in VOC vapor pressure; and • The vapor pressure ofthe m ixers never rises above ] atmosphere 4 

### (Fisher et al., 199 3). 

### The equation for ca l c u l ati

ng these emiss i ons i s based on equations found in Control of Volatile 

### Organ ic Compound Emissions fi·om Bmch Processes and is 

### shown in Equation 8.4-10 (EPA, 1994c): where:

Evor 

## = (PJTI 

## = • ll n • 

### M • CYC 

# • (8.4-10)

VOC 

### emissions fi·om mat erial heat- up in d1e process equipment (lblyr) ; Initia l part i al pressure of each VOC species x 

### in the vessel h eadspace at the i nitial temperature Tl 

### (psia); see Equations 8.4 - 3 

### and 8.4-4; 

### (PJn 

## = Final partial pressure of each VOC species 

### x in the vessel headspace at the final temperature T2 

### (ps ia); see Equ ations 8.4-3 

### and 8.4-4; 

### lln 

## = Number of pound-tnoles of gas displaced (lb-mole!cycle); 

## M. = 

### Average vapor molecular weight (lbllb-mole); and CYC 

## = Number of cycles per year (cycles/yr).

8.4 -12 Et/ P Volume II 

## VES015993313198 CHAPTER 8 • PAINT AND INK MANUFACTURING 

### The term 

## tm may be calculated using Equation 8.4 - 11:

Where: 

### An 

## = 

## v = 

### R 

### Pa 1 = 

### Pa 1 

## = T'l 

## = T2 An " 

## v * ( Pa 1

_

# P~) R Tl T2 Number of pound-moles of gas displaced (lb-mole/cycle ); Volwne of free space in the vessel (ft'); 

### Universal gas co ns tant at I 

### atmosphere of pressure, 10 .7 3 ps ia · ft' l lb-mole · • R 

### Initial 

### gas pressure in vessel (psi 

### a); Final gas pressure in vessel (psia); Initial temperature of vesse l 

### <-R); and Final temperature of vessel (-R). (8.4 - 11)

Pa, and Pal may be calcu lated using Equations 8.4 · 12 and 8.4 - 13:

where: Pa, 

## = Pa, 

## = (P,) TI 

## = (P,) n 

## =

EIIP Volume II 

### Pa 1 " 

### 14.7 - 

### I:(P

# Jn Pa2**~** 

### 14 . 7 - 

### I: (P,)n

Init ial gas pressure i n vessel (psia); F

inal gas 

### pre ssure in vessel (psia) : (8.4-12) (8.4-13)



### Partial pressure of each 

### VOC, in the vessel headspace (psia) at the initial temperature Tl; see Equatio ns 8.4-3 

### a nd 8.4-4 ; Partial pressure of each VOC , in the vessel headspace (psia) at the final temperature T2; see Equations 8.4-3 and 8.4-4.

8.4-13


### VES015994CHAPTER 8 • PAINT AND INK MANUFACTURING 313198 

### Specia t ed VOC emissions would be calculated using a modified vers i on ofEquation 8.4 - 10 

### as s hown in Equation 8.4-14:



### where: ( (P,)TI E = 14 . 7 - (P,)y 1 +



## ' (8.4 -1 4) 14.7 

### - (P,)n 

### •ll n • M 

## * eve 

## • E, (P , ) rt = (P,) n = 

### lln = 

## M. = 

## eve = 2 

### VOC species x emissions from material heat- u p in the process equip ment (lb/yr); 

### Partial pressure of VOC species x in the v essel headspace at the initial t emperature T l (psia); see Equations 8.4-3 

### and R.4 - 4; Partial pressure of VOC species x in the vessel headspace at the final 

### temperature T2 (psia); see Equatio n s 8.4-3 

### and 8 . 4 -4 ; Number of pound-moles of 

### gas displaced ( lb-mole/ cycle); see Equation 8.4 - 11 ; 

### Average vapor molecular weight (lbllb-mole) ; and Number of cycles/year. Example 8.4 - 2 illustrates the use of Equations 8.4-10 

### through 8.4-13. 

### Emiss ions are calcu l ated by following Steps I thro u gh 6 present ed on d1e next few pages.

8.4-14 EII P V o/vroo II 

## VES015995313198 CHAPTER 8 • PAINT AND INK MANUFAC TUR ING Example 8.4-2 Thi s example shows 

### how heat-up losses from a**spe~r** are calculated using Equations 8.4-10 through 8.4-13. Supporting equation s from Section 

### 4 . 1.1 (Equations 8 .4-3 and 8.4-5) are also used in this exan1ple. A 3,000- gallon , high-speed disperser contains 2 , 000 gallons of paint The fo llo wing data are given: • The pa i nt consists of 30 perc ent by weight toluene , 20 percent by weight methyl ethyl ketone 

### ( MEK ), and 50 percent by weight p i gments and nonvolatile 

### resins; • The initial temperature 

### (Tl) of the mixture i s 

### 7?-F or 537 " R 

### ("R = 

### •f 

### + 460) ; 

### The final temperature (T2) is 

### J05 • F (565•R); • The approx imate molecular weight (M) of the paint mixture is 85 lbllb-mol e; The average vapor molecu l ar weig ht 

### (MJ is 77 l bllb-mole (calculated us i ng E q u ati on 8 . 4-Q); and The mi xer goes through the given temper.tture cycle with this pa int formulation 25 t i mes!)'f (CYC). The volume of free sp ace in the vessel is 3,000 - 2 , 000 gal = I ,000 gal or 133.68 

### ft '.

EIIP Volume II 8.4-15 

## VES015996CHAPTER 8 - PAINT AN D INK MANUFACTUR ING 313198 

### Step 1 : A pply Equation 8.4 - 5 , Ca l c ulatiou of Liquid Mole Fraction (m , ) Liquid Mass Fraction , z, (lb o f xllb lolecu.lar Wei gbt, M , Uquid Mole Fraction, m, Co mponents ofliuuid) (lb o f xllb-nt ole o fx) (mole of x/m ole of liquld) Toluene 0.3 

### 92 .z/ M, = 0.3 / 9 2 I:(z,!M,) 1/ 85' = 028 

### MEK 0 . 2 72 

## .z..tM.. =Q.U1l I:(z,/M,) 1 1 85' =0.24 

### ' I f t h

e mo l ecu lar 

### weight of 

### the mixture i s known , 

### the follow i ng express ion 

### can be 

### used:

where : 

### tn

### ~ zjM, • !:(z / MJ 1 / M 1 

### Molecular weig h t 

### of tbe liq ui d 

### mi:<.ture, and aU 

### other temts 

### are defined as in 

### Equation 8 .4-5 . Step 2 : Appl y Equation 8.4-3, Calculation of Partial Vapor Pressure at Initial Temperature ( (P 

## JTt l Vapor Pre ss ure, VP, Liquid Mole Fra cti on, m, 

### @ 77 " F Partial Pressure at Tl, Comoonent x mol e of xlmole of liquid) (usia) (P 

### .)Tl (u si a ) T oluene 

### 0.28 0.58 m, 

## * VP, = 

### 0.28 • 0.58 = 0.16 

### ME K 0.24 1.93 

### m , • VP , = 

### 0.24 

## * 1.93 = 0.46

8.4-16 EIIP Volume II 

## VES0 15997313198 CHAPTER 8 ·PAINT AN D INK MANUFACTURING Step 3: Apply Equation 8 . 4 -3, Ca l c ulati o n of Par tial P re ssu re at Final Temp e.-at ure [ ( P 

## J.n l Vapor Pressure, Liquid Mole 

### VP , Fraction , m , @ 

### IOS • F Partial Pr ess u re at T2 , (P 

## J.n Componentx ( mole/ mole ) (p s i a) (psia) froluene 0.28 

### 1.16 

### m,. • VPx 

## =0.28 

### * 1.16 =0.32 

# f-mK 0.24 3.75 

### m,. • VP, =0.24 

## * 3.75 = 0.90 Step 4: A pply Equations 8.4-12 and 8.4-13, Calcu l a tion of Initi a l Pressure ( P a 1) and Final 

### Pr ess ure ( Pa,) 

### Pa 1 = 14.7 •**~(P, )-,** 

### 1 = 14.7 . (0.16 

### + 0.46) = 14.1 

### psia 

### Pa2 = 14.7 •**~PJ n**  

## = 14.7. (0.32 

### + 0 . 90) = 1 3.5 

### psia S t ep 

### 5: Apply Eq uation 

### 8.4-11, C al culation oflb - mole s Gas Disp l aced (ti n ) The volume of 

### free space in 

### the vessel (V) 

### is 3,000 gal- 2 , 000 gal= 

### 1,000 gal or 133.68 

### ft' . 

# ll 0 = 

## v • ( 

# Pa 1 _ 

# Pa,) R T , T 2

= 1 33.68 • ( 

# .!i:..!. . 13.5) 10.73 537 565 = 

### O.o3 lb - mo l es/CYC

EIIP Volume If 

### 8.4 - 17


### V E$015998CH APT ER 8- PAINT AND INK MANUFACTURING 313198 

### S te p 

### 6: Apply Equatio n 

### 8.4-10, Calculation of Tota l 

### V O C Emissio n s (Evoc) ( E(P )TI ' +

- 14.7 - E(P.)TI 

### B..· oc - 2 

### E (P,)n ) 14 . 7 - E(P 

# >n ' • .6. n • 

### M • CYC (0 . 16 + 0.46) ) ( (0.32 + 0.90) = 

### _._;;_ 14

_ . 7

_-__,_ (0

;;_ .1

;_: 6

_

+

_ 0

;;...

4 -'

6 "- ) '--:·_,_-=1-- 4

_

. 7_-_ ( o..:. 0..:.

3=.

2 _•_: 0 ;_: . 9 ...:. 0

!...1.... ) • 0. 03 • 77 

### * 25 

### 2 = 

### 3 .9 lb VOC sf yr 

### Ste p 

### 7: Ap pl y Equatio n 

### 8.4-14, Calc ul atio n ofTolu e u eEmlssions 

### ( Evoc ) 

### ( (P

# J T

1 + 

### (PJn 14.7 - (P,)n 14.7 - (P ,)n 

### Evoc =**-"----~~ -'-** **--- ~::L**  

### • .6. 

### n • M • CYC 2

= 

### (0.16 + 0.46) ) ( 1 4 . 7 - (0.16 + 

### 0.46) + 

### (0 . 32 + 

### 0 .90) ) 14 .7 - (0.32 + 

### 0.90) • O.o3 • 

### 77 • 25 

### 2 = 

### 0.96 lb toluenelyr 

### 4.1 . 3 EMI SSION MODEL FOR SP I LL S 

### A vaporization model developed by Clements can be used to estimate ti1e evaporation rate ofa l iquid chem ical 

### spill if the s ize (area) of the spill is known or cau be estimated. This 

### is a simple model, but other available 

### spill models are more complex and may require more input data (EPA, 

### 1987). Equation 

### 8.4- 1 5, used for 

### the simple 

### model, is 

### as follows: ( 8.4- 1 5)



### 8.4-18 EIIP Volume II 

## VES0 1 5999