Environmental Protection

ESTIMATE EMISSIONS

FROM

Depressurization
Activities
Jimmy Peress, P.E.,
Tritech Consulting Engineers

epressurization describes the release of

a non-condensible gas from a process
vessel or a storage tank kept under
pressure. The term also refers to the
evacuation of a vessel from atmospheric pressure to
a vacuum condition by means of a vacuum pump or
a steam jet. When the vessel contains a volatile organic component (VOC), the vented gas will be saturated with the VOC present in the vessel. Depressurization activities include:
pressure release from a batch pressure reactor
(or autoclave) at the completion of the reaction step
venting of blanketing gas maintained under
pressure from a storage tank containing a VOC
pressure relief from a batch pressure filter prior
to solids discharge
evacuation of a vacuum distillation column
prior to startup.
Engineers frequently need to estimate emissions
in connection with emission inventory and other
regulatory requirements. This article reviews existing methods and proposes a new and improved procedure for estimating emissions from depressurization activities.

Existing estimation methods

Two methods for estimating emissions from depressurization activities are documented in the technical literature.

Unlike other techniques,

this method is applicable
over a wide pressure range
and in cases where the
vapor pressure of the
VOC approaches the
operating pressure.

EPA method (1). This procedure is based on

arithmetic averaging of initial and final partial pressure ratios of condensibles to non-condensibles.
The working equation for this model is:
wc =

V ( Pt1 Pt 2 )( MWc )
RT

1
2

Pc
Pc
+

( Pt1 Pc ) ( Pt 2 Pc )

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Vent

Vt
V
Pt1
Pt2
Pc

= Total Volume
= Headspace Volume
= Initial Pressure
= Final Pressure
= Vapor Pressure
of VOC
T
= Temperature
MWc = Molecular
Weight of VOC

total system pressure) for the model, Hatfield inadvertently introduced an anomaly in the final working equation that becomes more pronounced as the vapor pressure of the VOC approaches the final system pressure.
Under the limiting condition of Pt2 Pc = 0, Eq. 3 becomes indeterminate.

Proposed estimation method

The new method presented in this article is intended to obviate the limitations of the Hatfield algorithm.
Consider the pressure reactor illustrated in the figure.
The total volume of the vessel is V t and the headspace
volume is V. The reactor is maintained at an initial
pressure P t1 and a temperature T. The vessel is vented
to a final pressure P t2 . The depressurization is assumed to proceed at a constant temperature. The vessel contains a VOC having a vapor pressure P c and a
molecular weight MW c .
At any given time during the depressurization, the total
amount of gas in the headspace can be expressed as:

Figure. Schematic of vessel depressurization.

nt = (PtV)/RT
Note that the nomenclature was slightly changed from
Ref. 1 to conform to the nomenclature used for this article.
This procedure will provide reasonable estimates of
VOC emissions only when the pressure range is narrow and when the vapor pressure of the VOC is much
lower than the system operating pressure. When the
vapor pressure of the VOC approaches the system
pressure, this procedure significantly overstates the
actual emissions.
Hatfield method (2). Hatfield recognized the limitations of the EPA method and suggested an improved algorithm for estimating emissions from depressurization
operations. In order to maintain consistency with the
EPA method, Hatfield related the amount of condensible
gas released to the partial pressure of the non-condensible in the system (rather than to the total system pressure), as follows:
dnc = (VPc/RT)(dPnc/Pnc)

(2)

Integration of Eq. 2 between the initial and final

pressure of the non-condensible gas followed by rearrangement and substitution of terms yields the following working equation:

wc =

( P Pc )
VPc MWc
ln t1

RT
( Pt 2 Pc )

(3)

By selecting the partial pressure of the non-condensible gas as the independent variable (rather than the

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(4)

For a small change in pressure, the amount of VOC

evaporated can be neglected, and the total gas released
during depressurization is given by:
nt1 nt2 = V(Pt1 Pt2)/RT

(5)

The moles of VOC in the gas released over a small

interval is related to the total gas present in the
headspace and can be determined by:
dnc = (V/RT)(dPt)

(6)

The weight of VOC present in the gas vented can

be determined by integrating Eq. 6 between P t1 and
P t2 and substituting w c = n c MW c . This give the following equation:

wc =

P
VPc MWc
ln t1
RT
Pt 2

(7)

Special case no liquid. When no liquid is present in

the vessel, there will be no liquid evaporation into the gas
phase and the mole fraction of the VOC will remain constant during the entire depressurization operation. Under
these conditions, integration of Eq. 6 results in:

wc =

VMWc Pc

( Pt1 Pt 2 )
RT
Pt1

(8)

Table. Comparison between proposed method and existing methods.

Case

Initial
Pressure,
mm Hg

Final
Pressure,
mm Hg

Temperature,
C

Vapor
Pressure,
mm Hg

VOC
Emissions
Proposed
Method, lb

VOC
Emissions
EPA
Method, lb

VOC
Emissions
Hatfield
Method, lb

Ratio of
EPA
Method to
Proposed
Method

Ratio of
Hatfield
Method to
Proposed
Method

1-1

5,930

760

60.0

78.61

3.71

7.64

3.88

2.06

1.05

1-2

5,930

760

80.0

174.96

7.78

18.43

8.66

2.37

1.11

1-3

11,100

760

60.0

78.61

4.84

14.53

5.02

3.00

1.04

1-4

11,100

760

80.0

174.96

10.15

35.25

11.08

3.47

1.09

1-5

11,100

760

100.0

351.10

19.28

94.38

23.51

4.89

1.22

2-1

2,570

760

26.7

248.24

3.92

6.94

4.86

1.77

1.24

2-2

2,570

760

35.0

349.11

5.36

11.49

7.43

2.14

1.38

2-3

2,570

760

55.0

731.72

10.56

281.54

36.17

26.67

3.43

2-4

2,570

760

10.0

116.36

1.95

2.83

2.14

1.46

1.10

2-5

2,570

760

56.1

759.82

10.93

46,037.04

82.84

4,213.18

7.58

3-1

760

100

25.0

4.58

10.90

20.94

11.12

1.92

1.02

3-2

760

100

50.0

18.62

40.85

90.64

44.50

2.22

1.09

3-3

760

100

75.0

59.00

120.18

504.88

168.23

4.20

1.40

3-4

760

100

85.0

88.58

175.38

2,540.66

352.27

14.49

2.01

3-5

760

100

88.0

99.52

195.42

66,850.24

697.14

342.09

3.57

Case 1: 1,000-gal hydrogenation reactor. Total volume is 133.68 ft3, and vapor space is 66.84 ft3. Vapor space contains a mixture of hydrogen
(non-condensible) and n-octane (VOC). MWc = 114.22. Antoine constants for n-octane: A = 6.9186, B = 1,351.9, C = 209.15.
Case 2: 1,000-gal Nutsche pressure filter. Total volume is 133.68 ft3, and vapor space is 66.84 ft3. Vapor space contains a mixture of nitrogen
(non-condensible) and acetone (VOC). MWc = 58.08. Antoine constants for acetone: A = 7.1171, B = 1,210.59, C = 229.66.
Case 3: Distillation column 7 ft ID 75.5 ft H. Total volume is 2,905.60 ft3, and vapor space is 2,905.60 ft3. Vapor space contains a mixture of air
(non-condensible) and cumene (VOC). MWc = 120.20. Antoine constants for cumene: A = 6.9367, B = 1,460.79, C = 207.78.

Estimating emissions
Example 1. A 1,000-gal reactor is used to hydrogenate 1-octene to n-octane. The reactor headspace is
500 gal (66.84 ft3). The reaction is carried out at a pressure of 100 psig (5,930 mm Hg) and a temperature of

Nomenclature
MWc
nc
nt
nt1
nt2
Pc
Pnc1
Pnc2
Pt1
Pt2
R
T
V
Vt
wc

= molecular weight of the VOC

= total mole of VOC released, lbmole
= total mole of gas in vapor space, lbmole
= total mole of gas in vapor space at initial pressure, lbmole
= total mole of gas in vapor space at final pressure, lbmole
= vapor pressure of the VOC at the vessel temperature, mm Hg
= initial partial pressure of non-condensible gas, mm Hg
= final partial pressure of non-condensible gas, mm Hg
= initial system pressure, mm Hg
= final system pressure, mm Hg
= universal gas constant = 998.9 mm Hgft3/lbmoleK
= temperature of the air in the system, K
= headspace volume, ft3
= total volume of vessel, ft3
= weight of VOC released, lb

60C in the presence of a hydrogenation catalyst. During the reaction, essentially all the 1-octene is converted to n-octane. At the completion of the hydrogenation
step the reactor is vented. Estimate the amount of n-octane leaving the reactor. The vapor pressure of n-octane
is 78.61 mm Hg at 60C and the molecular weight of noctane is 114.22.
Equation 7 is used to calculate the weight of VOC
leaving the reactor:
wc =

66.84 78.61 114.22

5, 930
ln
998.9 333.15
760

= 3.71 lb
Example 2. A slurry containing acetone is filtered in a
1,000-gal Nutsche-type pressure filter under a pressure of
35 psig (2,570 mm Hg). At the end of the filtration step,
the filter is depressurized. Estimate the VOC emissions
from this step. Assume that the headspace is one half of
the total filter volume. The vapor pressure of acetone is
248.24 mm Hg at 26.7C and the molecular weight of
acetone is 58.08.

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Equation 7 is used to calculate the weight of VOC

leaving the reactor:
wc =

66.84 248.24 58.08

2, 570
ln
998.9 299.85
760

= 3.92 lb
Using Eq. 1, the emissions calculated by the EPA
method are 6.94 lb. Using Eq. 3, the emissions calculated by the Hatfield algorithm are 4.86 lb.
Example 3. A distillation column is evacuated from
atmospheric pressure to a pressure of 100 mm Hg prior
to start-up. The temperature in the column during evacuation is 25C. The column is 75.5 ft high and has a diameter of 7 ft (total volume is 2,906 ft3). The column
headspace is assumed to be saturated with cumene. Estimate the VOC emissions from this step. The vapor
pressure of cumene at 25C is 4.58 mm Hg and the
molecular weight of cumene is 120.20.
Case 1 For this case it is assumed that there is residual liquid in the column to maintain the gas phase saturated
with cumene during the evacuation step. Equation 7 is used
to calculate the weight of VOC leaving the column:

wc =

2, 906 4.58 120.20

760
ln
998.9 298.15
100

= 10.90 lb
Case 2 For this case it is assumed that no residual liquid is present in the column and that the vapors
are initially saturated with the VOC. As the column is
evacuated, the mole fraction of the VOC in the column remains constant during the evacuation step.
Equation 8 is used to calculate the weight of VOC
leaving the column:
2, 906 120.20 4.58
wc =

(760 100)
998.9 298.15 760
= 4.66 lb

Comparing the methods

The table provides a side-by-side comparison of the
emissions calculated by the three methods. It shows that
the EPA methodology calculates emissions that are in most
cases at least twice those calculated by the new method
proposed here. In cases where the vapor pressure approaches the final operating pressure, the divergence is
even wider (Cases 2-3, 2-5, 3-4 and 3-5).
The Hatfield algorithm provides, in many cases, values that are within 1040% of the results obtained by

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the proposed method. As the vapor pressure of the VOC

approaches the final pressure, the discrepancy increases
considerably (Cases 2-3, 2-5, 3-4 and 3-5).
The new proposed depressurization model can be
used over a wider range than the Hatfield method.
Specifically, it can be used to estimate emissions from
depressurization activities when the vapor pressure of
the VOC approaches the final operating pressure. It also
can be used to estimate emissions in situations when
liquid evaporation does not occur. Thus, it is believed to
be superior to the existing methods and is recommended as a method of choice for estimating emissions from
depressurization activities.

Program available
A template to estimate emissions via the proposed
method, as well as the existing methods, is available on
an Excel spreadsheet. Readers interested in obtaining a
copy of the template free of charge may contact the auCEP
thor via e-mail at peressj@nyc.rr.com.

Literature Cited
1. U.S. Environmental Protection Agency, Control of Volatile
Organic Compound Emissions from Batch Processes Alternative Control Techniques Information Document, Publication
No. EPA-450/R-94-020, U.S. EPA, Research Triangle Park, NC
(Feb. 1994).
2. Hatfield, J. A., Improved Algorithm for Estimating Process
Emissions from Batch Depressurization, Environmental
Progress, 17 (3), pp. 195198 (Fall 1998).

Further Reading
Peress, J., Estimate Storage Tank Emissions, Chem. Eng. Progress,
97 (8), pp. 4445 (Aug. 2001).

JIMMY PERESS, P.E., is director of Tritech Consulting Engineers (Jamaica,

NY; Phone: (718) 454-3920; Fax: (718) 454-6330; E-mail:
peressj@nyc.rr.com). He has over 30 years of professional experience
in process engineering, process troubleshooting, software
development and regulatory compliance (emission inventories and air
permitting). Prior to starting his consulting practice in 1983, he was a
process development manager and a senior consultant for Chem
Systems, Inc. He earned a BSChE from the Israel Institute of
Technology and an MSChE from the City University of New York. He is
a Professional Engineer registered in New York, New Jersey and
Delaware, and he holds seven U.S. patents. He is a member of AIChE
and the American Chemical Society.