PROCESS DEVELOPMENTS

Develop more accurate prediction of flash points

New calculation improves estimating minimum flash temperature for petroleum products
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flash point of a hydrocarbon mixture is a very imporrant parameter especially with regards to the safe handiing, storage r,, and transportation of hydrocarbons. By definition, the flash point is the minimum temperature at which vapors from the mixtue would produce a momentary flash when subjected to a standard test flame. The two widely accepted test methods for fiash-point determinations are Pens Martins and Abels flash apparatus. Flash points are extremely dependent on the lighter ends of any petroleum fraction.

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For fractions up to 500"F, Eq. 2 predicts flash poinrs with

reasonable accuracy, while Eq. 1 is applicable for higher boiling

,:

point fractions.

Methods. Riazi and Daubert determined that for petroleum fractions, ASTM 10% is more appropriate for calculating flash points. They proposed two equations for predicting flash points:

Better prediction method. A slight modification can predict the flash point value even more closer to the experimental value. Instead of taking ASTM 107o, if one replaces the value of ASTM 10% with the average of the initial boiling point (IBP), 5o/o and 10% in Eq. 1, the calculated flash point values obtained are very much closer to experimental values. Tble 1 summaizes the observations for diesel flash points ofvarious units from a refinery.
rf

tfr, = -o.ot+568+(2.84e4t lr,)*(,.r0: " ro-')r"

where

r,

rr:

-o.or+s6s +(z.a4t47lr^"0)*

(r.loe,

ro-3

(r

)ua"o
(3)

is the

Q and I1

are

in'R *O

ASTM 10% temperature of petroleum fraction.

where f,,, ir {uun .

5% + 10%)/31

in 'R and

is the fiash

point in "R.

Tf = -t24.72+0.707047,(+

are

in'F)

Error analysis.
Q)

Tble 2 lists the error analysis berween experimental and predicted values using Eq. 3.

Calculated flash points of diesel with varying ASTMs for different refineries
ASTM distillation

Samples
Diesel Diesel

Density

IBP

1 816.5 162 2 824.3 194 Diesel 3 853.9 230 Diesel4 sil.- - is) Diesel5 8058 152
flash point, 'C D1 = flash point estrmated from Eq. l pont D2 = f ash estrmated from Eq. 2
Exp =

5o/o 'l0o/o 50% 185 195 256 220 233 213 255 268 314 260 275 317 '168 176 263

90!o
JJ
I

95o/o FBP
352 346
381

Flash
55

Exp pt
b9
97 103 45

Flash,

330 367

360

D2 Mod (0,5,10) f Flash, "C "C 'C 66.96 63.38 180.67 57.32 g0.24 90.40 215.67 A.0
Flash2,

Dl

392
3g7

10e.1 112.59 54.10

lti,..lg
11g.34

zsi.o

roo.jg

3to
348

385 358

372

49.94

257.33 103.74 '165.33 46.56

sps,r..,,

25

Modfed=FlashpointestimtedfrommodifredEq. l,bysubstituting(1BP+5%+'T0%)/3
in place of ASTM 1 0%

20

Error analysis between experimental and

predicted values

r
t' o
Mod
2.32

15

Samples
Diesel
1

D1
1'l .96

D2

Elo
5 0

8.38 21.24 17.99

16.g4
1

Diesel 2 Diesei 3 Diesel 4 Diesel

5

21.40 12.16 9.59

1.09

i.s
0.7 4

Diesel

't

Diesel

Diesel

Diesel

Diesel 5

e.io

4.94

1.56

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PROCESS DEVELOPM ENTS

Comparison of predicted flash points with various dieselfractions using the f (0,5,10) method

160 140
I

Samples r
Sample
1

Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 Sample 10 Sample
11

(0,5,10) 161 .3 162.6 163.6 164.6 166.3 169 110 177.3 17g 296.6 31 3.6

Dl
52

49.8 49.8
53.4
51 .2

57.5 76.5 88.6

66.29 124.1
13'r .6

D2 47.8 45.7 45.6 4g.2 41.1 53.4 88.1 62.6 139 51

'1

Mod
+31
44.6

Exp
41

120
O

l;;;pl
<*r*#l "L---rz_-\.-

'It-aroeatl

.^100
t

45

45.3
46.1

46
42 43

E o E

--v

360
40 20 0

,r'\

\d/
I

47.2 49.1 +:e.8

13.e

48 40 39 49 138
141

50.8
56.1

Samples

122.5

129.5

As is quite evident fromTable 2 and Fig. 1, using f (0, 5, 10)-Eq. 3-in place of only 10% yields a flash point value which is close to the experimentally determined value. AIso, from a safery viewpoint, predicting a lower flash value is always safer rvhen handling and transporting petroleum fractions. To further test its compatibiliry a comparison using different fractions rvas carried out. Table 3 and Figs. 2-4list the resulrs of this study. From Figs. 2-4, the modified Riazi and Daubertt eqi-ration is accurate for all fractions with minor deviations from the experimenta-l values in the mid range. Most modern simulation and chemical software packages take into account Daubert equation for predicting flash

160 140 --l

120

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+oz
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lLaroeazI

"-100

'e
o

80

\,r

860
40
U

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\/
,1

-*
t)

l0

12

Samples

r#K
fip- Iis"{r* #*rx
o
o t

160

140

_l+.No

120

l.c-

exp

l_
I

"-100

'6
iE

80

360
40 20
0

I
J
6 Samples

poir.rts of petroleum fractions. By considering the average of IB!,5o/o

and 10%, o.ne can predict flash points even more accurately. Since, at the IBB we get the first drop of the fraction, it is at this point that the flash is predominant. So, the average of the first three points will give a more accllrate prediction of the flash point. HP
LITERATURE CITED
r Riazi, M. R. and T.
F.. Dauberr, "Predicting flash ancl
1

pour points," Hylrocdrbon

Prorcsing,Scpternber

987, pp. 81-83.

K. R. Ramakumar is a product on engineer at Indian Orl Corp. Ltd., Gujarat, lnd a. He has a BS degree in chemical engrneering from Sardar Val abhbhai National lnstitute of Technology, Surat, Gularat, where he was a bachelor of chemica enqlneer nq
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Select 1 79 at www.HydrocarbonProcessing.com/RS