235

CHAPTER 21

Enthalpies and Enthalpy Transfers

Chapters 10 through 20 indicate that rapid, efficient multi catalyst bed S O 2 -k- 1~O2
SO3 oxidation requires:

(a) warm 1st catalyst bed feed gas (-690 K)

(b) cooling of gas between beds and before H2SO4 making.

Fig. 21.1 indicates how these requirements are achieved for a single contact sulfur-
burning acid plant with 3 catalyst beds. It shows that:

(a) 690 K 1st catalyst bed feed gas is obtained by cooling sulfur burning exit gas in a
boiler and steam superheater
(b) 700 K 2nd catalyst bed input gas is obtained by cooling -890 K 1st catalyst bed
exit gas in a second boiler
(c) 710 K 3rd catalyst bed input gas is obtained by cooling-770 K 2 nd catalyst bed
exit gas in a steam superheater
(d) 470 K H2SO4 making input gas is obtained by cooling-720 K 3 rd catalyst bed
exit gas in an economizer (boiler feed water heater).

The final products of the flowsheet are (i) cool SO3 rich gas ready for H2SO4 making
and (ii) superheated steam.

Steps (a) to (d) all require transfer of heat to water or steam.

This chapter examines these heat transfers. Its objectives are to calculate:

(a) the enthalpies of (i) catalyst bed input and output gases and (ii) H2SO4 making
input gas
(b) heat transfers that will give these enthalpies.

These values pave the way for Chapter 22's examination of catalyst bed and H2SO4
making temperature control.
236

690 K, 10 volume% SOa,

11 volume% Oa, 79 volume% Na
gas from sulfur burning
furnace and boiler/superheater

l L~ 893.3 K I~ - - - -I . . . . .

b~ ~ I--
,, 700 impervious plate

~,~. . . . .2.nd
'~... . . catalyst
. . . . . . . . . .bed
.. '~(,~
V.....
,;~..'t....,.-...,.~.'t......~.-...~,..~..~.,.~~.h
. . . . .

<t 773.2 K
team superheater 710 K impervious plate

t~.. , 3rd~,~_~_~.~.~,~.~,~.~
~.~.~"~,~_~.~_
,,,"','" catalyst .~bed ~-~.~'
~.~~,,
- ~ -'"'""

721.1 K

economizer (boiler
feed water heater)

470 K, SO3 rich gas to

H2SO4 making
Fig. 21.1. Heat transfer flowsheet for single contact, sulfur burning sulfuric acid plant. It is
simpler than industrial plants, which nearly always have 4 catalyst beds rather than 3. The
gaseous product is cool, SO3 rich gas, ready for HESO4 making. The heat transfer product is
superheated steam. All calculations in this chapter are based on this figure's feed gas composition
and catalyst bed input gas temperatures. All bed pressures are 1.2 bar. The catalyst bed output
gas temperatures are the intercept temperatures calculated in Sections 12.2, 15.2 and 16.3.

21.1 Input and Output Gas Enthalpies

Fig. 21. l's catalyst bed input and output gas enthalpies can be calculated directly on our
heatup path-equilibrium curve worksheets, Table 21.1. Table 21.1's 3 rd catalyst bed
input gas enthalpy is, for example"
w O
Hinputgas - kg-mole S O 3 in * H710
so 3
o
+ kg-mole SO2 in * H710
so2
o
+ kg-moleOEin * H7~0
02
o
+ kg-moleN2 in * H710
N2
 237

= B34 *-D28
+ B35 *-E28
+ B36 *-F28
+ B37 *-G28 (21.1)
where B34 etc. are Table 21.1 cell references.

Cells D28-G28 each contain -H ~ Eqn. (11.7). This explains their negative signs in Eqn.
(21.1).

Table 21.1's cell H43 contains Eqn. (21.1) exactly as shown in the cell beside it. It
shows that Fig. 21. l's 3 rd catalyst bed input gas enthalpy is:

-25.94 MJ
per kg-mole of 1st catalyst bed feed gas.

21.1.1 Output gas enthalpy

Table 21.1's 3 rd catalyst bed output gas enthalpy is calculated the same way. It is
described by the equation:
o
Houtput gas --" kg-mole SO3 out * H721.1
SO 3

o
+ kg-mole SO2 out * H721. l
SO2

o
+ kg-mole 02 out * H72~.~
02

o
+ kg-mole N2 out * H72~.~
N2

= B38 * H28

+ B 3 9 " 128

+ B40 * J28
+ B41 9 K28 (21.2)

where 721.1 K is the 3 rd catalyst bed intercept temperature.

Table 21.1's cell H44 contains Eqn. (21.2) exactly as shown beside it. It shows that Fig.
21.1's 3 rd catalyst bed output gas enthalpy is"

-25.94 MJ

per kg-mole of 1st catalyst bed feed gas.

238
0
0
.,,.~
t~
0
0
o'1
ID
E ~
r~
t~
~d::l
d~
[_, .-,
o.~
0
~Z
0
J r,~
 239

21.1.2 First and second bed enthalpies

1 st and 2 nd catalyst bed input and output gas enthalpies are calculated from Tables J.2
and M.2 exactly as described above. They are summarized in Table 21.2.

21.2 H2SO4 Making Input Gas Enthalpy

Fig. 21.1's H2SO4-making input SO3, 502, 02 and N2 quantities are shown in Table
21.1. They are the 3 rd catalyst bed exit (intercept) quantities.

However, their 470 K enthalpies are not shown in the table. They are accounted for by
the equation:

H H 2 S O 4making input gas -- kg-mole SOa out * (0.07144 * 470- 420.6)

+ kg-mole SO 2 out * (0.05161 * 470 - 314.3)
+ kg-mole O2 out * (0.03333 * 470 - 10.79)

+ kg-mole N2 out * (0.03110 * 470 - 9.797) (21.3)

= 0.098 *-387.0
+ 0.002 *-290.0
+ 0.061 * 4.88
+ 0.790" 4.82

-34.40 MJ per kg-mole of 1st catalyst bed feed gas.

where:

'kg-mole 503 out' is kg-mole SO3 out of the 3 rd catalyst bed and into H2SO 4 making

and:
o
(0.07144 * 4 7 0 - 4 2 0 . 6 ) is H470
SO3

and so on.

21.3 Heat Transfers

21.3.1 Heat transfer from 3rd bed exit gas to economizer water

This section calculates how much heat must be removed from Fig. 21. l's:

721.1 K 3 rd catalyst bed exit gas

240

to cool it to the figure's specified:

470 K H2SO4 making input gas temperature.

This heat removal is calculated by the equation:

Q = IAHI =l HH2sO4makinginputgas- H3rdbedexitgas[ (21.4).

The enthalpies in this equation are those calculated in Sections 21.1.1 and 21.2, giving:

Q = IAHI = 1-34.40-(-25.94)1

= 8.46 MJ per kg-mole of 1st catalyst bed feed gas.

So, per kg-mole of 1st catalyst bed feed gas, 8.46 MJ must be removed from 721.1 K 3 rd
catalyst bed exit gas to cool it to the specified 470 K H2SO4 making input gas
temperature. The heat is, of course, transferred to water in Fig. 21. l's economizer.

21.3.2 1 - 2 and 2 - 3 heat transfers

Heat transfers from gas between beds 1 and 2 and 2 and 3 are calculated exactly as
described above. They are tabulated in Table 21.2.

Table 21.2. Summary of Fig. 21.1's temperatures, enthalpies and heat transfers. Note the con-
tinuing decrease in the gas's enthalpy as heat is transferred from gas to water and steam in Fig.
21.1's boiler, superheater and economizer. All temperatures but the last are from Tables J.2, M.2
and 21.1. Note that a catalyst bed's input enthalpy is always the same as its output enthalpy. This
is due to our assumption that there is no conductive, convective or radiative heat loss from the
gas.
Gas Temp. K Enthalpy ~
1st catalyst bed feed gas 690 - 17.31
1st catalyst bed exit (intercept) gas 893.3 -17.31
heat transfer to 1-2 boiler water 6.50 #
2 nd catalyst bed input gas 700 -23.81
2 na catalyst bed exit (intercept) gas 773.2 -23.81
heat transfer to superheater steam 2.13 #
3 rd catalyst bed input gas 710 -25.94
3 rd catalyst bed exit (intercept) gas 721.1 -25.94
heat transfer to economizer water --, 8.46 #
H2SO 4 making input gas 470 -34.40
#MJ per kg-mole of 1st catalyst bed feed gas.
 241

21.4 Heat Transfer Rate

The rate at which heat is transferred from Fig. 21.1's 3 rd catalyst bed exit gas to its
economizer water is calculated from:
Section 21.3.1's heat transfer amount, MJ per kg-mole of 1st catalyst bed feed gas

and:

a specified 1st catalyst bed feed gas input rate, Nm 3 per hour, e.g. 100 000 Nm3/hour.

Heat transfer rate is given by the equation:

1st catalyst bed feed gas input rate, Nm 3/hr

heat transfer rate = Q * (21.5).
22.4 Nm 3 of feed gas per kg-mole of feed gas

With Table 21.2's 8.46 MJ economizer heat transfer (Q), it is"

catalyst bed exit

3 rd
gas to economizer =
heat transfer rate

MJ per kg-mole 100 000 Nm 3 of 1st catalyst bed feed gas per hour
= 8.46 of 1st catalyst *
bed feed gas 22.4 Nm 3 of feed gas per kg-mole of feed gas

(21.6)
= 38 000 MJ per hour.
21.4.1 Extension

This chapter has examined a very simple acid plant. Its techniques are, however,
readily extended to complex industrial acidmaking situations.

21.5 Summary

Catalyst bed gas enthalpies are readily calculated on our heatup path-equilibrium curve
intercept worksheets.

These enthalpies are conveniently used to calculate the amount of heat that must be
removed to cool a catalyst bed's output gas to a specified temperature.

The enthalpies and heat removal quantities are all calculated per kg-mole of 1st catalyst
bed feed gas.

The heat removal quantities (plus 1st catalyst bed fee:l gas input rate) are readily used to
determine the cooling requirements (MJ/hour) of each of Fig. 21.1's gas cooling
devices.
242

The next chapter builds on this information to show how catalyst bed and H2SO4
making input gas temperatures are controlled by bypassing gas around the cooling
devices.

Problems

21.1 Prepare a table like Table 21.2 for:

12.0 volume% S O 2
13.2 " 0 2
74.8 " N2

1st catalyst bed feed gas and the following catalyst bed gas input temperatures:

1st catalyst bed 675 K

2 nd " 685 K
3 rd " 695 K.

Assume that:

(a) the pressure in all catalyst beds is 1.2 bar

(b) heatup path-equilibrium curve intercepts are attained in all beds

(c) the 3 rd catalyst bed exit gas enters H2SO4 making at 470 K.

Hints

Use your Problem 12.3, 15.1 and 16.1 spreadsheets to calculate input and
output gas enthalpies (as described in Section 21.1).

. Use your Prob. 16.1 3 rd catalyst bed output quantities and Eqn. (21.3) to
calculate H2SO4 making's input gas enthalpy.

21.2 Calculate the rate, MJ/hour, at which heat must be transferred from 3 rd catalyst
bed exit gas to economizer water to obtain the above specified 470 K H2SO4
making gas. 100 000 Nm 3 per hour of 1st catalyst bed feed gas is entering the 1st
catalyst bed.