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FINAL REPORT
VOLUME II
APCO Contract No. CPA 70-45
A STUDY OF THE LIMESTONE INJECTION
WET SCRUBBING PROCESS
CHEMICAL RESEARCH . SYSTEM? ANALYSIS • COMPUTFR SCIENCE • CHEMICAL ENGINEERING
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.
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.
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FINAL REPORT
VOLUME II
APCO Contract No. CPA 70-45
A STUDY OF THE LIMESTONE INJECTION
WET SCRUBBING PROCESS
Presented to:
AIR POLLUTION CONTROL OFFICE
DEPARTMENT OF HEALTH, EDUCATION AND WELFARE
411 West Chapel Hill Street
Durham, North Carolina 27701
1 November 1971
CHEMICAL RESEARCH. SYSTEMS ANALYSIS. COMPUTER SCIENCE. CHEMICAL ENGINEERING
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TABLE OF CONTENTS
Technical Note 200-004-12
Technical Note 200-004-19
Technical Note 200-004-21
Calculation of the Enthalpy of
Aqueous Ionic Solutions
Description of the Radian Process
Model for the Prototype LIWS System
Equilibrium Calculations for Type I
APCO Inhouse Experiments
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TECHNICAL NOTE 200-004-12
CALCULATION OF THE ENTHALPY OF
AQUEOUS IONIC SOLUTIONS
Prepared by:
David W. DeBerry
Philip S. Lowell
25 August 1970
CHEMICAL RESEARCH. SYSTEMS ANALYSIS. COMPUTER SCIENCE. CHEMICAL ENGINEERING
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1.0
INTRODUCTION
Key ingredients in chemical process design or analysis
are the energy and material balances. This is true for the
lime/limestone wet scrubbing process. This process involves
gas, liquid, and solid stream components. The energy balance
involves sensible heats, latent heats, heats of reaction, and
heats of mixing.
This technical note is concerned with the aqueous
solution. It takes into account the various ionic and non-
ionic species present, their heats of reaction, and their heats
of dilution. With the ability to calculate the enthalpy of the
total liquid phase, data may be analyzed more accurately. Also
the effect of the chemical reaction system in the liquid phase
may be calculated. Without a computational scheme such as is
presented here, not even the order of magnitude of the ionic
reaction system and liquid phase non-ideality could be estimated.
A classical chemical engineering approach was used to
solve this problem. The total enthalpy of the solution is the
sum of the partial molal enthalpies of the solution components.
The partial molal enthalpy of each solution component was
calculated as the sum of the reference state enthalpy and the
difference between the partial molal enthalpy and the reference
state enthalpy.
In addition to this classical approach for enthalpy
calculation, the enthalpy and equilibrium calculations made by
Radian are put on a thermodynamically consistent basis. The
standard state heat of reaction is related to the change of the
equilibrium constant of that reaction with temperature. The
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heats of dilution of the solution components are related to the
change in the activity coefficients with temperature. These
relationships between equilibrium data and enthalpy data are
accounted for on a thermodynamically consistent basis.
The following method for calculating enthalpy is outlined
in this technical note. First the thermodynamic basis is given.
Second the derivation of the equations for the difference between
ideality and reference state are given. Then the means of
selecting the reference states are discussed. Finally a compari-
son is made between experlmental and calculated values.
2.0
THEORY
The Gibbs free energy of an actual reaction is given
in Equation 1.
6G = 6H - T 6S
( 1)
The heat of the reaction is given by the Gibbs-Helmholtz
equation, Equation 2.
-6H
r
=
o( 6G/T)
aT
(2)
The free energy may be considered to be composed of
two parts, a standard state free energy plus a deviation from
the standard state.
M
6,G = 6G 0 + 6G
(3)
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Hence the enthalpy may be considered to be composed
of two parts as in Equation 4.
-bH - o(bGo IT)
7 - oT
M
+ o(bG IT)
oT
(4a)
= - 6Ho
T:a
M
+ -6H
~
(4b)
The first term, the contribution in going from
reactant reference state to produce reference state, is
in Equation 5 for a J+l component system
J+l
bHo = I
j=l
given
n.H~
J J
(5)
The various He: values need to be determined.
J
consider the ionization of water
As an example
H:aO
~
H+ + OH-
(6)
The free energy of this reaction from standard state to
standard state is known as a function of temperature and hence
the standard state heat of the reaction is known from Equation
4. The enthalpy of water is known and the enthalpy of the
hydrogen ion at infinite dilution (reference state for H+) is
arbitrarily set equal to zero at 25°C. The enthalpy of the
hydroxyl ion may be calculated as shown in Equation 7.
HOH- = HH:aO - HH+ + bHR
(7)
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This method may be used to calculate the reference state
enthalpy of the various species in the solution. As may be
seen, there may be several different paths from which the
value of a reference state enthalpy may be calculated. An
effort must be made to use that path that seems to have the
most reliable data.
The second term in Equation 3 is the free energy
associated with the difference between reference state and
actual state conditions. For a J+l component system the free
energy of mixing is given by
M
{JG
=
J+l
RT I
j=l
n. tna.
J J
(8)
Substituting Equation 8 into Equation 4 yields the expression
for the heat of mixing.
M
- {JH
=
J+l
RTa I nj
j=l
otna.
1
oT
(9)
The problem of calculating enthalpies is that of evaluating
Equations 5 and 9 in the units that are appropriate to our
problem.
The total enthalpy,
partial molal enthalpies of
by the following equation.
H, of a system is related to the
the J+l constituents of the system
H = nlHl + naHa
+ ...
J+l
'\
= L
j=l
n.H.
J J
( 10)
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For aqueous
the species
molality of
solution it is convenient to use the molalities of
instead of the number of moles. We define the
th .th
e J- species in the following way.
n.
m. =--1-
J
nwMw
=
njmw
nw
( 11)
Mw is the molecular weight of water with the units kg/mole. It
is also convenient to express the partial molal enthalpy as the
sum of the deviation from standard state, H. - H'?, plus its
J J
standard state value, H~.
J
Hj = (Hj - Hj) + Hj
( 12)
With these definitions, the total enthalpy can be expressed
as in Equation 13.
J+l
H = ~ \' m.[(H.- H~) + H~J
mw . L1 J J J J
J=
( 13)
Separating the water term, we obtain Equation 14.
H = n {(H - HO) + HO
w w w w
+1-
mw
J
I mj [ (Hj - Hj) + H; J}
j=l
( 14)
This is the general equation which we will use for the energy
balance. The molalities of the species may be calculated using
the Radian chemical equilibrium program. The calculation of
the deviation terms and standard state entha1pies is discussed
below.
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The deviation from the standard state may be calculated
from the variation of the activity coefficient with temperature.
(Hj - Hj) = -RTa
aP,na.
1 =
aT
2
-RT
a p,n y.
1
aT
(15)
We will derive two separate expressions, one for the species in
solution, and one for water.
In the Radian model, the activity coefficients of the
species in solution are given by the following equation.
.k
2 [ -12
p,nYj = AZjP,nlO 1 + &.BI~
J
+bjIJ+UjI
(16)
For the present we must assume that only A and B are functions
of temperature.
6 ~
1.8246xlO
A = (DT) 0/2 d
0
50.29d ~
B = 1 0
(DT) 2
( 17 a)
(17b)
These coefficients contain the temperature as well as the
dielectric constant (D) and the density of water (do) which
are functions of temperature. Differentiating p,ny. we obtain
1-
Equation 18.
ap,ny.
1-
aT
.k
= z; (p,nlO){~~ [1 + ~~:I~
J
o
+ bjIJ + A ~~ [(1:~~BI~)2J}
.J
(18)
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In evaluating the derivatives of A and B we will use the
following definitions.
a ==
1 (oV)
V oT P =
~1 (odo)
o oT p
( 19)
T ==
1 oD + 1
D oT T
(20)
Differentiating A and B and using these definitions we obtain
Equations 21 and 22.
~~ = - ~ A (T + 3 )
(21)
oB - 1
oT - - 2 B (T + a)
(22)
Combining Equations 15, 18, 21, and 22, and using the
definition s. = ~.BI~, yields the desired expression for the
1. J. 1 J 1 1 h 1 f h . th . . 1.
re at~ve part~a mo a ent a py 0 t e J- spec~es ~n so ut~on.
:3 a
(Hj - Hj) = RT Az~tn10 {3(T + ))bjI -
I~[2SiT + 3( T + J)] \
(1 + Bj):3 J
(23)
The expression for the relative partial molal enthalpy
of water is analogous to that given for the solution species.
(H - HO') = -RTa otny
\ w w w
oT
a
= -RT
otnaw
oT
(24)
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The derivation of an expression for tnaw
Technical Note 200-004-02, 27 May 1970.
in Equation 25.
was given in Radian
The result is shown
- tnaw
J
- tn10 '\
- m L m.
w . 1 J
J=
a ~
{-AZ;I
~~
J
[~j - 2tn(1 + ~j) + l:j ~. ]
J
+ ~ [AZ;bj + Uj J} + ~w I mj
j
(25)
Once again we assume that only A and B are functions of
temperature
otnaw oA
aT = aT
o1..naw
aA
J
+ aB '\ ~
oT .L oB
J=l
o p,naw
08.
J
(26)
After performing the differentiations of tnaw, we can use our
previous results to obtain (Hw - H~).
2
(Hw - H~) = R~ {3( T
J
~) [ tnlO '\
+ "3 tnaw + rn:- L mj
j=l
(¥ + tntO)J
- A(,. + ~)
1: J a
I 2 n 10 m. Z .
X,n '\ 1 1
mw L ~~
j=l J
[- ~ tn( 1 + ~J')
~j
a
6 + 9~. + 2~.
+ J J
(1 + ~ j )2
J}
(27)
The remaining quantities necessary for the enthalpy
calculation are the standard state entha1pies, Hj', The standard
state heats of formation were chosen for this application. This
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enables us to select a certain number of "key" enthalpy values
and then calculate the rest from heats of reaction.
The selected standard state heats of formation of the
key species are given in Table I. The values for the aqueous
species are based on the assignment of Hi = 0 for H+(aq) at
25°C. The values given are those which are considered to be
the most accurate and which should give the best relative
accuracy in the computational chain.
The standard state heat of reaction may be calculated
from the variation of the equilibrium constant with respect
to temperature.
o.tnK -
~-
6Ho
.=::.:..a..
RTa
(28)
The data for .Q,nK as a function of temperature used in the
Radian chemical equilibrium program were used to calculate
6H~ at 25°C for each reaction. Using these heats of reaction
and the selected heats of formation, the remaining heats of
formation at 25°C were calculated by the following equation.
6H~ = \ e HOf (product) - \e Hfo (reactant)
L p. . L, r. .
j J J j J J
(29)
These values are given in Table II.
Heat capacities are necessary for calculating the
heats of formation at temperatures other than 25°C. The
literature survey and preliminary calculations indicated that
the mean heat capacities calculated by Criss and Cobble (CO-DOl)
from their entropy correspondence principle would give
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TABLE
I
HEATS OF FORMATION OF THE KEY SPECIES AT 25°C
Species Hf,298.16(kca1/mo1e)
H; O(.t) - 68.317
H+(aq) 0.00
SO:(aq) -216.90
NO;(aq) - 49.372
++ -129.77
Ca (aq)
SO; (g) - 70.93
CO:a(g) - 94.01
C1-(aq) - 40.023
++ -110.41
Mg (aq)
+ - 57.279
Na (aq)
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Species
H~O
H+
OH-
HSO;
SO;
SO:
HCO;
CO;
NO;
HSO~
H2 S03
H2 C03
Ca++
CaOH+
CaSO~
Ca CO~
CaHCOt
CaSO~
CaNOt
Mg++
MgOH+
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TABLE
II
STANDARD STATE HEATS OF FORMATION AND MEAN
HEAT CAPACITIES OF LIQUID SPECIES
o ( kca 1) TOOC( ca1 )
Hf,298.16 mole C~ 25 mo1eoK
- 68.317 18.04
0.000 23.
- 54.799 - 47.
-149.376 - 16.
-152.276 -121.
-216.900 - 99.
-164.729 - 27.
-162.126 -132.
- 49.372 - 49.
-211.660 - 13.
-145.516 + 7.
-166.971 91.
-129.770 45.
-183.320 2.
-279.736 - 76.
-289.720 - 87.
-293.118 18.
-344.033 8.
-173.445 4.
-110.410 51.
-162.839 4.
continued
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TABLE II (continued)
0 (kca1) ]600C( ca1 )
Species Hf,298.16 mole C; 25 mo1eoK
MgSO~ -260.707 - 70.
MgHCOt -274.063 24.
MgSO~ -322.469 - 48.
MgCO~ -270.226 - 81.
Na+ - 57.279 35.
NaOHo -112.078 - 12.
NaCO; -218.017 - 97.
NaHCO~ -222.008 8.
NaSO; -273.076 - 64.
NaNO~ -106.651 - 14.
C1- - 40.023 - 51.
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satisfactory results. Using this form, the heats of formation
at a temperature between 25 and 60°C are given by Equation 30.
60
Hf.(T) = Hf.(298.l6) + Cp,jJ
J J 25
(T - 298.16)
(30)
All of the pertinent values given by CO-OOI
Missing values were calculated from the oC
p
computational scheme similar to the one given for the enthalpies.
This procedure is subject to greater inaccuracies, however,
since the calculation of oC requires a second differentiation
p.
of tnK. Most of the equilibria data do not justify this opera-
tion. The calculated and adopted values for C .J60 are also
P,J 21!!
given in Table II.
were adopted.
of reaction and a
The equations and data necessary for the enthalpy
calculation were incorporated into a computer subroutine.
Functional forms for some of the coefficients such as a. and d
o
were obtained by curve fitting tabular data. The comparison
of experimental and calculated results is given in the next
section.
3.0
COMPARISON OF EXPERIMENTAL AND CALCULATED RESULTS
Thermodynamic values were calculated for several simple
systems and compared with experimental values. The integral
heats of solution at a given molality was used for most of
the comparisons. In terms of the calculated total enthalpy,
H, the integral heat of solution of a single salt in water at
a given temperature is given by:
OHsoln. = l/ns[H - nwH~ - nsH~J
(31)
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H~ and H~ are the heats of formation of water and pure solute
respectively, and nw and ns are the corresponding number of
moles of water and solute. This equation was used to calculate
6H 1 for HC1(g), CaCla(s), and Ca(OH)a(s).
so n.
The relative partial molal enthalpy of the total solute,
La, was also calculated for several cases. This is essentially
the "deviation" term given by
L =
a
J
\" (-
L Vj Hj
j=l
- Hj)
(32a)
Ll = (Hw - H~)
(32b)
where v. is the number of anions or cations which one electrolyte
J
molecule dissociates into. The results of these calculations
are given in Table III. In general the agreement is good. The
present model does not predict the maximum in La shown by NaCl.
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TABLE III
COMPARISON OF EXPERIMENTAL AND CALCULATED RESULTS @ 25°C
Experimental Calculated Experimental Calculated
Molality 6Hsoln 6Hsoln La La
Solute (mole/kg H~O) (cal/mole) (cal/mole) (cal/mole) (cal/mole)
HCL(g) 0.04 -17,800 -17,895
CaCla(s) 0.02 -19,560 -19,560 360 339
0.05 ------- ------- 490 443
0.10 ------- ------- 620 517
0.60 ------- ------- 1020 529
I
...... Ca(OH):a(s) 0.004 4,082 3,525
\J1
I 0.01 - 3,819 3,400
-
0.02 - 3,523 - 3,345
NaCl 0.06 ------- ------- 94 112
0.37 ------- ------- 42 181
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4.0
NOMENCLATURE
a
activity
o
a
ion size activity coefficient parameter
A
Debye-Huckel limiting slope constant
b
activity coefficient deviation parameter
B
Debye-lfuckel constant
Cp
heat capacity
do
density of water
D
dielectric constant of water
G
Gibbs free energy
H
enthalpy, total
H
partial molal enthalpy
HO
reference state enthalpy
M
H
heat of mixing
I
ionic strength
J
number of species except for water
K
equilibrium constant
L
relative partial molal enthalpy
m
molality
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. .
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M
molecular weight
n
mole
R
gas constant
S
entropy
T
absolute temperature
u
activity coefficient parameter
v
number of ions formed from one mole of solute
v
volume
z
ion charge
Greek
o.
derivative term defined by eq 19
s
k
the term aBI2
y
activity coefficient
T
derivative term defined by eq 20
Subscripts
.th .
J- specl.es
j
s
solute
w
water
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5.0
BIBLIOGRAPHY
CO-DOl
Criss, Cecil M., and J. W. Cobble, J. Am. Chern. Soc.,
86, 5385 (1964).
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TELEPHONE 512 . 454.9535
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TECHNICAL NOTE 200-004-19
DESCRIPTION OF THE RADIAN PROCESS MODEL
FOR THE PROTOTYPE LIWS SYSTEM
22 March 1971
Prepared by:
Delbert M. Ottmers, Jr.
Senior Engineer
CHEMICAL RESEARCH. SYSTEMS ANALYSIS. COMPUTER SCIENCE. CHEMICAL ENGINEERING
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I.
INTRODUCTION
Radian has developed a computerized process model for
the limestone injection - wet scrubbing (LIWS) process. The
process model is based upon (1) the ability to predict vapor-
liquid-solid equilibria for the CaO-MgO-NaaO-S02-C02-S03-N205-
HC1-H20 system and (2) a number of process assumptions with
regard to equipment characterization and the extent of various
chemical reactions.
Much of the theoretical basis for this process model
was developed under APCO Contract No. CPA 22-69-138 and is
described in the Radian Final Report "A Theoretical Description
of the Limestone Injection - Wet Scrubbing Process". The
computerized process model used (1) employs a modular approach
to performing process material and energy balances, (2) spe-
cifies the extent of various reaction steps by appropriate
equilibrium assumptions or model inputs, (3) characterizes the
various process vessels in terms of practical equipment descrip-
tions, and (4) converges the model's iterative parameters with
suitable numerical techniques.
This technical note presents a description of the
Radian process mode 1. A brief description of the LIWS process
with regard to its relationship to the process model will be
followed by listing of the model assumptions and parameters.
After these discussions, a detailed description of the model
will be presented.
The utility of this model to process development and
design is clear. Simulation results for the prototype LIWS
process are discussed in Radian Technical Note 200-004-18.
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II.
PROCESS DESCRIPTION
A qualitative description of how the Radian model
relates to process operation will be presented in this section.
The model description will be given in terms of the wet scrubbing
scheme which represents the essential features of the prototype
LIWS system being planned for TV A's Shawnee Plant at Paducah,
Kentucky. The process description for other process schemes
should follow by analogy to this one.
Figure 11-1 is a schematic diagram showing the various
process vessels and streams.
The scrubber serves as a gas-liquid contacting device
with some dissolution of limestone solids. In the present
model, the scrubber (S) is assumed to trap all of the solids
in the flue gas stream so that no solids leave with the stack
gas. For material balance calculations the inlet gas stream to
the scrubber has been divided into two fractions, a flue gas
stream (FG) containing only gaseous components and a limestone-
fly ash stream (LA) containing only solid components. The
solids are composed of two parts: limestone (LS) and flyash
(FA). In this model the stack gas (SG) leaving the scrubber is
assumed to be in equilibrium with the scrubber liquor (and
thus with the scrubber bottoms).
The scrubbei effluent hold tank (E) serves mainly as a
solids dissolution and precipitation vessel. This stirred
tank should approximate idealized backmix flow and in practice
should be designed to provide enough residence time and agita-
tion to hydrate and dissolve the major portion of the CaO and
MgO that dissolves in the system. In this model some CaO and
MgO entering the stream are taken to be unreactive. This amount
of CaO and MgO leaves the system unreacted in the filter
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GAS SPECIES
FGI SG
STACK GAS
SG
WATER
MAKEUP
VIM
I. SOz
2. COz
3. NOx
4. HzO V
5. Oz
6. CO SCRUBBER FEED PROCESS
7. Nz SCRUBBER WATER
S SF HOLD TANI<
P
SCRUBBER
FLUE GAS BOTTOMS
FG ~ SB SLURRY RECYCLE SR..
-
I
CLARIFIER ~
LIQUID
.' CL
LIMESTONE
FLY ASH SCRU8BER CLARIFIER
SOLI OS EFflUENT FEED.. CLARIFIER --
LA HOLD TANK po- C
CF
r. CoO E
2. MgO. CLARIFIER
3. CoS04 80TTO;/1S
4. MgS04 ' CB
5. COS03
6. M9S03 FILTER
7. COC03 -
F ~
8. MgC03 FILTER
LIQUID
9. FLY ASH FL
10. SOLUBLE No FIL TER
II. SOLUBLE CI BOTTOMS
FB
PROCESS SOLID SPECIES
(CFI SRI CO, FB, SF)
6. MgO
7. Mg(OHh
8. M9C03' XH20
9. Mg503 . X HzO
10. FLY ASH
I. Co 0
2. Co(OHh
3. COC03
4. Co 503 . X Hz 0
5. COS04 . xHzO
FIGURE 11-1 WET SCRUBBING SCHEME
-3-
PROCESS
LIQUID
SPECIES
SB, CF~ SRI C81
FB, CLlL, SF
I. H+
2.0H-
3. HS03
4. 503
5. S04
6. HC03
7. C03
8. HS04"
9. H2S03
10. Hz C03
II. Co++
12. CoOH+
13. Co S03
14. COC03
15. CoHCO~
16. COS04
17. CoNO!
18. N03
19. Mg ++
20. r.1g0H +
21. r'019S04
22. MgHCO!
23. MgS03
2 4. ~lgC03
25. No+
26. NoOH
27. NoC03
28. NoHC03
29. NOS04
30. NoN03
31.CI-
~
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1-
Radian Corporation
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bottoms (FB) stream. All of the remaining CaO and MgO which
enters the effluent hold tank (E) is assumed to be available for
reactions. The liquid leaving the effluent hold tank (E) is
assumed to be in equilibrium with respect to the liquid and
solid phases. This implies that several species will dissolve
or precipitate. A major portion of the precipitation in an
actual process will probably occur in the effluent hold tank.
The clarifier and filter vessels serve mainly as
solid-liquid separators. In the model presented, the clarifier
liquid (CL) was assumed to be in equilibrium with the solids
in the clarifier. The liquid in the clarifier bottoms (CB) was
assumed to have the same composition as the CL stream. This
model also assumes that the compositions of the solid and liquid
phases in streams leaving the filter (FB and FL) are the same
as the compositions of the solid and liquid in equilibrium in
the clarifier and filter. This situation would exist if the
clarifier and filter were operated at the same temperature, or
if the solid-liquid "shift" in the filter were insignificant.
The CL and FL streams can contain a small amount of solids due
to clarifier and filter inefficiencies which are specified as
model inputs.
The' process water hold tank (P) is a stirred tank which
serves as a liquid mixer. Here the clarifier and filter liquids
(CL and FL) and slurry recycle (SR) are diluted with water make-
up (WM) to produce the scrubber feed (SF) for the scrubber. In
this model, this tank is assumed to be an ideally backmixed
vessel that has attained solid-liquid equilibrium.
Figure 11-1 also shows the chemical species possibly
present in various process streams. Seven gaseous species are
listed for the flue and stack gases. The nitrogen oxides in
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the gas phase are designated NOx since not enough information
concerning (1) NOx composition in the gas phase, (2) oxidation
rates, and (3) chemical reactions in liquid phase has been
found in the literature. Due to this uncertainty, a realistic
fraction of the NOx in the flue gas will be taken as absorbing
and this NOx will show up in the process liquids as "equivalent
nitrates". A refinement of this approximation can be made if
enough information concerning the NOx system becomes available.
The limestone - fly ash stream (LA) could contain eleven
solid species, CaO and MgO being the major ones. The fly ash
component is not specified in further detail because fly ash
compositions vary to some extent and because the soluble nature
of the fly ash is not fully known at this point. For the pur-
poses of this model, the fly ash will be assumed to contain
Na20, NaCl, and inerts.
III.
MODEL ASSUMPTIONS AND PARAMETERS
The present Radian model is based upon the following
assumptions:
( 1)
The partial pressures of S02' CO2, and
H20 in the stack gas leaving the scrubber
are in equilibrium with the scrubber
liquid at the scrubber temperature.
(2)
After withholding a portion of the input
lime (CaD and MgO) as being chemically
unreacted in the system, solid-liquid
equilibrium is achieved in the scrubber-
effluent hold tank and the process-water
hold tank.
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(3)
The clarifier and filter are solid-liquid
separators only (no chemical change occurs).
(4)
Ionic reactions taking place in the liquid
phase are rapid and thus at equilibrium.
The first assumption is based on the premise that the gas-liquid
absorption step is not rate controlling, whereas the second
assumes the hold tanks are large enough to permit solid-liquid
equilibrium except for a portion of unreactive lime. This
unreacted lime (CaO and MgO) is fixed by model input.
The compositions for the system inlet and exit streams
[limestone (LS1 fly ash (FA), flue gas (FG), stack gas (SG),
and water makeup (WM)] and operating conditions for the process
are model inputs. Other model parameters are used to set the
"conversion" in the process due to various rate steps. That is
to say, the fraction of precipitating solids, limestone in the
flue gas entering the scrubber and dissolving, sulfite oxidizing,
and NOx absorbed in the scrubber are set by the model parameters.
A list of the model parameters along with their typical
units is given below:
1.
Theoretical Limestone ~Ol~~1~:Os62M~~ ~~ LS]
2 .
Lime Hydrating in System [1 - moles CaO + MgO in FBJ
moles CaO + MgO in LS
3.
Scrubber r~oles CaO+MgO from LS hYdrating]
Lime Hydrating in L moles CaO+MgO in LS
4.
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Radian Corporation
10.
11.
12.
13.
14.
15.
16.
17.
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5.
Recycled Solids Dissolving
[1 - Ca(OH)a + Mg(OH)a from SF left in SB]
moles Ca(OH)a+Mg(OH)a from SF
6.
L' C' . . [ moles MgO in LS ]
lmestone omposltlon moles CaO + MgO in LS
7 .
Fl A h L 1 [ wt. fly ash ]
y seve wt. sulfur in coal
8.
Soluble Sodium [wt. fro Na in FAJ
9.
Soluble Chlorine [wt. fro Cl in FAJ
SO a Level in Flue Gas [mole fro SOaJ
SOa Absorbed [moleS 806 abSOrbed]
mole ::; a In l'G
S If' ° 'd' d [mOleS SOa oxidizedJ-
u lte Xl lze mole SOa absorbed
COa Level in Flue Gas [mole fro COaJ
NO Level in Flue Gas [mole fro NOJ
NOa Level in Flue Gas [mole fro NOaJ
NO Absorbed [moles NO a~sorbed]
moles NO In FG
NO Absorbed [moles NOa a~SOrbed]
2 moles NOa In FG
Solids in Filter Bottoms [wt. fro solids in FBJ
Solids in Clarifier Bottoms [wt. fro solids in CBJ
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18.
F"l Eff" " [ wt. solids in FB I
~ ter ~c~ency wt. solids in filter inletJ
19.
[ wt. solids in CB ]
Clarifier Efficiency wt. solids in clarifi~r inlet
20.
Solids Precipitated in Scrubber [yes or no]
21.
Circulating Liquor Temperature [OF]
22.
[Gal. of SF ]
Scrubber Feed Rate 1000 ACF of FG
Actually, the temperature of the scrubber liquor is determined
by an energy balance about the scrubber. (Here, the humidity
and temperature of the flue gas are the dominant factors.)
Then the tempterature of the circulating liqu~r is set equal to
that of the scrubber liquor.
Process simulations have been conducted by specifying
the amount of S02 to be removed from a flue gas of known
composition and adjusting the amount of slurry recycle (SR)
(or the amount of scrubber feed (SF) in some cases) to obtain
this S02 removal. In these cases, the fractions of limestone
solids (LS) reacting in the scrubber have been specified as a
model input. In the same way, the fractions of solid species
in the scrubber feed (SF) stream that are available for reaction
are also model inputs.
All of the liquid-phase species are allowed to react in
the scrubber. Thus, for a fixed scrubber feed (SF) rate, the
amount of slurry recycle (SR) required to obtain the desired S02
removal is a measure of the scrubbing capability of the process.
High slurry recycle rates indicate a poor set of scrubbing
parameters.
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IV.
COMPUTERIZED PROCESS MODEL
The computerized process model consists of essentially
three parts: (1) an executive system that interconnects the
processing units in appropriate fashion and controls the
sequencing of computer operations, (2) equipment subroutines
that model each process unit, and (3) convergence subroutines
that force convergence of the model's iterative parameters.
The design of anyone of these parts is dependent upon
the design of the other parts. For example, a generalized
scheme for performing material and energy balance calculations
is attractive from the standpoint of model flexibility. How-
ever, this approach suffers from the need of greater programming
sophistication and from less specific (and thus slower) con-
vergency routines.
Radian has developed a computerized model that is based
upon a compromise between generalization for greater system
flexibility and specialization for improved computational
efficiency. The modular concept for equipment subroutines has
been used. This concept tends to allow greater flexibility in
simulating various processing schemes. These equipment sub-
routines are specialized only to the extent that more rapid
convergency can be obtained by using the engineer's knowledge
of the system. Wherever possible the equipment subroutines were
formulated to allow for extension to models which give a more
sophisticated description of the processing unit.
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A.
Executive System
The function of the executive system is to interconnect
the various process units in the appropriate fashion and control
the sequencing of the computer operations.
The process units are interconnected by means of a
"process matrix" during an initialization phase of computer
operations. In this phase, model input data are read into the
machine, the process matrix is used to define the processing
scheme, and each equipment box is initialized. The interconnec-
tion of equipment boxes for the prototype system is shown in
Figure IV-l. Here each processing unit is labeled by a number,
its name, and the subroutine designation. For example, the
subroutine used for the scrubber [equipment number (4)J is
designated SCRUBR. In .addition, the various process streams are
labeled by letter abbreviation and a stream number.
The "process matrix" used to define this processing
scheme is given on the first page of computer print-out for each
simulation case. An example simulation case (Prototype Simula-
tion No.2-B) is given in the Appendix. The "process description"
information defines the interconnection of process units. For
example, equipment number 4 is the scrubber (subroutine SCRUBR).
It has input streams numbered 2 and 15 and output streams
numbered 3 and 6.
The executive system also must be given the order in
which the process calculations are to be made. For the prototype
simulations, the order of the process calculations was fixed.
This order is indicated in the lower half of the first page of
computer print-out. The order was selected so as to maximize
computational efficiency. A block diagram showing the order of
process calculations is given in Figure IV-2.
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S:;3
5
(5) (13)
Reheater SGa I.D. Fan
(CLRI-rrR) 4 (PMPFAN)
WM
14
3 SG1
(3) (4) Pr ess
Cooler GSa Scrubber SF Water
(CLRHTR) 2 (SCRUBR) 15 Hold Tank
(EQMIXR)
6 SB SR
8
. (6) (7)
t-'
t-' Scrubber EB Tee CF Clarifier CL
I Effluent
Hold Tank 7 (DIVDER) 9 (CLRFYR) 10
(None)
11 CB
GSa SG1 (8)
Filter
2 System 3 FL
WM (OVALMB) FB (FILTER) 12
14 >- 13
FB
FIGURE IV-l SIMULATION OF PROTOTYPE SYSTEM 13
-------
Read
Input
Data
Calculate
EB Stream
(DIVDER)
Initialize
Equipment
Subroutines
Calculate
SF Stream
(EQMIXR)
Calculate
Cooler Duty
(CLRHTR)
Set .A
XA(C02)
No Adj us t
erform Overall LSR
Material
Balance and
Set Liquor
Te~erature
(0 ALMB) No Adj ust
XA(C02)
Calculate FL
and CB
Streams
(FILTER) Calculate Re-
heater and Fan
Duties (CLRHTR
and PMPFAN)
Calculate CL
and CF
Streams
(CLRFYR) Print
Desired
Results
Set LSR B
FIGURE IV-2
PROCESS CALCULATIONS FOR PROTOTYPE SIMULATIONS
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After the initialization phase has been completed, the
executive routine transfers control of computer operations to
the appropriate subroutines until the process calculations
have been converged. At this point, the calculated results are
printed. The last ten pages of computer print-out (refer to
attached case) show these results in the form of stream vector
information. Stream vectors are the means by which information
is transferred from one equipment routine to another.
B.
Equipment Subroutines
Simulation of the prototype system involved the use of
nine equipment subroutines.
1)
Cooler (CLRHTR) - determines the heat
exchange required to cool the flue gas
stream to a specified scrubber inlet
temperature.
2)
Scrubber (SCRUBR) - determines if the
scrubber feed stream contains enough
basic species to scrub the specified
amount of S02 from the flue gas and
forces iteration until convergence is
obtained.
3)
Reheater (CLRHTR) - determines the heat
exchange required to reheat the stack gas
stream to a specified outlet temperature.
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4)
1. D. Fan (PMPFAN) - determines the energy
required to pass the stac~ gas out of the
system based upon pressure losses in the
cooler, scrubber, and reheater.
5)
Process Water Hold Tank (EQMIXR) - combines the
process streams returning to the scrubber
(slurry recycle, clarifier liquid, and
filter liquid) with the water makeup and
allows the exiting scrubber feed stream to
reach solid-liquid equilibrium.
6)
Filter (FILTER) - provides for solid-liquid
separation based upon specified weight frac-
tion solids in the filter bottoms stream.
7)
Clarifier (CLRFYR) - provides for solid-
liquid separation based upon specified
amount of slurry recycle.
8)
Tee (DIVDER) - divides the exit stream from
the effluent hold tank into the slurry re-
cycle and clarifier feed streams.
9)
System (OVALMB) - determines the amount of
water vaporized in the scrubber and the
scrubber temperature using an approximate
scrubber energy balance and then determines
amount and composition of the filter bottoms
stream uS,ing a system material balance.
Actually, the ninth process unit is the effluent hold tank.
However, the System calculation routine eliminates the need
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8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454.9535
for effluent hold tank calculation. The same subroutine
(CLRHTR) can be used for the cooler and the reheater.
In addition to these equipment subroutines, four "source"
or "sink" type routines were required. Subroutines for the
gas-solid stream (FLUGAS) and for the water makeup stream
(WTRMKP) are used to "generate" the process input stream. Like-
wise, the exit stack gas. (STKGAS) and filter bottoms (FLTRBM)
stream are "discharged" as process exit streams. These last
four subroutines essentially convert units for input/output
purposes and provide a source or sink for the terminal proc~ss
streams.
Each of the individual equipment subroutines will now
be discussed in detail.
1.
CLRHTR
This subroutine is used to calculate the heat required
to cool or heat a process stream composed of a gas-solid stream
from one temperature T1 to another temperature Ta' In the
prototype simulations, the CLRHTR subroutine is used for the
cooler and reheater process units. Flow diagrams indicating
the usage of CLRHTR for these units are given below.
GS1 Cooler GSa SG1 Reheater SG2
- (CLRHTR) -
TGS TGS T S G (CLRHTR) T S G
1 a 2. a
\ '\
Qc QR
FIGURE IV-3. CLRHTR Flow Diagram
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The subroutine inputs include (1) the temperature of
the inlet gas-solid stream (T1), the press~re of the inlet
gas-solid stream (P1)' the number of moles of each gas and/or
solid species in the inlet stream [N1(JG) and/or N1(JS)], the
temperature of the exit gas-solid stream (T2), and the pressure
drop across the heat exchanger (-6PHE). The basic assumption
here is that all materials (both solid and gas) are at the same
temperature.
The heat added to the process (Q) is then calculated
by the relation:
Q = 6H 2 - 6H 1
( IV-l)
where 2 and 1 designate the outlet and inlet heat exchanger
streams. By convention, Q is positive for heat added to the
process. The enthalpies of process streams is calculated
relative to a reference temp~rature of 25°C by means of an
enthalpy subroutine.
The pressure of the outlet stream (P2) is calculated
by the relation:
Pa
=
P1 - (-6PHE)
(IV-2)
2 .
SCRUBR
This subroutine is used to determine if the scrubber
feed (SF) stream as calculated by means of other equipment
routines throughout the system will indeed remove the specified
fractions of 50a and CO2 removal. In this version of SCRUBR,
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the scrubbing liquor temperature is fixed by adiabatic humidifi-
cation of the flue gas stream. This calculation is made in the
OVALMB subroutine.
The input and output streams for the SCRUBR subroutine
are shown below.
,
SF
GS2 S SG,
(SCRUBR)
SB
FIGURE IV-4.
SCRUBR Flow Diagram
With the absence of rate correlations, the fractional
conversions for the various rate steps occurring within the
scrubber are specified by model assumptions or inputs. At the
present time, sulfite oxidation and solid-liquid mass transfer
rates are believed to be the rate controlling steps. Based
upon this premise, the following assumptions have been made in
this SCRUBR routine.
( 1)
The partial pressures of S02' CO2, and H20
in the stack gas leaving the scrubber are
in equilibrium with the scrubber exit
liquor (SB) at the scrubber temperature.
(2)
All of the solids in the scrubber inlet
gas-solid (GS2) stream are trapped in the
scrubber liquor.
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(3)
(4)
(5)
(6)
(7)
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The fractions of CaO and MgO in the GS2
stream that hydrate in the scrubber are
fixed by model inputs.
The fractions of solid species in the
GS2 or of the hydroxides formed from
that stream that dissolve in the scrubber
are fixed by model inputs.
The fractions of solid species in the
scrubber feed (SF) stream that dissolve
in the scrubber are fixed by model inputs.
The fraction of S02 entering the liquid
from the gas that is oxidized in the
scrubber is fixed by a model input. The
circulating S02 is not oxidized.
Solids precipitation can be allowed so
that solid-liquid equilibrium is achieved
with regard to the "reactive" chemical
species or no precipitation is allowed.
The first assumption is one of vapor-liquid equilibrium. This
describes scrubbers operated with the liquid-phase ideally
backmixed so that the exit gas is last in contact with a liquor
whose composition is the same as the scrubber bottoms (SB)
stream. Examples are the turbulent contact absorber or marble-
bed scrubber. For concurrent contactors (such as the venturi
scrubber), the backmixed assumption is not necessary. It does
not describe true countercurrent scrubbers.
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The SCRUBR subroutine consists of essentially three
parts. First, the total moles of "reactive" key species in
the scrubber bottoms (SB) stream are determined as the sum of
the "reactive" species entering the scrubber via the flue gas
(FG), limestone-flyash (LA) stream, and the scrubber feed (SF)
stream. For the nine key species (SO;, CO2, SOs, N20s, CaO,
MgO, Na20, HCI, H20),
NTSB(JT) = 6NsFT(JT) + 6NsOT(JT) + 6NAT(JT)
(IV-3)
where NTsB(JT) are the total moles of key-species JT that should
be considered in the equilibrium calculation of the SB stream,
6NsFT(JT) are the moles of key-species JT that are available
from the SF stream, 6NsoT(JT) are the moles of key-species JT
that are available from the LA stream due to dissolution, and
6NAT(JT) are the moles of key-species that result from absorption
from the FG stream. In these calculations, the species not avail-
able for reaction are withheld from the equilibrium calculation.
For example, a fraction of the calcium hydroxide in the SF stream
is specified by model input as reacting in the scrubber. The
remaining fraction of calcium hydroxide is "withheld" from the
scrubber equilibrium calculation.
The second phase of the SCRUBR routine involves "calling"
the Radian chemical equilibrium program. This program calculates
the equilibrium partial pressure of S02[P~e(SOa)] and the moles
of total CO~ in the SB liquid [NT* (CO;)]. Here the desired
'" s e
partial pressure of CO2 in the stack gas [PP(CO;)] is specified
as an equilibrium program input. The total moles of CO2 in
solution and compared with the total CO2 determined by summing
over the SF, FG, and LA streams [NTse(CO;)].
Tests for S02 and CO2 convergence are made using the
following criteria:
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\ PP(SO;) - P;(B (SO;) \
< E:SO
PP(SO;) . ;
(IV-4)
I NT S B (CO 2) - NT~( B ( CO .) I <
NTLA(CaO) + NTLA(MgO)
€C():a
(IV-5)
where PP(SO;) is the partial pressure of SO; in the stack gas
and NTLA(CaO) and NTLA(MgO) are the moles of total CaO and
total MgO entering the scrubber in the LA stream. If S02
and CO; convergence has not been attained for a given scrubber
calculation, control is transferred to a convergence promotion
subroutine whereby new values for the iterative parameters
(scrubber feed rate or slurry recycle rate for the partial
pressure of SOa and the fraction of CO~ absorbed for the moles
of CO; in SB) are selected.
The third and last phase of the SCRUBR subroutine
involves adjusting the elements in the SB stream vector for
quantities withheld in the scrubber equilibrium calculation.
In the present version of SCRUBR, the pressure drop
across the scrubber (-6Ps) is specified as an equipment parameter.
The pressure of the scrubber exit gas (PSG1) is calculated by
PSG1 = PGS; - (-~Ps)
(IV-6)
3.
PMPFAN
This subroutine calculates the power requirement of the
I.D. fan. The pressure of the stack gas entering the fan is
determined by the pressure losses through the cooler, scrubber,
and reheater. The desired pressure of the exit stack gas
stream is set by model input.
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w
SG:3
SG:3
I.D. Fan
PSG
:3
(PMPFAN)
PSG
:3
FIGURE IV- 5
PMPFAN Flow Diagram
The power requirement (-w) is then calculated by the
relation:
-w
=
CFQ' (PSG3 - pSG2)/YtF
(IV-7)
where CF is the appropriate units conversion factor, Q is the
gas flow rate, PSG and PSG are the exit and inlet gas pres-
:3 2
sures, and Yt is the efficiency of the fan.
F
4.
EQMIXR
This subroutine sums the total moles of key species for
all input streams and uses the equilibrium program to calculate
the composition of the vessel's output stream. Here, the input
streams are taken to be "known" streams and the output stream
is calculated.
Thus, for the process water hold tank in the prototype
simulations, the moles of key species in the slurry recycle
(SR), clarifier liquid (CL), filter liquid (FL), and water
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i
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makeup (WM) streams are summed to give the key-species amounts
in the scrubber feed (SF) stream, i.e.,
NTsp(JT) = NTsR(JT) + NTcL(JT) + NTpL(JT) + NTwM(JT)
(IV-B)
where JT is the index for total or key species. Again, the nine
key species are S02' CO2, S03' N?OS, CaO, MgO, Na?O, HCI and
HaO.
CL
P
(EQMIXR)
SF
WM
FIGURE IV-6
EQMIXR Flow Diagram
The process water hold tank is taken
vessel which closely approaches solid-liquid
the composition of the SF stream is computed
composition corresponding to the key-species
Equation (IV-B).
to be a well-stirred
equilibrium. Thus,
as the equilibrium
amounts given by
In this version of EQMIXR, the temperature of the vessel
is set equal to the temperature of the filter liquid (FL) stream.
This assumes that the circulating liquor system operates iso-
thermally.
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In addition to summing over the key species, EQMIXR also
sums over the four input streams to get the moles of "non-
equilibrium" solids, i.e.,
NTSf(JNS) = NTsR(JNS) + NTcL(JNS) + NT,L(JNS)+ NTwM(JNS)
(IV-9)
where JNS is the index for non-equilibrium solids. These
include CaO, MgO, MgS04, Na?O, NaCl, and insoluble fly ash.
5.
FILTER
This subroutine calculates stream vector quantities for
the filter inlet (CB) stream and the filter liquid (FL) product
stream based upon knowing stream vector information for the
filter solids (FB) stream. The basic assumptions here are that
essentially no chemical charge occurs within the filter and that
the filter operates isothermally. The temperature of the filter
and its process flow streams is fixed by the temperature of the
FB stream.
FL
CB
F
(FILTER)
FB
FIGURE IV-7
FILTER Flow Diagram
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In addition to knowing the FB stream, the filter
efficiency and weight fraction solids in the filter inlet (CB)
stream are set by model inputs as equipment parameters. Since
no chemical change occurs in the filter, the composition of the
liquid phase for the CB and FL streams can be set equal to the
liquid-phase composition of the FB stream. The relative amounts
of the solid and liquid phases for the CB and FL streams are
then determined by knowing the filter efficiency (XSOF) and the
weight fraction solids in the CB stream (XWSCB)' That is,
LCB = l~XSOF (l~S;B) (l~::R)
(IV-lO)
where LCB and LpB are the liquid flow rates of the CB and FB
streams, respectively. Then,
LpL
=
LCB - LpB
(IV-II)
and
XWSpL =
XSOF * ( XWSrR )(~)
1- XWS I' R L P L
1'+ XSOF * (XWSI'R )(~)
l-XWS P L
C B
( IV-12)
where L'L is the liquid flow rate of the FL stream and XWSpL
is the weight fraction solids in FL.
The moles of solid species in the FL stream rNpL(JS)]
are then calculated by the relation:
NpL(JS)
=
(XWS,~ - ~~CB)(~~PL) Nps(JS)
XWS C B P L ' B
(IV-13)
where the index JS refers to all solid species.
Then,
-23-
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 - 454-9535
Ncs(JS)
=
Nps(JS) + NFL(JS)
(IV-l4)
6.
CLRFYR
This subroutine calculates the clarifier feed (CF) and
clarifier liquid (CL) streams based upon the clarifier being
a solid-liquid separator only and upon the clarifier bottoms
(CB) stream being completely known. In this subroutine, the
CF stream is determined by process parameters exterior to this
routine. More specifically, the liquid flow rates of the
scrubber feed (SF) and slurry recycle (SR) streams are required
inputs for the CLRFYR subroutine. In addition, the amount of
solids in the CL stream are set by a clarifier efficiency
(XSOC).
CL
CF
C
( CLRFYR)
CB
FIGURE IV-8
CLRFYR Flow Diagram
The CLRFYR subroutine is basically composed of two
parts. The first part involves setting elements in the CF and
CL stream vectors equal to the equivalent elements in the CB
stream vector. The temperatures of the CF and CL streams are
set equal to the CB temperatures. Since no chemical change is
-24-
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l
Radian Corporation
8409 RESEARCH BLVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454-'1535
assumed to occur within the clarifier, the liquid-phase
compositions of CF and CL are set equal to those of CB.
The second part involves determining the amounts (LCF
and LcL) of these two unknown streams. These amounts depend upon
the systems iterative parameters LSF and LSR since the weight of
liquid water is not strictly conserved about the process water
hold tank. For example, the hydration of CaO to Ca(OH)2 consumes
liquid water. A total weight balance around the process water
hold tank is not possible at this point sfuce the compositions
(and thus densities) of the SF and SR streams are unknown.
The approach that has been used in the CLRFYR subroutine is
(1) to make the rather good approximation that the moles of
liquid water are conserved about the process water hold tank
and then (2) to iterate to correct any error involved with
this approximation. Thus for the first CLRFYR calculation
1 - °
LCF - LSF + LFe - LWM - LSR
(IV-IS)
1 1
Lc L = Lc F - Lc e
(IV-16)
Based upon these values for LCF and LCL' the EQMIXR subroutine
will subsequently determine a possibly different value for
LSF' say L~F' At this point, control is returned to the CLRFYR
subroutine and new values for LCF and LCL are determined by the
relations
(i+l)
LcF
=
(i+l)
L*
+ LFe - L~M - LSR
(IV-17)
(i+l)
Ln
=
( i+l)
Ln
- Lce
(IV-18)
. (i+l)
where L*
L* - Lo
SF - SF'
is an iterative parameter such that in the solution
-25-
-------
Radian Corporation
8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454-9535
Once LCF and LCL have been determined the weight
fraction solids (XWScp and XWSCL) and moles of each solid
species [Ncp(JS) and NCL(JS)], in these two streams can be
calculated as follows:
= (l-~SOC) (l~~S~~) (~)
( 1 )(XWSr A )(~)
1 + 1-XSOC 1-XWSCB Lcp
XWS C P
(IV-19)
XWSCL =
(}[WSC F )(Ln \
(XSOC) 1-XWScp ~)
(IV-20)
1 + (XSOC) (XWSCF )(~)
1- XWS C F L C L
NCL(JS) = (XWSCB - XWSCF) N (JS)
XWS c p - XWS C L C 8
( IV-21)
NCF(JS) = NCB(JS) + NCL(JS)
(IV-22)
7 .
DIVDER
This subroutine determines the elements of the stream
vector for the input stream and one output stream given the
elements of the other output stream. This program is used in
the prototype simulations to determine the effluent bottoms
(EB) and slurry recycle (SR) streams once the clarifier feed
(CF) stream is known.
-26-
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 787S8 . TELEPHONE 512 . 454-9535
SR
EB
Tee
(DIVDER)
CF
FIGURE IV-9
DIVDER Flow Diagram
In addition to knowing the CF stream
flow rate for the SR stream (LSR) is
routine input.
completely, the liquid
also required as a sub-
The program determines the size of the EB stream as the
sum of the SR and CF stream, i.e.,
LE e = Lc ~ + Ls R
(IV-23)
and sets the compositions of the EB and SR stream equal to that
of the CF stream. Thus, the program assumes no chemical change
and no solid-liquid separation occurs within DIVDER.
8.
OV ALMB
This subroutine first uses an adiabatic humidification
calculation for the scrubber to determine the amount of water
vaporized and liquor temperature in the scrubber. Then, using
this information along with a material balance for the overall
system, OVALMB calculates the amounts and compositions of the
filter bottoms (FB) and stack gas (SG) streams and the amount
of water makeup (WM).
-27-
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 - 454-9535
The diagram given below shows the solid-liquid stream
leaving the system as being the filter bottoms (FB) stream.
GS~ S
System
WM (OVALMB)
.L'
G1
B
FIGURE IV-10
OVALMB Flow Diagram
For systems without a filter, this stream would of course be
the clarifier bottoms (CB) stream.
The compositions of the gas-solid stream entering the
scrubber (GS2) and the water makeup (WM) are taken as known
inputs to the subroutine. In addition, the fractions of (1)
SO~ and NOx absorbed in the scrubber, (2) SO~ oxidized in the
scrubber, and (3) CaO and MgO hydrated in the system are also
known. Two equipment parameters, pressure drop across the
scrubber (-t:.Ps) and weight fraction solids in the filter bottoms
(XWSps)' are required inputs for OVALMB. For each iteration
through the OVALMB subroutine, the fraction of CO~ absorbed in
the scrubber [XA(CO~)] is also a fixed subroutine parameter.
The amount of water vaporized and the liquor temperature
in the scrubber are calculated by the simultaneous solution of
mass and energy balances about the scrubber. In the energy
balance, the scrubber is assumed to be adiabatic. The heats
of reaction, solution, etc., are neglected. The exit gas (SG~)
and liquid (SB) streams are assumed to reach the adiabatic
-28-
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454.9535
saturation temperature (TAS) and temperature of the entering
liquid (SF) is assumed to close enough to TAS such that this
sensible heat term can be neglected.
This phase of
the WAVAP subroutine.
Equation IV-2~
the OVALMB calculations is performed by
Here, the mass balance is written as
[NGSa - NGsa (HaD) - 6NAbs] *YSGl .(H20)
- NG S (H?O)
2
Nw v =
1 - YSG
1
(HaD)
= ~MB(TAS)
(IV-24)
In Equation IV-24 Nwv is the moles of water vaporized
(unknown), NGsa is the total moles of GSa, NGsa(H?O) is the
moles of H?O in GS2, 6NAbs is the moles of gas species absorbed
in the scrubber, YSG (HaD) is the mole fraction of HaD in the
1
stack gas stream and ~MB(TAs) represents the value of Nwv calcu-
lated by the mass balance. YSG (HaD) is a function of the
1
temperature TAS' i.e.,
YSG (HaD)
1
=
(~) *
PSG 1
5.22684-l750.286/(TAS-38.2)
10
(IV-25)
Nwv =
The energy balance is given by Equation
(CPGs\ * (TGS - TAS)
)mean a
(6Hvap)T
A II
IV-26
= ~EB(TA9)
(IV-26) .
-29-
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Radian Corporation
8409 RESEARCH BLVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 - 454.9535
In Equation
GS; stream,
is the heat
(~Hvap)T
A S
IV-26 (CPGs)mean is the mean heat capacity of the
TGs~ is the temperature of the GS2 stream, and (6Hvap)TAS
of vaporization for H20 at the temperature TAS.
is a function of temperature, i.e.,
\
(6Hvap)TAS = l3,630.6-10.464*TAS
(IV-27)
The quantity ~E8(TAS) is the value of Nwv calculated by the
energy balance. The solution is the value of TAS such that
~M8 = ~E8. The WAVAP subroutine solves this problem numerica~ly
using a Newton-Raphson technique. The result is valued for Nwv
and TAS. The process liquor circulating in the system is
assumed to have the temperature TAS.
The moles of key species leaving the system in the
filter bottoms (FB) stream can now be determined. Key-species
in the FB stream come from three sources: (1) the gas species
absorbed in the scrubber, (2) the solids from the limestone-fly
ash streams, and (3) the water makeup, i.e.,
NTFS(JT) = 6NAT(JT) + NDT(JT) + NTwM(JT)
(IV-28)
where NTFS(JT) and NTwM(JT) are the moles of the key species
JT in the FB and WM streams. As in the SCRUBR routine, 6NAT(JT)
is the moles of key species JT absorbed by the system from the
flue gas. The term NDT(JT) represents the moles of key species
JT that enter the system from the limestone-fly ash (LA) stream
except for "inert" solids. These inert solids include the
insoluble fly ash and the quantity of CaO and MgO that does
not hydrate in the system.
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Il
Radian Corporation
8409 RESEARCH 8LVD. . P.O. 80X 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454.9535
Based upon the process model assumptions, the chemical
species (excluding the unreactive portion of CaO and MgO) in
the FB stream are in solid-liquid equilibrium at the temperature
of the scrubbing liquid. Thus the Radian chemical equilibrium
program can be used to calculate the composition of the FB
stream. In this calculation, the moles of the first eight key
species (SO~, CO?, S03' N~Os' CaO, MgO, Na~O, and HC1) are
calculated by Equation (IV-28). For the first calculation, the
moles of water makeup (NWM) are unknown so that the key species
entering from this stream are neglected initially. Chemical
equilibrium is then calculated using an option of the Radian
program whereby the moles of the first eight key species plus
the weight fraction solids are specified as program inputs.
This version determines the resulting equilibrium composition
and the moles of total H?O species [NT,B(HgO)J. The moles of
water makeup (NWM) can then be determined by the relation:
NWM(H~O) = NT,e(HQO) + N~v
(IV-29)
where as before Nwv are the moles of
scrubber. An iteration loop is used
makeup species in Equation (IV-28).
water vaporized in the
to account for the water
9.
Other Subroutines
As mentioned earlier subroutines for material sources
(FLUGAS and WTRMKP) and sinks (STKGAS and FLTRBM) are also
. used by the Radian process model. These programs essentially
read input data and convert them into usable units or prepare
calculated data for output printing.
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. BOX 9948 . AUSTIN, TEXAS 787S8 . TELEPHONE SI2 - 454-9535
C.
Convergence
Two major iteration loops are required to converge the
simulation cases for the prototype LIWS system. First, a
composition of the scrubber bottoms (SB) stream must be obtained
such that the equilibrium vapor pressure of SO~ for this stream
is equal to the desired partial pressure of the stack gas (SG)
stream. In this case, the amount of slurry recycle (SR) or
scrubber feed (SF) is used as the iterative parameter for
"SO~ convergence". Secondly, the fraction of CO~ absorbed by
process [XA(CO~)J is also assumed to be controlled by the
equilibrium vapor pressure of CO2 above the SB stream. The
Radian process model assumes an initial value for XA(C0\:l) and
then a~usts this parameter until the molality of total carbonate
in the SB stream coincides with the molality required to give
the CO~ partial pressure of the stack gas.
The approach used to converge the prototype simulation
cases is to iterate on SO::! via a "loop" im:ernal to the COg
convergence loop. This approach was chosen based upon the
observations that (1) the molality of total CO~ in SB will be
essentially constant (corresponding closely to the partial
pressure of CO~ in the flue gas since a small fraction is
absorbed) and (2) the XA(CO::!) influences the OVALMB calculations.
Since the molality of total CO~ in SB will
as XA(CO?,) is varied, the values of slurry
feed) rates obtained by sag convergence at
will be relatively close to the SR rate at
level.
not change significantly
recycle (or scrubber
one level of XA(COg)
another XA(COg)
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 - 454-9535
The SO~ convergence technique is a modified version of
. *
the Method of False Position whereby a straight line interpola-
tion is used to find the next SR (or SF) rate. The "poles" or
known points are continually updated so as to use values
closest to the solution. The logarithm of the SO~ partial
pressure is used in the straight line interpolation.
The CO~ convergence routine uses a straight line
relation between the moles of total COa in the SB[NTsa(C02)]
and the fraction of COg absorbed from the flue gas, i.e.,
NTse(COs) = A * XA(C02) + B
(IV-3l)
Since A is known, one point is required to determine a new
value of XA(CO~) for the next iteration.
The procedure used in the prototype simulations was to
select an initial value for XA(COQ) and perform the simulation
calculations to obtain values for NTse(CO~) and NTta(COg).
Here, NTsa(COa) corresponds to the value obta~ned from Equation
(IV-3D) and NT~a(COa) corresponds to the value obtained from
the equilibrium calculation in the scrubber. To obtain the next
iterative value for XA(CO~), NT~a(COa) is used in Equation
(IV-3D) and a value for XA(CO~) is calculated.
*
Kunz, K. S., Numerical Analysis, McGraw-Hill Book
Company, Inc., New York, 1957.
-33-
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Radian Corporation
8409 RESEARCH BLVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 - 454-9535
Va
CONCLUDING REMARKS
Radian has developed a computerized process model for
the LIWS process. The present model is based upon a number of
process assumptions which reflect the current knowledge of
process rate steps and equipment characteristics. Insofar as
possible, the computerized system has been designed for
flexibility so that a number of control schemes can be simu-
lated. Specialization has been used when a significant improve-
ment in computational time would result.
The
development
improved by
data become
present model represents a valuable tool to process
and design. The model could be significantly
including rate correlations when appropriate rate
available.
-34-
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Radian Corporation
8409 RESEARCH 8LVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454.9535
APPENDIX
Example Simulation Case
(Prototype Simulation No.2-B)
-------
PROTOTY PE S : -1UL AT 10N,NO. 2- B
PROCESS DESCRIPTION
EGU P. NO. EQUIP.N~ME IN PU T ST RE AMS our PU T ST RE AM~
1 FLUG AS 0 1
2 WT PMKP 0 1 If
3 CLC?~TR 1 2
'f S C PU BP 2 IS 3 6
5 CLRHTR 3 4
6 DIVOER 7 8 9
1 CL R F Y R 9 1 0 11
B FI L T ER 1 1 12 13
9 EOT-tIXR 8 10 12 14 15
10 ov ~L MB 2 14 3 13
11 FL T R BM 13
12 ST KG AS 5
13 PM PF AN 4 5
ORDER OF PRO CESS CALCULATIONS
I 1. 2, 3 ( 10,8 C1. 6,9,4)) S. 11,13. 12.
t-'
I
R E CY CL E LO OP FRO,", 10 TO 4
RECY CL E LOOP FROM 1 TO 4
-------
04 AUG 70
10:51:09.307
PROTOTYPE 51~llILATION NO.. 2-3
PQOCr.SS CCNOITIONS
RATE = 1GOOOO.OOACFM AT TFG = 215. f)~G. f AND PFG =
lt9S0R8EO = 90.0 ~ NO ABSORBED = 10.00 t
OXIDIZED = 50.0 % NO? ABSOR8EO =
PSI A
FLUE GAS
$02
S02
14.7
100.
..
.
LlpIIESTONE PUE = 31.4
LI~ESTONE COMPOSITION =
LIME REACTEO IN BOILER =
NO PRECIPITATION ALLOWED IN
LIME HYDRATED
IN SYSTEM
CAO =
MGO =
IN SCRUBBER
CAO =
MGO =
75.0
75.0
LB5/MIN - 15 O. % THEORET lCAl
-
. COO M OLE5 ( M G )/ MOL ES (C A + M'~)
.000 %
SCRUeBER
SOLIDS 0 ISSOLV ED INS C RU 811 E R
LA SF"
CACOH)2 - 40..0 " 35.0 %
-
MGCOH)2 - 40..0 t 35.0 %
-
CAC03 - 40..0 % 35.0 .
- '"
MGC03 - 40.0 % 35.0 %
-
MGS 04 - 40..0 % 35.0 %
-
NA20 - 40.0 % 35.0 %
-
NA CL - 40.0 % 35.0 :t
-
LBS/MIN - 3.35 LBS F 61 LB SULFUR TN COAL
-
%
%
20.0
20.0
%
%
I
N
I
FLY ASH RATE =
EQUIPMENT PARAMETfRS;
SOLIDS IN CLARIFIER BOTTOMS =
SOL IDS IN F!t T ER BOT TOMS =
TEMP. OF COOLED ~-S STREAM -
1.0. FAN EXIT PRESSURE = 14.7
UNIT PRESSURE LOSSES.PSIA
COOLER = .144
INITIAL VALUES;
SCRUBBER FEED RATE =
=
1400.00 GPM H20
':0 .0
CLARIFIER EFFICIENCY =
fILT ER EF FI CIENCY =
TEMP. OF REHEATED STACK r-I\S =
30.0 WT.%
6 0.0 W T . %
2 25 . DE G F
PS 14
99.0 %
99.0 %
25 o.
SCRUBBER =
.288
REHEATER =
.144
G?M H20 SF/iooe ACFM FG
14.0
INPUT STREAM COMPOSITIONS:
FLUE GAS tIMESTONE
COMP. MOLE % CO~P. WT.%
502 = .200 CAO - 100.
C02 = 14 .5 M GO - . 00 C
NO - .450-01 CAC03 = .000
N02 = .500-02 MGC03 = .000
02 - 3.00 CAS03 = .000
CO - .000 MGS03 = .000
N2 - 74.2 CAS04 = .000
HCL = .000 HGS04 = .000
H20 = 8.00
FL Y AS H
COM?
N A20
N ACl
INS OLU 8L E
FLY ASH =
=
WT.%
.112
.746
WATER MAKEUP
COMP. MG/L
S03 = .ceo
C03 = .oco
504 = .oeo.
N03 = ..OGO
CD. - .000
~G = .000
NA - .000
CL - .000
-
99.1
.--
o E~. F
-------
REACT ANT
I
lJJ
I
H20
H2S0 3
H503
HS04
H2C03
HC03
CAOH+
CAS 03
C ACO 3
CAHC03+
CAS04
CAN03+
CAC03CS J
CAS01HS J
CAS 0 :3 C S )
CACOH)2(S)
MGOH+
M GS 0'3
MGHC03+
M GS 04
MGCO 3
MGCOH)2(S)
MGS03(S>
MGC03(SJ
NAOH
N A CO 3-
NAHC03
NAS04-
N ANO 3
PPCS02)
PP(C021
K (25 C)
1.0129-14
1.2957-02
G. 2207-08
1.0396-02
4.4513-07
4.6817-11
4.2229-02
3.~999-04
G. 299.6-04
5.5002-02
4.8969-03
4.8'485-01
4.8695-09
2.4000-05
8.4004-08
5.6281-06
2.6001-03
1. 1997-03
1.1001-01
5.E;636-03
3.9999-04
1.2552-11
5.3272-05
2.1500-05
3.7154+00
5.40 02-G 2
1.7783+00
1.9024-01
2.5119+00
1.2158+00
3.4215-02
.. ::MPER ATUR::
K n E MP J
S .1 028- 14
B . \) \) 5 6- (0 3
4 . 3 32 6- 0 B
5 . a 24 5- 03
5.1559-:17
6 . 6 64 2- 11
3.6137-02
2 . q <:J 88- 04
4 .8025- ('4
4.6298- 02
3.5939-03
2 . 3 82 &- 01
1 .8 83 3- 09
1 . 7 4 3 3- OS
8.4004-08
3.4099-06
1.9347- 03
9.3729-04
'3 . 6 20 0- [')?
3 .G96 7- 03
2.9988- 04
9.5400- 12
5 .9 14 4- 05
1 .2 4 I; 5- 05
3.1154+00
4.541 G- 02
1.7783+00
1.6579-01
2.511 g+ 00
5.5630-01
1 .917 1- 02
48. 791
JEGR ::ES C
EQUILIBRIUM CONSTANTS
A
14.4710+03
-(').43(;7+02
-6.3384+02
4.7514+02
3.4047+03
2.'3024+03
-2.73CO+02
- 5. 04 80 + G 2
.:-4.7548+02
- 3. 01 e5 +02
2.:.721+03
-1.2450+03
-1.C:~OO+03
4.5440+03
O. CO 00
7.£560+02
- 5.1199+02
-1+.325G+~2
-2.35013+02
-1.0573+03
- 5. 04 80 +0 2
-Q.6085+CZ
8.0220+02
- 9. 51:) 11+ +02
0.00 CO
-3.0341+02
o. GO 00
-2.4100+02
0.0000
-1.3700+03
-1.0150+03
B
O.OGIJO
o .0 GO (I
o . GOO a
0.0000
O.OOO~
o .0000
0.0000
0.0 OC 0
o .0 GO 0
0.0 GO 0
2.3150+01
o .0 OD 0
o .D 00 0
3.1745+01
0.0000
4.4700-07
0.0000
o .000 0
O.GOOO
O.CGOG
0.0000
0.0000
0.0000
O.OGOO
0.0 GO 0
C .0000
1).0000
0.0000
0.0000
0.0000
0.0000
c
1.7C(.0-02
O.r.~80
O.OOCO
1.8222-02
3.2766-02
2.3790-02
0.0000
O. S ~ 00
0.0000
0.0000
o. 0000
O. CO ('10
0.00 DO
0.0000
O. CO GC
1. 71 Z 5 -0 2
0.0000
0.0000
o. ('1[)OG
0.0000
G.OOG!]
0.0000
G.DGOD
o. (1000
O.OIlCO
0.0')00
O. DO 00
0.0000
0.0000
0.0000
0.0000
HYDRATES If PRECIPITATED ARE MGC03*3H20,MGS03*3H20,CAS03.n/2)H20
THIS PROGRAM DEVELOPEO BY RADIAN CORP. UNDER NAPCA/HEW SPONSORSHIP
D
6.0875+00
-4.1111+00
-9.3320+00
5.0435+00
1.4843+01
fi.4980+00
-2.2900+00
-5.0910+00
-4.7954+00
-2.272C+OO
6.3t.OO+01
-4.4 ~!OO"'OO
-1 .31390"'01
1.05:3(+02
-7.0751+00
2.4240+00
-4.3223..(10
-4.3115+00
-1.7470+00
-5.7<350"'00
-5.091~...no
-1.2514+01
-1.5830+00
-7.8710+CO
5.7000-01
-2.2852"00
2.5000-01
-1.52~O"'OO
4.0000-01
-4.5100+CO
-14.8700"00
-------
O~ AUG 70 10:53:2b.l03
STREAM NUMBER
TOTAL STREA,.,
FLOW RATE tG/SECJ
(G- MOLEIS EC )
TEMPERATURE (DEG. K)
PRESSURE (ATM)
ENTHALPY tCAL/SEC)
SOL 10$ (WT t)
GAS PHASE
FLOW RATE
(G/5EC)
(G-MOLE/S EC J
tCAl/SEC)
(G-MOLES/SE C)
I
.p.-
I
ENT HAlPY
C011P
S02
C02
NO
N02
OZ
CO
N2
HCL
H20
lIGU ID PHASE
FLOW RATE
(G/SEC)
(G- MOlESI SE C)
( CALI S E C )
(G-MOLES/SE CI
ENT HALPY
COMP
S02
C02
S03
N205
CAO
HGO
N420
HCL
H20
DENSITY (G/HL
IONIC STRENGTH
AT TI
1
42437.
1411.6
408.16
1 .0 OQ 0
-.26356+08
1.2718
41 a 98.
1409.3
-. 2~ 761 + 08
2.8181
204.35
.G3Lf:?0
.701467- 01 .
42.280
.00000
1046.4
.00000
112.75
.00000
.('0000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.0 (( 0
2
PROTOTYPE SIMULATION NO. 2-9
3 4
5
42437 .
1417.6
360.38
. 99 G2 0
-.26653+08
1 .271 8
~ 18 99 .
1 409. 3
-.25055+08
2.8181
2014.35
.63LfZO
.10467- 01
42.280
.00000
1046.4
. 0000 0
112.75
. 0000 0
. 00000
.00000
. ('0000
. 00000
.00000
.00000
.0000 a
. ('0000
. CO 00 0
.00000
.00000
. 00000
.00000
.00000
42739 .
lL163.3
321.95
. 97 G'; 0
- . 28 78 e.. 08
. 00 00 0
427 33 .
1463. :!
- . 2~ 1fi 8+ 08
. 2~ 1 ~ 1
2 04 .2 5
.57078
. 00000
41. sa 1
. GO 00 0
1046. 4
. 00 00 0
1 70 .23
. 00 00 0
. DC 00 0
.00 000
. Orl 00 0
. 00 CO 0
. CO OG 0
. oe 00 0
. (Ie 00 0
. 00 00 0
. 0000 0
. 00 co 0
. ('0000
. 00 00 0
. 00 000
. 0000 0
42739.
1463.3
394 .27
.9608 I
-.28000+08
. 00 00 (1
42739.
146 3. ~
-.28000+08
.28187
20~.25
.57c.1~
. 0000 ('
41.581
.00000
104f,.4
.00('00
110.23
.00000
.0000 (I
.00 co 0
. 00000
.~ooor.
.0000 (I
.OOOOQ
.00000
.00('00
.00000
. co 00 0
.00000
. coooo
.00000
.00000
42739.
1 4f 3.3
3 ~4 . '2 7
1 .0 co 0
-.2ROOO+08
. 00000
42739.
14r;3.3
-.;?~ OCO"08
.28181
7.04.25
.~707P.
. noooo
41.$~1
. CO 00 Q
1(14(.4
.00000
1 70 . '- 3
. co 00 0
.00000
.00000
.00 GO 0
. 00 00 0
.00000
. os as a
. DO ('0 0
.00000
. ~o DC 0
.00 COO
.GOOGO
.00000
.00000
.00000
~
92034.
4868.4
321.95
. 0 C 00 0
-.33736+09
2 .640 1
. 00 co 0
.00 GO 0
. 00 00 0
. 00000
. 0000 0
. OC co 0
. DC 00 0
. 00000
. 00 co 0
. 00000
. 00000
.00000
89604.
4839.7
-.33042+09
1 .2925
.20587
2.1138
1 2. O') 9
13. S8 4
. 00 GO 0
4.4(.29
6.9539
4798.7
1 .0209
.51387
4.0588
-------
'I
VI
1
04 AlG 70 10:53:26.346
STR ~A~ Nt ~ BER
LIQ. H20 RATE (KG/S EC)
COMP CG-MOLES/KG H20)
H+
OH-
H S 0 3-
503=
S04=
HC 0 3-
C03=
N03-
HS 04-
H2S03CL)
H2C03 CL J
CA++
CII.OH+
CAS03CL)
CAC03CLJ
CAHC03+ J
CAS04(LJ
CAN03+
MG++
MGOH+
MGS03(L)
MGHC03+
MGS04CLJ
MGC03(L)
NA+
N AOH (U
NACOJ-
NAHC03CL)
NAS04-
N ANO 3-
CL-
SOLID PHASE
F LOW RAT E (GI SEe)
(G- MOLESI SE C)
ENTHALPY (CAL/SEC}
. coooo
.00000
.00000
.00000
.O'JOOO
.00000
.00 OC 0
.00000
.00000
.oooeo
.00000
. 0 G 00 0
.00 DC 0
.OCOOO
.00000
. 00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
. 00000
.00000
. 00 00 0
. OOOC 0
.0000 a
.00000
.00000
539.73
8.2302
-.15944+07
2
. 00000
. co 00 0
.0000 a
. 0(\ ao 0
. CO 00 0
.00000
.00000
. OC 00 G
. CO 00 0
. CO 00 0
.00000
. 0000 C
., (JL; 00 0
. aD 00 0
.00000
. 00000
. 0000 0
. CO 00 C
.00000
. 00000
. 00000
. 00000
. OC 00 0
.00000
. co 00 0
. 0000 0
. 00000
. 00000
. co 00 0
. OC 00 0
. OC co 0
. 00000
5 39 .1 3
8.2302
-.15914+07
, ? OT 0" Y ):: S I MU LA" : 0 IJ In. 2-9
3 4
.00000 .00000
. 0000 0
. 00000
. GO CO 0
. 00000
. 00 00 0
. 00 00 0
. co 00 0
. 00 os 0
. 00 O'J a
. 00 00 0
.. 00 00 0
. 00000
. 0000 0
. 00000
. co 00 0
. 08 00 0
. 00 00 0
. 00 00 0
. 00000
. 00 OD 0
. 00 DO 0
. 00 CD 0
. 00 DC 0
. 0000 a
. CO 00 0
. 00 00 0
. GO 00 0
. 00000
. 00000
. 00 00 0
. co 000
. 0000 0
. co 00 ('
. 0000 0
.00000
.00000
.00010
. ao oa a
.OOOGO
.00000
.00000
.0000 C
.00000
.0000 d
.0000 a
.00 co 0
.0000':1
.00000
.00000
.coonn
. 00 00 0
. co 00 n
.00000
.00000
.00000
. co 00 n
.80000
.00000
.00000
.0000 I]
.cooor.
.00000
.00000
.00000
. 00000
.00000
.00000
.00000
5
.0000 a
.r.OGOO
. 00 co 0
. Of) 000
.00000
.oonoo
.0000 0
.00000
. OfJOOO
. cacao
. 00 co 0
.00000
.01lu00
. ro OCO
.00000
.00000
.00 GO 0
.GCOOO
.0000 (I
.00 co 0
.08000
.00000
.('GOOO
.00000
.00000
.00000
.OCOOO
. 0000 a
.00000
.00000
.00000
.00000
.00000
.00 co 0
. 00 00 0
G
8 (,.50 1
.97427-04
.19750-09
.14398-01
.25607-04
.1193 ~-01
. 2 3 1 5 8- 04
.63!50-10
.25515
.36638-04
.93813-04
.23428-02
. 1 2 7C 9
. GS 86 4-09
. 4244 f.- 0 3
.. 655 (, 8- 0 9
.13491-04
.11565-01
.21414-01
.00 00 0
. 00000
.00000
.0000 0
. DC 00 0
.OC(100
.99114-01
.10016-10
.24827-10
.54915-06
.8'3167-03
.31757-02
.80391-01
2429.8
28.714
-.69394+01
-------
04 ~UG 70 10:53:26.584 PROT OTYPE S I MU l~ T ION NO. 2-B
S1'REAH NUMBER 1 2 3 14 5 6
C:OHP (G-MOLES/SEC!
CAO 4.2279 4.2279 . 00000 .00000 .00000 6.3€-94
CA(OH)Z .00000 . 00000 . 00 00 0 . 00 CO n .OCODO 1.1494
C~C03 .00000 .00000 . 00 CO 0 .00 OD 0 . GO 00 0 . 18278
CAS 03 .00 DO 0 .00000 . 00000 .00 co 0 .00000 .00 DC 0
CAS03*1/2H20 .00000 .00000 . 00 DC 0 .00000 .00000 3 .3302
CAS 04 .00000 . 00000 . 00 00 0 .0000 Q .00 COG 3.302 S
CAS04.2H20 .00000 .00000 . GO CO 0 . 00 00 (' .0'1000 .00000
MGO .00000 .00000 . 00 co a . 00000 . f.moco .00000
MGCOH,Z .00000 . 00000 . Of) GO 0 .00000 .00 00 0 .00000
MGC03 .00000 .00000 . 0000 0 .00COr. .00 co 0 .00 (10 0
MGC03*3H20 .OODOO . CO 00 0 . CO co 0 .0000 r .OrlODO .00000
MGC03.SH20 .00000 .00000 . 00 00 0 . 00000 .00000 .00 GO 0
M GS 0 3 .00 co 0 . co 00 0 . 00000 . 00 00 0 . 00000 .00 co 0
MGS03*3H20 . 00000 . CO 00 0 . 00 00 (I . 00 00 (I .00000 .00 GO 0
MGS03*6HZO .(10000 .00000 . co 00 0 .00000 .00 co 0 . 0 C 00 0
MGS04 .00000 . GO 00 0 . co 00 0 . DO OO!J .OOOGO .00000
I NA20 .54735- 02 .54735- 02 . 0000 0 .00000 .00000 .3284 t-02
0'\
I INSOLUBLE FLY ASH 3.QS82 3 .9582 . 00 00 0 .00000 .00000 14.353
NACl .38605- 01 .38605-01 . 00 00 0 .00000 .00000 .23 16 3- 01
SUMMARY IN ENGINEERING UNITS
TOT FLOW R4TE ClBS/MIN) 5613.4 561 3. 4 S6:; 3.7. 5653.2 5653.2 121 74 .
C l 8- MOL E S / M IN) un .51 187.51 193.5 {; 193.5f; 193.56 643.Q7
GAS FLOW RATE (lBS/MIN) 5542.0 5 S4 2.0 5653. '2 5653.2 Sf,S3.2 . 00 co 0
ClB-MOlES/MIN) 186.42 1 86 .42 193 .5 (; 193 .S; 1 ~3 .Sf, .00 CO 0
C A Cf M) 100000. . 00 GO 0
LIQ t='lOW RATE (lBS/ HI N) .00000 . 00000 . 00 00 C . 80000 .:)0000 11852.
( L B- MOL E S / '"f IN) .00000 . 00 GO 0 . 00 00 0 . 00 co (I .00000 640.1t3
(1000 Las H~O/HIN) .00000 . 00000 . ('0 00 0 .0000 C .onooo 1 1.442
(GAL/MIN) .00000 . 00000 . CO 00 0 .0000 C .coooo 1386.9
L 1Q DENSITY (lBS/ GA LiiI T> .00000 . 00 00 0 . 00 co 0 .00000 .OOOOQ 8.5198
SOL FLOW RATE (LBS/MIN) 11.392 11.392 . 00 00 0 . 00000 .00000 321 .4 1
C L B- HOLES/ MI N) 1.0886 1 .0886 . 00 00 0 .00000 .00000 3 .198 1
-------
04 AUG 70 10:53:21.) ,(
STREAM Nt' ER
TOTAL STREAM
FLOW RATE (G/SEC)
(G-f10lE/SEC)
TEMPERATURE (DEG.. K)
PRESSURE (UM)
ENTHALPY (CAl/SEC)
SOLIDS (WT %)
GAS PHASE
FLOW R4TE
(G/SEC)
(G- MOlE/S EC )
( CAL/SEC)
(G- MOLES/SE C)
I
~
I
ENTH4LPY
COMP
S02
C02
NO
N02
02
CO
N2
HCL
H20
lIQUID PHASE
FLOW RATE
(G/SEC)
(G-MOLES/SE C)
(CAL/SEC)
(G- MOLES/SE C)
ENTH4LPY
COMP
S02
C02
S03
N205
C AO
MGO
NA20
HCL
H20
DENS ITY (GI ML
IONIC STRENGTH
PH
AT T)
7
92035.
4864.6
321.95
.00000
-.3 J 743+ 09
2.~ 151
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
89352.
4835.1
-.32986+09
.23789- 01
. 35 82 6- 03
.83364
12.099
13.151
.00000
4.4118
6 .9711
4791. 6
1.0184
.48217
11.34 If
8
, R J. O' . Y ): s t ' J - A T ION NO. 2-8
<3 10
1 1
66139.
3495.8
321.95
.00000
-.24248+09
2.9151
.0000 a
.0000 a
. 00 000
.00000
.00000
. 00000
. 00000
.00000
. GOOOO
.00000
.00000
. 00 00 a
G 42 11 .
3474.(;
-. 23704 + 09
. 1109E.-Ol
.25745-03
. 5'3901
8.6344
<3 .4 50 '3
.00000
3.2178
5.0139
3441. 7
1.0184
. 48277
1 1. 34 f+
2 5!3 96 .
1 36 ~. R
321.95
. 00000
-. 9494 3+ 08
2.9151
. OC 00 0
. 00000
. 00 Of) 0
. co 00 0
. 00000
. 00000
. co 00 0
. 00000
. 00000
. 00 00 0
. 00 00 0
. 00000
25142.
1 35 o. 5
-.92814+08
.66937-02
. 10 Ga 1- 03
. 23 4S 1
3 .4 04 3
3 .. 7 00 5
. 00 00 0
1 .259 <3
1.9632
1 349. 9
1.OlB4
. 48277
1 1. 34 "
23~01.
12Gb.a
321 .9 c:;
.0000 (I
-.863133+08
.3225<\-01
.oooor
.ooono
. CO 00 n
.00000
.0000 C
.00000
.00000
.00000
.0000 0
.00000
.00000
. 00 00 n
2 3 394 ..
1265.9
-.86367+08
.62284-02
. 9319 ~-04
.21821;
3..161f;
:3 .443:2
.00000
1..172~.
1 .. 8261
1256. 1
1.01114
. 48 211
11 . 3i+.4
2495.2
10'-.78
321.95
.00000
-.85606+07
2').951
. OC 00 0
.onooo
. no 00 0
.00000
.00000
.00000
. co 00 0
.00000
.00 00 0
.00000
.(10000
.00(100
1147.9
9la.5-33
-.£:4525+07
.46535-03
.10~gI-05
.11;301-01
. 2 ~ 66 7
.25 n 6
.0000.0
.87592-01
. 1 3 64 8
93.848
1 .0 164
. 4 ~ 271
1 1. 34..
12
1260.9
61.911
321.95
.00 co 0
-.46485+07
.59269
.00000
.00000
. 00000
.0000 a
. DC 000
.00000
. 00000
.00000
.00000
. 00000
.00000
. 00000
1253.5
61.829
-.46214+01
.33372-03
. SO 25 8-0S
.11695-01
. 1 I) 97 3
.18449
.00 GO 0
.62816-01
.97877-01
{) 1. 302
1 .0184
.48211
11.3'Pi
-------
04 AU G 7 a 10: 53: 27.261
ST RE AM NU MBER
LIG. H20 RATE (KG/SEC)
COMP (G-MOLES/KG H20)
H+
OH-
HS 0 3-
S03=
504 =
He 0 3-
CO 3=
N03-
HS04-
H2S03(LJ
H2C03(lJ
CA+.
CAOH+
CAS 0 3 (L J
CAC03fl)
CAHC03+J
CAS04(L)
CAN03+
MG..+
MGOH+
MGS03 (L)
MGHC03+
MGS04 fL)
MGC03CLJ
N A+
N AOH (U
NACO 3-
NAHC03(L)
N AS 0 4-
N A.NO 3-
CL-
I
00
I
SOLID PHASE
FLOW RATE fG/SEC)
f G- MOLESI SE C)
ENT HALPY C C Al/S EC)
7
86.475
.510Q9-11
.15467-01
. 4 90 IJ 8- 03
.1€4al-04
.4~039- 02
.71292-08
. 3£; S3 7 7 - 06
.25f.33
.79571-12
. 1 {; 763- 18
. 31 P- 6 4- 1 3
. 11 545
.11723-01
. 2 S 8 {; 2- 03
.36133-D5
. :3 q 4 4 5- 03
. 44 57 7- 02
.201 CHG
. 51 C8 9- 11
.15467-01
.49008-09
. 164:3 1- 04
.49039-02
.71292- 08
. 36877- 06
. 2S 633
.79571-12
.16703-18
. 37864- 13
. 11 545
. 11 72 3- 01
. 2S 86 2- 03
. 3f, 13 3- 05
. 3844 5- :J~
.44577-02
.20192-01
. 00000
. 00000
. co 00 0
. 00 DO 0
. OC 00 a
. 00000
. 99 G8 9- 01
.19639-03
.14974- 06
.172:3fJ-09
. 37 86 8- 0:3
. 32986- 02
.80684- 01
1 92 8. 0
21.142
-.54384+07
.51089- 11
. 15 4~ 7- 01
.4900 R- 09
.1~4S1-D4
. 48 03 9- 02
.11292-08
. :'6877- 06
. 2S (':.3 3
.79571-12
. 16 76 3- 1 8
. 31 ~G 4- 13
. 11 54 5
.1l72!-01
. 2S E6 2- 03
. 3613 3- 05
. 3844 S- 08
. 44 S 7 7- 02
. 20 1 9 2- 01
. 00000
. 00 00 0
. 00000
. 00000
. 00 00 0
. 00 00 0
.99689-01
.}<}E,39- 03
. 14 '374- 06
.17239-09
.37868-03
. 32 q8 6- 02
.8069~01
154 .89
8.2180
-.21294+07
.. 5 1 08 9- 11
.15467-01
.4900~-09
.16481-04
.148039-02
.71292-08
.3h877-06
.25633
.79511-12
.167C':-18
.37 8~ 4 -13
. 11 54 c:;
.11723-01
.25867.-03
.36133-05
..3gq4~-08
.44571-02
.20192-01
.00000
.oooor.
.00000
..oooor.
.0000(1
.00001)
.99689-01
.19639-03
. 14 97 4 - Of;
. 1173~-09
.378;8-03
.3298f-02
.80~84-01
7.S48~
.82180-01
- 2 12 94 .
.51 OR 9-11
. 15461-01
.4900B-09
.H~431-04
.«iQ039-02
.71292-08
. 3c.877-06
.25633
.79571-12
.1r-7~3-18
. ~78f)4-13
.1lS'~S
.11 723-01
.7.~8(;2-03
. 3C; 113-05
.3~44S-C8
..44571-02
.201~2-01
. on 00 0
.00000
. co 00 0
.00 co 0
. DC 000
.'JOOOO
.933
.79.571-12
.16763-18
.31864-13
. 11 545
.11723-01
.25862-03
.3h133-0S
.38445-08
.44577-02
.20192-01
.00 co 0
. oe 00 0
.00000
.OOGOO
. 0000 0
.0eGOO
.99689-01
. 1
-------
(4 AUG 70 10:53:27.543 P R OT 0 . Y ) E 5 : Ml LA" : 0 N NO.. 2-B
STRE~M NUMBER 1 8 9 10 1 1 12
COMP (G-MOlES/S EC)
CAO 3.8321 2 .7 54 3 1 .0134 .10B4-01 1.0f,1E .1067(-01
CA(OHI2 1 OlE 644 1 . 1 96 1 .'i;;833 .4683~-02 .uS354 .46364-02
C II.C03 .38829 . 27903 . 10925 .l092C,-02 ..10816 .10816-02
CAS 0 3 .00000 .. OC 00 0 . 00 GO 0 . CO 00 0 .. co 00 0 .. 00000
CAS03*1/2H20 4.5989 3 .J 04 9 1 .2 94 0 ..12940-01 l.2Pll .12811-01
CAS04 4.5826 3.2932 1.2(1<34 .12894-01 1 .2166 .121Gf.-Ol
CAS04*ZHZO .00000 . 00000 . GO 00 0 .0000 [1 .00000 . 00 00 0
MGO .00000 .00 00 Q . CO 00 0 .0000 r .. OOCGO . GO 000
MG(OH)Z .00000 .. 00000 . 00000 .ooooe .Gcor;o .. 00 DO 0
MGC03 .00 00 0 . 00 DC 0 . 00 CO 0 .00000 .00000 . 00 00 0
MGC03*3H20 .Ocooo . OC 00 0 . 00 CO 0 .00 CO r . CO 00 0 . 00000
MGC03*5H20 .00000 .00000 .. 00 00 0 .00000 .00000 . 00000
MGSO 3 .00000 . 00000 .0000'0 . 0000 0 .00 GO 0 . 00000
MGS03*3H20 .00000 .00000 . 00000 .00000 .00000 . CO 00 0
MGS03*6H20 .00000 .00000 . 00 DC 0 .ooooc ..00000 . 0000 a
MGS04 .00000 .0000 0 . 00 DO 0 .0000 D .00000 .00000
NA20 .00000 .00000 . 00000 .00000 .~OOOO .00000
I INSOLUBLE FLY ASH 14.353 10.314 4.0386 .40386-01 3.q982 .39982-01
1.0 NACL .00000 . 00000 . 00 00 0 .OOOOf) .00000 . 00000
I
SUMM ~RY IN ENGINEERING UNITS
TOT FLOW RATE (LaS/MINI 121 74 . 8748.. 5 3 42 ~. 5 3095.4 -330.05 lE-6.19
( L 8- MOL E S / M IN) 643.46 462.41 181.05 167.4(, 1 ~. 5'35 8.9630
GAS FLOW RATE (LBS/MIN) .00000 .00 co 0 . DC 00 0 .00000 .00000 .. 00 00 0
( L 8- MOL E S I M IN) .00000 .00000 . 00 00 0 .00000 .00000 . 00000
(ACFM1 .00000 .00000 . OC 00 0 .00000 . no 00 0 . DC 00 0
LIG FLOW RATE (LBS/~IN) 11819. 8493.5 3325.6 3094.4 231.20 165.80
( L S- MOL E S I M IN) 63'3.51 459.61 1 79 .96 1 b 7.45 12.511 8 .972 1
( 1000 LBS H20/MIN) 11.438 8.21'99 3 .Z 18 5 l..994? .22375 .. 1604 f
(GAL/MIN) 1386.5 996.31 3 90 .1 3 363.00 27.122 19.450
LIG DENSITY (LBSI GAli~T) 8.4963 8 . 4 98 3 8.4983 a .4983 8.4983 8 .4 98 3
SOL FLOW RATE (LaS/MINI 354.88 255.02 99. 854 .99854 98.855 . 98855
(l B- MOLESI MI N) 3.8915 2 .7 96 5 1 .0950 . 1 0 95 0- 01 1.081f-0 .1064 Q-Ol
-------
04 AUG 70 10:S3:28.D76
STREAM NUMBER
LIQ. H20 RATE CKG/SECt
COMP tG-MOLES/KG H20)
H+
OH-
H S 0 3-
S03=
S04=
HCO 3-
C03=
N03-
HS04-
H2S03CLt
H2C03CLJ
C6++
C AOH+
CAS03CL}
C ACO 3CL t
CAHC03+J
CAS04CL)
CAN03+
MG++
MGOH+
fo'IGS03CLJ
MGHC03+
MGS04(l)
MGC03CLJ
NA+
NAOHCL)
NACO 3-
NAHC03CL)
N AS 0 4-
N ANO 3-
CL-
I
......
o
I
SOLID PHASE
FLOW RATE CG/SEC)
C G- HOLES/ SE C)
ENTHALPY (CAL/SEC)
1 3
.47841
. 51 ca 9- 11
.15467-01
.49n08-09
. 1 6 u 8 1- 04
. 48 03 9- 02
.71292- oa
. 36R77- 06
.:?5E33
.79571- 12
.161;3- 18
.37864-13
. 11 545
.11723- 01
.25~62-03
. 3" 1 3 3- 05
. 38 4 ~ 5- 03
.44571-02
.201 9 2- 01
.00000
.00000
.00 OC 0
.00000
.00000
.00000
.99689-Ql
.19639-03
. 1 q 97 4- 06
. 1 72 } 9- 09
. 37A.68- 03
.32986- 02
. 80E-8 4- 01
739.87
a.1133
-.20870+01
14
1 .533 G
PiHITOTYPE SIMULATION NO. 2-8
1 5
87.530
.22603-06
. 22 6C 3- 06
. 0000 c
.00000
.00 DO 0
.00 co 0
.00 00 0
. 0000 a
. 00000
. 00 00 0
. 0000 0
. 00000
.00000
.GOOOO
. CO 00 0
. 0000 0
. 00000
. GO 00 0
. 00000
.00000
.0000 []
.0000 a
. co GO 0
. 00000
. 00000
. 00 DC 0
.00000
.0000 C
.00000
.00000
.0000 C
. 00 00 0
. 00000
.00000
. 50 31 4- 11
. 1 5 56 1- 0 1
.4') 23 1- 09
. l{; 57 ~- 04
. 4 ~ 18 2- 02
.11(.20-08
. 3709 }- 06
. 25 199
. 60098- 12
. 16 18 8- 1 8
.31923-13
. 11 311
.11658-01
. 25 81 3- 0 3
. 36179- OS
.3823(,- 08
. 44 G 3 q- 02
. 1 q 11 7- 01
. 00 CO 0
. 00 00 0
. 00 00 0
. 00 GO 0
. 00 00 0
. CO 00 0
.97959- 01
.19~Sl-03
. 14 90 7- 06
. 1707 f,- C9
.377GC-03
.32080- 02
. 79210- 01
1939. 0
21.261
-------
J4 AJG 70 10:53:27.907
STREAM NUMBER
TOTAL STREAM
FLOW RATE (G/SEC)
(G-MOlE/S EC)
TEMPER~TURE (DEG. K)
PRESSURE (ATM)
ENTHALPY rCAL/SEC)
SOLIDS (WT %)
GAS PHASE
FLOW RATE
(G/$EC)
( G- MOL E / S EC )
( CAL/SEC)
(G- MOLES/ SE C)
I
......
......
I
ENTHALPY
COMP
S02
C02
NO
N02
02
CO
N2
HCL
H20
LIQUID PHASE
FLOW RATE
(G/SEC)
(G- MOLESI SE C)
( CAL/SEC)
(G-MOLES/SEC)
ENT HALPY
COMP
S02
C02
S03
N205
CAO
MGO
NA20
HCL
H20
DENSITY (G/ML
IONIC STRENGTH
PH
AT T)
13
1234.3
34.867
321.95
.00000
-.3'3122+07
59.944
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
.00000
494.40
26.753
-. 1 8 25 1 .. 07
. 1 J 16 3- 03
.19823-05
.4612 G- 02
. G (; <34 4- 01
.12768- 01
.00000
. 24 11 ~- 01
.38605-01
2 (;. 546
1.0184
.48217
11.344
14
1 533. 6
85.122
321.95
. 0000 a
-. 57 18 7.. 07
.00000
. 0000 0
. 00 GO 0
. 00 GO 0
. co 00 0
. OC 00 0
. co 00 a
. 00000
.00000
. 00000
. 00000
.00000
.00000
1533.6
85.122
-.57187+07
.00000
. 0000 C
. 00 co 0
. 00000
. 00 00 0
.00000
. 00 O~ 0
.0000 G
85.122
. 98 86 1
. 22603- 0;
6.6461
)~OTOTYPr. 511, LATION ~O. 2-B
1 5
92334 .
491 4. 9
321 .95
. 0000 0
2 .1 00 0
. 00 00 0
. 00 00 0
. co 00 0
. co co 0
. 00 co 0
. 00 00 0
. 00 DO 0
. co 00 0
. 00 00 0
. 0000 0
. 00 00 0
. 0000 0
903 95 .
4893. G
-.33382+09
. 7.4 11 5- 01
. 3631 (- 03
..R4541
.12.032
13.118
. 00000
4.45'30
6 .9 38 5
4856.2
1.0179
. 47 54 8
1 1. 34 6
-------
04 AUG 10 10:53:27.907
STRE~:-1 NUMBER
TOTA.L STREAM
FLOW RATE (G/SEC)
(G-MOlE/SECJ
TEMPER~TURE (DEG. K)
PRESSURE (ATM)
ENTHALPY (C~L/SEC)
SOL 10S HIT %)
GAS PHASE
FLOW RATE
(GISEC)
( G- MOL E IS EC )
( CAL/SEC)
(G-MOlES/SEC)
I
.....
N
I
ENTHALPY
COMP
S02
C02
NO
N02
02
CO
N2
HCL
H20
LIQUID PHASE
FLOW lUTE
(G/ S E C)
(G- MOLES/ SE C)
( C A L/ S E C)
(G-HOLES/SEC)
ENTHALPY
COMP
S02
C02
S03
N20S
CAO
MGO
NA20
HCL
H20
DENSITY (G/ML
IONIC STRENGTH
PH
AT T)
13
1234.3
34.867
321.95
.oooco
-.3QI22.01
59.944
.00000
. a 0 OC 0
.00000
.00000
.00000
.COOOO
.oooao
.00000
.00000
.00000
.00000
.00000
494.40
2'>.153
-. 18251 + 01
. 1 J 1 6 3- 03
.IQ823-C5
.46126- 02
. 66 <3 II 4- 01
. 72 1 G 8- 01
.00000
.2417~-01
.38605-01
2 ~. 546
1.0184
.48271
11.344
14
PROTOTYPE. SIMULATION NO. 2-B
1 5
1 533. 6
8 S. 122
321.95
. 0000 C
- . 57 78 7.. 07
.00000
. 00 OC 0
. 00000
.00000
. co 00 0
. OC co 0
. 00000
. 00 GO 0
. 00000
. 00 co 0
. 00000
.00000
.00000
1533.6
85.122
- . 57 18 1. 07
.00000
.0000 C
. 00000
. 00000
. 00000
. 00000
.00000
.0000 G
85.122
. 98 86 1
.22603-06
6.6461
923 34 .
491 II. '3
321 .95
. 00 00 0
2 . 1 00 0
. 00 00 C
. 00 00 0
. co 00 0
. 00 00 0
. 00 00 0
. 00 00 0
. 00 00 0
. co 000
. co 00 0
. 00 00 0
. 00 00 0
. 00 00 0
903 qS .
4893. 6
-.33382"09
. 24 11 5- 01
. 3631 (- 03
. ~ 454 1
12.032
13.118
. 00 OC 0
4.4530
6 .9 38 5
485 E. 2
1 .Q 119
. 4754 8
1 1. 34 (.
-------
04 AUG 10 10:53:28.259
STREAM P.JUMBER
COMP (G-MOlES/SECJ
C 6.1)
CA{OH)Z
CbC03
C r-S03
CAS03*1/2H20
CAS04
CAS04*ZHZO
MGO
MGtOH)2
MGC03
MGC03*3H20
MGC03*SH20
M GS 03
MGS03-3H20
MGS03*6H20
MGS04
NA20
INSOLUBLE FLY ASH
NACL
,
.....
v.>
,
SUMMARY IN ENGINEERING UNITS
TOT FLOW RATE (LBS/MIN)
( L B- MOL E S / t.1 IN)
GAS FLOW RATE (LBS/MIN)
( l 8- MOL E S / ~ IN)
(A ~F M)
LIQ FLOW RATE (L9S/MIN)
eLB-MOlESI MIN)
(1000 LBS H20/~IN)
(GAl/MIN)
lIQ DENSITY (LBS/GAL~T)
SOL FLOW RATE (LBS/MIN)
CL B- MOLES/ MI N)
13
1.0510
.45901
. 10 708
.oaoco
1.2633
1.2638
.00000
.00000
.00000
.coooo
.00000
.00000
.00000
.00000
.00000
.00000
.00000
3.'3582
.00000
163.26
4.6120
..00000
.00000
.00000
65.396
3.5388
.632<30-01
1..6116
8.49;J3
91.861
1.0132
14
. 00000
. CO 00 0
.00000
. OC 00 0
.00 co 0
.. 00000
.GO~jQO
. GO 00 0
. co GO 0
.00000
.00000
. 00000
.00000
.. 00 GO 0
. 00000
.. 00 00 a
. co 00 0
.00000
. 00000
7.02.85
1 1.259
.. 00000-
. OC 00 0
.0000 0
202.35
11.259
.. 20265
2". 588
8.2499
.00000
. 00000
PROT OTYPE SIMULI\T ION NO. Z-B
15
2 .7 7S 7
1.1f!29
.213120
.00 os 0
3 .3 302
3.3025
. CO 00 0
. 00 00 0
. 00 00 0
.. 00000
. co 00 0
. co 00 0
. 00000
. 00 00 0
. 00 CG 0
. 00 00 0
. 00 (10 0
1 U. 395
. 00 00 0
1 22 14 .
6 50 . 1 1
. 00 00 0
. CO 00 0
. DC 00 0
11~57.
641.30
11.578
1403. ..
8.4943
Z 56 .4 9
2.8131
-------
)
PROTOTYPE SIMULATION NO. 2-8
EQUIPMENT OUTPUTS
014 AUG 70
10:53:28.411
1.0. FAN POWER REOUIEMENTS;
HORSEPOWER: 3.0868+02 K!LOWATTS: 2.3019+02
COOLER/REHEATER; .
Cooler HEAT DUTY :-297063.75CAL/SEC
Reheater HEAT DUTY: 787sa3.S1CAL/SEC
I
......
~
I
-------
Radian Corporation
8409 RESEARCH BLVD.
.
TELEPHONE 512 - 454.9535
AUSTIN, TEXAS 78758
.
TECHNICAL NOTE 200-004-21
EQUILIBRIUM CALCULATIONS FOR TYPE I
APCO INHOUSE EXPERIMENTS
11 March 1971
Prepared by:
James L. Phillips
CHEMICAL RESEARCH. SYSTEMS ANALYSIS. COMPUTER SCIENCE. CHEMICAL ENGINEERING
-------
Radian Corporation
~£~~.~~~ . t!! a~10H'3.'JT . II2\!
8409 RESEARCH BLVD. . P,O. BOX 9948 . AUSTIN, TEXAS 1~~"\1()~If~nw~b~W35
1.0 j
IN'rRODUCTION
This technical note gives the results of equilibrium
calculations made during analysis of data from APCO's inhouse
S92 scrubbing experiments. These experiments were conducted
at the Division of Process Control Engineering's Cincinnati
I ,
laboratory facilities during the period August to December,
1970.
3"
2.0
EXPERIMENTAL APPROACH
The test program for the Type I experiments was
described in detail in Radian Technical Note 200-002-05.
The primary purpose of this experimental series was to
observe the approach to vapor-liquid equilibrium in a venturi
scrubber during S02 absorption. The ability to accomplish this
objective is based on the computational scheme developed by
Radian Corporation during APCO Contract 22-69-138. Using this
equilibrium subroutine, S02 (and CO2) partial pressures above
a given scrubber liquor can be calculated provided accurate
chemical analyses are obtained. These calculated equilibrium
partial pressures can then be compared to measured experimental
partial pressures for the flue gas in contact with the liquor
at the scrubber outlet. This comparison provides a quantitative
index of vapor-liquid 'mass transfer capability. Appropriate
test parameters can be varied to examine a range of scrubber
performance.
3.0
EQUILIBRIUM CALCULATIONS
Copies of computer outputs for equilibrium calculations
based on chemical analyses of appropriate scrubber liquors are
-------
Radian Corporation
8409 RESEARCH BLVD. . P.O. BOX 9948 . AUSTIN, TEXAS 78758 . TELEPHONE 512 . 454.9535
attached. Important aspects of the format for this output
are described below and are indicated by numbered brackets
on the first case.
For each of the Type I Runs, measured chemical species
(aqueous) included equivalent concentrations of 802' CO2, 80s,
N20s, CaO, MgO, Na20, and HCl. These values are shown as
inputs to each equilibrium calculation [1]. The scrubber
liquor temperature is also input to the program [2].
Equilibrium concentrations, activities, and activity coefficients
for all important species are calculated by the routine and
printed as output [3]. The equilibrium partial pressures of
CO2 and 802 above a liquor of the compo~ition given by the
input species are also calculated and printed [4]. Finally,
the pH and ionic strength [5] are calculated and printed.
The calculated value of pH is derived from the electro-
neutrality constraint for the liquor. Thus, it provides an
important indicatibn of the accuracy of the input species
analyses. If one or more cation analyses are high, for
example, electroneutrality wou.ld require that the calculated
value of pH be higher. If anion analyses were high, the cal-
culated pH would be lower than the actual pH.
-2-
-------
27 JAN 71
11:411:38.730
. INPUT MOLES
502
C02
503
I NA20
I
~
I
=5.00000-03
=3.98000- 04
=1.93000-03
=6. isoao-04
I
i
3
COMPONENT
H20
H+
OH-
HS 03-
50 3--
504--
HC03-
C03--
N03-
HS Olf-
H2503
H 2CO 3
C4++
C AOH+
C 4503
C ACO 3
CAHC03+
C &504
C ANO 3+
M6++
"GOH+
MG503
MGHC03+
MGS04
"GC03
NA+
NAOH
NACO 3-
N AH C 03
N 150 q-
TEMPERATURE
APCO INHOUSE EXPERIMENTS - TYPE I, NO.1
N20S = 1.07000- 014
HCL =1.49000-03
CAO
H20
= 1 . 31 00 0- 03
=5.55062"01
MGO
=6.96000-0q
AQUEOUS SOLUTION EQUILIBRIA
MOLALtTY
3. 8 1 8- 03
6. CSIf-12
3. 8 9 5- 03
8. 5 ~ 2- 08
1.319-03
6.267- 08
1 . 33 5- 1 5
2.135- Olf
3.939- 014
1.105-03
3. 9 !W- 04
1. 110- 03
1. 1 43- 1 3
1.146-01
-1.16E--15
9. 1 4 9- 1 0
1.397-:J1f
4.258- 07
6.239-04
1.031-12
1 . 990- 08
2. 3 g 0- 10
1.211- 05
9.764-16
1.230- 03
1 . 603- 1 5
2.161-11
3. 4 1 2- 11
5.642- 06
A CT IV IT Y
3.451-03
S.408-12
3 .4 84- 0 3
5.498-0e
8.257-04
5 .60~- 08
8.861-16
1.887-04
3.519-04
1.108-(;3
3.988-04
1.528-04
1.021-13
1.150-01
1 .1 10- 15
B.113-10
1.400-C4
3.804-01
3.913- 04
9.21l-1~
1.~94-0e
2.126-10
1.232-05
9.184- 16
1 .104- 0 3
1.607-15
1.930-17
3.479-11
5.040-06
ACT IV ITY COEFFICIENT
9.997-01
9.039-01
8.933-01
3.944-01
6.399-01
6.261-01
8.944-01
6.399-01
8.836 -rn
8.933-01
1.002+00
1.002+00
6.435-01
8.933-01
1.002+00
1.002+00
8.933-!H
1.002+00
8.933-'11
6.368-01
8.933-01
1.002+00
3.933-01
1.002+00
1.002+'J0
8.972-01
1.002+00
8.933-01
1.002+00
8.933-01
I 3:5 . :5 30 DE G. C I
I
2
-------
A JPS02
q. ~CO 2
I
.p-
I
N ANO 3
Cl-
= 1. II II 7 8- 0.3
= 1.44268- 02
IPH =
ATM.
ATt'!.
2.462
8.273-08
1.1190-03
8 .290- 08
1.330-03
1.002 +00
8.928-01
MOLECULAR WATER = 9.99S13-01 KGS.
IONIC STRENGTH = 1.17484-021
I
5
Page 2
TYPE I. NO. 1
\:,
RES. E;'N. =
-1.733-10
-------
21
I ~: 7
. : 2 3: 25. : 73
TEHP~RA'. ~~
S02 =".76000-03
C02 =3.98000- 04
S03 =2.39000- 03
NI20 =7.80000-04
INPUT MOLES
APCO INHOUSE EXPERIMENTS - TYPE I, NO. lA
N205 = 1. 07000- 04 CIO = 1. 50000- 03 MGO = 5. 02GOO-CIf
HCL = 1. 80000-03 H20 =5.55062+01
AQUEOUS SOLUTION EGU IL 19 RI A
COMPONENT MOLALITY A CT IV IT Y A CT IV IT Y COEFFICIENT
H20 =J .997 -0 1
H+ q. 310- 03 3 .8 84 - 0 3 9 .0 11 -0 1
OH- S. 4aD- 12 If .805-12 8 .8 98 -0 1
HS 03- 3.612- 03 3.217-03 8.909-01
S03-- 7.153-08 4.512-08 5.299-01
S04-- 1.604- 03 9.874-01J 6 .1 54 -3 1
H CO 3- 5. S91- 08 1f.981-08 8 .909 -0 1
C03-- 1.111-15 6.997-16 6.299 -01
N03- 2. 134- 04 1 . 8 17 - 0 4 8.193-!H
I HS 0 4- 5.322- C4 4.135-04 8 .8 9B -0 1
VI
I H2S03 1.149-03 1.151-03 1.002+00
H2C03 3.980- 04 3.989-04 1.002 +!)Q
CA++ 1.315-03 8.331-04 6.337 -0 1
C IOH. 1.128-13 1.004-13 8.898-01
C ASO 3 1. 01f2- 01 1.045-07 1.002+00
C ACO 3 1. 02e- 15 1.022-15 1.002+00
C AHC03. 9. tTJ5-10 8.0 3q-l 0 8.898-01
CAS 0 II 1.849-04 1.853-04 1 .002 +00
C ANO 3. 4.701-C7 4.188-07 8.89g-rn
MG.+ ".419- 04 2.169-04 6.26.1-01
f4GOH+ 6. en 2- 13 5.105-13 8.898-01
MGS03 1. 1 38- 08 1.140-08 1.002+00
MGHC03. 1.4~1-10 1.317-10 8 .898 -0 1
HGS 0.. 6.015-05 6.028-05 1 .002 +00
MGC03 5.314-16 5.386-16 1.002+00
NA+ 1.552- 03 1.381-03 8.938-01
NIOH 1.189-15 1.793-15 1.002 +00
N ICO 3- 2. 1 52- 11 1.915-11 8.998 -0 1
NAHC03 3. a 16- 11 3.885-11 1.0C2+!J0
N AS04- 8.510- 06 7.571-06 8.898-f.'n
33.33(
DE 6. C
-------
NAN03
CL-
PS02 = 1.26274- 03
PC02 =1.4fJ29C3-02
PH =
I
0\
I
ATM.
ATM.
2.411
1.031&- 01
1.800- 03
1.036-07
1.601-03
MOLECULAR WATER = 9.99912-01 KGS.
IONIC STRENGTH = 1.27363-02
1.002 +oq
8.892 -01
Page 2
TYPE I, NO. lA
RES. E.N. =
-2.866-08
-------
09 )C. 70
T EMP'=-R~ '.URE
.3 : 56: 39. 2 GO
INPU T MOLE'S
502
C02
503
N420
=4.70000-03
= 2 . 5 1 0 0 0- 0 3
=1.27000-03
= [.. 56 00 0- 0 II
N20S = 1. 32000- C4
HCl =1.53000-03
APCO INHOUSE EXPERIMENTS - TYPE I - NOo 2
no
H20
=1.2.8[,00-03
=5.5S0;2+D1
MGO
=5.140')0-04
~GU£OUS SOLUTION (GUll BRI4
COM P 0 N E NT MOl~LITY ~ CT I V IT Y ~ CT IV IT Y COEFFICIENT
H20 '3 . 9 «37 - 0 1
H+ 3. OQ6- 03 2.804-03 '3.C85-S1
OH- 1. 4 0 2- 1 2 ~.655-12 3.991-Gl
H 5 0 3- 3 . ~n S- 0 3 3.434-03 9.001-':)1
5 0 3 -- 1 . !J 1 (- 07 5.1;69-08 6.5&4-01
504-... 9.014-04 5.804-04 £.439-01
H CO 3- 4.832-07 4.343-01 3.001-01
C03-- 1.2~9-14 8.461-15 5.5t;4-!Jl
N03- 2.634-04 2.34~,-04 3.905-('1
I H S 0 4- 2.2!S-04 2.010-04 8.9'H-~1
"" H 25 0 3 8.85!=-04 ~.81C-04 1.002+'0
I
H 2C 03 2.510-03 2.514-03 1.002+00
C ~++ 1 . 11 B- 03 7.171-04 6.596-fi1
C AOH+ 1 . 44 2- 13 1.297-13 a.991-01
CAS 0 3 1.438-01 1.440-07 1.002+00
C ACO 3 1.151-14 1.153-14 1.OD2+f10
C AHC03+ 7.;?31-09 f.~46-C'3 3.991-Ql
CAS 0 4 1.014-04 1.016-04 1.002+00
C ~NO ~+ 5.429-07 4.882-07 8.991-01
~r,++ 4.144-04 3.100-04 0.535-01
MGOH+ 9.839- 13 8.846-13 3.391-01
~GS 0 3 1 . 8 ~ 4- 08 1.381-08 1.802+(10
'1GHC03+ 1.432- 09 1.Z?S-09 8.3~1-Gl
MGS04 3. 91;Q- 05 3.9£7-05 1.002+00
MGC03 7. 278- 15 7.2'31-1S 1.002+']0
Nt\+ 1. 3 O~- 0:3 1.18C-03 9.02[,-t")1
N AOI-/ 2.111-15 2.114-15 1.002+CO
N ~C 0 3- 2. I q 2- 1 6 1.'311-1[, 8.9'31-Gl
N AH CO 3 2 . 8 c; 2- 10 2.687-10 1.002+']0
N ASO 4- 4.214- Gf, 3.788-0E 3.391-S1
33.330
DE G. C
-------
N ANO 3
CL-
PS 0 2 = 9. 7 2 <3 8 1- 04
PC02 =9.03596-02
PH =
I
00
I
ATM.
ATM.
2.552
1 . 1 00- 07
1.590-03
1 .102- 0 7
1.429-03
MOLECULAR WATER = 9.99889-01 I
-------
09 0:' 1)
.3:56:43.~ 11
'PPf.R4.'.RE
$02
C02
S03
NA20
=4.60000-03
=2.55000-03
= 1.69000- 03
=6.42000-G4
IN PU T MOLES
APCO INHOUSE EXPERIMENTS - TYPE I, NO.3
33.330
DE S. C
MGO
=4.6080:)-04
COMPONENT MOLALITY A CT IV IT Y A CT IV IT Y COEFfICIENT
H20 '3.9(n-j~1
H+ 3.751-03 3.400- 03 9.066-('1
'OH- 6. 1 2 11- 1 2 5.488-12 3.3(.1-01
HS 0 3- 3.!:.92-03 3.225-03 8.~71-Cl
SO 3- - 7.951-03 5.1 E S- 0 8 0.496-01
504-- 1.169-03 7.439-04 6.3tE-Ol
H CO 3- 4 . 0 5 9- 07 3.644-07 8.977-01
CO 3-- 9. 0 a 1)- 1 5 5.840-15 6.490-01
N03- 2.494-04 2.214-04 3.871-01
I HS 04- 3.4~3-04 3.123- 0 4 3.9£7-01
\0
I H 25 0 3 1 . (I a 8- 0 3 1 .0 10- 0 3 1.002+80
H2C03 2.550-03 2.555-03 1.0Q2+00
C A++ 1. 1 3 5- 0 3 1.414-04 5.529-01
C AOH+ 1 . 1 3 g- 1 3 1.020-13 8.9£'7-Dl
C AS 03 1.062-07 1.064-07 1.002+00
C AC 03 7. 5 8 8- 1 5 7.603-15 1.002+80
CAHC03+ 5. 8 3 F;- 0 '3 5.233-09 8.367-01
CAS 04 1 . 24 0- 0" 1.242-04 1.002+00
C ANO 3+ 4.904- 07 4.391-07 8.967-0}
MG++ 4 . 1 -6 c- 04 2.690-04 6.465-01
MGOH+ 7.05 g- 13 6.329-13 9.961-r)1
MGS 0 3 1.2;6-08 1.268-08 1.1]02+00
MGHC03+ 1.044-0'3 9.36S-1G 8.9E7-01
MG504 4. 1+ a 3- 0 5 14.411-05 l.coz+no
MSC03 4. 3 5 2- 1 5 4.37G-15 '1.002+'":0
N A+ 1 . ? 7 9- 0 3 1.1~'1-C3 9.003-':11
NAOH 1.~97-15 1.701-15 I.C02+00
NACO 3- 1.4~1-1£ 1.328-15 3.9~,7-01
NAHC03 2.355-10 ? . ~ ~. 9- 10 1.002+00
N AS 0 4- 5.?~n-C6 4.73f.-CE 8.'3£7-':11
N20S =1.250aIJ-04
HCL = 1. 600'J0- 03
C~O
H20
= 1. 26000- 03
=5.55062+01
AQUEOUS SOLUTION EQUILIRRIA,
-------
N ~NO 3
Cl-
Pc.; 0 2 = 1 . 1 C 8 1 2- 0 3
PC02 =Q.2ti2ti!-02
PH =
I
~
o
I
ATM.
ATM.
2 ... G8
1 . cn 3- 07
1 . ;; 0 0- 03
1.015-07
1."3ti-0~
MOL £ CU L A R W ATE R = 9. 9 9 8 g 1- 01 K G S .
IONIC STRf.NGTH = 1.S8532-02
1.002+00
8.963-(\}
Page 2
TYPE I, NO.3
RES. F.N. =
-3.531-11
-------
27 ..AI 71
Jl : 3 5 : L 1 . 8 99
TE'PC:RATURE
502
C02
503
NA20
=4.58000-03
=3.75000-04
= 1 . 4 2000- 0 3
=7.80000-04
INPUT MOLES
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 3A
N20S =1.47000-04
YCL =1.90000-03
C40
H20
= 1. 41 000- 03
= 5. S 5 06 2 + 01
MGO
=5.10GOO-04
AQuEOUS S OLUT ION EGU IL lBRI II
COMPONENT MOL AL ITY 4 CT IV IT Y A CT IV IT Y COEFFIClfNT
H20 9.997-01
H+ 3.104- 03 2. a 13- 03 9.064-01
OH- 7. 3 <39- 1 2 6.632-12 a.9£4-Gl
HS 03- 3.,117-03 3.33f-03 8.914-01
503-- 9.954-08 6.451-08 5.487-')1
504-- 1.004-03 6.383- 04 6.356-f)1
HC03- 7.216- 08 6.47£-08 8.974-01
CO 3-- 1.43 36- 15 1.25t:;-15 6 .487 -e!l
N03- 2. «3 32- 04 2.602-04 8.873-01
I HS 04- 2.474- 04 2.21B-04 3.9f,4-81
.....
..... H2S0 3 8.630-04 8.647-04 1.002+GG
I H2CO 3 3.750-04 3.757-04 1.002+00
CA++ 1.289-03 8.403-04 6.521-01
CAOH+ 1 . 5 5 9- 1 3 1 .398- 13 a.964-~1
CAS 03 1 . 5 0 5- C\7 1.508-07 1.002+00
C ACO 3 1.847-15 1.851-15 1.002+00
CAHC03+ 1.116- 09 1.054-09 8.964-01
C A50 4 1.206-04 1.208-04 1.002+00
C ANO 3+ 6.533-01 5.856-07 8.964-01
MG++ 4 . 6 76- 04 3.019- 04 6.457-01
MGOH+ 9.578- 1 3 8.58(-13 3.964-01
MG503 1.77F-08 1 .779- 08 1.002+00
~GHC03+ 2. 08 3- Ie 1.867-10 8.964 -fn
MG504 4.240-05 4.249-05 1.002+0G
MGCO 3 1 . 0 52- 1 5 1.054-15 1.0Q2+00
NA+ 1.554-03 1 .399- 0 3 9.000-01
NAOH 2.493-15 2.498-15 1.0G2+~O
N A C 0 3- 3.868- 17 3.467-11 3.964-01
NAHC03 5 . 0 9 5- 11 5.095-11 1.OG2+f!Q
N A50 4- 5.509-06 4.938-06 8.964 -en
33.330
DE G. C
-------
N ANO 3
Cl-
PS02 =9.48432-04
0e02 =1.35903-02
PH =
I
~
N
I
ATH.
ATH.
2.551
1.44£.-07
1 . 91)0- 0 3
1.449-07
1 .702- 03
MOLECULAR WATER = 9.99931-01 KGS.
IONIC STRENGTH = 1.09326-02
1.002+00
8.960-01
Page 2
TYPE I, NO. 3A
RES. E.N. =
-9.442-09
-------
21 )::C 7(
, 11: 23: 3~.. 9"
T EHP~IU", E
INPUT HOLES
S 02 =6.04000- 03
C02 =2.83000-04
503 =3.59000-03
NA20 = 1. 56000- 03
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 3B
N205 = 1.01000- 014
HCl =1.00000-03
=1.36000-03
= 5.55062+ 01
"GO
CAO
H20
= 3. 40 000-04
AQUEOUS SOLUTION EGUILIBRIA
COMPONENT MOl~lITY e, CT IV IT Y A CT IV IT Y COEFfICIENT
H20 9.996-01
H+ 6. 5 2 3- 0 3 5.825-03 8.930-01
OH- 2.614 7- 12 2.321-12 8.193-01
HS 0 3- 5.62£- 03 4.953-03 8 .804 -0 1
SO 3-- 8.265- 08 4.967-08 6.009-01
504-- 2.340-03 1.366-03 5.840-01
HCO 3- 2. 5 17- 08 2.269-08 8.804-01
C03- 3. 27 2- 16 1.966-16 6.009-01
N03- 2. 1 ! 5- 04 1 .8149- 04 8.663-01
I HS 04- 9.117- 04 8.591-04 8.793-01
t-' H 25 0 3 2.415-03 2.1422-03 1.003+00
UJ
I H2CO 3 2.830-04 2.838-04 1.003+00
CA.. 1.156- 03 1.002-04 6.056-01
C AOH+ 4.509- 14 3.965-14 8.793-01
C AS 0 3 9. 115- 08 9.141-08 1.003+00
C ACO 3 2.285- 16 2.291-16 1.003+00
C AHCO 3+ 3.385-10 2.916-10 8.193-Ql
C ASOft 2.036-04 2.042-04 1.003+00
C ANO 3+ 3.438-01 3.023-07 8.793-01
HG++ 2.932- 04 1.153-04 5.977-01
HGOH+ 1 . 878- I 3 1.652-13 8.793-rn
MGS03 7. 5 5 3- 09 7.574-09 1 .003 +00
MGHC03+ 4.208-11 3.100-11 8.193-rn
"GSOft 4.683- 05 .. .697-05 1 .003 +00
MGCO 3 9. 0 34- 11 9 .0 60 - 1 7 1.003+00
NA. 3.091- 03 2.138-03 8.841-01
NAOH 1 . 71 0- 1 5 1.115-15 1.003+00
NAC03- 1.169-11 1.028-11 8.793-01
NAHC03 3.484- 11 3.494-11 1.003+00
NAS04- 2.291-05 2.014-05 8 . 7 93 -0 1
2 ~ .8 90
DE G. C
-------
NAN03
eL-
PS02 =1.28385-03
pe02 =9.180'13- 03
"H =
I
....
~
I
ATM.
AT".
2.23S
2.010- 07
1.000- 03
2.016-01
8 .186- 0"
1.003+00
8 . 7 84 -0 1
MOLE aJl4R V4 TER = 9. 9~ 842- Cl K GS .
IONIC STRENGTH = 1.63085-02
Page 2
TYPE I, NO. 3B
RES. E .N. =
-2.5H~-09
-------
(43 OC. 70
13:156:5..995
TEMPERATURE
IN PU T MOL E 5
502 =4.08000-03
C02 =1.43000-03
50:3 = 1.57 CO 0- 03
NA20 =£.73000-04
APCO INHOUSE EXPERIMENTS - TYPE I, NO.4
=1.34000-03
=5.55052+01
N205 = 1. 43000- 04
HCL = 2.04000- 03
CAO
H20
MGO
=4.43(100-04
AOUE OU5 5 OLUT ION EQU IL IH RI A
C OMP ONENT MOLALITY ~ CT IV IT Y A CT r V IT Y COEFFICIENT
H20 9.997-01
H+ 3 . 4 3 5- 0 3 3 . 11 G- 0 3 3.07.0-01
bH- 6 . b 7 5- 1 2 5.989-12 3.972-01
He; 0 3- 3.1::31-03 2..'353-03 3.982-01
503-- 7.672- 08 4.994-08 5.51C-Ol
504-- 1.099-03 1.011-04 5.381-01
H C 0 3- 2.482-07 2.230-07 3.982-01
CO 3-- 5.9'37- 15 3.904-15 6.510-01
NO 3- 2.853-04 2.534-04 8.883-1)1
I HS 04- 3.007-04 2.598-04 8.972-1)1
t-' H 25 0 3 8. 1 9 8- 04 8.203-04 1.002+00
V1
I H2C03 1.430- 0"3 1.433-03 1.002 +00
C A+ + 1.214-03 7.'345-04 6.543-01
C AOH+ 1 . 3 3 D- 1 3 1.193-13 8.912-01
C AS 0:> 1.101-01 1.103-01 1.C02+00
CAC03 5 . 4 3 C- 1 5 5.440-15 1.002+00
CAHC03+ 3.825- 09 3.431-09 3.972-01
C A5 0 4 1.252-!J4 1.255-04 1.002+00
C ANO 3 + 6. 010- 07 :; . 393- 0 7 8.972-01
MG++ 4 . 028- 04 2.610-04 6.480-01
MGOH+ 7.4C;c;-13 f.1DI-I! 8.912-01
M GS 03 1. 1 a 8- 08 1 .1 90- 08 1.002+00
M6HC03+ E.194-1D S.557-10 13.972-01
M GS 0 4 4.026-05 4.034-0S 1.002+00
MGC03 2.827- 15 2.832-15 1.002+0C
N A+ 1.341-03 1.208-03 3.008-01
NIIOH 1.343-15 1.'347-15 1.IJ02+GO
NAC03- 1.0"37- 16 9.305-17 8.972-01
NlIHC03 1.51 2- Ie 1.514-10 1.002+00
NilS 0 4- 5.219-00 4.682-06 3.312-01
33.330
DE G. ~
-------
N ANO 3
CL-
PS02 =8.99802- 04
PC02 =5.18249-02
PH =
I
t-'
0\
I
ATM.
ATM.
2 . 5 06
1 . 21 6- 07
2 . 04 0- 03
1.219-01
t .830- 0 3
MOL.ECULAR WATER = 9.99916-01 KGS.
IONIC STRENGTH = 1.01264-02
1.002+00
8.968-01
Page 2
TYPE I, NO.4
RES. E.N. =
-1.301-09
-------
09 0 :.. '1(
,4:08:13.281
Tnpf!U".~~
IN PU T MOLES
502 =2.54000-03
C02 =1.55000-03
S03 =4.10000-03
N A 2 0 = E . 9 300 Q- 04
APCO INHOUSE EXPERIMENTS - TYPE I, NO.5
CAG
H20
= 1. 32QQO- 03
= 5. 55 06 2 + 01
N20S =1.07000-04
HCL =2.0SQOo-03
MGC
=4.40000-04
AQUEOUS SOLUTION EQUILIBRIA
COMPONENT MOL Al ITV A CT IV IT V A CT IV IT Y COEFFICIrNT
H20 9.997-01
H+ 6.12£-03 5.492-03 8.966-01
OH- 3.843- 12 3.3~7-12 8.841-01
HS 0 3- 1.756- 03 1.554-03 8.852-01
SO 3-- 2.S1Q-0~ 1.541-08 6.141-01
S04-- 2.590- Q 3 1.550-03 5.983-01
H CO 3- 1 . 5 5 0- 07 1.372-07 8.852-01
C03-- 2.219-15 1.363-15 6.141-01
N03- 2. 1 3 (.- a 4 1.863-04 8.723-01
I HS 04- 1 . 1 8 9- 03 1.051-03 8.841-01
~ H 25 03 7.845-04 1.865-04 1.003+00
-...J
I H2C03 1.550-03 1.554-03 1.003+00
CA++ 1.096-03 5.115-04 0.183-01
C AOH+ 6,.470-14 5.720-14 8.841-01
C AS 0 3 2.8;9-08 2.876-08 1.003+00
C ACO 3 1.6~1-15 1.605-15 1.003+00
CAHC03+ 2.019-09 1.785-09 8.841-01
C AS 04 2.318-04 2.344-04 1.003+00
C ANO 3+ 3.7'30- 07 3.350- 0 7 8.841-Gl
MG++ 3.642- 04. 2.225-04 C .1 08 -0 1
MGOH+ 3.f;6E-13 3.241-13 3.8'11-01
MGS 03 3.122-09 3.129- 0 9 1.C03+00
~GHC03+ 3.298-10 2.915-10 3.841-01
MGS04 7.5 g 2- OS 7.601-05 1.003+!::O
HGC03 8.401-16 3.428-16 1.003+'30
NA+ 1.374-03 1.221-03 8.885-f'J1
N 6.0 H 1. 11 4- 1 5 1.117-15 1.003+r.O
NAC!J3- 3. 71 !=- 1 7 3.284-17 8.841-i11
N AH CO 3 9.398-11 9.422-11 1.003+00
N AS 0 q- 1.18&1-05 .1.046-05 8.841.-01
33.330
OE G. C
-------
N ANO 3
CL-
PS02 =8.62702- 04
PC 02 = S. G 219 }- 02
PH =
I
.....
00
I
ATM.
ATM.
2 .2 60
9.033-08
2.050-03
9.056-08
1.81l-03
MOlECUL4R WATER = 9.99895-01 KGS.
IONIC STRENGTH = 1.44410-02
1.003+00
8.834-01
Page 2
TYPE I, NO.5
REes. E.N. =
-2.326-08
-------
,-
21 JAN 11
502
C02
503
NA20
I
t-I
\D
I
11:35:46.511
-= 1 . B 8000- 0 2
=1.09000-03
=3.00000-03
=1.46000-02
COMPONENT
H20
H+
OH-
HS 0 3-
S03--
S 04--
HC03-
CO 3--
N03-
HS 04-
H 2S 0 3 .
H 2CO 3
CA++
CAOH+
CAS 03
C AC03
CAMC03+
CASOIf
C ANO 3+
MG++
""GOH+
MGSO 3
MGHC03+
MGS04
MGC03
NA+
NAOH
NACO 3-
NAHC03
~JAS 04-
INPUT MOLES
TEMPERATURE:
APCO INHOUSE EXPERIMENTS - TYPE I, NO.6
N 205 = 1 . 25 a 0 0- 04
HCL =1.9CGOQ-03
CAO
H20
= 1. 380CO-C3
= 5.55 OE 2 + 01
MGO
=4.73000-04
AQUEOUS SOLUTION EQUILIBRIA
MOLAL !TV
3. ~ 1 7- 01
7.174-08
1.35f-02
4.0b1-03
2.711- C 3
7.036-04
2. 1111- 01
2.480- 04
5.156-03
3.230-01
3.750-04
3 . 5 79- 04
3 . 1 q 2- 1 0
9. 702- C~
3.182-08
2.4?0-06
4.951- 05
1.140-07
2.357- 04
3.5 1 6 - 09
2.053-04
1.639-01
3.126-05
3.249-08
2 . 8 9 9- 02
3.~11-1C
5. ~ 47- 08
8.023-06
2.0n'-04
A CT I V I T V
3.115-01
5.38(,-08
1 .1 :!3- C 2
1.980-03
1.249-03
5. g 17- 04
1.029-01
2.001-04
1+ . B 0 3- 08
3.251-07
~.775-04
1.774-04
2.6E.3-10
9.7£6-G4
3.203-08
2.020-06
4.990-05
9 . 5 10- 08
1.143-04
2.934-09
2.066-04
(, .41f.- 07
3.147-05
3.270-08
2.443-02
3.937-1C
4.963-CB
3.01F.-CS
1.687-04
ACT IV !TV COEFFICI~NT
9.991-01
8.612-C1
a.34s-rl
8.3514-01
4.870-:11
4.595-'::1
3.354-~1
4.37G-01
3. C 70 -PI
8.345-~1
1.OQ7+QC
1.007+QG
4.958-01
8.34S-r'11
1.007+00
1.007+00
3.345-01
1.007+00
3.345-31
4.850-01
a.345-01
1.001+00
.3.345-Cl
1.007+00
1.007+00
3.428-01
1.007+!J0
8.345-::)1
1.007+S0
8.345-C1
33.330
DE G. C
-------
N ANO 3
Cl-
PS02 =3.56814-07
PC02 =1.36651-02
PH =
I
N
o
, ,
ATM.
ATM.
6.507
1.934- 06
1.900-03
1.947-06
1 .580- 0 3
MOLECULAP WATER = 9.99882-01 KGS.
IONIC STRENGTH = 3.15598-02
1.001+00
d.315-01
Page 2
TYPE I, NO.6
RES. [.N. =
2.071-10
-------
21 OEC 10
11 : Z 3: 4".884
T PPfRA T . RE
INPUT MOLES
S02 =2.15000-02
C02 = 1 . 09000- 0 3
S03 =5.30000-03
NA20 = 2.12000- 02
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 6A
N205 = 1.15000- 014 CAO = 8. 90000- 04 MGO =3.20000-014
HCL =1.15000-03 H20 =5.55062+01
AOUEOUS S 0 lU T ION E GU IL fa RI A
COMPONENT MOLALITY A CT IV IT Y A C1 IV IT Y COEFFIClf:NT
H20 9.988-01
H+ 1 . q 72- 07 1.2148-07 8.4114-01
OH- 1 . If 5 2- 07 1.178-07 8.112-01
HS 0 3- 1. 1 06- 02 8.972-03 8.109 -01
S 03-- 9.5"2- 03 ".126-03 14 . 3 2.. -0 1
S 04-- 4.81 Z- 03 1.920-03 3.991-01
HC03- 8.854- 04 7.180-04 8 .1 09 -0 1
C03-- 6. 8 5 1- 07 2.965-01 4.3214-01
N03- 2.216- 04 1.757-04 7.719 -01
I HS 04- 3.Z99-08 Z.6 76-08 8.11Z-01
N H 2S 0 3 9.5Z4-08 9.620-08 1.010+00
...
I H2C03 1.@84-04 1.903-014 1.010+00
C A.+ 1.47t-04 6.559-05 4.1143-01
C AOH+ 2. 3 3 5- 10 1.894-10 8.112 -0 1
C ASO 3 7. 1 q 3- 014 7.215-011 1.010+00
C ACO 3 3. Z II 1- 08 3.280-08 1.010+00
CAHC03. 1.097- 06 8.898-01 8.112-01
C ASO.. 2.697- 05 2 . 7 2 4- 05 1.010+00
C ANO 3+ 3. q 3 q- 08 2.185-08 8.112-01
MG.. 1.113-0" 5.019-05 II .329 -('1
MGOH. 3.029-09 Z.457-09 8.112-(11
MGSO 3 1.827- 014 1.846-04 1.010.00
MGHC03+ 4.Z11-07 3.416-07 8.112-fH
MGS04 1.951-05 1.911-05 1.010+00
MGC03 3.975-08 ".015-0e 1.010+00
NA+ 4. 195- OZ 3.445-02 8.213-01
NAOH 1.081-09 1.092-09 1.010+00
NACO 3- 2.424- 01 1.966-07 8.11Z-01
N AH CO 3 1.311- 05 1.391-05 1.010+00
N ASOq- 4.421-04 3.586-04 8.112-01
30.000
DE G. C
-------
NAN03
::l-
PS02 =CJ.43203-08
PC02 =6.33582- 03
PH =
I
N
N
I
ATM.
ATM.
6.CJ04
2.386-06
1.150- 03
2.410-06
CJ.268-04
1.010+00
8.058-01
MOLEaJLAR W'TER = 9.99899-01 KGS.
IONIC STRENGTH = 5.10966-02
Page 2
TYPE I, NO. 6A
RES. E.N. =
2.020-09
-------
APCO INHOUS E EX? ~ CMENT S - 'Y? ~ I, NO.7
0°7 O-E C 7 0
08 :-22: 39.295
S02
C02
S03
NA2D
= 2 . 11 GO 0- a 2
=5.20000- 04
= 1. 59000- 03
= 1. 88000- 02
I
N
U-'
I
C IJ M P ON ~ NT
H20
H+
OH-
HS 0 3-
S (' 3- -
S 04--
H CO 3-
CO !--
N03-
HS 0 4-
H 2S 0 !
H 2CO 3
C ~++
CAOH+
C 45 0 ~
C 4CO 3
CAHC!J3+
CAS 0 If
C AND 3+
MG++
MGOH+
MGS03
MGHC03+
M G'5 04
MGC03
N.A+
NAOH
~UCO 3-
N AH CO 3
N 4304-
N20S =1.86GOC-04
HCl =1.95000-83
A.GUf. 0.US
MOLIlLITY
E..787-08
1f.454-G1
7.~54-03
1 . 2 5 3- Q 2
1.443-03
4.668-04
a.3Q7-07
3 . F 'j 4- 04
5.412-[9
3. 2;:"'}- DB
4.421-05
2 . 0 5 9- 04
1 . 0 S 8- 0 ~
1 . 4 S 0- 0 3
c. 1 1. 3- r. '3
8. ~ 56- 'J 7
1.255- OS
9.2;2-08.
1.(47-0«+
1.417-08
3.(32-04
3.263-~n
9.737-05
1.~, 3 G- 08
3.747-02
2.~'3S-09
2.ElC2-07
f.S«+S-06
1.;:47-::4
INPUT MOLES
CAp
H20
= 1 . t. 7 00 0- 03
= ~. . 55 Of, 2 + 01
50LUTION :QU IL DR! A
II CT I V IT Y
S.762-03
?~3f,-01
-- .::'31-03
!;.:::1?-8:
:: .3'3C-04
~.8[;3-04
3.5'3P..-07
2.;F5-C~
4.408-09
3.Z(H-O~
4.461-05
~.345-05
3.615-10
1.4f.3-03
5.180-08
~,.'3E.g-a7
1.266-05.
7.545-08
7.249-05
1.154-03
3.71(.-04
2.&53-07
3..1321-0f.
7.60C-OR
3.089-02
~.r '-(J9
2.2b2-07
E.t:.Q(;-Oh
1.Glr-ou
T EMP:-R A TURE
MGO
=5.43000-04
ACTIVITY COEFFICIENT
<3.'390 -1') 1
8.489-1)1
8.145-81
3.145-01
4.4D4-()1
4.081 -(11
8.146-01
4.404-01
7.777-0.1
S -.1 4 S -~ 1
-1.0C9+SS
I.C09+"0
4.516-01
3.145-1"')1
1.009+nO
1.0c?,.no
.j.1US-1"'1
1.0("3+1"'0
3.145-'11
4.402-~1
;3.145-'11
1.CI]9+"0
3.14S-~1
1.009+[10
1.C09+!"'Q
8..244-i'J1
1.a0'3+0'1()
3.145-"1
1.(:r:9+"0
~.145-"1
3S.0SQ
DE G. C
-------
N ANO 3
CL-
PS02 =3.81986-08
PC 0 2 = 1 . 6 8 34 1- 0 3
PH =
I
N
.p-
I
AT M.
ATM.
'.239
3.491-06
1.950-03
3.523-06-
1.519-03
MOLECULAR WATER = 9.9~9I.iG-O} I'\G.5.
rONIC STRENGTH = S.2556B-C2
1.009+DO
3.098-01
Page 2
TYPE I, NO.7
RES. E.N. =
1.1114-09
-------
08:22: 24.429
APCO INHOUSE EXPERIMENTS - TYPE I, NO.8
TEHPfR~TURE
1)7 DEC 70
S02
C02
S03
HA20
INPUT HOLES
= 2. 21 00 0- 02
=5.00000-04
=5.40000-03
= 1. 92000- 02
C~O
H20
H205 =1.86000-04
HCL =2.25000-03
= 1. 50000- 03
= 5. 55 06 2 + 01
HGO
=7.16000-04
33 .3 30
OE G. C
AQUEOUS SOLUTION EQUILI8R!~
COMPONENT MOLALITY , CT IV IT Y 4 CT IV IT Y COEFFrCIENT
H20 9.988-01
H+ 3.195-07 3.230-01 8 .5 11 -0 1
OH- 7 . 0 5 7- 08 5.173-08 8.180 -01
HS 0 3- 1.632-02 1.335-02 8.183-01
S03-- 5.022- 03 2.252-03 Lf.483-al
S 04-- 4 .8 30- 0 3 2.013-03 4.168-01
I H CO 3- 3.206- 04 2.623-04 8.183-01
N CO 3-- 9.884- 08 4.431-08 4.483-01
VI
, N03- 3.683-04 2.883-04 7 .829 -J'! 1
HS 04- 9. a 1 5- 0 B 3.029-08 g.lBO-~l
H 25 0 3 3.9 ! 8- 07 3.973-07 1.009+00
H 2CO 3 1. 732- 04 1 . 7 4.1J~ 0 4 1.009+00
C A++ 3.!;CH-04 1.691-04 4.592 -(] 1
CAOH+ 3 . 0 C 4- 10 2.457-10 8.180-01
C ~S 0 3 1. Q 5 3- 03 1.0E:?-03 1.OO~+OO
C ACO 3 1.!IJS-CB 1 .319- 0 8 1.009+00
C AHCO 3+ 1.054-06 .g.;;2£-01 3.180-':'11
CAS 04 7.630-05 1.591-05 1.003+00
C ANO 3 + 1 . 6 0 2- 01 1.311-01 8.180-01
MG++ 3.393-04 1.519-04 4.478-01
MGOH+ 4.5'37-09 3 . 1 f. 0- 0 g 8.18'J-~1
M GS 03 3.G~S-04 3.122-04 1.009+f)O
t'lGHC03+ 4. E- 53- 01 3.3GFi-07 a.1RO-01
KGS 0 4 6.f84-05 6.143-05 1.009+00
MGCO 3 1. E! 5 5- 08 1.811-08 1.009+[')0
N'''' 3.797-02 3.142-02 8.216-fH
N aOH 4. ~4,}-lC 4. f - -1: 1.OO~+';Q
N AC 03- 3 . '3 S c- ('a ~.1"d-G8 3.180-11
N AHCO 3 4.~,q;:J-C; 4.;:;'''Q;:-Of 1.iJC:9+,,:r
---------
NA504- I.j. 21':.,- 04 !.4~3-a4 8.180-81
-------
N ANa 3
Cl-
PS02 =4.36168-07
PC02 =E. 32547- Q3
PH =
I
N
0\
I
ATH.
4TM.
6.491
3.576-06
2.250-03
3.607-06
1.831- 03
MOL E CU L A R W ATE R = 9. 99 85 7- 01 K GS .
TONIC STRENGTH = 4.99505-02
1.009+00
8.136-01
Page 2
TYPE I, NO.8
RES. E .N. =
1.396-09
-------
21 DEC 70
TEMPER~TURE
11:23:57.140
INPUT HOLES
S 0 2 = 2. b :3 000- 02
C02 = 9 . II 3000- 04
S03 =3.10000-(;3
N420 =1.78000-02
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 8A
C~O
H20
N20S = 1.01000- 014
HCL = 1.20000- 03
= 1. Of, 00 0- 0:3
=5.55062+01
MGG
=3.30S00-04
AQUEOUS SOLUTION £GUIlBRI4
C OM PONE NT MOLALITY 4 CT IV IT Y A CT IV IT Y COEFr:"IClfI\JT
H20 9.989 -rn
104+ 7. F 5 2- 07 6.551-07 8.561-fH
OH- 3.721- 08 3.076-08 8.2f,S-fn
HS 03- 2.229-02 1.844-02 8.212-01
S03-- 3.21 8- 03 1 .506-03 4.681-('11
S04-- 2.789-03 1.224-03 4.387-('11
H CO 3- 4.1154-04 3.685-04 8.272-01
C03-- 6 . £. 7 2- 08 :3 .1 23- a 8 4 .6fH -81
N03- 2. 1 ? 0- 04 1.C:;81-0Lf 1.9S~ -I; 1
I HS 04- 1.239-07 1.024-07 3.2;5-01
N H 25 03 1. 1 30- O£ 1.1:!9-05 1.008+'10
-...J
I H2C03 4. 8 98- 04 4.935-04 1.C08+f1C
C A++ 3. 3 66- 0.. 1.;08-04 4 . 718 - Q 1
CAOH+ 1 . 5 1 2- 1 a 1.250-10 3.2(,5-01
CAS 03 S. 71 5- 04 (,.B27-04 1.n08+~Q
CACOJ 8. 8 S 8- 09 Q.925-09 1.003+00
C AHCO 3+ 1.4'JQ-06 1.151-0(, Q.2f,S-Ol
CAS 0 4 4.461-05 4.494-05 1.008+00
C ANO 3 + 9.091-08 7.511f-G8 8.265-01
MG++ 1.eS9-0fl 8.678-01) tf.667-'l1
MGOH+ 1. 404- 09 1.161-09 8.2:;.5-01
MGS03 1 . 1 q 8- 0 tf 1.207-04 1.003+00
MGHC03+ 3. 7 1 8- 07 3 .013- 0 1 8.265-01
MG'SO~ 2.391-05 2.403-05 1.005+00
?'-GC03 7. 5 80- 0 <3 1.638-09 1.008+00
Nil,.. 3 . 5 J ~- 02 7.954-02 8 . 3 55 -0 1
NAOH 2. 4 2 7- Ie '1.445-10 1.008+00
N6.C03- 2.221-ca 1.836-08 B.2f,S-Ql
N AHC,:>3 6.')74-06 c.120-0f> 1.008+00
NtSOI.4- 2.4 3 ~- 04 2.011-04 a.2f.5-1J1
34.44:)
D( G. C
-------
N ANO 3
CL-
PS02 = 1. 29719- 06
PC02 =1.83666-02
PH =
I
I\.)
00
I
ATM.
UM.
6 .1 84
1.968- 06
1.200- 03
1.983-06
9.877-04
MOLECULAR WATER = 9.99797-01 KGS.
IONIC STRENGTH = 4.29329-02
1.008 +(,!Q
8.229-01
Page 2
TYPE I, NO. 8A
RES. f.N. =
4.179-10
-------
07 OEC 70
APCO INHOUSE EXPERIMENTS - TYPE I, NO.9
T EMPt:RA TURE
08:22:49.222
INPUT HOLES
S02 =2.04000-02
C02 =f..73'D00-04
SO 3 = 5 . GOO 00- 03
N A 2 0 = 2. 0 1 000- 0 2
N205 = 1. 07000- 04
HCL =2.25000-03
CAO
H20
= 1.51000- 03
=5.55062+01
MGO
=5.84000-04
AQUEOUS SOlUTICN EQUILIBRIA
COMPONENT MOL~LtTY A CT IV IT Y A CT IV IT Y COEFFICIEN,T
H20 9.989-[n
H+ 1.573-07 1.335-07 3.485-(')1
OH- 1.5:.'5-07 1.241-07 8.133-(')1
I HSO 3- 1.063-02 .3.644-03 3.133-01
110.) SO 3-- 8.212-83 :5 . E 19- a 3 4.315-']1
\0
I S 04-- 5.054- 03 2.046-03 4.048-01
H CO 3- 5. 4 1 0- 04 4 .4 CC- 04 8.1-:B-!Jl
C 03-- 3. qq6- 07 1.748-01 4.375-01
N03- 2.118- 04 1.643-04 7.7S5-Gl
HS 0 4- 3.942-08 3.206-08 8.133-Cl
H2S 03 1.017-07 1.027-07 1.810+fJO
H 2C 03 1.211- 04 1.228-04 1.010+00
C A++ 2 . 7 a 3- 04 1 .2 14- 04 4 .490 -fn
CAOH+ 4. 5 .3 9- 1 0 3 . 733- 1 0 8.133-01
CAS 03 1. 1 R 4- 0:3 1.19E-03 1.010+00
C A C O. 3 3. f 14- 03 3.549-08 1.010+\;0
C AHC03+ 1.2S6-0t; 1.021-06 :3.133-01
C AS 04 5.4 25- 05 5.477-05 1.010+00
CANO:!+ 6.237- 08 5.073-08 8.133-01
MG++ 2.250- 04 9.845-05 4.37;-01
MGOH+ 6. 3:] 2- 0 '3 5.126-09 03.133-'11
~GS 03 3.1S4-04 3.195-04 1.010+00
'1 G1-4 C/O 3+ 5.037- C7 4.091-07 3.133-11
~GS04 4 . 2 1 0- 0 5 4.250-05 1.010+')0
."I6CO 3 4.f41-08 4.o85-0~ 1.010+00
N Go+ 3.974-02 3.272- a 2 3.233-r;1
NaOH 1 . :" 3 2- C '3 1 . C -o~ 1.218+ns
N A C 0 3- 1."311-G7 1 . 1 15- J 1 a .1 n -,-, 1
N AH CO 3 8.:19-8S ~.8C3F-Q~ I.Q10+(1;;
NA.SOu- 4.5i)::,-Qu 3.SFtI-C4 3.133-01
31.660
DE G. C
-------
N ANO J
Cl-
PS02 =1.06560-01
PC02 =4.26551- 03
PH =
I
W
o
I
ATM.
ATM.
6 . 9 14
2. 120- 06
2. Z 50- 0 3
2.140-06
1.B19-0:!
MOlECUl~P. WAtER = 9.99917- 01 KGS.
IONIC STRENGTH = 5.45561-02
1.010+00
8.083-01
Page 2
TYPE I, NO.9
RES. E .N. =
6.369-09
-------
27 JAN 71
TE,",P[R4TURE
11:36:02.144
INPUT MOLES
soz
C02
S03
NA20
=2.310CO-02
=8.5 &000- 04
= 1 . 0 30 a 0- 0 3
= 1 . 4 2000- 0 2
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 9A
= 1.06GOQ-03
=5.55062+01
MGO
=3.70000-04
N 205 = 9.00000- 05
HCl =1.10000-03
CAO
H20
AQUEOUS SOLUTION EQUILIBRIA
COMP ONENT MOL Al rry 4CTIVITY A CT IV IT Y COEfFICIENT
H20 9.991-~1
H+ 6.359-01 5.501-07 8.662-01
OH- 2.2?2-G8 1.310-08 3.416-01
H$ 0 3- 1.871-02 1.576-02 8.42S-rJ1
501-- 3.520-01 1.114-03 '3.038-')1
S04-- 9. 3 94- 04 4.48e-04 4.118-(11
HCO 3- 4 . 1 7 9- 04 3.521-04 8.425-01
CO 3-- 5. 9 f. 9- 08 3.008-08 5.038-01
N03- 1.786-04 1.453-04 8.U;S-01
I HS 04- 2. 844- 0 S 2.394- 0 8 3.416-01
VJ H 2S 0 3 6.;<32- 81 5.732-01 1.006+'10
to-'
I H 2CO 3 4.311-04 4.343-04 1.00£; +QO
C A++ 3.199-04 1.63B-04 5.121-01
CAOH+ 8.634-11 7.2 E 5- 11 8.416-01
C ASO 3 7.248-04 7.284-04 1 .006 + r) G
C A('O 3 7.7 q 5- 09 1.S42~G~ 1.0C6+(10
CA"'C03+ 1.248-06 1.eSO-OE 3.416-(11
CAS 04 1.496-05 1 . 505- 0 5 1.00;+no
C AND 3+ 5.896-08 4.'3~2-0e 8.416-Gl
MG++ 2.078-04 1.G42-G4 S.OlE-f)1
MGOH+ 8.Q11-10 7.521-1C B.41E-S1
MGS03 1.~.3f-04 1 . 545- C 4 1.0C5+QQ
~GHC03+ 3.910- C7 3.341-07 8.416-01
MGS04 8.263-Q6 6.313- C E I.GOf,+r;c
HGCO 3 7.a14-01 7.861-09 1.006+(10
N A+ 2.833-02 2.4(;6-02 8.493-01
"HOH 1.2~4-1~ 1.211-1C 1.CO;+"D
NACO 3- 1.5~5-::S 1.34:!-08 .'3.u1f,-nl
NAHCC3 4 . 1 3 E,- 0 E 4.764-0£ 1.QQ6+00
N AS 04- 6.756- os 5.£85-05 3.415-01
25.23'::1
DE: G. C
-------
N ANO 3
C.L-
PS02 =5..58775-07
pe02 = 1. 27835- 02
PH =
I
W
N
.
AT.M.
ATM.
6 .259
1.388- 06
1.100-03
1.397-06
9.230-011
MOLECULAR WATER = 9.99830-01 KGS.
IONIC STRENGTH = 3.Q3761-02
1.006+00
8 . 3 90 - 0 1
Page 2
TYPE I, NO. 9A
RES. E.N. =
1.941-10
-------
27 JAN 71
11:35:56.453
TEMPERATURE
INPUT MOLE~
S02
C02
S03
NA20
APCO INHOUSE EXPERIMENTS - TYPE I, NO. 10
= 1.13000- 02
=6.50000-04
=4.00000-03
=9.81000-03
N20S = 2. 29000- 04
HCL = 2.25000- 03
CAO
H20
= 1 . 51000- 03
=5.55062+01
MGO
=5.120QO-04
AGUEOUS SOLUTION EQUILI3RYA
COMPONENT ,",OLALITY ACT IV ITY A CT IV IT Y COEFFTCrrNT
H20 9.993-01
H+ 1.101-06 9.601-07 8.729-01
OH- 2.219-08 1.941-08 8.519-01
HS 0 3- 9.761-83 3.3:!,2-03 8.531-01
S03-- 8.917-04 4 . 72 3- 04 5 . 296 -0 1
S04-- 3. 5 5 2- 03 1.199-03 5.064-1]1
HC03- 2.401- 04 2.054-04 8.531-01
CO 3-- 2.202- 08 1.166-08 5.296-01
N03- 4.550-04 3.782-C4 8 . 311 -01
I HS 04- 2.505- 01 2.134-07 3.519-Dl
(,.0)
(,.0) H 25 0 3 1.340-07 1 . 375- C 7 1.005+'10
I H 2CO 3 4.049- 04 4.068-04 1 . 0 05 + 0.0
C A++ 1.863-04 4.219- 04 5.366-:)1
CAOH+ 2.411-10 2.054-10 8.519-(n
CAS 03 5.512- 04 5.539- G 4 1.00S+DO
C ACO 3 8 . 5 8 9- 09 8. t; 30- 0 <3 1.005+00
CAHC03' 1 . 9 7 c- a 6 1.619-0f. B.519-l'n
CAS04 1.7!J1-04 1 .110- 04 1 .005 +00
C AN03 + 5. 0 1 6- :J 1 4.214- a 7 8.519-01
MG+.+ 3.9~6-04 2.100-04 5.261-11-
MGOH+ 2. C 5 2- 0 <3 1 .148- G 9 8.519-01
MGS 03 <3. 0 0 8- OS 9.051-05 1.005+00
MGHC03+ 4.834-07 4.l1S-07 3.519-01
MGS04 8.287- 05 8.321-05 1.005+80
MGC03 6.173- 09 6.805-09 1.005+QO
NA+ 1 . <342- a z 1.66€-02 3.588-01
NAOH 8.675-11 8.717-11 1.00S+!"Q
N 4CO 3- 4.5006-09 3.6:!9-0C3 8.513-01
N'AHC C 3 1.917-06 1.926-COS 1.005+10
N AS 0 4- 1.948-04 1.659-04 3.51'3-01
33.330
DE G. C
-------
N ANO 3
CL-
PS02 =8.09286-07
PC02 = 1.47238- 02
PH =
I
U)
~
I
ATM.
ATM.
6 .0 17
2.499-06
2.250- 03
2.511-06
1 .91 3- 0 3
MOLECULAR WATER = 9.99923-01 KGS.
IONIC STRENGTH = 2.74251-02
1.005+00
8.S0C-OJ
Page 2
TYPE I, NO. 10
RES. E'.N. =
- 1 . 71 2-10
-------
2. DEC 70
11 : 2": 09 . 378
T [HPERA TURE
INPUT MOLES
S02 =1.18000-02
C02 =2.93000-04
SO 3 =2.20000- 03
NAZO =5.91000-03
APCO INHOUSE EXPERIMENTS - TYPE I, NO. lOA
= 1. 43000- 03
= 5.55062+ 01
"GO
=Ct.OOOOO-OIi
N205 = 1. ..0000- 04
HCl = 1.10000- 03
CAO
H20
AGUEOUS SOLUTION EQUILIBRI.
COMPONENT MOLALITY A CT IV IT Y A CT IV IT Y COEFFICIENT
H20 <3.995-01
H+ 1.155-03 1.024-03 8.863-01
OH- 1.522-11 1.324-11 8.703 -01
HS 0 3- 1 . 098- 02 <3.569-03 8 .7 15 -0 1
S 0 3-- 9.464- 07 5.460-07 5.769-!)1
S04- 1. 8 08- 03 1 .009- a 3 5.580-01
HC03- 1.534-07 1.337-07 8.715-01
CO 3-- 1 . 1 4 3- 1 4 6 .594- 1 5 5.769-01
N03- 2. 186- 04 2.382-0Ct 8 .550 -0 1
I HS 04- 1.282- 04 1.116-04 8 .703 -01
UJ H 2S 0 3 8.194-04 8.222-04 1.003+00
\JI
I H 2CO 3 2.929-0Ct 2.939-04 1.003+00
C A++ 1.270-03 1.395-04 5.823-01
C AOH+ 2.738-13 2.383-13 8 .. 1 03 - 0 1
C AS 0 3 1.058- 06 1.062-06 1.003+00
C ACO 3 8. 0 8 S- 1 5 8.116-15 1.003+00
CAHC03+ 2. 1 2 8- 09 1.852-09 8.103-01
CAS 0.. 1.587-04 1.593-04 1.003+00
C ANO 3+ 4.724- 07 4.112-07 8.103-01
MG++ 3.593-04 2 .061- 0 If 5 . 1 31-0 1
MGOH+ 1.270- 12 1 .105- 1 2 a.703-01
MGS 03 9.761-08 9 . 7 9S - 0 8 1 .003+~O
f'4GHC03+ 2 . 9.. 6- 1 0 2.564-10 8.703-Cl1
f'4GS04 If. 066- 05 .. .080-05 1.003+00
"GC03 3.561-15 3.573-15 1.003+00
N .+ 1. 1 76- 02 1.030-02 8.758-01
N r-OH 3.658-14 3.610-14 1.003+00
NACO 3- 1."89-15 1 .296- 1 5 8.103-01
Nr-HC03 7. 71 4- 10 7.740- 10 1.003+00
N AS 0 4- 6." 27- 05 5 .594-0 5 8.703-01
28 . 8 90
DE G. C
-------
N ANO 3
Cl-
PS02 =7.75.376-04
PC02 =9.50673-03
PH =
I
lA)
0\
I
ATH.
UH.
2.990
9.730- 07
1.100- 03
9.763-07
9.562-011
MOLECULAR WATER = 9.99879-01 KGS.
IONIC STRENGTH = 1.96086-02
1.003+00
8.692-01
P s:r.E e 2
TYPE I, NO. lOA
RES. f.N. =
1.251-09
------- |