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1178 C-C. CHEN

CHEMICAL EQUILIBRIUM RELATIONSHIPS

The solution chemistry dictates the true species in solution and imposes equality
constraints on the composition of the true species. The chemical equilibrium relationship
for reaction j may be expressed as follows:

1nK=v1lna1 (1)

where I( is the chemical equilibrium constant, v.,j is the reaction stoichiometric

coefficient of component i, and a-j is the activity of component i.

Note that salt precipitation equilibrium constraints are active only when salt
concentrations reach or exceed salt saturation limits. Below salt saturation limits, salt
dissolves in the solution and the salt precipitation equilibrium constraint need not be
active.

It is important that chemical reactions be properly identified for a system to be

simulated. Physical interactions in solutions are sometimes described by postulating
chemical reactions at equilibrium. The chemical theory of solutions should be used only
for real chemical reactions. Inaccuracies in simulating reactive chemical systems are
often due to incorrect assumptions about the solution chemistry.

Chemical equilibrium constants are often available in the literature (refs. 13, 14). If
such chemical equilibrium constants are not available, they may be estimated from the
reference state free energies of the reaction—participating components (ref. 15).

SIMULATION APPROACH: APPARENT COMPOSITION VS. TRUE

COMPOSITION
In general, there are two simulation approaches in treating reactive chemical systems. The
true composition approach represents the system composition in terms of concentrations of
the true species that exist in chemical equilibrium. The apparent composition approach
represents the system composition in terms of concentrations of the apparent components
that exist prior to the reactions that occur in solution. These two approaches are
equivalent since a set of apparent components with chemical equilibrium relationships
uniquely defines the compositions of the true species in chemical equilibrium. The
composition based on the true species is connected to that based on the apparent components
with mass balance equations and chemical equilibrium expressions (ref s. 7, 8, 16—18).

From a process simulation viewpoint, the true composition approach requires that process
specifications be given in terms of the true species. The true species and their
compositions are to be carried in each process stream and each unit operation. This
approach requires development of an array of new unit operation computational algorithms to
solve the chemical equilibrium relationships in addition to the unit operation describing
equations (refs. 5, 9, 19).

The apparent composition approach requires that process specifications be made only in
terms of apparent components. The solution chemistry and the true species are transparent
to process flowsheets and unit operations. The apparent composition approach makes it
possible to use existing unit operation computational algorithms, such as flash algorithms
for vapor—liquid equilibrium, liquid phase splitting algorithms for liquid—liquid
equilibrium, and distillation algorithms. Note that rigorous representation of the
effective partial molar properties of apparent components requires solution of the chemical
equilibrium and knowledge of the partial molar properties of the true species (ref s. 18,
19).

The choice between the apparent composition approach and the true composition approach
often is a matter of personal preference. Generally, the apparent composition approach is
preferred for simple reactive chemical systems. It offers the advantage that only apparent
components need to be taken into account. When the system becomes more complex and it is
difficult to select the apparent components, true composition is the desired approach.
Sometimes it may be most convenient to use the true composition approach for the modeling
of some unit operations and the apparent composition approach for other unit operations.

THERMOPHYSICAL PROPERTY MODELS

In the computer—aided process simulation environment, it is essential that the following
thermophysical properties be computed at given temperature, pressure and composition:
fugacity
molal enthalpy
reference state free energy
 Process simulation for reactive chemical systems 1179

These properties are necessary to perform phase equilibrium calculations, chemical

equilibrium calculations, and mass and energy balance calculations.

Often, the most critical properties for process simulation are the fugacities, which
determine the amounts, compositions and phases involved. Table 1 summarizes some of the
models that are widely used in process simulation.

TABLE 1. A summary of fugacity models

None lectrolytes:
Activity coefficient models Equation of state models
Ideal solution Redlich—Kwong
Van Laar Redlich—Kwong--Soave
Margules Peng—Robinson
Wi lson BWR—Starling
NRTL
UNIQUAC
UNIFAC
Electrolytes:
Activity coefficient models
Debye—Hückel
Davis
Bromley
Pitzer
Electrolyte NRTL

Although there are thermophysical property models that adopt the chemical theory of
solutions, most thermophysical property models attempt to account for physical interactions
between the true species. There are two categories of models commonly used for
nonelectrolytes: liquid activity coefficient models and equation of state models (refs.
20, 21). The liquid activity coefficient models are more accurate for highly nonideal
chemical mixtures, but at high pressures the equation of state models are generally more
convenient. Among the models available for nonelectrolytes, the UNIFAC model is
particularly interesting since its group contribution method provides a reasonable
methodology to estimate physical interactions between the true species (ref. 12).

The liquid activity coefficient approach is preferred for electrolytes particularly because
ionic activity coefficients are required for chemical equilibrium calculations, and because
the development of equations of state for electrolytes is a relatively new endeavor (ref 5.
22, 23).

Until recently, the treatment of electrolytes in process simulation has been greatly
limited by the lack of generally applicable models for activity coefficients of the
molecular and ionic species present. In most cases empirical correlations have been used
that are applicable only to one particular system, over a limited range of conditions.
However, the empirical correlations do not provide a framework for treating new systems or
for extending the range of existing data.

Recently there have been a number of significant developments in the modeling of

electrolytes. Among the models available, the electrolyte NRTL model (ref S. 24—26) may
prove to be the most valuable engineering model. The model is applicable to the entire
electrolyte concentration range, it requires only binary interaction parameters, and it
provides a continuous thermodynamic framework for aqueous electrolytes, mixed—solvent
electrolytes, and nonelectrolytes.

Given temperature, pressure, compositions of the true species, and physical interactions of
the true species in solution, thermophysical property models compute thermophysical
properties for the true species and the mixture of the true species. If the apparent
composition approach is used in process simulation, thermophysical properties of apparent
components must be computed from the properties of the true species and their compositions
(refs. 7, 17). For example,

a = a
(x/ x (2)

where y-j and x are, respectively, the activity coefficient and mole fraction of true
species i in solution; and 1a and x1a are, respectively, the effective
activity coefficient and mole fraction of component i in the apparent composition approach.
1180 C-C. CHEN

DATA REGRESSION
Data regression is an essential step in representing thermophysical properties in process
simulation. Most of the thermophysical property models used in process simulation require
interaction parameters to be determined from experimental data through data regression.
With the presence of the solution chemistry, chemical equilibrium and solubility product
constants need to be determined in addition to the interaction parameters.

The most general mathematical formulation of data regression uses the maximum likelihood
principle (or generalized least squares criterion) (refs. 27, 28). The maximum likelihood
principle can be extended for reactive chemical systems (refs. 7, 17). One key
consideration in the extension is that the chemical equilibrium constraints of the solution
chemistry must be satisfied.

Often, experimental measurements of thermophysical properties of reactive chemical systems

are available as thermophysical properties of apparent components. Typical measurements
are listed below:

—solute properties, such as mean ionic activity coefficients

—solvent properties, such as osmotic coefficients
—fugacity coefficient data, such as vapor pressure depression,
vapor—liquid equilibrium data and liquid—liquid equilibrium data
—solution properties, such as heat capacity, enthalpy
—solubility or salt saturation limits

PROCESS SIMULATION WITH THE SOLUTION CHEMISTRY

Typically process simulation of reactive chemical systems may involve flowsheet simulation
with several unit operation blocks that are to be simulated with unit operation models such
as those listed in Table 2. The solution chemistry may be associated with any of the unit
operation models. Different solution chemistries may be involved in different unit
operation blocks. The chemical reactions may take place in vapor, aqueous, or organic
liquid phases. The true species may be molecular solvents, molecular solutes, ionic
solutes, or solid salts.

TABLE 2. A summary of unit operation models

Single stage unit operation models:

mixer flow splitter
component separator pump
compressor/turbine heater/cooler
flash heat exchanger
stoichiometric reactor specified yield reactor
chemical equilibrium reactor continuous stirred tank reactor
plug flow reactor stream duplicator
stream multiplier
Multiple stage unit operation models:
distillation multiple column distillation
absorber/stripper liquid—liquid extractor

Chemical equilibrium calculations are the core of process simulation with reactive chemical
systems. With the apparent composition approach, the chemical equilibrium expressions are
solved for the computation of apparent component thermophysical properties, which are
required by unit operation models. With the true composition approach, the chemical
equilibrium expressions are solved with the unit operation describing equations.

Numerous mathematical algorithms have been proposed for solving the chemical equilibrium
expressions (refs. 29, 30). Some solve the sets of nonlinear algebraic equations from the
numerical point of view. Others adopt minimization techniques. Some require knowledge of
the stoichiometric coefficients for a linearly independent set of reactions from the
problem specification point of view. Others require atomic matrix, ionic charge, and
product component specifications.

In the process simulator environment, it is very important that the algorithm adopted for
solving chemical equilibrium expressions be both efficient and robust. Solving chemical
equilibrium expressions, a computing—intensive task, is an integral part of the process
simulation and is performed repetitively. For example, in solving a typical flash model
with the apparent composition approach, it is estimated that 90% of computing effort goes
to apparent component thermophysical property calculation, of which 60% of computing effect
is consumed by solving chemical equilibrium expressions. Without an efficient algorithm
for solving chemical equilibrium expressions, prohibitively excessive computing time may be
encountered for large flowsheets.
 Process simulation for reactive chemical systems 1181

With proper selection of numerical algorithms, intelligent checking of the solution

chemistry to avoid solving redundant reactions or infeasible reactions, and with the
progress in computing power, it is feasible to have a reasonably efficient and robust
algorithm to meet the needs of process simulation with reactive chemical systems.

STRUCTURE OF PROCESS SIMULATORS

General purpose steady—state process simulators have been developed to treat reactive
chemical systems (refs. 10, 19). These simulators have been designed to simulate any
process with reactive chemical systems, consisting of any number of unit operation blocks,
reactions in the solution chemistry, and components.

Key elements of these process simulators can be summarized as follows:

1. user—friendly input language for simulator users

2. system databanks containing the information necessary to calculate thermophysical
properties of pure components and mixtures
3. a library of state—of—the—art thermophysical property models
4. a facility for solving the chemical equilibrium expressions and computing
apparent component thermophysical properties
5. data regression facility to allow users to develop user databanks from
proprietary data
6. a facility to generate thermophysical property tables/plots
7. a library of unit operation models, including flash models and multistage column
models
8. a facility for flowsheet simulations, such as flowsheet convergence, feed forward
controller, feedback controller, etc.
9. a facility for case study and sensitivity analysis
10. a facility for costing, sizing and optimization
11. a facility for simulation report generation

INDUSTRIAL APPLICATIONS
There are numerous industrial applications for process simulation of reactive chemical
systems. Examples include sour water stripping in the petroleum industry, caustic brine
evaporation and chlorine recovery in the chlor—alkali industry, acid gas removal in the
chemical, gas and power industry, nitric acid separation in the nuclear industry, trona
mining in the soda ash industry, organic salt separation in the biochemical industry, black
liquor evaporation in the pulp and paper industry, etc. Important process insights and
significant economic benefits can be realized through process simulation.

There are two key steps in building a simulation model for reactive chemical systems. The
first step is to build a solution "chemistry model which consists of the knowledge of the
chemical reactions, the true species, and the physical interactions between the true
species. The second step is to build a "process" model which consists of flowsheet
topology, feed stream conditions, unit operation conditions, and optionally, feed forward
controller and feedback controller. Once a simulation model is developed, engineering
studies can be carried out easily to examine sensitivites of key process variables and to
optimize the process.

Four small—scale simulation examples are given below to illustrate some typical industrial
applications. Specifically, these examples illustrate how a simulator assists users in
analyzing reactive chemcial systems. More flowsheet—oriented examples are available
elsewhere (ref S. 8, 19). These examples were developed with the ASPEN/ASPEN PLUS simulator
(see APPENDIX).

SATURATION PRESSURE OF WATER-FORMALDEHYDE SYSTEM

The thermophysical property table generation facility of the simulator is used to compute
and plot the saturation pressure of a water—formaldehyde mixture as a function of water
content at 373.15 K.

Maurer (ref. 12) has examined the solution chemistry of a water—formaldehyde system and
reported the formation of methylene glycol and polyoxymethylene in the aqueous phase as
follows:

CH2O + <——> (3)

H2O CH2(OH)2
HO_(CH2O)n1_H + CH2(OH)2 <——> (n> or =2)
HO_(CH2O)n_H ÷ H20 (4)
1182 C-C. CHEN

Maurer also reported chemical equilibrium constants for the reactions and the UNIFAC
parameters for the physical interactions of the true species.

Figure 1 shows the simulation input file. Figure 2 gives a print—plot of the saturation
pressure as predicted by the Maurer's model. The profound "L" shape curve of the
saturation pressure is a result of the solution chemistry.

TRUE SPECIES COMPOSITIONS OF AQUEOUS SULFURIC ACID

The thermophysical property table generation facility of the simulator is used to compute
and plot compositions of the true species of aqueous sulfuric acid as a function of
sulfuric acid content at 298.15 K.

Goldfarb and Chen have recently reported a solution chemistry model for aqueous sulfuric
acid (ref. 31). In the aqueous phase, the following two reactions are considered:

H20 ÷ H2S04 <——> H3O + HSO4 (5)

<——> + (6)
H20 ÷ HSO4 H3O SO42
Water and sulfuric acid are the apparent components. The true species are the
undissociated molecular species water and sulfuric acid, and the ionic species hydronium,
bisulfate, and sulfate. The Electrolyte NRTL model parameters for molecular—electrolyte
interactions have been reported by Goldfarb and Chen (ref. 31). This solution chemistry
model is available in the simulator.

Figure 3 shows the simulation input file. Figure 4 shows the computed true species
compositions of aqueous sulfuric acid. As predicted by the model of Goldfarb and Chen,
bisulfate ion is the main sulfuric acid species up to 90 wt.% sulfuric acid. Above 90
wt.%, sulfuric acid exists primarily as undissociated sulfuric acid. Sulfate ion
concentration is very low throughout the entire concentration range.

PRECIPITATION OF FERROUS CHLORIDE IN AQUEOUS HYDROCHLORIC

ACID SOLUTION

The simulator is used to establish the saturation limit of ferrous chloride in aqueous
hydrochloric acid solution at 298.15 K. A hydrogen chloride stream is gradually added to
an aqueous ferrous chloride solution to precipitate ferrous chloride. A sensitivity study
is performed to compute saturation limit of ferrous chloride in aqueous solution as a
function of hydrogen chloride concentration.

The solubility of ferrous chloride in aqueous hydrochloric acid solution has been examined
by Chen (ref. 32). The solution chemistry involves the following reactions:

HC1 ———> H ÷ Cl (7)

FeCl2
———> Fe2 + 2Cl (8)
Fe2 + 4Cl <——>
FeCl2 (9)
Fe2 + 2C1 + ———> (10)
2H20 FeC12.2H20
Fe2 ÷ 2C1 + ———> (11)
4H20 FeC12.4H20
Fe2 + 2Cl + ———> (12)
6H20 FeCl2.6H20
Hydrogen chloride, water, and ferrous chloride are the apparent components. The true
species include the ionic species hydrogen, chloride, ferrous, ferrous tetrachloride, the
molecular species water, and the solid salts ferrous chloride dihydrate, ferrous chloride
tetrahydrate, and ferrous chloride hexahydrate. The chemical equilibrium constants, the
solubility product constants, and the Electrolyte NRTL model parameters for
molecular—electrolyte interactions and electrolyte—electrolyte interactions have been
published in the literature (ref. 32).

Figure 5 shows the simulation input file. Figure 6 shows the computed results of the
ferrous chloride saturation limit. The ferrous chloride solubility drops significantly as
the concentration of hydrogen chloride increases. Figure 7 shows the stream compositions
including flow rates for various true species. Ferrous chloride dihydrate is the
precipitated solid salt.
 Process simulation for reactive chemical systems 1183

TGS
IN—UNITS SI
RUN—CONTROL MAX—TIME= 100
5.00+06
identify all species
(OMPONENTS WATER H20 /
FA CH2O / MGi C2H602 / MG2 C2H602 / M
MA
MG3 C2H602/ MG4 C2H602 / MG5 C2H602 A
define the chemistry A
CHEMiSTRY MAURER A
A
STOIC 1 WATER—i / FA —i /MG1 1 A
STOIC2 MGi —2/ MG21/WATER1 1.00+06 A
STOIC3 MG2 —1 /MG1 —1 /MG3 1/WATER 1 A
S A
STOIC4 MG3 —i/MG1—l/MG41/WATER1 A
STOIC5 MG4 —l/MGJ—l/MG51/WATER1 5.00+05 A
K—STOIC 1 —125.1608 11211.35 16.53361 0 A
A
K—STOIC 2 151.9185 —8666.626 —21.50844 A A
K—STOIC 3 152.4102 —8523.298 —21 .69641 A
K—STOIC 4 152.3118 —8502.615
—21.69418 A
K—STOIC 5
use UNIFAC model
152.3669 —8491.151
—21.69644 /S A
A
A
PROPERTIES SYSOP7K CHEMISTRY=MAURER TRUE—COMPS=O / SYSOP15 Q AA
8 1.00+05
Use ideal gas vapor phase PHIVMXOO
PROP-OPTIONS SYSOP1K SYSOP1 PHIUIX PHILMX39/
PHIVMX PHIVMXOO
5.00+04
Ignore Poynting correction, use PHIL®
MP—ROUTE PHILMX39 PHILMX 5 PHILMX39
MODEL GMUFAC
MPROP PHIL PHIL®
SP—ROUTE XTRUEO1 XTRUE 1 XTRUEO1
MODEL GMUFAC
define UNIFAC groups
UNIFAC groups: 1010 -> —CH2—
1200->-OH 0.00 0.2000 0.4000 0.6000 0.8000
;
MOLEFRAC WATER
1300 —> H2O
1610 —> —CH2O— (ETHER)
4000 —> CH2(OH)2
Fig. 2. A print—plot for saturation pressure
GROUPS GW 1300 / GE 1610 / GH 1200 / GC 1010 / GM 4000 of water—formaldehyde system at 373.15 K.
enter physical property data
PROP—DATA
UNIFAC parameters
TGS
PROP—LIST UFGRP RUN—CONTROL MAX—T1ME= 100
PVAL WATER 1300 1 IN—UNITS SI
PVAL FA retrieve information on chemistry, true species, and
1610 1
PVAL MGi 4000 1 physical property data for aqueous sulfuric acid
PVAL MG2 1200 2 1010 1 1610 1 INSERT GLOBAL MH2SO4 H2O H2S04
PVAL MG3 1200 2 1010 1 1610 2 PROP—SET XTRUE XTRUE PHASE=L COMPS=H2SO4 HSO4— SO4—2 H2O
PVAL MG4 1200 2 1010 1 1610 3 use physical propertc table generation facility to plot
PVAL MG5 1200 2 1010 1 1610 4 ture species compositions
PROP—TABLE FRAC PROPS
PROP—LIST GMUFR / GMUFQ MASS—FLOW H2S04 .5 / H2O .5
PVAL GH
1.0 / 1.2
STATE TEMP=298.l5 PRES=1O1325
PVAL GE
0.9183 / 0.18 VARY MASS—FRAC COMP=H2S04
PVAL GC
0.6744 / 0.54 RANGE LOWER=O.Ol UPPER=.99 NPOINT=5O
PVAL GW
0.9200 / 1.40 TABULATE PROPERTIES=XTRUE PRINT—PLOT=YES GRID=NO
PVAL GM
2.6744 / 2.94
PROP—LIST GMUFB
BPVAL GH GE 28.06 Fi. 3. ASPEN PLUS input file for true species
BPVAL GH GC 156.40
BPVAL GH GW
BPVAL GH GM
353.5
353.5
— compositions of aqueous sulfuric acid.

BPVAL GE GH 231.7
8PVAL GE GC 83.36 DO
DODD
BPVAL GE GW 240.0 000
BPVAL GE GM 240.0 DOD
BPVAL GC GH 986.5 DO
000
BPVAL GC GE 251.5 DO
BPVAL GC GW 1318.0 0.8000+ DO
BPVAL GC GM 1318.0 DO
BPVAL ON GH —229.1 0
BPVAL ON GE —149.0 DO
BPVAL ON GC 300.0
x 0
BPVAL ON GM 0.0
BPVAL GM GH —229.1
I 0.6000+
DO
0
BPVAL GM GE —149.0 U 0
BPVAL GM GC 300.0
E O A1
A
O
+ 0 A+
BPVAL GM ON 0.0
PROP—LIST MGi / MG2 / MG3 / MG4 / MG5 O
88
A!
CVAL MW 48.04/ 78.07 /108.09 /138. 12 /168. 14
Q
U
I 0.4000+
DO
0
0 B
88 AA
B8A +
PROP—LIST PLXANT
0 O B8 BA
PVAL WATER 23. 19636 —3816.44 —46.13 0 0 0 0 300 450 OS *
PVAL FA 21.37026 —2204.13 —30.15 0 0 0 0 300 450
PVAL MG1 S
17.98455 —1991.20 —142.12 0 0 0 0 300 450
PVALMG2 —20 000000300450 S O AS
585 O AS
PVALMG3 —20 000000300450 AS
PVALMG4 -20 000000300450 0.2000+
BBS
55
SB O
O
O AS
AS
PVALMG5 —20 000000300450 SB OA B
use physical property table generation facility to plot 8888 DA S
saturation pressure 888 DA B
88588 DA S
PROP—TABLE Fl FLASHCURVE 88888
MASS—FLOW WATER .796/ FA .204 5888885 ADD
STATE TEMP=313.15 VFRAC=O 0.00 0.2000 0.4000 0.6000 0.8000 1.000
VARY MOLE—FRAC COMP=WATER MASSFRAC H2S04
RANGE LOWER=O UPPER=i INCR=.O2
TABULATE PROPERTIES=P PRINT—PLOT=YES Y—SCALE=LOG GRID=NO * A: 82504 *
PROP—SET P PRES * B: 6504— *
* C: S04—2 *
* 0: 620 *
Fig. 1. ASPEN PLUS input file for saturation
pressure of water—f orrnaldehyde system. Fig. 4. A print—plot for true species compositions
of aqueous sulfuric acid at 298.15 K.
1184 C-C. CHEN

A
A+
M
A
M
0. 1OO0. A ÷
M
IN—UNITS SI
A
RUN—CONTROL MAX—T IME=500
DATABANKS AQUEOUS/SOLIDS 8 A
; specify all apparent components and true species SB
0.0150+ 858 AM
COMPONENTS H20 H20/HCL HCL/FECL2 FECL2/ 88 M
Hi- H÷/FE+2 FE+2/CL— CL—/FECL4—2 504—2/ B88B
2H FECL2/4H FECL2/6H FECL2 B8 M
BBBB M
; specify the solution chemistry 88 M
CHEMISTRY FECL2 8588 M
0155 FECL2 FE÷2 1/ CL— 2 B8 A
DISS HCL Hi 1/ CL— 1 0.0500÷ **BB
A BB
STOIC 1 FE÷2 —1/ CL— —4/ FECL4—2 1 M 88
K—STOIC 1 1.998 —5683.9 A 88
SALT 2H FE+2 1/ CL— 2/ H20 2 M BB
A 8888
SALT 4H FE÷2 1/ CL— 2/ H20 4 M 88
SALT 6H FE+2 1/ CL— 2/ 1120 6 M BSBB
0.0250÷ M 88
K—SALT 2H —8.1916 1135.2 88
K—SALT 4H —389.66 19432.1 55.919 AM 88
K—SALT 6H —14.069 2118.5 M 88
5888
PROPERTIES SYSOP15 CHEMISTRY=FECL2
enter physical property data AM
PROP—DATA
PROP—LIST HENRY 0.00 20.00 40.00 60.00 80.00 100.0
BPVAL HCL H2O 60.812 —8891.4 0 0 273 500 TOTAL MASSFLOW IN STREAM HCL SUBSTREAII MIXED
PROP—LIST t *
PVAL 2H 162.7838 * A: HCL MOLE FRAC
PVAL 4H 198.8146 * B: FECL2 MOLE FRAC *
PVAL 6H 234.8454
PROP—LIST GMELCC / GMELCD / GMELCE / GMELCN
PPVAL H2O (FE÷2 CL—) 3.284 / 1716.7 / —10.764/ .2 Fig. 6. A print—plot for ferrous chloride
PPVAL (FE÷2 CL—) H2O —2.333 / —723.3 / 0 / .2 saturation limit vs. hydrochloric acid
PPVAL HCL (FE+2 CL—) 0.001 concentration at 298.15 K.
PPVAL (FE+2 CL—) HCL —0.001
PPVAL H20 (Hi. CL—) 39.141 / 5115.4 / —10.585/ .03
PPVAL (Hi. CL—) H20 —20.961 /—2164.O / 5.871/ .03
PPVAL HCL (Hi. CL—) 0.001
PPVAL (Hi. CL—) HCL —0.001
PROP—LIST GMELCC / GMELCD
PPVAL (FE÷2 CL—) (Hi. CL—) 0.630 / —357.5
specify process flowsheet FECL2 HCL OUTPUT
FLOWSHEET
BLOCK CRYST IN=FECL2 HCL OUT=OUTPUT
specify feed stream conditions
STREAM ID FECL2 HCL OUTPUT
STREAM FECL2 TEMP=298.15 PRES=100000 NPHASE=l PHASE=L &
FROM CRYST
MASS-FLOW= 1000
TO : CRYST CRYST
MASS—FRAC H2O .5 / FECL2 .5
STREAM HCL TEMP=298. 15 PRES= 100000 FLASH—OPT IONS=NOFLASH &
SUBSTREAM: MIXED
MASS—FLOW= 100
PHASE: LIQUID MIXED MIXED
MASS—FRAC HCL 100
COMPONENTS: KMOL/SEC
specify unit operation block conditions H2O 21.7546 0.0 20.4749
éLOCK CRYST HEATER
HCL 0.0 2.7421 0.0
PARAM TEMP=298.15 PRES=I00000
FECL2 0.0 0.0 0.0
perform sensitivity study Hi. 0.0 0.0 2.7427
SENSITIVITY SOLUBILITY FE+2 3.9447 0.0 0.3016
DEFINE FH MOLE—FLOW STREAM=OUTPUT COMPONENT=H÷ CL— 7.8894 0.0 3.3396
DEFINE FFE MOLE—FLOW STREAM=OUTPUT COMPONENT=FE÷2 FECL4—2 1.9334—06 0.0 3.1875—03
DEF INE FFE 1 MOLE—FLOW STREAM=OUTPUT COMPONENT=FECL4—2 2H 0.0 0.0 3.6399
DEFINE FH2O MOLE—FLOW STREAM=OUTPUT COMPONENT=H2O 4H 0.0 0.0 0.0
XFECL2 = (FFEi.FFE1)/(FHi-FFE÷FFE1÷FH2O)
F
F XHCL = FH/(FHi.FFE÷FFE1÷FH2O) 6H 0.0 0.0 0.0
TOTAL FLOW:
VARY STREAM—VAR STREAM=HCL VARIABLE=MASS—FLOW KMOL/SEC 39.5881 2.7421 30.5018
RANGE LIST=l 10 20 30 40 50 60 70 80 90 100 KG/SEC 1000.0000 100.0000 1099.9998
TABULATE 1 'XHCL COL—LABEL='HCL' 'MOLE' 'FRAC' CUM/SEC 0.5591 MISSING 0.5812
TABULATE 2 XFECL2 COL—LABEL='FECL2' 'MOLE' FRAC' STATE VARIABLES:
PLOT GRID=NO TEMP K 298.1500 298.1500 298.1500
PRES N/SQM 1.0000÷05 1.0000÷05 1.0000÷05
Fig. 5. ASPEN PLUS input file for precipitation VFRAC 0.0 MISSING 0.0
LFRAC 1.0000 MISSING 0.8807
of ferrous chloride in aqueous hydrochloric SFRAC 0.0 MISSING 0.1193
acid solution. ENTHALPY:
J/KMOL —2.3942÷08 MISSING —2.5091÷08
J/KG —9.4782+06 MISSING -6.9593÷06
WATT —9.4182÷09 MISSING —1.6552÷09
ENTROPY:
J/KMOL—K —2.3925÷05 MISSING —1 .8188÷05
J/KG—K —947 1.5046 MISSING —5043.2560
DENSITY:
KMOL/CUM 70.8102 MISSING 52.4796
KG/CUM 1188.6488 MISSING 1892.5921
AVG MW 25.2591 36.4610 36.0634

Fig. 7. True species flow rates with

precipitation of ferrous chloride in
aqueous hydrochloric acid solution.
 Process simulation for reactive chemical systems 1185

SOUR WATER STRIPPER

The simulator is used to examine two configurations for a sour water stripper. The
configuration of the sour water stripper is shown in Fig. 8. The feed compositions of the
two feed streams to the stripper are summarized in Table 3. It is desired to determine the
effect of changing the caustic feed location on the concentrations of hydrogen sulfide,
carbon dioxide, and ammonia in the bottoms product. The simulator will be used to compute
the change in column composition profiles, pH profile, and bottoms composition due to
changing the caustic feed location from stage 4 (Case 1) to stage 9 (Case 2).

Fig. 8. Sour water stripper configuration.

TABLE 3. Composition and flow rates of feed streams to

the sour water stripper

Stream Feed Caustic

Total 1.00 kgmole/sec 0.002 kgmole/sec

H2S 0.02 kgmole/sec
NH3 0.02 kgmole/sec
C02 0.002 kgmole/sec
H20 0.958 kgmole/sec 0.0016 kgmole/sec
NaOH 0.0004 kqmole/sec

The sour water stripper system has been examined by many investigators (refs. 2, 24). The
solution chemistry involves seven aqueous phase reactions:

H20
<——> H -'- OH (13)
<——> + OH (14)
H20 ÷ NH3 NH
H2S
<——> H -'- HS (15)
HS <——> H i- S2 (16)

H20 + CO2 <——> H +

HCO3 (17)

HCO3
<——> H +
C03 (18)
NaOH ———> Na + OH (19)

Water, ammonia, carbon dioxide, hydrogen sulfide, and sodium hydroxide are the apparent
components. The true species include the ionic species hydrogen, hydroxide, bisulfide,
sulfide, bicarbonate, carbonate, and the undissociated molecular species water, ammonia,
carbon dioxide, hydrogen sulfide. The chemical equilibrium constants and the physical
interaction parameters have been well established in the literature for the sour water
stripper system (ref. 24). This solution chemistry model is available in the simulator.

The simulation input files for Cases 1 and 2 are given in Figs. 9 and 10, respectively.
Based on the computed column profiles, substantial effects can be seen when the caustic
feed inlet location is changed. The effects are illustrated with the changes in
vapor—liquid equilibrium K—values and compositions of ammonia and hydrogen sulfide and
computed pH profiles in the column. Such changes are shown via print—plots, given in Figs.
11—16. The hydrogen sulfide concentration at the bottom of the column drops from 100 ppm
by mole to less than 1 ppm by mole when the caustic feed location is changed from stage 4
to stage 9.
1186 C-C. CHEN

RUN—CONTROL MAX-TIME= 1000

IN—UNITS SI
retrieve the sour water chemistry model
INSERT GLOBAL SOUROH H20 NH3 H2S C02 NAOH SYSOP15 0
specify the flowsheet
(LOWSHEEI
BLOCK COLUMN IN = FEED CAUSTIC OUT = TOP SOT
specify feed stream conditions
STREAM FEED TEMP=313 PRES=300000
MOLE—FLOW H2S .02/ NH3 .02/ CO2 0.002/ H2O .958
STREAM CAUSTIC TEMP=313 PRES=300000 NPHASE=l PHASE=L .-. Fig. 9. ASPEN PLUS input file for sour water
MOLE-FLOW NAOH .0004/ H2O .0016 stripper, Case 1.
specify the distillation column conditions
BLOCK COLUMN RADFRAC
PARAM NSTAGE=lO MAXOL=3O
case 1, casutic enters stage 4
FEEDS FEED 3 / CAUSTIC 4
PRODUCTS TOP 1 1 / BOT 10 0
P—SPEC 1 250000 / 10 310000
COL-SPECS RDV=l D= .07 RR=2 u.oo÷--
T—EST 1 363 / 10 383
TRAY—REPORT TRAY—OPTION=ALL—TRAYS PROPERTIES=PHVALUE & A
A!
PRINT—PLOT=YES GRID=NO A+
PLOT 1 KVL=H2S NH3 Y—SCALE=LOG GRID=N0 A!
A!
PLOT 2 Y=H2S NH3 Y—SCALE=LOG GRID=NO M
PROP—SET PHVALUE PH25 PHASE=L 11.50÷ MAMA +
STREAM—REPORT NOZEROFLOW AM
AM
M
P U
RUN—CONTROL MAX—T IME= 1000 H M
IN—UNITS SI 2
5 A
retrieve the sour water chemistry model 11 A
INSERT GLOBAL SOUROH H20 NH3 H2S C02 NAOH SYSOP15 0 I A
A
specify the flowsheet Q A
FLOWSHEET U A
BLOCK COLUMN IN = FEED CAUSTIC OUT = TOP SOT A
specify feed stream conditions 0 A
STREAM FEED TEMP=3l3 PRES=300000 10. 50+
MOLE-FLOW H2S .02/ NH3 .02/ C02 0.002/ H20 .958
STREAM CAUSTIC TEMP=313 PRES=300000 NPHASE=1 PHASE=L
MOLE-FLOW NAOH .0004/ H20 .0016
specify the distillation column conditions
BLOCK COLUMN RADFRAC
PARAM NSTAGE=lO MAXOL=30 10.00÷
case 2, casutic enters stage 9 MAMAA
FEEDS FEED 3 / CAUSTIC 9 AM
AM
PRODUCTS TOP 1 1 / BOT 10 0
P—SPEC 1 250000 / 10 310000
COL—SPECS ROV=l D=.O1 RR=2
T—EST 1 363 / 10 383
TRAY—REPORT TRAY-OPT ION=ALL—TRAYS PROPERT IES=PHVALUE & 0 2 4 6 8 0
PRINT—PLOT=YES GRID=NO TRAY NUMBER

PLOT 1 KVL=H2S NH3 Y—SCALE=LOG GRID=NO

PLOT 2 Y=H2S NH3 Y—SCALE=LOG GRID=NO Fig. 11. A print—plot for pH profile in sour
PROP—SET PHVALUE PH25 PHASE=L water stripper, Case 1.
STREAM—REPORT NOZEROFLOW

Fig. 10.ASPEN PLUS input file for sour water

stripper, Case 2.

A
Mi AAAAM A
U K U A
U M M
A V U M
12.00 A + A
A 10. 00÷ BB'BBBBBBBBBBBBBBBBBBBBBBI
A 1 U 888 A
A BBBBBBBBB A
A I BB M
5.000+ B8 A
P
A
A
1
I / BB A
H 11.50 A +
2 A 1
5 A M
A 0
I A
A
I
1 AM
A M
11.00 A + B U
A 1.000 U
0 MM
MMM
0.5000
U
10.50+ A
AAAAAA AAAAAA
A
A
U
M MMM
U
M
M
10. 00+

AM 0 2 4 6 8 10
AM TRAY NUMBER

* A: COMPONENT H2S *
* B: COMPONENT NH3 *
0 2 4 6 $ 10
TRAY NUMBER
Fig. 13. A print—plot for vapor—liquid
Fig. 12. A print—plot for pH profile in sour equilibrium K—value profile in sour water
water stripper, Case 2. stripper, Case 1.
 Process simulation for reactive chemical systems 1187

50.00÷
A88
M88
V 0.1000 M
MAMA M A ABS
M MM • A8858
M AMAAA A 0 A B
M UAMMAMA A
A
B
88
10.00+ A 88
888 A H A B
888888888 A A 0.0 100 • A B
88 A S A 88
5.000÷ 88 A + • A 88
88 A A B
A M A B
A I 0 A 88
A 1 A 88
A A B
A I 1.00—03 • A B
A I M 88
A M 88
A I A M B
A 1.000+ A + C AMA B
A 1 MAMA 88
A
A 0
+ MW
0.5000÷ A
A
N 1.00—04
B!
8÷
A
A 88
A
A
A
A
M 0 2 4 6
MM 8 10
TRAY NUMBER
2 4 6 a jo
TRAY NUM8ER
* A: COMPONENT H2S *
* B: COMPONENT NH3 *
* A: COMPONENT H2S *
* B: COMPONENT NH3 *
Fig. 15. A print—plot for vapor compositionr
Fig. 14. A print—plot for vapor—liquid profile in sour water stripper, Case 1.
equilibrium K-value profile in sour water
stripper, Case 2.

A 88
A 8888
A 88
A 88
M 88
A B
A B
1.00-03÷ A 88
A 88
A B ÷
A B I
A 88 1
A 88 1

1.00—04+
A
A
M
B!
8
8÷
1

A B!
A 88
A
A
A
A
A
1.00—05÷ A
A
A
A A Fig. 16. A print—plot for vapor composition
A profile in sour water stripper, Case 2.
A
A
0 A
1.00-06+ A
A
A
A

MMAM
•
0 2 4 6 8 10
TRAY NUMBER

* A: COMPONENT H2S *
* B: COMPONENT 883

CONCLUDING REMARKS
The recent developments in computer—aided process simulation technology represent
significant advancements in the modeling of reactive chemical systems. Such technology
advancements and simulation tools enable scientists and engineers to analyze complex
reactive chemical systems as routinely and conveniently as hydrocarbon systems.

Acknowledgements
The author wishes to thank the organizers of the Eighth International Symposium on
Solute—Solute—Solvent Interactions for the invitation to deliver the plenary lecture upon
which this paper is based. The author also wishes to thank Aspen Technology, Inc. for the
permission to present and publish this article. The manuscript benefited from
constructive reviews by Joseph F. Boston, Lawrence B. Evans, Herbert I. Britt, Paul W.
Gallier, Willie K. Chan, Suphat Watanasiri, M.S. Sivasubramanian, Bill Mock, and Carolyn
Kintisch, who made many helpful suggestions for improvements.
 8811 N3H3'3-3

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