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The system is flowing at 1000 kg/hr and the atomic wt of Ni is 58670mg/mol.
Thus the minimum solubility achieved is 2.42 mg/kg (ppm). Thus, even when
CN
-
is at a fairly low concentration, 10 ppm, the soluble Ni requirements are no
longer maintained. Why is this?
Considerations
In the presence of CN
-1
and above 7.5 pH, Ni(CN)
4
-2
is the dominant aqueous species. This very stable complex
increases overall Ni solubility by 10,000x. Given this stability, we can estimate Ni solubilization by merely
knowing the CN addition. Ni atomic weight is 58,67, CN formula weight is 26.02. The complex Ni(CN)
4
-2
is
Chapter 3 Analyzer Mechanics, Multiple Point Calculations 3-23
comprised of 58.67 g Ni and 104.08 g CN. Thus, for every 10 ppm CN in solution, up to 5.64 ppm Ni dissolves.
Thus, if CN concentrations exceed a few ppm, the plant will never be able to maintain a 1 ppm Ni content. For
the sake of the course, lets assume that 10ppm CN- is entering the stream and there is no way to stop it. We
will need some new ideas to remove nickel to below 1ppm.
Chapter 4 Analyzer Mechanics, Mixers 4-1
Chapter 4 Analyzer Mechanics,
Mixers
Chapter 4 Analyzer Mechanics, Mixers 4-2
4.1 A Mix Block Calculation
Overview
This is a simple calculation, it is two steps. First create two new streams, 0.1 molal HF and 0.1 molal CaCl2, Then
you will mix them at equal amounts. What will be the mixed pH?
How to do it
Create a stream using the
following information
Stream Name HF
Unit Set Default
Names Style Formula
Temperature 30
o
C
Pressure 1 atm
H2O 55.508 mol
HF 0.1 mol
Perform a single point
isothermal calculation.
Here is the shorthand notation
Add Stream > Rename Stream
> Definition > Add Conditions
> Add Single Point > Select
Isothermal Calculations >
Calculate
Create a new stream using
the following information.
Stream Name CaCl2
Unit Set Default
Names Set Formula
Temperature 30 C
Pressure 1 atm
H
2
O 55.508 mol
CaCl
2
0.1 mol
Perform a single point
isothermal calculation.
Chapter 4 Analyzer Mechanics, Mixers 4-3
Mix calculation set up
Select Streams from the Menu
Bar and select Add Mixed
Stream.
Confirm that the Mix block is using
the Default units and not the
Course units. If the units set is not
default, then change it.
Highlight the stream HF in the
Available Streams box and
click the right double-arrow
(>>).
Repeat for the stream
CaCl2.
Select Single Point Mix in the
Type of survey button.
Select Isothermal with the
Type of calculation button.
Calculate.
We have just defined two streams and we will now mix them together.
The summary box displays the results.
The pH is 1.44.
Considerations
Why the unusual pH behavior? Mixing an acid and a base should result in a neutralized solution. In this case, the
pH is lower than the starting streams.
Chapter 4 Analyzer Mechanics, Mixers 4-4
4.2 Mix Block - Neutralizing two streams
Overview
This example is a follow-up to the Mix Block examples. The purpose of this example is to familiarize the user
with the three mixing options, Ratio, Proportion, and Volume. Some of this was already covered in the previous
examples, and this calculation will serve as a comparison analysis.
We are going to use two refinery waste waters, a spent caustic and a spent sulfuric acid stream.
How to do it!
Create two streams with the
following composition.
Stream Name Spent Caustic
Unit Set Mass Fraction
Names Style Formula
Temperature 50
o
C
Pressure 1 atm
Stream Amount 1000 kg
H2O balance
NaOH 0.9 wt%
CH4S 0.2 wt%
NaCl 0.2 wt%
H2S 0.5 wt%
Phenol 0.2 wt%
Naphthenic acid 0.15 wt%
NH4Cl 0.07 wt%
Run a single-point isothermal
calculation
Stream Name Spent Sulfuric
Acid
Unit Set Mass Fraction
Names Style Formula
Temperature 42
o
C
Pressure 1 atm
Stream Amount 1500 kg
H2O balance
H2SO4 1.5 wt%
Na2SO4 0.5 wt%
Na2S2O3 0.3 wt%
Lauric Acid 5.2 wt%
Run a single-point isothermal
calculation
Review the units selected for this block. Make sure that it is set for either
mass or moles (in Version 2.0 and below, mass and mole fraction units
are not allowed)
Chapter 4 Analyzer Mechanics, Mixers 4-5
Select Streams from the menu
bar and select Add Mixed
Stream
Name the Mix Block
Titration Apparatus by Ratio
Highlight the Spent Caustic
and H
2
SO
4
streams just
created and move them to the
Selected field.
Select Ratio from the type of
survey button.
Click the Specs button.
Set the range from 0.0 to 4.0
and change the increment to
0.25
Click on the General object in
the Category field
Select Spent Caustic as the
adjustable variable.
Click OK to close.
Calculate.
Click the Plot tab and select
pH as the Y-axis variable
(located under Additional
stream parameters). Select
Volume Flow Aqueous as
the Y2-Axis.
The ratio calculation adjusts the amount of one of the specified streams.
By selecting this stream, you chose to adjust the Spent Caustic stream
from zero four times the ratio displayed on the definition grid. In this
example, a ratio of 1:1 means that 1000 kg Spent Caustic is reacted with
1500 kg Spent acid.
Chapter 4 Analyzer Mechanics, Mixers 4-6
Considerations
The mixing results are secondary to the objective of comparing the different mixing scenarios.
Ratio Survey This survey calculation adjusts the inflow mass of the selected stream only. Its mass is multiplied
by the Ratio value.
Stream Mass * Ratio = Total Inflow Mass
The second (third, fourth, etc.) stream inflows are kept constant.
Volume Survey This survey calculation adjusts the inflow volume while keeping the other stream volumes
constant.
Proportion Survey The Proportion survey calculation adjusts both inflow streams using the following rule
Selected Stream Mass * Proportion = Inflow Mass
Sum of Other Stream Masses * (1-Proportion) = Other Mass
In this survey calculation, the overall inflow mass is kept constant.
Chapter 4 Analyzer Mechanics, Mixers 4-7
4.3 How to create a titration curve?
Overview
A titration curve is the mixing of two reagents, typically an acid and base. The OLI Analyzers can mix two or
more reagent streams to produce a typical titration curve. In this example a 0.1 molal solution of citric acid will
be titrated against a 0.1 molal solution of sodium hydroxide.
How to do it!
Create a new stream using
the following information.
Stream Name Citric Acid
Names Style Display Name
Unit Set Default
Temperature 25C
Pressure 1atm
H2O 55.508 mol
Citric Acid 0.1 mol
Calculate
Create a second stream using
the following information.
Stream Name NaOH
Names Style Formula
Unit Set Default
Temperature 25 C
Pressure 1 atm
H2O 55.508 mol
NaOH 0.1 mole
Calculate
Select Streams>Add Mixed
Stream from the menu bar
Name it Titration Apparatus
Highlight the Citric Acid and
NaOH stream and move them
to the selected field.
Chapter 4 Analyzer Mechanics, Mixers 4-8
Select Ratio from the Type of
Survey button.
Click the Specs button.
You should see the Survey
Range tab. If not, then click
on the Variable Ratio object
in the Category section.
Set the range from 0.0 to 4.0
and change the increment to
0.05
Click on the General variable
in the Category field.
Highlight NaOH (if not already
highlighted).
Click OK to close
Calculate.
Click the Plot tab and
X-Axis Ratio
Y-Axis - pH
(pH is located under
Additional Stream
Parameters).
The ratio calculation adjusts the amount of one of the specified streams.
This will adjust the selected stream (selected next) from 0 to 4 times the
amount displayed on the definition grid. In this case we will select the
NaOH stream which is approximately 1 liter. Thus we will adjust the
stream from 0 liters to 4.0 liters. The Citric Acid stream is about 1 liter.
Considerations
The equivalence point seems to occur at approximately a pH of 9.4 with a ratio of 3.0. From this we could back
out the equilibrium constant for the acid.
Chapter 4 Analyzer Mechanics, Mixers 4-9
4.4 How do you enter data into Laboratory Analyzer?
StreamAnalyzer is developed to accommodate two input types, molecular and ionic. We have already seen how
molecular inflows are handled. When we are working off a water analysis, we use the LabAnalyzer screens,
either as a plug-in to StreamAnalyzer or in its Stand-alone version.
The LabAnalyzer databank recognizes several entries for a cation or anion. The database is populated with up to
a dozen synonyms for each ion. This gives you flexibility on how to type in the name. Two examples, Na
+
and
CH
3
COO
-
are shown below.
If you misspell or use an unrecognized name, the name will be moved to the neutral list and a red X appears to
the left of the name you entered. You will need to delete this cell to proceed.
There are approximately 2,000 cations and anions and 15,000 synonym entries in the database. You can access
the database by clicking on the down arrow within the input cell. To exit the list you need to select a species.
The escape key does not work within the list.
Sodium Acetate
Na+ C2H3O2-
Na+1 C2H3O2(-)
Na(+) C2H3O2(-1)
Na(+1) C2H3O2(1-)
Na(1+) C2H3O2-1
Sodium ion(+1) Acetate ion(-1)
NAION Acetate ion (-1)
Sodium ion ACETATEION
Natrium ion
Natrium ion(+1)
Chapter 4 Analyzer Mechanics, Mixers 4-10
How to do it
Create a new Lab Analysis
Entry by clicking on the Global
Icon and selecting Add Water
Analysis
Enter the following Brine
Analysis into the screen that
opens
Cations
Na
+
10,000 mg/l
Ca
+2
500
Mg
+2
1,200
Sr
+2
200
Ba
+2
5
Fe
+2
5
Anions
Cl
-
19,000 mg/l
SO
4
-2
2,700
B(OH)
4
-
180
HCO
3
-
145
AsO
4
-3
- 12
Formate
-
20
Acetate
-
50
Propanate
-
25
Thiocyanate
-
2
H
4
DTPA
-
56
pH 7.8
Density 1.013
TDS 36,500 mg/l
Select Add Reconcile on the
right-side of the screen. A
new window appears.
Click on the Specs button and
review the Electroneutrality
options
A new screen appears that looks like the following
If you cannot create the correct species, you can find it using the list.
Type in the first two or three characters. Then click on the down arrow to
the right of that input cell. When the list appears below the cell, it should
be near or even on the species you need. If you see more than one name
for the same component, select it. They are synonyms.
You will note that some of the names will change. The H4DTPA- ion
changes to H4(C14H18N3O10)-, because the Names Manager is set to
formula. You can change this by selecting from the menu, Tools>Names
Manager>Display Name or OLI Tag.
LabAnalyzer will reconcile the charge imbalance and calculate the fluid
properties.
.
Chapter 4 Analyzer Mechanics, Mixers 4-11
Electroneutrality
Dominant Ion
The largest species concentration of the deficient charge is
added
In this case Na
+
ion was added since there is an excess of
negative charge.
Proration
An equal percentage of all deficient species is added.
Na+, Cl-
Sodium is added when there is an excess of negative charge,
chloride is added when there is an excess of positive charge.
User Choice
The user specifies the cation or anion required to balance
the sample.
Since there is an excess of negative charge, only the cations
are available for selection with this option. 708.915 mg/L of
Ca
+2
is needed to balance the sample.
Make Up Ion
The specified ion is either added or subtracted to balance the charge.
With the make-up ion option, either a cation or anion can be used to adjust the Electroneutrality. Since in this
example, there is an excess of negative charge, selecting a cation has the same result as the User Choice option.
In the figure above, chloride ion has been selected. Since there is an excess of negative charge, 1254.212 mg of
Cl
-
must be removed.
Make sure the Type of
Balance button is set to Na/Cl
and the click the OK button.
Exit the screen and return to
the main worksheet
Click on the Auto NaOH/HCl
button within the Reconcile
pH area
Calculate
The Summary box is now updated with the current Electroneutrality
Chapter 4 Analyzer Mechanics, Mixers 4-12
Review the Summary section
Click on the Report Tab and
review the Scale Tendencies
(about one-third the way
down)
According to the calculation, 813 mg/l Na is needed to balance charge
In addition, 12.3 mg/l (0.34 mol/l) HCl is needed to fix the pH at 7.8
Lastly, some solids precipitated during
the titration
In order to see what solids formed, we
will review the Report
Three solids are calculated to precipitate (Their scale tendency =1.0), one
of which is CaCO3. Since CaCO3 removal is removal of alkalinity, then the
pH would naturally decrease. It is now the decision of the analyst to
decide if this solid truly existed in the solution during the experiments. It
is reasonable for this solid to not form, i.e., remain metastable, If that is
the case, then we may remove the solids from the calculation, and allow
the carbonate to remain in solution. We can review the species list and
see how much carbonate mass was removed from solution.
Chapter 4 Analyzer Mechanics, Mixers 4-13
Scroll down the report to the
Species Output (True
Species) section
Click on the Customize button
in the upper right corner.
Click on the Species Output entry
within the Category field
Next, select the Options tab
There is a Row Display field
with an option: Only rows
where any value is greater
than..
Click on that radio button and
enter the value 5.
Click OK to exit the window
From the menu, click on
Chemistry>Model Options,
and then click on the Phases
tab.
Remove the check from the
Solids entry within the
Include Phases field
Make sure that the Calculate
Scale Tendencies box is
checked
Click OK to exit the window
Re-Calculate by pressing the
F9 key
The Species output list is extensive, there are over 100 entries. We can
reduce the list size by adding a filter located in the Customize window.
Lets cut off the list a 1ppb. The new window contains formatting
features that add or remove specific report sections and to also
add/remove specific components within each section.
We will focus on the Species Output section of the Report
The 5 value correlates with the units chosen. For the ppm Aqueous, it is
5ppm, so any value greater than this will appear. The list length is
reduced by 75%.
Solids mass is in the far right row. SrSO
4
solids are 338 mg, followed by
127 mg CaCO
3
and 8.4 mg BaSO
4
. The 127 mg (or 1.27 mmol/l) CaCO
3
is
equivalent of 2.54 mmol/l carbonate alkalinity. This is much more than
the 0.34 mmol/l HCl added to increase pH. Thus, the CaCO
3
precipitation
had a greater impact on final pH then the HCl. If we re-reconcile this fluid
with these solids still dissolved, we can see what the pH initially was just
prior to precipitation.
(You will notice that BaSO
4
is on the list, but only has a value of 3e-3 ppm,
lower than this filter. This is because the solid phase is 8 mg, which
exceeds the filter value for the solid phase. Therefore it also appears.)
Chapter 4 Analyzer Mechanics, Mixers 4-14
Scroll down to the Scaling
Tendencies section.
Review the top four entries
Return to the Reconciliation
Tab and review the Summary
section. How much NaOH
was added?
Turn off the pH reconciliation
Recalculate
From the menu, click on
Chemistry>Model Options,
Phases.
Turn the solids back on
Click OK to exit the window
Calculate
Review the pH
Two sulfate and two carbonate solids are supersaturated, with BaSO
4
having the greatest supersaturation. When we ran the calculation, only
three solids precipitated. No SrCO
3
solid formed, despite its
supersaturation. This is because of competing ion effect among the four
potential phases.
Instead of adding 12 mg/l HCl, 58
mg/l HCl is needed. This difference
represents the impact of CaCO
3
precipitation on overall pH.
Lastly, lets see what the pH is
without reconciling.
The calculated pH is 8.9, much higher
than the 7.8 recorded. This is a big
difference and adds to the uncertainty.
There is one final calculation option; the
pH when solids are turned on. Lets look
at that calculation before we make a
conclusion
The pH is 7.94, close to the measured
value. This value is close enough to the measured pH to keep. Thus, we
can probably use the system as-is, and not add any HCl. The pH will be off
slightly, but with this approach, we are not changing any chemistry
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-1
Chapter 5 Analyzer Mechanics,
Water and Oil Analyses
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-2
5.1 Entering data into Laboratory Analyzer
StreamAnalyzer is developed to accommodate two input types, molecular and ionic. We have already seen how
molecular inflows are handled. When we are working off a water analysis, we use the LabAnalyzer screens,
either as a plug-in to StreamAnalyzer or in its Stand-alone version.
The LabAnalyzer databank recognizes several entries for a cation or anion. The database is populated with up to
a dozen synonyms for each ion. This gives you flexibility on how to type in the name. Two examples, Na
+
and
CH
3
COO
-
are shown below.
If you misspell or use an unrecognized name, the name will be moved to the neutral list and a red X appears to
the left of the name you entered. You will need to delete this cell to proceed.
There are approximately 2,000 cations and anions and 15,000 synonym entries in the database. You can access
the database by clicking on the down arrow within the input cell. To exit the list you need to select a species.
The escape key does not work within the list.
Sodium Acetate
Na+ C2H3O2-
Na+1 C2H3O2(-)
Na(+) C2H3O2(-1)
Na(+1) C2H3O2(1-)
Na(1+) C2H3O2-1
Sodium ion(+1) Acetate ion(-1)
NAION Acetate ion (-1)
Sodium ion ACETATEION
Natrium ion
Natrium ion(+1)
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-3
to do it
Create a new Lab Analysis
Entry by clicking on the Global
Icon and selecting Add Water
Analysis
Enter the following Brine
Analysis into the screen that
opens
Cations
Na
+
10,000 mg/l
Ca
+2
500
Mg
+2
1,200
Sr
+2
200
Ba
+2
5
Fe
+2
5
Anions
Cl
-
19,000 mg/l
SO
4
-2
2,700
B(OH)
4
-
180
HCO
3
-
145
AsO
4
-3
- 12
Formate
-
20
Acetate
-
50
Propanate
-
25
Thiocyanate
-
2
H
4
DTPA
-
56
pH 7.8
Density 1.013
TDS 36,500 mg/l
Select Add Reconcile on the
right-side of the screen. A
new window appears.
Click on the Specs button and
review the Electroneutrality
options
A new screen appears that looks like the following
If you cannot create the correct species, you can find it using the list.
Type in the first two or three characters. Then click on the down arrow to
the right of that input cell. When the list appears below the cell, it should
be near or even on the species you need. If you see more than one name
for the same component, select it. They are synonyms.
You will note that some of the names will change. The H4DTPA- ion
changes to H4(C14H18N3O10)-, because the Names Manager is set to
formula. You can change this by selecting from the menu, Tools>Names
Manager>Display Name or OLI Tag.
LabAnalyzer will reconcile the charge imbalance and calculate the fluid
properties.
.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-4
Electroneutrality
Dominant Ion
The largest species concentration of the deficient charge is
added
In this case Na
+
ion was added since there is an excess of
negative charge.
Proration
An equal percentage of all deficient species is added.
Na+, Cl-
Sodium is added when there is an excess of negative charge,
chloride is added when there is an excess of positive charge.
User Choice
The user specifies the cation or anion required to balance
the sample.
Since there is an excess of negative charge, only the cations
are available for selection with this option. 708.915 mg/L of
Ca
+2
is needed to balance the sample.
Make Up Ion
The specified ion is either added or subtracted to balance the charge.
With the make-up ion option, either a cation or anion can be used to adjust the Electroneutrality. Since in this
example, there is an excess of negative charge, selecting a cation has the same result as the User Choice option.
In the figure above, chloride ion has been selected. Since there is an excess of negative charge, 1254.212 mg of
Cl
-
must be removed.
Make sure the Type of
Balance button is set to Na/Cl
and the click the OK button.
Exit the screen and return to
the main worksheet
Click on the Auto NaOH/HCl
button within the Reconcile
pH area
Calculate
The Summary box is now updated with the current Electroneutrality
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-5
Review the Summary section
Click on the Report Tab and
review the Scale Tendencies
(about one-third the way
down)
According to the calculation, 813 mg/l Na is needed to balance charge
In addition, 12.3 mg/l (0.34 mol/l) HCl is needed to fix the pH at 7.8
Lastly, some solids precipitated during
the titration
In order to see what solids formed, we
will review the Report
Three solids are calculated to precipitate (Their scale tendency =1.0), one
of which is CaCO3. Since CaCO3 removal is removal of alkalinity, then the
pH would naturally decrease. It is now the decision of the analyst to
decide if this solid truly existed in the solution during the experiments. It
is reasonable for this solid to not form, i.e., remain metastable, If that is
the case, then we may remove the solids from the calculation, and allow
the carbonate to remain in solution. We can review the species list and
see how much carbonate mass was removed from solution.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-6
Scroll down the report to the
Species Output (True
Species) section
Click on the Customize button
in the upper right corner.
Click on the Species Output entry
within the Category field
Next, select the Options tab
There is a Row Display field
with an option: Only rows
where any value is greater
than..
Click on that radio button and
enter the value 5.
Click OK to exit the window
From the menu, click on
Chemistry>Model Options,
and then click on the Phases
tab.
Remove the check from the
Solids entry within the
Include Phases field
Make sure that the Calculate
Scale Tendencies box is
checked
Click OK to exit the window
Re-Calculate by pressing the
F9 key
The Species output list is extensive, there are over 100 entries. We can
reduce the list size by adding a filter located in the Customize window.
Lets cut off the list a 1ppb. The new window contains formatting
features that add or remove specific report sections and to also
add/remove specific components within each section.
We will focus on the Species Output section of the Report
The 5 value correlates with the units chosen. For the ppm Aqueous, it is
5ppm, so any value greater than this will appear. The list length is
reduced by 75%.
Solids mass is in the far right row. SrSO
4
solids are 338 mg, followed by
127 mg CaCO
3
and 8.4 mg BaSO
4
. The 127 mg (or 1.27 mmol/l) CaCO
3
is
equivalent of 2.54 mmol/l carbonate alkalinity. This is much more than
the 0.34 mmol/l HCl added to increase pH. Thus, the CaCO
3
precipitation
had a greater impact on final pH then the HCl. If we re-reconcile this fluid
with these solids still dissolved, we can see what the pH initially was just
prior to precipitation.
(You will notice that BaSO
4
is on the list, but only has a value of 3e-3 ppm,
lower than this filter. This is because the solid phase is 8 mg, which
exceeds the filter value for the solid phase. Therefore it also appears.)
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-7
Scroll down to the Scaling
Tendencies section.
Review the top four entries
Return to the Reconciliation
Tab and review the Summary
section. How much NaOH
was added?
Turn off the pH reconciliation
Recalculate
From the menu, click on
Chemistry>Model Options,
Phases.
Turn the solids back on
Click OK to exit the window
Calculate
Review the pH
Two sulfate and two carbonate solids are supersaturated, with BaSO
4
having the greatest supersaturation. When we ran the calculation, only
three solids precipitated. No SrCO
3
solid formed, despite its
supersaturation. This is because of competing ion effect among the four
potential phases.
Instead of adding 12 mg/l HCl, 58
mg/l HCl is needed. This difference
represents the impact of CaCO
3
precipitation on overall pH.
Lastly, lets see what the pH is
without reconciling.
The calculated pH is 8.9, much higher
than the 7.8 recorded. This is a big
difference and adds to the uncertainty.
There is one final calculation option; the
pH when solids are turned on. Lets look
at that calculation before we make a
conclusion
The pH is 7.94, close to the measured
value. This value is close enough to the measured pH to keep. Thus, we
can probably use the system as-is, and not add any HCl. The pH will be off
slightly, but with this approach, we are not changing any chemistry
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-8
Follow-up example
In efforts to reinforce the above case, we will run this example again using a few different water analyses. The
first one is an Arabian Gulf seawater. The other is a groundwater with unique composition. Run both cases, and
perform two reconciliations, a basic equilibrium and a pH reconciliation. Note the amount of additive required
to achieve the set pH and also note the solids content in each of the reconciliation calculations.
Name Arabian Gulf seawater 6,000 m well
Units Set WaterAnalysis
Concentration
WaterAnalysis
Concentration
Names Style Formula Formula
Stream Amount 1 L 1 L
Temperature 30 C 15 C
Pressure 1 bar 1 bar
Recorded Properties
pH 8.2 4.6
Density 1.029 (g/ml) 1.09
TDS 42,528 (mg/l) 211,197
Conductivity 0.050 (1/ohm-cm)
Neutrals
B(OH)3 31 43
SiO2 2 300
Cations (mg/l)
Li+ 0.25 ---
Na+ 13,440 55,895
K+ 485 9,730
Ca+2 520 17,163
Mg+2 1,765 473
Sr+2 1 121
Ba+2 0.08 630
Fe+2 0.008 469
Pb+2 3.6
Zn+2 1.3
Anions (mg/l)
F- 1.5 3.1
Cl- 24,050 126,700
Pb
+2
82 ---
Zn
+2
0.25
SO4-2 3,380 9.2
HCO3- 165 1.1
CO3-2 88 ---
We will look at the results on the projector.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-9
Crude Oils
Crude oils are complex groups of organic molecules containing hundreds, perhaps thousands of pure
components in a single oil. Modeling crude oils using pure components is impractical, because analyzing for
each pure component is cost prohibitive and the number of species would make calculations overwhelming. A
convenient solution to this problem and to modeling the properties of a crude oil is to create
pseudocomponents. Crude Oil properties may be defined through a distillation curve, where each boiling point
range is a progression of molecular weights, densities, solubilities, viscosities and other properties associated
with that section. It is reasonable for low boiling point molecules to be low molecular weight, low density, low
viscosity, and more soluble in water. We can dice boiling point curves using well accepted methods standard to
create pseudocomponents, that in combination reflect the property of the whole oil. Below is an example of a
distillation curve that is segmented into ten pseudocomponents.
There are two ways to create a crude oil stream on the Analyzers. The first is to start with a PVT curve and
create pseudocomponents using one of the three thermodynamic methods coded into the software. The
second is to enter the pseudocomponent data directly and using the same theremodynamic methods to predict
the component properties.
The three thermodynamic methods are API (version 5), Lee Kesler, and Cavett. At the time of writing, the
software implementation specifications for these methods were not in hand. Thus the specifics of each method
are not detailed in this document+.
0
50
100
150
200
250
300
350
400
450
0 10 20 30 40 50 60 70 80 90 100
T
e
m
p
e
r
a
t
u
r
e
,
C
Liquid Vol % Distilled
Distillation Curve
PC10 PC9 PC8 PC7 PC6 PC5 PC4 PC3 PC2 PC1
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-10
5.2 Entering a PVT Analyses
You will create a simple PVT analysis in order to see how the most recent features of the Analyzer studio works.
The idea is fairly simple. You will create enter an Assay name and activate the assay editor, which is a subgrid in
the worksheet. You then will enter the experimental data, and upon creating a single-point calculation,
compute the crude properties.
How to do it
Create a new Stream
Name the Stream Crude Oil
Select Chemistry>Model
Options>Phases and turn on
Second Liquid phase
Type PVTCurve in a blank cell
and press Shift-Enter.
Enter the following data in the
subgrid that appears
Stream Name Crude Oil
Inflow name PVTCurve
PVT Curve 1000 mole
Analysis ASTM D86
Density Type API Gravity
Bulk Density 31
Distillation Cuts 5
Thermo Method API
H2O Mass 5 mole
Click the Edit button in the
Distillation Data grid and
enter the following data
Distillation data
Vol% Dist Temp, C
1 20
5 30
10 50
20 60
40 80
60 120
80 150
90 180
95 200
99 220
100 240
Click on Add Calculation and
select Single Point
Calculate
The second liquid phase is turned off by default. If you want to turn it on
indefinitely, you can select the Streams icon in the tree view and then
turn on the second liquid phase there.
The Shift-Enter action instructs Analyzer to create an Assay rather than
look for a database species (pure component).
The software contains user input options. They the Assay Data type (the
experimental procedure that is run), the density units, and the
thermodynamic method used to compute pseudocomponent properties.
You can change these by clicking on the cells and selecting on of the
choices. The defaults are ASTM D86, specific gravity, and API.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-11
View the report
Return to the definition tab
and change the Type of
Calculation to Vapor Fraction.
Make the Known: Vapor Frac
value 0.5 mol/mol
Calculate
View the results, Total and
Phase flow and Species
Output
The five pseudocomponents are distributed between the aqueous and
organic (2
nd
liquid) phase. The component name designations are created
by the software. The normal boiling point temperature of each cut is
embedded in the name. Note that the aqueous solubility of these
components decrease with increasing boiling point, and the range
computed is five orders of magnitude.
The vapor fraction calculation distributes the mass (in terms of moles)
evenly between the vapor phase and liquid phase. Note right now that
the software places the organic liquid into the aqueous column. This is a
bookkeeping issue, in that the first liquid phase is put into the aqueous
column, even though it is not an aqueous phase. OLI is working on a
solution to this. As of version 3.0.58 this is the current configuration.
.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-12
Follow-up example
OLI software computes the critical properties of these pseudocomponents using one of the three models
discussed above. To see this data you (presently) need to open a text file that is stored in the work directory. If
you open an explorer window and look for PSEUDO1.txt and PSEUDO10.txt you can view this information.
Below is formatted information from PSEUDO1.txt for the first pseudo-component. If your data does not look
like this, dont worry. This is a snapshot of a particular case in a particular software version. Our interest is to
look at the available variables.
PVTCu_294K
General Information Vapor Level Aqueous Level
IDNO 6001 ACEN 1.623583E-01 HREF -1.141830E+05
FORM C4H6 TCRI 4.873340E+02 GREF -1.682110E+05
CHEM C4H6 PCRI 6.313467E+06 SREF 2.246544E+02
MOLW 54.093 VCRI 2.094492E-04 CPRE 2.891333E+01
MATC 8800 CP -1.406283E+01
2.786379E-01
6.715268E-03
-1.221312E-04
4.200226E-15
HKF 0.0 0.0 0.0 0.0 -
3.391220E+02
1.745077E+06 -
1.952198E+06
STOI 1.0 HREF -1.198393E+05 VREF 0.000000E+00
GREF -1.881348E+05 ZRAC 2.750119E-01
SREF 2.982775E+02
CPRE 5.815640E+01
EQUA PVTCu_294KVAP=
PVTCu_294KAQ
The general information is the created pseudocompoiunt. In this case, it is a C4H6 molecule with a 54 amu
molecular weight. =The MATC is a material code identified by the software, and STOI is the stoichiometry of
this material (1 moles of 8800 or 1 moles of C4H6). The thermodynamic properties for the vapor and aqueous
species are as shown. Critical temperature is 487K (215C) and critical pressure is 6.31e
6
Pa (~63atm).
Your task, should you choose to accept it is to regenerate these pseudocomponents using the Lee Kesler and the
Cavett models. How do they differ?
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-13
5.3 Entering Pseudocomponents to a Stream
Many clients have their own PVT analysis models, and thus they can create pseudocomponent properties
directly. The Pseudocomponent entry option lets users enter their information. Users can enter two fo the
three properties, boiling point, molecular weight, or density. OLI software then uses one of three
thermodynamic models, API, Lee Kesler, or Cavett to calculate the critical properties. You will find that this
procedure is fairly simple, with a limited number of tasks.
How to do it
Create a new Stream
Name the Stream Crude to
Stills
Select Chemistry>Model
Options>Phases and turn on
Second Liquid phase
Type PC1 in a blank cell and
press Ctrl-Enter.
Enter the following data in the
subgrid that appears
Inflow name PC1
Inflow rate 100 moles
Thermo Method API
Boiling Point 20 C
Specific Gravity 0.72
Enter four additional
pseudocomponents using the
above procedure.
Change the H2O rate to 20
moles
Change Temperature to 15 C
Click on Add Calculation and
select Single Point
Calculate
View Report
The CTRL-Enter action instructs Analyzer to create a pseudocomponent
rather than look for a database species (pure component).
Pseudo-
component
Rate
(moles)
Method Normal Boiling
Point, C
Specific Gravity,
H2O=1
PC1 100 API 20 0.72
PC2 200 API 60 0.76
PC3 250 API 100 0.8
PC4 250 APi 140 0.85
PC5 180 APi 190 0.9
.
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-14
As with the PVT analysis, critical properties are created for the pseudocomponents also. Here is what the first
pseudocomponent looks like. Compare your results and see if they differ
_U9
General Information Vapor Level Aqueous Level
IDNO 6001 ACEN 1.603606E-01 HREF -1.070512E+05
FORM C5H4 TCRI 4.731703E+02 GREF 1.014195E+04
CHEM C5H4 PCRI 4.835700E+06 SREF 2.546778E+02
MOLW 54.64.0884 VCRI 2.478505E-04 CPRE 9.475090E+01
MATC 8501 CP -5.278970E+00
3.566437E-01
1.230597E-03
-1.445405E-04
1.239677E-15
HKF 0.0 0.0 0.0 0.0 -
3.808792E+02
1.923808E+06 -
2.199844E+06
STOI 1.0 HREF -1.170190E+05 VREF 0.000000E+00
GREF -1.337601E+04 ZRAC 2.852654E-01
SREF 3.263531E+02
CPRE 8.820565E+01
EQUA EQUA _U9VAP=_U9AQ
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-15
Follow-up example
As a last follow-up, we will run a whole fluid calculation. If we assume for the sake of learning that the case in
question is a gas-condensate-black oil fluid being produced from a newly developed field. The field produces
50,000 bbl/day oil and 3MMscfd gas. We have a whole fluid analysis that includes pure component data, a PVT
curve and pseudocomponents for the high ends. In addition, the new well produces 1000 bbl/day of brine. This
is what the data looks like (this is the real thing, so dont be surprised that it takes you a long time to work this
example).
Water Analysis Whole Fluid Analysis
Cations ppm Pure
Component Mole %
Assay
Na 2700 H2O 0.8 Vol % Temp, C
K 30 N2 0.32 1 175
Mg 169 CO2 0.106 10 195
Ca 3200 H2S 0.001 20 215
Sr 7.9 C1 49.55 40 245
Ba 6.6 C2 2.07 60 275
Fe 28 C3 2.48 80 300
Mn 1.1 iC4 0.50 90 315
Zn 1.8 nC4 1.51 95 325
iC5 0.60 99 345
Anions ppm nC5 0.83 100 350
Cl 10150 C6 0.97 Density@25 (g/cc) 0.80
HCO3 46 C7 1.15 Data type TBP
SO4 13 C8 1.10 Thermo Method API
C9 0.77 # of Cuts 5
Neutrals ppm C10 0.88
SiO2 12.7 Pseudocomponents
B(OH)3 38.3 Balance Mole% PC1 (mole%) 7.6
C10+ Assay 17.45 NBP, C 400
pH 4.7 PC1 7.6 MW 350
Density 1.01 PC2 6.4
Calc type pH &Alk PC3 3.1 PC2 (mole%) 6.4
NBP, C 450
MW 420
PC3 (mole%) 3.1
NBP, C 550
MW 630
For the Asssay,
Chapter 4 Analyzer Mechanics, Mixers and Water Analyses 5-16
Mixing the three inflow types, PVT, pseudocomponents,
and pure components
All three of the inflow types, pure component, PVT analysis, and pseudocomponents can be combined into a
single stream. We will show that here. You are asked to create a combined analysis, in which the lights are
defined by pure components, the middle-range is a PVT and two pseudocomponents are used to model the high
boiling point components.
1.000 190.0
10.00 195.0
20.00 210.0
40.00 220.0
60.00 235.0
80.00 250.0
90.00 265.0
95.00 275.0
100.0 290.0