Ryan and Kyle- RO

Experiment/Analysis
Abstract
The objective for the team was to run reverse osmosis experiments using the
DuPont membrane to see if it could separate NMP form water. If successful, the
wastewater from DuPont can be sent through their reverse osmosis system to be
purified for reuse. In order to run this experiment, the team needed to have a
method to accurately analyze the concentration of NMP in water at low
concentrations. The team looked into three pieces of equipment available in Rowan
Hall to analyze the samples. The refractometer was able to detect the NMP in the
mixtures but it did not give enough significant figures to distinguish between the
extremely low concentrations. The gas chromatograph was able to detect and
quantify the concentration of NMP but there was too much inconsistency between
samples. It was determined that the GC would need maintenance performed to
remove the errors. The ultraviolet visible spectrometer was the most consistent and
accurate analysis tool the team used. Calibration curves were made using standards
with concentrations similar to the feed and permeate concentrations of the RO. The
team ran an experiment using the DuPont membrane and a feed concentration of
0.15% NMP. Analysis of the streams using the UV-vis showed a rejection of NMP of
99.98%. The team concluded the membrane was able to purify the NMP-water
system and the use of this membrane to purify the wastewater at the DuPont
facility was a feasible option.

Refractometer
The refractometer was the first piece of equipment tested to see if it would be able
to accurately analyze the NMP and Water samples. This was a piece of equipment
which we knew was working properly and had a fairly simple method. There was
one doubt in this piece of equipment; we did not know if it would be accurate
enough at the low sample concentrations that we were dealing with.
Once a sample is placed in the receptacle, a beam of light is passed through the
sample. Depending on how the light bends and/or slows down a refractive index is
calculated for the sample using the Brix scale. On the machine that was used in our
analysis, all of scaling was done by the machine and a refractive index value was
digitally displayed.
Four samples, all with a different weight percent NMP were analyzed using the
refractometer. The four values that we tested and the results can be seen in Table
1.

Table 1 Refractometer calibration curve data

wt% NMP
50
1
0.5
0.1

Refractive Index
1.417
1.333
1.332
1.331

Using the above data a calibration curve was plotted for the refractometer, which
can be seen in Figure 1.

Refractometer Results
1.42
1.4
1.38
1.36
Refractive Index

1.34
1.32
1.3
1.28
0

10

15

20

25

30

35

40

45

50

Wt% NMP

Figure 1 Refractometer calibration curve

After looking over the results, it was concluded that the refractometer was not a
viable option for analyzing low concentration samples. The reason for this is
because the machine does not calculate enough significant figures to be able to
differentiate the low concentrations from each other. This can be seen by how close
together the results are for the three low concentrations that were tested.

Gas Chromatography
Gas chromatography (GC) is one of the most accurate laboratory analysis tools used
today. It is able to differentiate and analyze samples with varying concentrations.
With expected concentrations from the reverse osmosis process ranging from 0.15%
to 0.0015%, gas chromatography is an ideal analysis tool for this process.
The team was initially told, the gas chromatograph at Rowan University had not
been used often and has not had maintenance for many years. The team first had to
get the machine up and running before testing could be done. The computer system
attached to the GC was down and would not turn on. After following all of the wires
and cables going in and out of the computer the team found the power strip circuit
breaker had been tripped. After resetting the circuit breaker, the computer turned
on. The next issue that arose was the computer system required users to sign in.
The account name was already in the system but the team had no password. After
looking through the system manuals and Rowan experimental lab procedures the
team was unable to find the password. Moving around the equipment, the team
found a sticker on the computer which had the information required. After finally
logging into the computer another issue arose. The mouse attached to the
computer was not functioning and there was no way to navigate the system
efficiently. With help from Chris, a Rowan Hall lab technician, the team found
multiple mouses which could be used. None of the other mouses solved the
problem. Using the keyboard, the team was able to navigate through the computer
settings to the mouse settings. From this menu it was found the computer was
using the wrong driver for the mouse that was attached. After changing to the
correct driver, the mouse could be used.
The next step was to learn how to navigate and operate the GC control program.
The team used a Rowan experimental lab procedure write as a guide through the
program. The document allowed the team to get a basic understanding of how to
use the program to run samples with the GC. However, the document did not have
any information on how to change settings on the machine or how to use the data
analysis tools in the program. The team decided to create a writeup of a procedure
to use the GC which would include this information.
With a working knowledge of the program the team could begin running the GC. The
first thing which the team noticed, was the helium carrier gas was empty. Chris put
in an order for a new tank. Once the new tank came in, the system lines were
reconnected. Chris and a lab technician form the Chemistry Department went
through the GC settings and set them properly to allow the team to run the GC and
get accurate results.
In order to see if the GC was working properly, the team decided to run a method
which was already loaded in the system. This method was used the last time the GC
was operational for analysis of methanol and water samples from one of the senior
labs. This method gave accurate results the last time it was used. The first goal was

to run samples to create a calibration curve to see if the GC could be used for that
simple system. With the help of another Rowan professor, Jesse VanKirk, standard
were made with known weight percentages of methanol and water. The standards
made were 90%, 78.6%, 68.5%, 50%, 24.9% and 9.4%. The samples were run in the
GC and the results can be seen in Table 2. The full GC data files can be found in
APPENDIX XX.
Table 2 Methanol raw GC data

Sample
Wt%
68.5
68.5
90
90
24.9
24.9
9.4
9.4
78.6
78.6
50
50

GC Wt
%
73.4912
71.0637
2
89.0411
9
89.4222
6
33.4591
43.9884
3
9.24485
9.25645
79.2251
4
78.8602
7
45.4059
4
44.3746
8

A calibration curve was created using the data from the methanol method. Figure 2,
shows the calibration curve which was generated. At high and low concentrations of
methanol, the GC gives accurate and consistent results. The issue was between the
concentrations, the GC was not able to generate accurate or precise concentrations.
In order for a proper calibration curve to be generated, the GC needs to give
consistent values. The calibration curve allows for there to be some error between
the real concentrations and the concentrations given by the GC but if the GC cannot
give the same value every time the same sample is run through the system then
there is no point to run the experiments.

100
90

f(x) = 0x^2 + 0.8x

R = 0.99

80
70
60

Actual wt%

50
40
30
20
10
0

10

20

30

40

50

60

70

80

90

100

GC wt%

Figure 2 Methanol GC calibration curve

In order to determine if there was an issue with the GC itself or if there could have
been errors within the method, the team decided to focus on the NMP and water
system. This was the overall goal of getting the machine running properly at the
beginning of the semester. In order for the system to separate NMP and water, the
specifications for the GC needed to be changed. A new method was created to
separate the NMP and water. The major difference between the NMP method and
the methanol method was the temperature which the oven was set at. The boiling
point of NMP is higher than methanol so the oven temperature was changed from
110C to 210C. This change makes sure that the NMP and water mixture will all
vaporize and be sent through the column.
The team created new standards using NMP and water to create a calibration curve
for the new NMP method. The standard created were 10.1%, 5.07%, 1.1%, 0.54%,
0.133%, and 0.0436%. Figure 3, shows the calibration curve generated from running
the samples through the GC using the NMP method. The issues that occurred with

the methanol and water system also appear with this system. The GC is not able to
give reproducible values for the runs. In order for the GC to be a viable analysis tool
the variability between samples needed to be eliminated.
12

10

Actual wt%

GC wt%

Figure 3 Calibration curve for the initial run of NMP standards

In order to troubleshoot this issue, Agilent Technologies was contacted. Agilent

Technologies is the company which makes the GC and equipment the team used in
this experiment. They mentioned many things that could be contributing to this
reproducibility issue. One of the comments was general maintenance needed to be
done on the machine because it has not been run in so many years. General
maintenance consists of cleaning out and replacing certain parts of the machine
that could have worn out or have broken, also general cleaning of the machine and
parts in the housing. Another comment was replacing some of the more common
parts which are known to go bad over time. These parts include; the liner, the
septum, the gold bearing seal, and the split vent trap. They also suggested that the
team clip the end of the column by 6 to 12 inches. This would not affect the results
because the column is very long but they explained there could be a large amount

of buildup of undesired material in the beginning of the column which could be

causing the issues. Besides general maintenance there are many variables that can
be changed to make the machine produce more repeatable data. Reducing the
injection volume from 1 microliter to 0.5 microliter was suggested because our
solution contains water, when water solutions are vaporized they expand
tremendously which may oversaturate the liner. Making this change helped in the
consistency. Another variable is the injection path, which can be split or splitless.
Having a splitless pathway sends the entire injected sample into the column, a split
pathway only sends a ratio of the sample into the column to be analyzed (this
allows the peak to be more crisp). The ratio can be adjusted in the GC computer
program, which is another variable that needed to be optimized. Figure 4, shows the
difference in accuracy which was achieved by changing the split ratios. The team
found a split ratio of 30:1 gave the most consistent and repeatable concentrations.
0.6

0.5

0.4

GC NMP Weight Percent

0.3

0.2

0.1

0
50:1

30:1

10:1

Figure 4 0.54% NMP sample tested with different split ratios

The team then ran more standards through the GC using the new optimized split
ratio. Figure 5, shows the calibration curve with these new settings. The runs
became slightly more reproducible but they are still not consistent enough for
analysis of our lower concentrations.
0.6
f(x) = - 0.52x^2 + 1.49x
R = 1

0.5
0.4

Actual wt%

0.3
0.2
f(x) = - 6.62x^2 + 2.01x
R = 0.96

0.1
0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

GC wt%

Figure 5 Calibration curve for GC using 30:1 split ratio

After speaking on the phone with Agilent, a service order was issued for the
machine (#8100341061). The team asked for quotes regarding the replacement
parts described above to see if they could be contributing to the issue. The quote
for these parts and the quote for the GC maintenance can be seen in APPENDIX XX.
The team had the parts ordered so they could be replaced. The part numbers are
the following:
5 pack of Liners 5190-3164
Gold seal 5188-5367
Split Vent Tray Filter 5188-6495
Once the parts came in, the team looked into how to install and remove the old
parts of the machine. It was found that procedures for replacing all of the parts
could be found in the operation manuals for the GC. The team then turned off the
GC and began to replace the old parts. The new liner was optimal for water systems
because it had a high expansion factor. The team also replaced the septum, where
the needle is inserted. When replacing the gold seal, the column had to be
removed. Since it was out, the team decided to trim the end of the column. About
two inches were cut off the end of the column before it was attached to the GC.
Once the parts were replaced the team ran a few more samples through the system

0.45

0.5

to see if there were was any improvement in the consistency. The samples did not
show any improvements over the trials which were done before the parts were
replaced.
The last option the team looked into was a temperature ramp for the system. By
starting the temperature low and slowly increasing it. There should be better
separation of the species since they will boil off at different rates. ADD IN
TEMPERATURE RAMP INFORMATION!!!!!!!
After going through all of the recommendations and tips given to the team from the
calls to Agilent, replacing all of the parts, and editing the method, there was not a
significant improvement to the reproducibility of the GC. Taking all of these factors
into consideration. The team decided to look into getting Agilent to come and
perform maintenance on the GC. The maintenance should eliminate the errors and
improve the results so the GC can be used to analyze the samples.

GC Operation
GC Operation
1. Turn on Computer and log in to the computer using password: 3000hanover
2. Turn on the Gas Chromatographer by pressing the light grey button on the
bottom left of the machine. Once the GC is on the display will light up and it
will run through the startup process.

3. From the desktop, open the program, Instrument 1 Offline.

4. Once the program initiates choose the correct method in top dropdown menu.
Select STANDBY.M from the menu. Once the method is selected close out of
the program.

5. Ensure that the gas tanks are open and set at the correct pressures. To open
the tanks, fully turn the large knob on the top of the canister. To adjust to the
correct pressure use the small blue knob. Turn clockwise to increase the
pressure. Adjust the pressures until it is above the required pressures for
each gas. These values change depending on the method which is being run.

6. From the desktop, open the program: Instrument 1 Online

7. Once the program initializes, click on the Oven button to open the adjustment
window for the method.
8. Go to Inlets tab. Make sure the drop down menu on the right side of the
window is set to FRONT. The boxes for Heater, Pressure and Total Flow should
all be unchecked. If they are not click on the box to deselect that option.
Once the boxes are unchecked click on the Apply button on the right side of
the window.

9. Allow time for GC to warm up. To check on the status of the GC press the
Status button on the GC control panel. This screen displays all of the errors or
warnings that need to be addressed. If messages continue to appear. Look in
the operation manual for troubleshooting for the error.
10.Once the GC has reached the settings from the Standby Method, choose the
method to be run. Go to dropdown menu at the top of the screen and select
the correct method.
11.Allow GC to warm up to the new temperatures and adjust to the new settings.
If errors for Front Flows appear on the GC display, repeat steps 7 and 8
above.
12.Once the GC is ready it will indicate on the GC display that a Prep Run needs
to be done. Press the Prep Run button on the front of
the GC panel. After the Prep Run, the display will
indicate that it is ready for an injection.
13.Take the syringe out of the box and remove the tube
protecting the needle. Use the 5 L syringe. Take the
sample and insert the syringe. Take out between 0.5
and 1 L of sample depending on the concentration
and method that is being run.
14.Insert the needle half way into the septum at the
inlet port. Continue to fully insert the needle as the
plunger is depressed. Immediately press the Start
button on the GC control panel and remove the
syringe.
15.When the method is finished running, data will
appear on the screen. Data can be printed or edited
under the Data Analysis drop down menu in the top
left corner of the program. The first page displays
the graphs of the results. The following pages give
analysis of each of the graphs. The TCD can usually
be found on one of the last two pages of the report.

NMP Method Instrument Values

NMP.M

Valves
o Configure
Valve #1 Other
Inlets
o Back
Mode: Split
Gas: He
Heater: 250 C
Pressure: 32.32 psi
Total Flow: 112 mL/min
Split Ratio: 30:1
Split Flow: 107
o Front
Mode: Split
Gas: He
Heater, Pressure, Total Flow- OFF
Columns
o Column 2
Mode: Const Pressure
Inlet: Back
Detector: Back
Next psi: 32.32
He Flow
Pressure 32.32 psi
Flow: 1.9 mL/min
Average Velocity: 48 cm/sec
Oven
o Oven ON
o Setpoint: 225 C
o Oven Configuration
Maximum: 225 C
Equilibration min: 3.00
o Oven Ramp
Next: 220 C
Hold: 2.5 min
Post Run: 100 C
Hold min: 0.00
Detectors
o Front
Heater: 250 C
H2 Flow: 40 mL/min
Air Flow: 450 mL/min
Makeup Flow: He, 45

Back

Aux
o

Flame- ON
Electrometer- ON
Lit Offset: 2.0
Heater: 250 C
Reference Flow: 20 mL/min
Makeup Flow: He
Const Col + Makeup: 10 mL/min
Negative Polarity- OFF
Filament- ON

Heater 50 C
Turn OFF if error appears on GC

UV VIS method/ data

The UV-Vis Spectrophotometer was one of the better options for analyzing the
concentration of NMP in water. This piece of equipment measure the intensity of
light that passes through a sample. It generates an absorbance value by comparing
the sample to a reference (distilled water).
Before the team could start running the samples in the Spectrophotometer we
needed to determine what wavelengths NMP absorbed light at. This was done by
running samples and determining what wavelength was generating the best and
most consistent data. This point happened to appear where the wavelength vs.
absorbance graph was smooth with a negative slope. It is also noticeable that there
are a lot of jagged sections on the graph, this is an example of a wavelength which
would not be consistent. This graph can be seen below.
GRAPH
It was determined that the best wavelength was between 220 and 230 nanometers
based off the above information. Table 3 and Table 4, show what concentrations we
tested and the absorbance values we obtained.
Table 3 High concentration data for UV-vis calibration curve

NMP weight
Percent
Run 1
Run 2
Average

0.078
1.337
4
1.332
3
1.334
85

0.095
4
1.457
1
1.452
7
1.454
9

0.120
6
1.613
5
1.611
6
1.612
55

0.154

0.206

1.701
4
1.716
6

1.764
6
1.759
2
1.761
9

1.709

Table 4 Low concentration data for UV-vis calibration curve

NMP weight
Percent

0.0177

Run 1

1.2102

Run 2

1.2108

Average

1.2105

0.011
6
0.6715
2
0.6696
5
0.6705
85

0.004
99
0.3174
4
0.3208
3
0.3191
35

0.001
49
0.0769
04
0.0763
18
0.0766
11

0.05
1.869
5
1.902
7
1.886
1

All of the values shown above acted as our premade standards. The weight
percentages that we chose represent numbers that we expected to get from our RO
experiment, which will be discussed further on in the report.
Using the data from the premade samples two calibration curves were made; one
for concentrations near the feed (0.15 wt%), and another for predicted permeate
concentrations which are very low. Making two calibration curves instead of one,
allowed us to have a more accurate trend line (equation) for the concentrations that
we were interested in. Figure 6 and Figure 7, show the calibration curves for the
high and low concentrations respectively.

2
1.8
1.6

f(x) = - 33.44x^2 + 12.8x + 0.54

R = 1

1.4
1.2

Absorbance [Au]

1
0.8
0.6
0.4
0.2
0
0.06

0.08

0.1

0.12

0.14

0.16

NMP Concentration wt%

Figure 6 High concentration calibration curve for UV-vis

0.18

0.2

0.22

2
f(x) = - 762.1x^2 + 75.96x
R = 1

1.8
1.6
1.4
1.2

Absorbance [Au]

1
0.8
0.6
0.4
0.2
0

0.01

0.02

0.03

0.04

0.05

0.06

NMP Concentration wt%

Figure 7 Low concentration calibration curve fot Uv-vis

A detailed method of how to run the machine can be found below.

1.
Make sure the computer is turned on and the Spectrophotometer is also turned
on.
a.
The power button for the spectrophotometer is near the bottom behind the
cuvette holder
2.
Open the UV-Vis online program on the desktop. Make sure you choose
online.

3.
Once the program is open, wait for it to initialize and set up. This is the screen
that will appear.

4.
This is the main screen of the program. Before any samples are run, a
literature search should be done to see what range of wavelengths is absorbed by
the compound you are using.
5.
We can now begin to run samples in the machine, first we will run samples to
see if the literature value you obtained is correct.
6.
7.
Click the setup button on the main page. The dialog box on the left is what will
pop up
8.
First make sure that there is no background correction and the data type is
absorbance.
a.
Where is says Use Wavelengths you can input the wavelengths you found in
literature; I would recommend adding a few others above/below literature values.
These values will appear in a chart layout with absorbance numbers for the
wavelengths you input.
b.
Where it says Display Spectrum you should input a range of wavelengths
that you seem fit, similar to the ones in literature. This data will be graphed;
absorbance vs. wavelength.

9.
We can now prepare to run the analysis. Locate the glass cuvettes (usually in
the top drawer under the computer). Clean with acetone and dry. Fill with distilled
water. Place cuvette in sample holder. *NOTE the cuvettes have two clear sides
and two frosted sides; Make sure the light will shine through the clear sides when
placed in holder. Do not get fingerprints on clear sided this will impair results (use
Kim wipes).

10. The distilled water is going to act as our reference sample. Click Blank, it will
take about 20 30 seconds to get results.

11. The absorbance should be zero or very close to zero. Remove the cuvette.
Clean with acetone and dry. Fill cuvette about full with sample. Place in sample
holder in the same way presented in step 9. Now hit the sample button which is
right below Blank
12. It will take 20-30 seconds to run, and then results will pop up. The screen will
look similar to the screen below after multiple samples are run.
a.
More wavelengths will appear in the chart depending on how many you
entered in the setup dialog box.
b.
You are able to enter in name for you samples as seen to the right just by
clicking and typing.

c.

You should run at least 2 tests for each sample.

13. Make sure that in between samples you clean and dry the cuvette thoroughly.
14. Once all samples are run you can transfer data to excel. *NOTE this
computer is not connected to internet and only takes floppy disks. You may just
have to type in the data to your own laptop.
15. A calibration curve can be generated using the data you collected. Make sure
to select a logical range for your curves.
16. You are now ready to run unknown samples.
17. Make sure to turn off machine when you are done or the light will burn out.

Reverse Osmosis Experiment

The process DuPont is currently running does not reuse the wash water; the
wastewater is disposed of and new water is supplied. The new water is purified
using a reverse osmosis (RO) system where there are three membranes in parallel.
The teams goal was to see if it was possible to avoid the wastewater disposal and
determine if it would be possible to reuse the water. A spiral wound membrane was
purchased from GE Water and Process Technologies. The specific model is
AG2521TM, the spec sheet for this membrane can be found in the appendix, this is
membrane the DuPont currently uses in the RO system they run the new water
through.
The wastewater that DuPont creates has about 0.15 wt% NMP. This is the
concentration that would be fed into the RO system and will be the basis for the
team's experiment. The purpose of running a reverse osmosis experiment was to
determine if it would be feasible to separate NMP out of the wastewater solution.
This was done by running the RO system and analyzing the permeate stream and
feed stream using the UV-Vis calibration curves. Through this analysis,
concentrations of the feed and permeate of the RO system could be calculated.
These concentrations could then be used to find the percent rejection of NMP for the
membrane.
The RO system was run at a pressure of 300 psi and had a feed flowrate of 1.75
GPM. A more comprehensive layout of the variables taken into account can be
seen in Table 5. The pure water represents the purge/prime run, and the 0.15wt%
represent the system variables at the two times we the streams were sampled.

Table 5 Reverse osmosis experiment raw data

Feed
Soluti
on

Conducti
vity Feed
[ms/cm]

Perme
ate
Flow
[GPH]

Retent
ate
Flow
[GPM]

Permeat
e
Conducti
vity
[us/cm]

Feed
Flow
[GPH]

Feed
Flow
[GPM]

Pressu
re [psi]

0.415

24.17

1.966

0.948

26

1.75

300

0.41

22.21

2.01

0.82

25

1.75

300

0.412

22.23

2.008

0.804

25

1.75

300

Pure
Water
.15 %
NMP
.15%
NMP

Results
The RO system was run for about 30 minutes. At this time a sample was taken from
the permeate stream and the feed stream. Five minutes after the first sample a
second sample was taken from both the permeate and feed streams. A sample of
the water source was also taken and used as a blank/reference when using the UVVis. The absorbance shown below are the values given by the UV-Vis. Using the
equations generated from the calibration curves discussed earlier, concentrations
were solved for. These values can be seen in Table 6, along with the concentration
range which is representative of what calibration equation was used.
Table 6 Reverse osmosis experiment UV-vis data and calculated concentrations

Sample

UV VIS Measured [Au]

Calculated
Concentration

Calibration
Curve Used

Feed

1.762201

0.203

High

Permeate 1

0.278066

0.003

Low

Permeate 2

0.24032

0.003

Low

Retentate 1

1.94770

N/A

N/A

Retentate 2

1.95470

N/A

N/A

With the concentrations of the permeate and feed calculated, a percent rejection
was calculated using the following equation:

%R= 1

Permeate Concentration
100
Feed Concentration

The experiment resulted in a 99.98% rejection

Conclusions
Throughout the process of determining how to analyze our samples; it was
discovered that the refractometer could not differentiate at low concentrations.
After working on the GC for about one and a half months, it was concluded that
maintenance from Agilent is necessary and currently being looked into. The piece of
equipment that was used to analyze our samples was the UV-Vis spectrophotometer.
This piece of equipment was deemed accurate and was able to analyze our sample
and produce reliable and consistent data. In the long run, the RO experiment acts
as a preliminary test to see if our original idea of reusing the waste water was
feasible. A rejection of 99.98% supports the initial idea and suggests that it is
feasible.

Future Work
Now that we confirmed the DuPont reverse osmosis and membrane system is able
to reject NMP to an acceptable extent, the team can continue to perform RO
experiments and analysis. Future experiments would be used to more accurately
model the DuPont wastewater stream and how the RO system separates the
components. Experiments would include testing the membrane with different
concentrations of NMP and running the system with other binary mixtures to see
how the membrane separates the other chemicals in the waste water.
Once the gas chromatograph has the maintenance done, more complex systems
can be run through the membrane. The GC will allow the team to find the exact
concentration of multiple species in the mixture. Using this we can accurately model
the DuPont wastewater stream, run the reverse osmosis system and analyze the
concentrations of the chemicals in the purified water.

Appendix