Separation of Acetonitrile from Hazardous Waste

Honors Senior Thesis

**********************************
PASS WITH DISTINCTION
Kristi Folsom
University Honors 451
Washington State University
April 18, 2000
ABSTRACT
This paper will discuss the collection of parameters necessary for
separation of acetonitrile from hazardous waste by rotary evaporation and
spinning band distillation using parameters from previous trials for acetone and
ethyl acetate performed by Ronald Newton, Instructional Laboratory Supervisor
at Washington State University Department of Chemistry. Analysis by nuclear
magnetic resonance spectroscopy, gas chromatography, infrared spectroscopy,
and mass spectrometry were used to determine the purity of the final product by
testing for the presence of waste components. At the completion of this
research, 75% of the processed waste was recycled, the other 25% was sent
offsite for hazardous waste processing.
INTRODUCTION
In the past chemistry and research laboratories produced large volumes of
hazardous waste product. Waste was routinely bottled, labeled and shipped for
disposal. Most laboratory disposal continues assuming that waste recycling is
too costly (Fenton 1986). However, solvent recovery is a simple task. It provides
researchers the opportunity to reduce the amount of hazardous materials
entering the waste stream as well as reducing annual costs through the use of
recycled solvents thus saving new chemical purchases and shipping costs.
Solvent recycling can take place either on or offsite. A problem for many
research facilities is that off-site recycling is available only in limited areas, and is
typically restricted to recycling of nonhalogenated solvents for fuel (Valkenburg
1993). In 1997 Washington State University began onsite recovery and recycling
of usable solvent components from hazardous waste produced by researches in
both Organic Chemistry and the Biochemistry departments. Onsite recovery
allows recycling of both halogenated and nonhalogenated solvents without the
worries of transportation off site for recycling (Valkenburg 1993).
Washington State University is presently collecting data for recovery of the
ten basic solvents most utilized within the Chemistry and Biochemistry
Departments. Data collection of parameters for acetonitrile was obtained by
processing hazardous waste received in the solvent recovery laboratory located
in the Organic Chemistry Division of the Chemistry Department. The data
collection process involved finding the appropriate temperature ranges in the
rotary evaporator which would cause acetonitrile to vaporize and be collected in
the receiver flask. The collected acetonitrile was then processed through the
spinning band distillation apparatus a multiple of times until the appropriate
collection range was determined. To document the process of purification,
samples were analyzed by mass spectroscopy, gas chromatography, infrared
spectroscopy, and nuclear magnetic resonance spectroscopy.
METHODS AND MATERIALS
The solvent recovery laboratory used was equipped with two walk-in
hoods containing chilled water units. One hood houses the Labconco vertical
condenser three-liter rotary evaporator, while the other hood contains the BIR
Industries 9600 Series Spinning Band Distillation System, which has a three-foot
spinning-band column. The laboratory is also equipped with a flammable storage
2
container and cabinets which function to hold a wash area and vacuum pumps
(Newton 1999).
The hazardous waste material used for data collection was waste received
in the solvent recovery laboratory of the Organic Chemistry Department. Once
received, the chemical composition of the material in the bottle was recorded
along with the boiling points. The boiling points were analyzed to ensure that an
adequate range was present for separation. The waste was then stored in
flammable waste storage cabinets until processing.
Determining the Parameters for Rotary Evaporation
To determine the temperature range for separation of acetonitrile on the
rotary evaporator, data from the separation of acetone was used. The boiling
point of acetone is 56C and can be separated in the rotary evaporator at a bath
temperature of 23C. The bath temperature for the separation of acetonitrile was
set at 28C for initial testing. The temperature was then adjusted on subsequent
runs until desired collection results were obtained.
Determining the Collection Range for the Distillation Apparatus
The BR Industries Spinning Band Distillation apparatus used in the solvent
recovery laboratory must be programmed with the correct parameters to obtain
separation of the undesired waste and the collection of the desired solvent.
Previous data collection by Ronald Newton on ethyl acetate was used to program
the still for the initial trial run of acetonitrile. The collection ranges for ethyl
acetate which boils at 77C was adjusted for the estimated collection ranges of
acetonitrile (BP= 81C). The settings entered for the trial run are seen below.
3
TABLE 1
Test Parameters for Distillation
Ethyl Acetate Acetonitrile
Initial Mantle Rate 35 36
Motor on Temp 30 30
Equilibration Hours 0 0
Equilibration Mins 15 15
Open Cut 1 30 30
Close Cut 1 72 78
Mantle Rate 30 31
Reflux Ratio 10 10
Add Cut 2 Yes Yes
Equilibration Hours 0 0
Equilibration Mins 0 0
Close cut 2 78 82
Mantle Rate 28 29
Reflux Ratio 40 40
Add Cut 3 No No
End Run Temp 80 83
This data is for an altitude of 2500 feet
The parameters were adjusted until complete separation had been
obtained. The correct collection ranges were then programmed in to the memory
storage unit within the computer of the solvent recovery system.
Testing for Usable Drying Agents
To test for a drying agent to remove the water from acetonitrile, two
popular drying agents were chosen and tested: sodium sulfate, and magnesium
sulfate. Infrared (IR) spectroscopy was performed on acetonitrile known to
contain water as a standard. Five grams of each agent was added to twenty
milliliters of the acetonitrile and an IR spectroscopy was taken. The process was
repeated adding five more grams of drying agent and obtaining an IR spectrum
each time.
Testing for Purity
4
A Gas Chromatography Mass Spectrometer (GCMS) was used to
document the progress of separation. Heavy contamination of the acetonitrile
prevented obtaining a reading prior to rotary evaporation. After rotary
evaporation and distillation, samples were sent through the GCMS to determine
the chemical contents. A sample of reagent grade acetonitrile was also run
through the GCMS for use as a standard.
RESULTS
Correct Settings for the Rotary Evaporator
To successfully collect acetonitrile in the receiver flask, the bath
temperature of the rotary evaporator must be set between 26-28C.
Experimentation determined if the waste has a high water content the bath
temperature must be set at either 27C or 28C. For separation of acetonitrile
from waste containing low percentages of water and high percentages of low
boiling components the bath must be set at 26C to prevent rapid boiling and
collection of undesired materials.
Correct Parameters for the Distillation Apparatus
Data collection revealed the following parameters were most efficient
to separate acetonitrile from all other contaminants in the waste bottles at an
altitude of 2500 feet:
5
TABLE 2
Correct Parameters for Distillation of Acetonitrile
Acetonitrile
Initial Mantle Rate 36
Motor on Temp 30
Equilibration Hours 0
Equilibration Mins 15
Open Cut 1 30
Close Cut 1 76
Mantle Rate 31
Reflux Ratio 10
Add Cut 2 yes
Equilibration Hours 0
Equilibration Mins 0
Close cut 2 80
Mantle Rate 29
Reflux Ratio 40
Add Cut 3 No
End Run Temp 81
This data is for an altitude of
2500 feet
Finding a Usable Drying Agent
Of the three drying agents tested it was determined that only calcium
chloride successfully removed water from the acetonitrile. Adding CaCb to
acetonitrile before distillation resulted in removal of nearly all water present in the
waste, allowing successful distillation to take place.
DISCUSSION
To begin the process of recycling acetonitrile, waste was collected from
the laboratories within the chemistry department. Once received in the solvent
recovery laboratory, the contents of the waste bottles were read from the
hazardous waste labels affixed to each bottle and recorded into the incoming
waste logbook and assigned a number for record keeping purposes.
6
After ten bottles of acetonitrile had been collected---enough to begin
experimentation---a bottle was chosen to begin the process. The boiling points
were checked to ensure there were no components of the waste, which had
boiling points within 5-10
o
C of acetonitrile (81.6C). This is a necessary step
since all separation is done by temperature. If any components of the waste had
boiling points in the range of 71 C-91 c they would not separate out during rotary
evaporation or distillation.
The next step was to begin trials on the rotary evaporator which was used
to remove the higher boiling impurities before processing in the still. In order to
determine a bath temperature to begin trials, the data for separation of acetone
was used. During trials in November of 1997, Ronald Newton, who began the
solvent recycling program at WSU, determined that acetone which boils at 56C,
requires a bath temperature of 23C for separation. This data was used to
estimate a required bath temperature setting of 28C to collect acetonitrile. At
28C, all components of the waste, which boil below 90C, should be drawn, or
come across to be collected in the receiving flask (see chart one for
components) .
It was estimated that approximately 90% of the material would be
collected if the run was successful. The run took two hours to complete and as
expected 90% of the liquid had been collected. The remaining waste was bottled
as still pot residue and stored. The collected solvent was stored in a four-liter
bulk storage container.
7
Although the run was successful in collecting the desired solvent, during
collection the solvent was seen to condense near the top of the condensing coil
enabling high boiling impurities to condense with the desired low boiling solvents
and collect in the receiving flask. In an attempt to prevent this, the second run
was performed with a water bath temperature of 27C. This run proved
successful in collecting the solvent but also showed condensation at the top of
the coil. When the water bath temperature was reduced to 26C, the
condensation level was reduced to the middle of the coil as intended, and
successful collection of the low boiling solvents was obtained.
A problem arose with an attempt to process bottle two with a bath
temperature of 26C, because bottle two had a water content of 56.5% (see chart
1). Acetonitrile is known to have a strong azeotrope with water, such that the
water was preventing the acetonitrile from turning into a vapor and condensing
on the column. In order to solve this problem, the water bath temperature was
raised to 27C, which proved successful and still allowed the liquid to condense
at the middle of the column as desired.
This data along with subsequent trials of 18 bottles of acetonitrile waste
revealed that the best collection results were obtained when the rotary
evaporator was set to a bath temperature of 26C. However if the waste has an
extremely high water content (50% or higher), the bath temperature should be
raised to 27C to achieve the desired collection of acetonitrile.
Once processed, the contents of the receiver flask from bottle two was
stored with the collected solvents from bottle one and a GCMS was performed on
8
the contents. The results of the GCMS showed Acetonitrile was present along
with the other expected low boiling impurities such as dichloromethane (Figures
1 &2). Subsequent tests on the collected solvents from the remaining bottles
revealed similar results.
Once eight liters of solvent had been collected from the rotary evaporator,
trials began on the spinning band distillation apparatus. The first trial run used
the collected solvents from the first four bottles of processed waste. Bottles three
and four contained the same components as bottle one, while the components of
bottle two were different (see chart 1). The collected acetonitrile was poured into
the distillation flask. Boiling sticks and a temperature probe were added and the
system was sealed. The memory storage unit on the still was programmed for a
trial run based upon the known values for distilling ethyl acetate found by Ronald
Newton during previous testing. The values entered into the computer can be
seen in table one.
The entire distillation took five days to complete. On the third day the
probe temperature read 77.5C. This value indicates that the boiling point of
acetonitrile at an altitude of 2500 feet is actually 77.5C not the literature value of
82C. While this first distillation was successful it was necessary to adjust the
settings of the still based on the boiling point of Acetonitrile at 2500 feet. This
adjustment further ensured the purity of the distilled Acetonitrile by only collecting
components that boil at or near 77.5C.
The second trial run on the distillation apparatus was performed on the
contents of bottles 5-8. The parameters programmed into the memory storage
9
unit can be seen in table two. The close temperature of cut one was altered to
76C, which would send all impurities that boil below acetonitrile into the forerun
barrel. Cut two was modified to end at 80C which prevented all high boiling
impurities from collecting in the collection barrel with the desired acetonitrile.
Ending the run at 81C instead of 83C further prevents transfer of undesired
materials and allows the distillation to be completed in a more timely manner.
This run however, proved to be unsuccessful. In an attempt to gain
separation the still was restarted under the same parameters. Unfortunately no
separation occurred. The acetonitrile in this run boiled at 72C indicating the run
failed due to impurities lowering the boiling point of acetonitrile, thus preventing
separation. A Nuclear Magnetic Resonance Spectroscopy was performed on the
contents of the forerun barrel. The spectrum revealed contamination of
substances other than acetonitrile as well as an extremely high water content
(Figures 10 & 11). A run on the gas chromatograph was also performed. The
run showed contamination with a substance having a boiling point extremely
close to that of acetonitrile (Figure 14). This contaminant was suspected to be
affecting the run on the still. The contents of bottles 5-8 were examined for
possible contaminants.
After examination of the contents, it was hypothesized that diphenyl
hydrazine from bottle seven was contaminating the solution. To test this
hypothesis, benzaldehyde and acetophenone were added to small samples of
the acetonitrile from the failed trial. If diphenyl hydrazine were the contaminant,
the aldehyde added to the acetonitrile would react with the diphenyl hydrazine to
10
form diphenyl hydrazone, which would form a precipitate, eliminating the
contaminant from the solution. A small precipitate was seen in the
acetophenone, while none was seen with benzaldehyde. The precipitate seen in
the addition of acetophenone was filtered out and another run was performed on
the gas chromatograph. A small part of the second peak was eliminated,
however this did not confirm diphenyl hydrazine as the contaminant (Figure 15).
Unable to confirm the contaminant preventing separation, the sample was
placed in bulk storage containers until a new hypothesis could be developed. In
the mean-time a fourth distillation trial was performed on the contents of bottles
9-14. The still was once again set at the parameters seen in table two.
However, on this run the acetonitrile was found to boil at 73.7C---again lower
than expected, and no separation was obtained.
A sample was taken from the forerun barrel and run through the infrared
spectrometer (IR). The spectrum showed a peak at 3531.8 cm-
1
indicating high
water content (Figure 17). The sample was then dried using calcium chloride, a
known drying agent, and another IR was performed. This spectrum showed no
water peak (Figure 18). To test whether calcium chloride would successfully
remove water from the acetonitrile, solving the distillation problem. In order to
begin distillation eight liters of acetonitrile were dried using calcium chloride.
While attempting to dry eight-liters of acetonitrile with calcium chloride, a
reaction between calcium chloride and the solution occurred. The reaction
resulted in the formation of two layers with acetonitrile being the less dense top
layer. The bottom layer was a dense viscous layer. Samples were taken from
II
both layers for analysis on the IR. The top layer proved to be dry acetonitrile
(Figure 19) when compared to the spectrum of reagent grade acetonitrile (Figure
16), while the spectrum of the bottom layer was unable to be analyzed due to the
unreadable spectrum. The bottom viscous layer was determined to be the
contaminant preventing distillation and the top layer was filtered off and stored for
later processing on the still. In order to completely dry eight-liters of acetonitrile,
nearly one kilogram of calcium chloride was used.
Before attempting the run on the still, samples from each four-liter bottle of
dried acetonitrile were run on the IR. Both spectrums (Figures 19 &20) revealed
no evidence of a water peak. Once the dry acetonitrile had been placed in the
distillation flask, the distillation apparatus was started under the parameters of
table two Upon completion of the run, a successful separation was obtained and
acetonitrile was found to boil at 77.8C. A sample of the distillate was taken for
analysis on the NMR and GCMS to check for purity.
Upon analysis, the GCMS obtained on the distillate (Figure 9) was
identical to the spectrum of reagent grade acetonitrile (Figure 3). The spectrum
showed no impurities, verifying a pure product was obtained. The NMR
performed on the sample revealed a 1H peak at 2.1 ppm consistent with the
expected results (Figure 12). Because the protons are on a carbon next to an
unsaturated center, the peak was expected to appear between 1.5-2.5 ppm as
seen. When blown up the peak remained smooth indicating all the water was
extracted from the distilled acetonitrile (Figure 13). The NMR spectrum also
12
revealed no impurities. The results of both the GeMS and NMR show that it is
possible to recycle acetonitrile and obtain a pure and usable product.
In order to reduce processing costs, tests were performed to find other
usable drying agents. Two known drying agents, sodium sulfate and magnesium
sulfate, each less expensive than calcium chloride were used in this test. To
begin the test 40 ml of acetonitrile, which had been processed through the rotary
evaporator, was collected. A sample was then taken for analysis on the IR for
use as a standard. The spectrum of this sample showed a large water peak at
3548cm-
1
(Figure 22). After the IR was performed 5g of sodium sulfate and
magnesium sulfate were added to 20ml of acetonitrile, and an IR was performed.
The spectrums of both drying agents still contained a large water peak indicating
no drying had occurred (Figures 23 & 24). Once this step had been completed,
five more grams of each drying agent were added to the samples. In the test
tube containing magnesium sulfate, this addition resulted in the absorption of all
the acetonitrile, proving magnesium sulfate would not be an alternative to
calcium chloride. An IR spectrum was taken on the sample containing 10g of
sodium sulfate, which showed no decrease in the water content (Figure 25).
Another spectrum was taken after the addition of another 5g, but once again no
decrease in water content was seen (Figure 26). This attempt to find a usable
drying agent proved unsuccessful.
In order to reduce production costs future research will be performed
using different techniques for drying acetonitrile. Data will be collected to
determine if using two-thirds less calcium chloride will still remove impurities and
13
enough water to allow a successful distillation. Another known method for drying
acetonitrile will also be tested. Acetonitrile can be dried initially by stirring over
potassium carbonate for 24 hours. Placing acetonitrile over 3A sieve will also
give a relatively dry solvent, however much better results can be obtained by
stirring over phosphorus pentoxide for 24 hours and then distilling. There are
possible problems to drying with this method, phosphorous pentoxide is
extremely reactive and could pose a hazard if any reactive impurities remained in
the solvent before distillation. It also can lead to the formation of substantial
amounts of colored residue, and the possibility of contamination with acidic
impurities (Leonard et al. 1995). Future experimentation will determine whether
these methods will be successful in obtaining a pure product at reasonable costs.
During the course of this experiment 80 liters of hazardous waste
containing acetonitrile was processed. Of that 80 liters, 60 liters were recovered
and bottled for redistribution among the Chemistry Department, leaving only 20
liters to be sent out for processing, a reduction of 75%.
Similar results were seen during experimental trials performed on acetone
and ethyl acetate in the Washington State University Solvent Recovery
Laboratory. During the first six months of operation, the laboratory processed
210 liters of hazardous waste. Of those 210 liters 24 liters were lost to
evaporation, 42 liters were sent out for processing as hazardous waste, and the
remaining 144 liters were purified and reused in the instructional and research
laboratories. During the 1997 experimental phase researchers saved $625 by
purchasing the recycled solvents. Reduction of hazardous waste shipping cots
14
saved the university another $67 resulting in a total savings of $692. The trials
during 1998 also proved successful in saving Washington State University
money. The school was able to save $427 in shipping costs, while the
researchers were able to spend $610 less by purchasing recycled solvents,
resulting in a total savings of $1037 for this test year (Newton 1999). When in full
operation the savings potential could possibly be as high as ten fold.
Cost savings were also seen in experiments performed at Energy Labs in
Billings Montana. In this facility both freon-113 and methylene chloride were
being recycled. Through data collection that minus direct expenses such as
hourly wages and expendable materials that processing three sixteen-liter
batches a week would result in an annual projected savings of $47,026 in the
recycling of freon-113 alone. An addition $20,932 could be made by recycling
three batches a week of methylene chloride (Valkenburg 1999). This cost
savings does not factor in the additional cost savings resulting from less
hazardous waste introduced into the environment and its associated cleanup
costs.
CONCLUSION
The data collected during the course of this research proves that onsite
recycling is a feasible option for research laboratories who wish to cut down on
the amount of hazardous waste deposited into the waste stream and reduce
research costs. Washington State University has now collected the data for and
is in the process of recycling acetone, ethyl acetate, methanol and acetonitrile,
greatly reducing the amount of waste sent into the environment by the
15
Department of Chemistry. Further research of this acetonitrile recycling program
will result in greater monetary savings and more thorough data on the amount of
this waste that will be prevented from entering the environment.
16
References
Fenton J. J. 1986. Solvent Recovery. International Hospital Federation Official
Yearbook.
Leonard, J., B. Lygo and G. Procter. 1995. Advanced Practical Organic
Chemistry. Chapman and Hall. New York, NY, U.S.A
Mangravite, J. A, D. Gallis and R. Foery. 1983. The recovery of organic solvents
from liquid scintillation waste. American Laboratory.
Newton, R. 1999. Recovery of Usable Solvents from Hazardous Waste.
Washington State University.
Pavia, D. L., G. M. Lampman and G. S. Kriz. 1995. Introduction to
Spectroscopy. Saunders College Publishing. New York, NY, U.S.A
Valkenberg, C. A, W. T. Brown and K. P. Kelly. 1993. Recycling Organic
Solvents. Environmental Lab Magazine. October/November.
Valkenberg, C. A, J. K. Hill, B.D Williams and R. R. Roark. 1999. Recycling
Laboratory Solvents by Distillation: Performance Data for DCM & Freon 113.
17
- . -. -. -. - -, - ., . - ._. --_. -
Name Percent Composition
Acetonitrile 72
Tetrazole 0.1
Acetic Anhydride 0.1
2.6-Lutidine 0.4
Telrahydrofuran 14.4
Methyllmodazole 0.2
Trichloroacetic acid 0.2
Dichloromethane 11.7
Iodine 0.4
Water 0.5
Bottle 2
Name Percent Composition
Acetonitrile 40
Water 56.5
Tetrahydrofuran 2
Acetic acid 0.5
Bottle 6
Name Percent Composition
Acetonitrile 47
Water 52.99
Sulfuric Acid 0.01
Bottle 7
Name Percent Composition
Acetonitrile 99
Dinitrophenyl hydrazine 1
Bottle 8
Name Percent Composition
Acetonitrile 76
Water 23.99
Sulfuric acid 0.01
Bottle 9
Boiling Point
81.6
-
139.9
143.7
66
-
196
39.8
184.3
100
Boiling Point
81.6
100
66
118
Boiling Point
81.6
100
280
Boiling Point
81.6
solid in sol.
Boilin!=! Point
81.6
100
280
Name Percent Composition Boiling Point
Acetonitrile 20 81.6
Water 69.9 100
Trifluoroacetic acid 0.1 71.8
Acelicacid 5 118
Trimethylamine 5 2.87
- - ---- --
I
Name
Acetonitrile
Water
TrifJouroacetic acid
Bottle 12, 18, 19
Name
Acetonitrile
Water
Trifluoroacetic acid
Bottle 17
Name
Acetonitri Ie
Purified water
Trifluoroacetic acid
Bottle 20
Percent Composition
50
49.9
0.1
Percent Composition
85
14.9
0.1
Percent Composition
49.95
49.95
0.1
Boiling Point
81.6
100
71.8
Boiling Point
81.6
100
71.8
Boiling Point
81.6
100
71.8
Name Percent Composition BoilinQ Point
Acetonitrile 40 81.6
Water 56.5 100
Tetrahydrofuran 2 66
Acetic acid 0.5 118

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STANDARD IH Da5ERVE
Pulse Sequence: s2pul
Solvent: CDC13
Ambient temperature
!Forerun Barrel from Distillation Three I
Mercury-300 "nmrlab"
PULSE SEQUENCE
Relax. delay 1.000 sec
Pulse 35.8 degrees
ACQ. time 1.998 sec
Width 4500.5 Hz
8 repetitions
OBSERVE H1, 300.0413150 MHz
DATA PROCESSING
FT size 32768
Total time 0 min, 25 sec
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STANDARD lH OBSERVE
Pulse Sequence: S2pul
Solvent: COC13
IBlown Up
Ambient temperature
Mercury-300 "nmrlab"
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DATA PROCESSING
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99/11/15 13: 14 WA. STATE UNIV.
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