Professional Documents
Culture Documents
ABSTRACT
In order to simplify and accelerate the analyses of oil and grease in industrial wastewaters, particularly those
discharged from various parts of the oil-refining process, an ultraviolet fluorescent sensor sensitive to polycyclic
aromatic hydrocarbons (PAH) was tested. The correlation between total oil-in-water concentration and the concen-
tration of the model PAH compound was found to be attainable in samples containing stable contents of oils.
INTRODUCTION
The analysis of oil and grease in industrial process waters, conjugate bonds (Figure 1) allowing for the fluorescent
wastewater in general, and then particulary in the oil refin- properties of these substances.
ing industry presents a real challenge due to the variability
in the analytes and the matrix. This variability depends The subject of this testing an ultraviolet (UV) fluores-
largely on the applications where the water is used; the cence probe was chosen based on the potential applica-
challenge rises most sharply in areas where on-line analy- bility to all refined and crude oils which is due to the fact
sis is implemented. One major task in applying methods that the method is sensitive and quite specific to PAH,
other than direct oil-in-water (OIW) laboratory analysis is which are considered to be constituents of all such prod-
to prove the correlation between the oil concentration and ucts.
the instrument readings. A general description of existing
methods for measuring OIW along with their respective Since the BTEX and PAH are both detectable with spec-
advantages and drawbacks is presented in Table 1. trophotometry, it was interesting to compare this method
with fluorometry.
The challenge of establishing the correct correlation
becomes particularly important when a method is based
H H
on the response of a specific model compound found in 142 pm 137 pm
the oils and not in the water matrix. Ideally, this model H H
compound should be present in all kinds of oil so that it is
139 pm 140 pm
not necessary to restrict the type of product to be ana-
lyzed. Furthermore, it should generate a strong enough H 121 H
signal, free of interference, to be detected and correctly Double bonding => fluorescence
H H
interpreted by the measuring instruments.
Figure 1:
There are several compounds regularly found in crude oil
and refined oil products that can serve as a model for opti- Structural formula of naphthalene as an example of PAH.
cal methods; these are aromatic hydrocarbons repre-
sented by two major groups of substances monocyclic
aromatic hydrocarbons (benzene, toluene, ethylbenzene,
xylenes a.k.a. BTEX), and polycyclic aromatic hydrocar-
EXPERIMENTAL PART
bons (PAH).
Based on data compiled in Table 1, UV and Vis fluores-
Polycyclic aromatic compounds present in oils are mostly cence techniques were selected for our experiments.
derivatives of naphthalene, anthracene, and phenan- Probes tested needed to be medium-priced, compact-
threne; their common structural feature is a system of sized sensors able to provide reagentless measurements
Table 1:
Comparison of different methods for OIW measurements.
specific to oil content. Physical dimensions of the sensors range: excitation = 370460 nm / emission = 520715 nm
varied based on what light source was implemented, depending on the intended analyte. Such sensors are less
which also resulted in different ranges of light spectrum expensive and have a smaller physical size; therefore, a
analyzed by the probe. Our main interest was placed on a Vis fluorescence probe designed for crude oil detection
UV fluorescence probe pictured in Figure 2 (left), where was also tried in this study. The testing conducted for the
the light source was a standard xenon flash lamp with an Vis fluorescence sensor was minimal; the main focus was
interference filter producing light at 254 nm (excitation) on the UV probe. Therefore, most of the information found
and collecting feedback at 360 nm (emission). below is related to the latter instrument. General sche-
matic for both UV and Vis probes is presented in Figure 2
An alternative to the UV fluorescence sensor was a visible (right).
light-based fluorescence probe (Vis fluorescence), where
the light source was a light-emitting diode (LED) whose Both types of sensors can be purchased with either a
major characteristics are normally within the following stainless steel or titanium body, and they produce an ana-
Xenon UV-lamp
Lens 1
Reference
photodiode
IF
Dichroid
Sample
photodiode
Lens 2
Window
Parameter Specification
chain (submersible)
Mounting options in-line (in-pipe mounting hardware)
bypass (flow cell)
Table 2:
UV fluorescence sensor technical specifications.
log signal that can be registered by a standard controller. matrix effect analysis was also conducted on a few of the
The UV-probe used in this study generated a 420 mA representative oils.
signal that was processed by an sc1000 controller. The
readings were displayed in either raw format (mA) or in rel- The results of the laboratory calibrations are presented in
ative (% of scale) or absolute concentration of oil in water. Figures 3 and 4.
The main technical specifications for the tested UV fluo- Figure 3 shows linear response of the sensor calibrated to
rescence sensor are presented in Table 2. The measure- phenanthrene concentration (y-axis) to the prepared oil
ment range limits are set to the factory settings and the concentration in deionized water (x-axis). The calibration
calibration standards are also available for both low and coefficients (slope and offset) can be easily established
high range sensors (Table 2). based on the linear regression for several of the oil prod-
ucts such as diesel fuel, gasoline, gear oil and motor oil. At
Currently, there is also some optional equipment available, the same time, the chainsaw oil, being a natural product
such as an automated cleaning system that would also derived from a biological raw material, does not show any
prove to be very helpful during this study. presence of the model compound.
80 4
60
2
40
20 0
0 1 000 2 000 3 000 4 000 5 000 6 000 7 000 8 000
0
0 1 000 2 000 3 000 4 000 5 000 Calculated DF Concentration [g kg 1 ]
Prepared Oil Concentration [g kg 1 ]
Figure 4:
Figure 3: UV fluorescence: diesel fuel (DF) calibration test results.
Calibration curves for series of available oil products in water.
The UV sensor comes with daylight automatic compensa- however, multiplying the analyte concentration by 10
tion; therefore, it was not necessary to take any precau- provided a clear response, even in this type of matrix
tions to avoid ambient light. (Figure 6).
A set of experiments was conducted to define the matrix Therefore, the UV fluorescence probe may be considered
effect on the measurement of OIW concentration with the suitable for wastewater applications, since the limit of
UV-based sensor (Figure 5). The test results presented detection for diesel fuel was found to be significantly lower
here were performed in deionized water, tap water, river than 1 mg L1 (ppm), which is considered satisfactory.
water and wastewater. A significant influence of the water
matrix requires in-process calibration of the sensor (grab The comparison of performance of the UV fluorescence
sample analysis) or in the process sample (standard addi- and UV spectrophotometric (Hach UVAS instrument,
tions method) as preferred calibration procedures. As 254 nm) sensors was conducted to identify key differ-
seen in Figure 5, the signal of 500 g L1 (ppb) of diesel ences between these technologies. Test for sensitivity to
fuel in wastewater was very small due to the matrix effect; pure phenanthrene in water revealed that monitoring
60 150
40 100
20 50
0 0
DI Water Tap Water River Water Waste Water DI Water Tap Water Waste Water
Figure 5: Figure 6:
Water matrix influence at 500 g L1 of diesel fuel. Water matrix influence at 5 000 g L1 of diesel fuel.
DI deionized
Industry Application
WWTP inlet
Monitoring direct and indirect discharge
Wastewater Storm water runoff
Membrane plants (water reuse)
Ground water reclamation sites
Table 3:
Potential applications for OIW sensor.
5 000
6 000
OIW Concentration [g kg 1 ]
5 000 4 000
Sensor Signal [g kg 1 ]
2 000 1 000
1 000
0
6/20/08, 00:00
6/20/08, 12:00
6/21/08, 00:00
6/21/08, 12:00
6/22/08, 00:00
6/22/08, 12:00
6/23/08, 00:00
6/23/08, 12:00
6/24/08, 00:00
0
9:00
9:05
9:10
9:15
9:20
9:25
9:30
9:35
9:40
9:45
9:50
9:55
10:00
10:05
10:10
10:15
10:20
10:25
10:30
10:35
10:40
Time [h:min] 6/11/08
Time [m/d/y, h:min]
Figure 7:
Experiment at a wastewater treatment plant, high-range sensor. Figure 8:
Real-life oil accident at a wastewater treatment plant, high-range
sensor.
50 2.5
12/19/08, 06:00
12/19/08, 18:00
12/20/08, 06:00
12/20/08, 18:00
12/21/08, 06:00
12/21/08, 18:00
12/22/08, 06:00
12/22/08, 18:00
12/23/08, 06:00
12/23/08, 18:00
OIW background (see pink dot on chart, Figure 9) and
shortly after this, an event was registered by the instru-
ment (Figure 9).
Because the event happened right before the weekend,
Time [m/d/y, h:min]
the incident could have gone unnoticed; however, the OIW
monitor registered it. Therefore, based on this finding, a
Figure 9:
decision was made to equip the monitoring point with an
Wastewater treatment plant test in Russia initial results.
autosampler connected to the same controller and driven
by the OIW monitor.
Thus, in further testing, the automatic grab sampling rou- tory analysis too expensive and did not make use of the
tine was triggered when the OIW concentration exceeded opportunity; however, merely combining the autosampler
the pre-programmed threshold, which was set at the level with the OIW monitor can certainly be very effective.
of 3.5 mg L1 OIW that corresponded to ~25 % of the
scale (Figure 10).
Refinery Testing (Wastewater) In conversations with
The autosampler provided the customer with an opportu- petrochemical customers, three potential applications
nity to analyze the stored water samples later in a labora- were identified as most valuable for refineries: wastewater
tory (within 4 h from the sampling) to determine the (after API separators but prior to the bioreactor), desalters,
absolute concentration of oil products at the time of event. and cokers. The desalter and coker applications normally
This would also help to pinpoint the source of contamina- involve high sample temperatures and high concentra-
tion. Unfortunately, the customer considered the labora- tions of chloride (desalter), and therefore require special
body materials, i.e., titanium. The wastewater (WW) appli- The installation was conducted at a refinery in Wyoming
cation does not require special precautions, such as tita- where customers have already tried several methods to
nium body material or intrinsically safe electronics; for this monitor the OIW concentration in WW discharge into the
reason, it was chosen as the most appropriate for field biotreatment. During biotreatment, excess of oil can wear
testing at a refinery. out the bacteria, which is costly to replace. The
customer implemented an induced-air flotation
(IAF) procedure right after the API separator to
120 reduce the amount of oil in WW going into the
bioreactor. This refinery tried a full-scale on-line
Relative OIW Concentration [%]
100
OIW analyzer based on a chemical method sev-
eral years ago. However, due to its high mainte-
80
Automatic
nance requirements and unreliable results, the
grab sample Grab sampling instrument was abandoned. The refinery cur-
60 trigger
events
rently conducts several different lab analyses of
40 the sample along with on-line turbidity monitor-
ing (surface scattering) in order to evaluate the
20 OIW content and keep it under control.
0
The two sensors, UV (low-range, 0500 g L1)
2/26/09, 12:00
2/27/09, 00:00
2/27/09, 12:00
2/28/09, 00:00
2/28/09, 12:00
3/01/09, 00:00
3/01/09, 12:00
3/02/09, 00:00
3/02/09, 12:00
3/03/09, 00:00
3/03/09, 12:00
3/04/09, 00:00
3/04/09, 12:00
3/05/09, 00:00
3/05/09, 12:00
3/06/09, 00:00
3/06/09, 12:00
3/07/09, 00:00
3/07/09, 12:00
3/08/09, 00:00
3/08/09, 12:00
3/09/09, 00:00
3/09/09, 12:00
3/10/09, 00:00
3/10/09, 12:00
3/11/09, 00:00
and Vis fluorescence (crude oil), were installed
on the same sample line with the surface scat-
terer after the IAF device and the data were col-
lected with a single multiparameter controller
Time [m/d/y, h:min] (Hach sc1000) Figure 11, left. The sensors
and controller were mounted on a panel along
Figure 10: with a flow chamber made out of available
Russian wastewater treatment plant long-term trial with autosampler. materials.
Figure 11:
Refinery installation wastewater stream after induced-air flotation and before the bioreactor.
ing. 10 40
8
30
Another challenge was with the nature of the oils 6
in the sample according to the customer, there 20
4
was never only a single type of crude oil being 10
2
treated at the refinery at a time. Therefore, the
0 0
sample content was never consistent in terms of
6/16/08, 00:00
6/21/08, 00:00
6/25/08, 00:00
7/01/08, 00:00
7/06/08, 00:00
7/11/08, 00:00
7/16/08, 00:00
7/21/08, 00:00
7/26/08, 00:00
7/31/08, 00:00
the type of oil and consequently also with the
PAH content in the sample. This resulted in
inconsistency of the readings received from
both sensors with the grab sample analyses
Time [m/d/y, h:min]
(Figure 12). All attempts to calibrate the sensors
using the grab sample data failed due to the
abovementioned limitations. Figure 12:
Refinery wastewater application test results.
On the positive side, it should be noted that
there was a similar trend found between the
results collected from both sensors; however, the Vis fluo- Auto Parts Plant (Industrial Wastewater) This test
rescence provided a significantly narrower range and only involved the same UV fluorescence probe (low-range,
therefore was excluded from later experiments (Figure 12). 0500 g L1) that demonstrated a wider range of
response to the OIW concentrations in previous trials. The
Given the discovered limitations, the next test was con- sensor was installed in an open channel (chain-mounted)
ducted in an industrial application with lower-to-no varia- at the inlet to the wastewater treatment facility of an auto
tion in oil types found in the wastewater discharge. parts plant in Michigan (Figure 13).
Figure 13:
Installation.
OIW [mg kg 1 ]
15
The entire test continued for approximately two months
and the data were logged by the controller, which also
10
allowed for remote wireless access to all data and the
controller's functions. The process calibration, described 5
below, was performed in the middle of the test using
the grab sample technique presented in Figures 14 and 0
4 6 8 10 12 14 16 18 20
15.
Sensor [mA ]
12/06/08, 12:00
12/09/08, 00:00
12/11/08, 12:00
12/14/08, 00:00
12/16/08, 12:00
12/19/08, 00:00
12/21/08, 12:00
25
Time [m/d/y, h:min]
20
Grab sample
Sensor Signal [mA ]
Figure 16:
15
Auto parts plant in Michigan (industrial wastewater) test
results.
10
12/02/08, 01:26
12/02/08, 03:21
12/02/08, 05:16
12/02/08, 07:12
12/02/08, 09:07
12/02/08, 11:02
12/02/08, 12:57
12/02/08, 14:52
120
60
40
20
8/12/09, 00:00
8/17/09, 00:00
8/22/09, 00:00
8/27/09, 00:00
9/01/09, 00:00
9/06/09, 00:00
9/11/09, 00:00
9/16/09, 00:00
9/21/09, 00:00
9/26/09, 00:00
Time [m/d/y, h:min]
After several days of normal operation with readings close to the extremely remote location of the test site, no such
to zero, an oil leak from the heat exchanger was detected service could be provided by the major US wireless carri-
(Figure 18). The contamination cost the customer more ers in the area.
than $1,000 in loss of oil. Besides the direct oil loss, the
company had to complete a series of procedures to clean Nevertheless, the sensor proved itself very useful by sav-
up the cooling water which involved the use of a biocide, ing the customer a significant amount of money at a nom-
oil absorbing mats, higher chlorine injection, followed by inal cost which was not exacerbated by maintenance
draining the entire cooling tower water to re-establish its requirements. Regular maintenance of the system involves
chlorine and polymer levels. All these actions required the cleaning of the sensor window; the frequency of clean-
approximately 8 hours of work time and an additional ing depends on the respective application. For example,
material cost of $1,000. when the sensor is submersed in a slow moving dirty sam-
ple, the cleaning may occur daily depending on the sam-
The accident cost was high enough; however, it could ple conditions and its origin (application). The cleaning fre-
have been even more costly if there had been no sensor quency can be significantly minimized either by using an
installed at the time. According to the customer, without air-blast auto cleaning system (for submersible installa-
such early detection, the leak would have been discov- tions) manageable from the same controller or by employ-
ered only after the shutdown of the compressor on low oil ing the flow-through cell. In the latter case, the mainte-
level. This could have led to a possible plant shutdown or nance can be nothing more than an occasional cleaning of
damage to the compressor necessitating an extensive the strainer installed in the sample line feeding the flow
cleanup of the cooling tower, which would have resulted in cell.
the loss of many thousands of dollars for the company.
As a matter of fact, in the presented case study, after more
As seen from Figure 18, the accident apparently went than 45 days of testing, there was no maintenance con-
unnoticed for about two days, because the communica- ducted on the sensor. There was some expected fouling
tion between the controller and the plant's monitoring sys- found in the flow cell and on the sensor window during the
tem had not yet been established. The controller was post-test inspection (Figure 19); however, it obviously did
equipped with a relay card allowing it to send an analog not prevent the probe from producing correct readings. As
signal to either the central monitoring post or to display an seen from Figure 18, the sensor was operating well during
alarm locally in case the prescribed oil-in-water level was the entire test.
exceeded. The other possibility for remote access and
control was the wireless communication option enabled
through GPRS (Global Packet Radio Service) and pro-
vided by most cell phone companies. Unfortunately, due
Figure 19:
Post-test inspection of the flow cell and sensor window.