Embodiments of the subject matter disclosed herein generally relate to a sensor for detecting benzene and/or other substances, and more specifically, to a laser-based system that uses cavity-enhanced absorption spectroscopy for determining trace amounts of benzene and/or other substances in ambient air.
Benzene (C6H6), also known as benzol, is a colorless liquid with a sweet odor. Benzene evaporates into air very quickly and dissolves slightly in water. Benzene is highly flammable. Most people can begin to smell benzene in air at approximately 60 parts of benzene per million parts of air (ppm) and recognize it as benzene at 100 ppm. Most people can begin to taste benzene in water at 0.5-4.5 ppm. One part per million is approximately equal to one drop in 40 gallons. Benzene is found in air, water, and soil. Benzene comes from both industrial and natural sources.
Benzene is found in air from various emission sources, such as gasoline service stations, vehicle exhaust, refineries, and petrochemical processing facilities. Benzene is largely used in the petrochemical processing facilities or other facilities for making other chemicals, like styrene, ingredients for resins, and ingredients for nylon and synthetic fibers. Measured levels of benzene in outdoor air have ranged from 0.02 to 34 parts of benzene per billion parts of air (ppb). The World Health Organization (WHO) categorizes benzene as a major public health concern. Fatal diseases such as cancer and aplastic anemia have been linked to human exposure to benzene.
To prevent or be aware of benzene contamination, various benzene sensors are used at the benzene processing facilities for determining any escape of this chemical into the environment. For this reason, there is a large demand for new and improved benzene sensors as the existing commercial sensors lack in many respects. It is desired to have reliable, accurate, sensitive, and real-time diagnostic methods and sensors for benzene detection at various facilities where benzene emissions are likely.
However, the existing sensors are slow, not very accurate, and not very sensitive to small amounts of benzene. Thus, there is a need for a new sensor that can overcome these limitations.
According to an embodiment, there is a laser-based detection system that includes a laser device configured to emit a laser beam, a measuring chamber configured to receive in an internal cavity ambient air and the laser beam, where the measuring chamber is configured to bounce the laser beam inside the internal cavity multiple times, and a photosensor configured to receive an output laser beam from the measuring chamber.
According to another embodiment, there is a laser-based detection system that includes a laser device configured to emit a laser beam that includes a wavelength of 3.3 μm, a measuring chamber configured to receive at an internal cavity ambient air and the laser beam, where the measuring chamber is configured to bounce the laser beam inside the internal cavity multiple times before exiting the measuring chamber; a photosensor configured to receive an output laser beam from the measuring chamber; and a data acquisition system configured to receive a measurement from the photosensor and to detect an amount of benzene in the ambient air based on the wavelength of 3.3 μm.
According to yet another embodiment, there is a method for determining a presence of benzene in ambient air, the method including introducing ambient air into a measurement chamber that has an internal cavity; emitting with a laser source a laser beam having a wavelength around 3.3 μm; directing the laser beam into the internal cavity and bouncing the laser beam multiple times between mirrors located in the internal cavity; measuring with a photosensor an absorption of the 3.3 μm wavelength by the ambient air; and estimating with a data acquisition system an amount of benzene in the ambient air based on the absorption of the 3.3 μm wavelength.
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate one or more embodiments and, together with the description, explain these embodiments. In the drawings:
The following description of the embodiments refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. The following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims. For simplicity, the following embodiments are discussed with regard to a laser-based detection system that uses an additional laser for alignment of the various optical components and also a dehumidifier for reducing the humidity in a cavity where the measurements take place. However, the embodiments discussed herein are not limited to such a configuration, but they may be applied to a system that has no additional laser and no dehumidifier.
Reference throughout the specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with an embodiment is included in at least one embodiment of the subject matter disclosed. Thus, the appearance of the phrases “in one embodiment” or “in an embodiment” in various places throughout the specification is not necessarily referring to the same embodiment. Further, the particular features, structures or characteristics may be combined in any suitable manner in one or more embodiments.
According to an embodiment, a laser-based detection system 100 is shown in
Although benzene has absorption bands in the ultraviolet (UV) wavelength region, the broad features of most hydrocarbons in this region do not permit interference-free selective measurements. In other words, the benzene and many other hydrocarbons have similar signatures in the UV region and thus, the presence of one hydrocarbon cannot be distinguished from the presence of another hydrocarbon. For this reason, in this embodiment, the laser device 110 is specifically selected to generate an infrared light beam as the infrared (IR) absorption spectrum provides better opportunities for the highly selective detection of benzene and other pollutants.
Based on the IR spectrum of benzene, the best wavelength for detecting the benzene presence is near 674 cm−1 (i.e., a wavelength of 14.837 μm). However, the inventors have observed that this wavelength region is currently not accessible by commercially available semiconductor lasers. In a previous work [1], low amounts of benzene were measured near the 9.6 μm wavelength using a quantum-cascade laser array. The selected wavenumber 1038 cm−1 (note that the wavenumber is defined as being the reciprocal of the wavelength of the laser beam, and thus, the wavelength for this case is 1/1038=9.6 μm; however, in this application, the terms wavenumber and the wavelength are sometimes used interchangeably) has a strong spectral interference from ozone, which can be a challenge in many geographical locations.
Therefore, for the embodiment illustrated in
A process for selecting an appropriate IR range for the wavelength of the laser device 110 is now discussed.
To minimize the interference of the absorbance signal due to the water, as illustrated in
A possible implementation of the laser-based detection system is now discussed with regard to
The embodiment shown in
Before the laser beam 110 is used to detect the benzene and/or other substances (e.g., ethylene, methane, water vapor), the various components of the laser-based detection system 400 need to be optically aligned. Note that the laser-based detection system 400 also includes mirrors 432 and 434 located inside a cavity 431 formed inside the measurement chamber 130, a convergent lens 440, and the photosensor 140. As the main laser device 110's beam is not visible (being in the infrared range), the alignment laser device 410 is selected to emit a visible laser beam that can be used for alignment purposes. Thus, the laser beam 412 from the alignment laser device 410 needs to be coupled, only for alignment purposes, to the other optical components of the laser-based detection system 400. This is achieved with the flip mirror 120C. For a given orientation, as shown in
After the laser beam 112 leaves the last mirror 120E, it enters inside the measurement chamber 130. The measurement chamber 130 includes two mirrors 432 and 434, located in the cavity 431, which are designed to reflect multiple times the incoming laser beam 112. In one application, two ZnSe mirrors of 99.97% nominal reflectivity (LohnStar Optics) were used to form a cavity in a sampling cell having a length L (e.g., 50 cm). The length of the cavity can be modified. The laser beam 112 is aligned in an off-axis mode (i.e., not entering along a symmetry longitudinal axis X of the measurement cavity), which suppressed the spurious coupling noise significantly compared to the on-axis cavity. A reflection pattern 435 of the incoming laser beam 112 is illustrated in
At each reflection on the mirror 434, part of the light 112 passes the mirror and exits from the measurement chamber 130 as output laser beams 112j. These output laser beams 112j are then collected via a focusing lens 440 (e.g., a convergent lens) on the photosensor 140. In one application, the photosensor 140 is a photodetector, for example, a 1.5 MHz AC-coupled, TE-cooled photodetector (Vigo Systems). The data collected at the photosensor 140 is then transmitted to data acquisition system 150 for processing.
As previously discussed, for the selected wavelength of 3.3 μm, the air that enters inside the measurement chamber 130 is assumed to be very low in humidity or otherwise the absorbance of water may interfere with the benzene and/or other elements absorbance. Thus, if the ambient air is high in humidity, a dehumidifier 310 may be added to the laser-based detection system 400, as shown in
The dehumidifier 310 may be any known dehumidifier. In one application, a CaSo4 dehumidifier has been used to remove the humidity from the incoming ambient air 512.
To force the incoming ambient air 512 to enter the dehumidifier 310 (if present) and the cavity 431 of the measurement chamber 130, a pump 320 may be used. The pump 320 may be connected to the outlet port 134 of the measurement chamber 130 so that the dehumidified air 512A, follows the path 510C and 510D to the pump 320 and then 510E out of the pump. In one embodiment, the pump 320 is a vacuum pump, which is configured to reduce the pressure inside the cavity 431. This is desired when the signal measured by the photosensor 140 needs to be calibrated.
More specifically, in one application, a valve 132A may be placed on the inlet port 132. This valve is closed so that no air is entering the measurement chamber 130. Then, the vacuum pump 320 is activated, for example, by the data acquisition system 150. The vacuum pump 320 may be run until the pressure inside the cavity 431, as measured by the pressure sensor 436, is below a certain threshold. When the pressure is below this threshold, it is considered that the cavity 431 has been emptied. Then, the laser device 110 is activated and a signal is measured with the photosensor 140. This signal constitutes the background signal, which needs to be compared to the actual signal measured with air in the cavity 431 at atmospheric pressure.
Once the evacuation is performed, the valve 132A is opened, which forces the air 512 through the dehumidifier 310 (if present) and into the cavity 431, so that a measurement of the benzene and/or other substances presence in the ambient air 512 can be performed. Note that after the initial evacuation of the system by using the vacuum pump 320, it is possible to either replace the vacuum pump with a compressor, or to use the vacuum pump not at full capacity, but only to reduce the pressure inside the cavity, to force the ambient air into the cavity due to a differential pressure. Alternatively, it is possible to remove the vacuum pump and use a compressor for circulating the ambient air through the cavity. The compressor 320 may also be connected to the air inlet port 132, or to the inlet of the dehumidifier 310 when only used to circulate the air through the measurement chamber.
In another embodiment illustrated in
The reflectivity of the mirrors 432 and 434 in the cavity 431 affect the sensitivity of the absorbance measurements performed with the laser beam inside the measurement chamber 130. Although a manufacturer provides the nominal mirror reflectivity of the sold mirrors, the inventors have noted that these manufacturer provided values are not always accurate. As these values impact the selection of various measurement parameters, it is desired to know the actual reflectivity of these mirrors. For this reason, experiments were performed by the inventors, with known amounts of benzene near 3037 cm−1 in the system 400, and the measured CEAS absorbance spectrum was compared with the single-pass simulated absorbance. The mirror reflectivity was calculated using the formula: R=eA
Then, measurements were performed with mixtures of benzene and nitrogen with the system 100.
This experiment shows that the laser-based detection system discussed herein has a very high sensitivity for detecting the benzene in ambient air, which is unmatched by any known device. This system may be packaged to be portable as now discussed with regard to
The laser-based detection system 1000 includes, optionally, a dehumidifier 310 connected to the inlet port 132 of the measurement chamber 130, and a pump 320 located anywhere along the air path 510. For simplicity, the pump 320 is located in
The laser-based detection system 1000 further includes a data acquisition system 150 that is configured to control each of the components of the system. The components of the system may be supplied with power from a power source PS. The power source may be a portable source, e.g., battery, fuel cell, etc., or a fixed wired source, i.e., the laser-based detection system 1000 is plugged to a conventional power source, e.g., a generator.
In one application, the laser-based detection system 1000 may also include a monitor 1010 that is attached to the housing 1002. The monitor 1010 can be configured to display an indication about the benzene concertation, based on the analysis provided by the data acquisition system 150. For example, the monitor 1010 may display a graph showing the concentration of the benzene in the ambient air for a given measurement location. In another application, the laser-based detection system 1000 may have a transceiver 1020 equipped with an antenna 1022 for transmitting a signal indicative of the presence of the benzene to a server or to a user. For example, if the laser-based detection system 1000 is used in a petrochemical facility, the system 1000 may be configured to transmit in a wireless manner an alarm to a command center of the facility, when a level of detected benzene is above a given threshold.
A method of measuring the level of benzene is now discussed with regard to
The method may also include a step of pumping with a pump the ambient air into the measuring chamber, and/or a step of focusing with a convergent lens an output laser beam from the measuring chamber, onto the photosensor, and/or a step of aligning the laser beam with the measuring chamber by using an additional laser beam that emits a visible laser beam, and/or a step of evacuating the measuring chamber by creating vacuum in the internal cavity and measuring the absorption in vacuum.
The system discussed above can be used to measure other substances or benzene mixed with other substances. For example, in one embodiment, the system was used to simultaneously measure benzene and ethylene. Ethylene was added to benzene in nitrogen so that the total absorbance is measured. Multi-dimensional linear regression is applied to the total absorbance in order to calculate the concentration of each species separately. Table 1 shows a comparison between the manometric and measured concentrations of nine different mixtures of benzene and ethylene. The large error in the ethylene measurements is due to the weak absorption spectrum compared to benzene. High accuracy for benzene detection was maintained even in the presence of ethylene.
In another embodiment, the same system was used to simultaneously measure benzene and methane. Methane was added to benzene in nitrogen so that the total absorbance is measured. Multi-dimensional linear regression is again applied to the total absorbance in order to calculate the concentration of each species separately. Table 2 shows a comparison between the manometric and measured concentrations of four different benzene and methane mixtures. The low error in the methane measurements is due to the strong and well-resolved absorption spectrum compared to benzene. Note that high-accuracy for the benzene detection was maintained even in the presence of methane.
In still another embodiment, the system discussed above has been used to simultaneously measure the benzene and water vapor. Water vapor was added to benzene in nitrogen so that the total absorbance is measured. Multi-dimensional linear regression is again applied to the total absorbance in order to calculate the concentration of each species separately. Table 3 shows a comparison between the manometric and measured concentrations of 12 different benzene and water vapor mixtures. It can be seen that the benzene is measured with high-accuracy even in the presence of the water vapor. Note that the previously employed low-pass filter cannot be used anymore in data processing as it will smoothen the water vapor feature, so another filter of higher cutoff frequency is used instead. This increases the minimum detection limit of benzene to 2 ppb.
In yet another experiment, air samples were collected from inside the lab, outside the building, a parking garage, and a gas station. All of the aforementioned species were measured in these samples and the results are shown in Table 4.
The high concentrations of ethylene and methane in the laboratory are due to the presence of gas cylinders of these species that might leak some amounts into the air. It is also noticeable that the amount of benzene decreases significantly in the parking garage from a weekday to a weekend due to the reduced usage of this garage by cars on weekends.
Benzene was measured with a Gas Chromatograph (GC) in some of the aforementioned samples for varication. Table 5 shows good agreement between the measurements performed with the system 400 and the GC.
The disclosed embodiments provide a novel configuration for a laser-based detection system that is capable to determine a lower level of benzene in air than the existing sensors, down to 2 ppb in the presence of interfering species. The embodiments are intended to cover alternatives, modifications and equivalents, which are included in the spirit and scope of the invention as defined by the appended claims. Further, in the detailed description of the embodiments, numerous specific details are set forth in order to provide a comprehensive understanding of the claimed invention. However, one skilled in the art would understand that various embodiments may be practiced without such specific details.
Although the features and elements of the present embodiments are described in the embodiments in particular combinations, each feature or element can be used alone without the other features and elements of the embodiments or in various combinations with or without other features and elements disclosed herein.
This written description uses examples of the subject matter disclosed to enable any person skilled in the art to practice the same, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the subject matter is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims.
This application claims priority to U.S. Provisional Patent Application No. 62/781,128, filed on Dec. 18, 2018, entitled “CAVITY-ENHANCED BENZENE SENSOR FOR ENVIRONMENTAL MONITORING,” and U.S. Provisional Patent Application No. 62/846,003, filed on May 10, 2019, entitled “LASER-BASED SYSTEM FOR BENZENE DETECTION,” the disclosures of which are incorporated herein by reference in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/IB2019/059582 | 11/7/2019 | WO | 00 |
Number | Date | Country | |
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62846003 | May 2019 | US | |
62781128 | Dec 2018 | US |