Patent Application
20230414819
The present application claims priority to Korean Patent Application No. 10-2022-0079206, filed Jun. 28, 2022, the entire contents of which is incorporated herein for all purposes by this reference.
The present disclosure relates to a method of monitoring and removing odor-causing substances in a flue gas of industrial facilities.
With the rapid expansion of industrial facilities, ever-increasing environmental pollution problems have become a critical social issue. Among such problems, odorous gases, along with environmental noise, are becoming the most common public complaint. Hence, odor regulation is becoming increasingly strict, and demand for deodorization technology capable of removing odorous gases is thus growing.
Odors typically refer to unpleasant and repulsive smells caused when irritating substances, such as hydrogen sulfide, mercaptans, amines, and the like, stimulate the human sense of smell. In addition, complex odors refer to unpleasant and repulsive smells caused when two or more types of these irritating substances are combined and stimulate the human sense of smell.
Under the current Korean law, odors are regulated by the Korean Odor Prevention Law, which defines odors as 22 types of designated odorous substances and complex odors. Similar provisions may exist in other countries including in the United States. The designated odorous substances are measured using instrumental analysis methods, and the complex odors are measured using the air dilution sensory method based on the Official Test Method enacted by the Ministry of Environment according to Article 6, Paragraph (1), Item 4 of the Environmental Testing and Inspection ACT. Standards for permissible emissions of complex odors under the current law are shown in Table 1 below.
Here, the dilution factor refers to a factor obtained by diluting the collected Example with odorless air in a stepwise manner until no odor is detected. As can be seen here, the evaluators had no choice but to evaluate the level of complex odors subjectively by smelling, unlike in the case of designated odorous substances. Real-time monitoring of complex odors based on more objective criteria is necessary for businesses not to exceed the regulated standards for permissible emissions. In addition, even though there are methods of using gas chromatography equipment and the like as conventional methods of determining odor-causing substances, analysis preparation for such methods and the analysis itself require a lot of time and manpower, not to mention that such equipment is also expensive.
Furthermore, although odor-measuring devices are used to determine odors in some cases, such devices have poor accuracy, and real-time measurement is difficult due to inconvenient measurement processes. Moreover, there is a problem in terms of maintenance because sensor replacement and calibration are periodically required.
According to a first aspect of the present disclosure, a method is provided for monitoring odor-causing substances in real time in a flue gas by measuring the absorbance of the odor-causing substances. The method may comprise: providing a flue gas containing odor-causing substances; introducing the flue gas into an odor removal unit; producing a gas-phase stream; dissolving a portion of the gas-phase stream in a solvent to produce a liquid-phase stream; and measuring an absorbance of the liquid-phase stream to identify the odor-causing substances.
According to an embodiment of the present disclosure, the odor-causing substances may comprise ethanol, benzene, trimethyl benzene, benzaldehyde, benzoic acid, toluene, phenol, styrene, α-methylstyrene, indole, pyridine, skatole, methylcyclohexane, xylene, o-cresol, m-cresol, methyl ethyl ketone, methyl isobutyl ketone, ammonia, methylamine, ethylamine, dimethylamine, trimethylamine, acetaldehyde, propionaldehyde, butyraldehyde, n-valeraldehyde, valeraldehyde, ethyl acetate, butyl acetate, propionic acid, n-butyric acid, n-valeric acid, i-valeric acid, i-butyl alcohol, ethyl acrylate, sulfur dioxide, hydrogen sulfide, dimethyl sulfide, dimethyl disulfide, diethyl disulfide, methyl ethyl sulfide, methyl mercaptan, ethyl mercaptan, carbon disulfide, methyl diethanolamine, diisopropylamine, acrolein, chlorine, fluorine, or a combination thereof.
In an embodiment of the present disclosure, the flue gas may be introduced into the bottom of the odor removal unit, and the odor removal unit may be a scrubber, a combustion device, an adsorption device, or a combination thereof.
In an embodiment of the present disclosure, the odor removal unit may be the scrubber, and water may be supplied to the top of the scrubber.
In an embodiment of the present disclosure, the solvent may comprise water, an aqueous solution, an organic solvent, or a combination thereof.
In an embodiment of the present disclosure, the aqueous solution may comprise a sodium hydroxide (NaOH) solution or a sulfuric acid (H2SO4) solution.
In an embodiment of the present disclosure, the absorbance may be measured using a spectrophotometer or optical sensor at a wavelength range of ultraviolet and visible light.
In an embodiment of the present disclosure, the absorbance may be measured in a wavelength range of 170 nm to 280 nm.
In an embodiment of the present disclosure, the method may further comprise: analyzing the odor-causing substances based on the measured absorbance to obtain an analysis result with a type and amounts of odorous substances in the flue gas; and controlling operating conditions in the odor removal unit based on the analysis result.
Using a monitoring method provided herein, types and concentrations of odor-causing substances generated from odor removal equipment can be monitored in real time at low costs.
In addition, using the standard absorbance data for each odor-causing substance, not only real-time analysis of the odor-causing substances generated in flue gas but also control of operating conditions in the odor removal equipment according to the analysis results are automatable. As a result, the operation can be optimized, and manpower and costs thus can be additionally reduced.
Even though the above and other objectives, features, and advantages of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, the present disclosure is not necessarily limited thereto. In addition, when it is determined that the detailed description of the known art related to the present disclosure might obscure the gist of the present disclosure, the detailed description thereof will be omitted.
A first aspect of the present disclosure relates to a method of monitoring odor-causing substances in flue gas.
The method comprises: providing a flue gas containing odor-causing substances; introducing the flue gas into an odor removal unit; producing a gas-phase stream; dissolving a portion of the gas-phase stream in a solvent to produce a liquid-phase stream; and measuring an absorbance of the liquid-phase stream to identify the odor-causing substances.
In the present disclosure, “flue gas” refers to gas derived from stationary sources, such as petrochemical plants, power plants, and the like, and mobile sources, such as vehicles, buses, trains, and the like, but is not limited thereto. In addition, any gas containing the odor-causing substances may fall within the target gas to be processed in the present disclosure.
In the present disclosure, “odor-causing substance” refers to a substance that causes the odor described above, and is not particularly limited as long as it is mixed in the air and causes odor. In particular, the odor-causing substance is not construed to be limited to the 22 types of designated odorous substances described above. In an embodiment of the present disclosure, the odor-causing substance may comprise ethanol, benzene, trimethyl benzene, benzaldehyde, benzoic acid, toluene, phenol, styrene, α-methylstyrene, indole, pyridine, skatole, methylcyclohexane, xylene, o-cresol, m-cresol, methyl ethyl ketone, methyl isobutyl ketone, ammonia, methylamine, ethylamine, dimethylamine, trimethylamine, acetaldehyde, propionaldehyde, butyraldehyde, n-valeraldehyde, i-valeraldehyde, ethyl acetate, butyl acetate, propionic acid, n-butyric acid, n-valeric acid, i-valeric acid, i-butyl alcohol, ethyl acrylate, sulfur dioxide, hydrogen sulfide, dimethyl sulfide, dimethyl disulfide, diethyl disulfide, methyl ethyl sulfide, methyl mercaptan, ethyl mercaptan, carbon disulfide, methyl diethanolamine, diisopropylamine, acrolein, chlorine, fluorine, or a combination thereof.
For example, sulfur compounds, such as methyl mercaptan, are characterized by the smell of rotten onions and rotten cabbages, and hydrogen sulfide is characterized by the smell of rotten eggs. In addition, nitrogen compounds, such as ammonia and methyl amine, are characterized by the smell of excrement and rotten fish. Aldehydes, such as acetaldehyde, are characterized by an irritating, sour, and burning smell, and hydrocarbons, such as ethyl acetate and propionic acid, and fatty acids are characterized by the irritating smell of paint thinners. Furthermore, halogens, such as chlorine and fluorine, are characterized by an irritating smell. Such odor-causing substances described above make those who smell the odor unpleasant and disgusted, and longer periods of smelling may accompany dizziness and/or headaches.
In the present disclosure, the flue gas comprises the odor-causing substances described above. For example, the flue gas may comprise odor-causing substances at concentrations (ppm v/v/) equivalent to or higher than the lower limit regulated by the Ministry of Environment. The minimum detectable concentrations of major chemicals according to the Enforcement Rules of the Clean Air Conservation Act are shown in Table 2 below.
In the present disclosure, the flue gas comprising the odor-causing substances is introduced into the odor removal unit. While passing through the odor removal unit, the odor-causing substances in the flue gas may be removed, or the number of the odor-causing substances may be reduced.
In the present disclosure, the odor removal unit refers to a device, a system, a means, and the like capable of removing the odor-causing substances in the flue gas. The odor removal unit is not particularly limited as long as the unit is an odor removal means having a structure where the flue gas is introduced, and the gas with the reduced number of the odor-causing substances is discharged. For example, the odor removal means may comprise scrubbing, combustion, adsorption, chemical process, cooling condensation, biological process, and the like.
In an embodiment of the present disclosure, the odor removal unit may be a scrubber, a combustion device, an adsorption device, or a combination thereof. In another embodiment of the present disclosure, the odor removal unit may be composed of a plurality of devices arranged in parallel and/or series, where the plurality of devices may be the same or different from each other.
A scrubber reduces the number of odor-causing substances by spraying water (or a combination of water and an absorbent) onto the introduced flue gas to bring the odor-causing substances in the flue gas into contact with water. In addition, an adsorption device reduces the number of odor-causing substances by using the characteristics of the odor-causing substances being adsorbed in between the pores of an adsorbent when flue gas introduced into the device allows the adsorbent present in the device to pass through. Furthermore, a combustion device reduces the number of odor-causing substances by allowing the odor-causing substances in flue gas introduced into the device to undergo oxidation combustion or thermal degradation at high temperatures. In the present disclosure, when using the scrubber as the odor removal unit, the scrubber produces a water stream, and the water stream is discharged from the bottom of the scrubber. In the present disclosure, the water stream refers to scrubber wastewater comprising odor-causing substances brought into contact with the water supplied to the scrubber.
In an embodiment of the present disclosure, the flue gas may be introduced into the bottom of the odor removal unit. In the odor removal unit, as the flue gas flows upward from the bottom to the top, the number of the odor-causing substances is reduced. Lastly, the flue gas is discharged from the top of the odor removal unit as a gas-phase stream to be described later.
In an embodiment of the present disclosure, the odor removal unit may be the scrubber. In this case, water may be supplied to the top of the scrubber from the outside, and the supplied water then contacts with the flue gas while flowing downward in the scrubber. On the other hand, in the case of performing the monitoring method of the present disclosure in an environment involving odor-causing substances such as lipophilic substances, an organic solvent, instead of water, may be used in the scrubber.
The odor removal unit produces the gas-phase stream. In the present disclosure, the gas-phase stream refers to flue gas in which the number of the odor-causing substances is reduced through the odor removal unit. The gas-phase stream is discharged from the top of the odor removal unit.
In the present disclosure, a portion of the gas-phase stream is dissolved in the solvent to produce a liquid-phase stream, which is used for absorbance measurement of the odor-causing substances as described later. The portion of the gas-phase stream may be dissolved in an extremely small amount with respect to the total amount of the gas-phase stream. The solvent used herein is not particularly limited as long as the solvent does not adversely affect the absorbance measurement to be described later and is capable of dissolving the odor-causing substances well. In an embodiment of the present disclosure, the solvent may comprise water, an aqueous solution, an organic solvent, or a combination thereof. Here, when using a random combination of the water, the aqueous solution, and the organic solvent as the solvent, the portion of the gas-phase stream is not dissolved in a random mixture of the water, aqueous solution, and organic solvent. Rather, the water, the aqueous solution, and/or the organic solvent are used independently from each other when dissolving the gas-phase stream. In the present disclosure, as the organic solvent, n-pentane, n-hexane, dichloromethane, methanol, ethanol, 2-methylbutane, ethyl acetate, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and the like may be used. However, the organic solvent is not limited thereto. In addition, the examples of the organic solvent may be used solely or in combination.
Depending on the types of odor-causing substance, the liquid-phase stream may vary in acidity. In an embodiment of the present disclosure, the pH of the solvent may be appropriately adjusted to increase the solubility of the liquid-phase stream.
For example, when the odor-causing substances are acidic, an aqueous solution of NaOH may be used as the solvent. In addition, when the odor-causing substances are basic, an aqueous solution of H2SO4 may be used as the solvent.
The dissolving of the portion of the gas-phase stream may further comprise removing solids. The gas-phase stream before the dissolving and the produced liquid-phase stream may comprise solids. Such solids may cause error in the absorbance measurement. Thus, the solids are preferably removed from the liquid-phase stream before the absorbance measurement to reduce errors. A means to remove the solids is not particularly limited, and the solids may be removed by mechanical means such as a filter or centrifugation.
Next, the absorbance of the liquid-phase stream produced above is measured. In an embodiment of the present disclosure, the absorbance of the liquid-phase stream may be measured using a spectrophotometer or optical sensor. The spectrophotometer may be an ultraviolet (UV) spectrophotometer or ultraviolet-visible (UV-Vis) spectrophotometer. The electronic structure of atoms or molecules of the odor-causing substances, as well as the compositions thereof, may be analyzed at peaks in a specific wavelength where light is absorbed. In addition, concentrations of the odor-causing substances may be analyzed using the absorbed light level (that is, absorbance).
In the present disclosure, the absorbance may be measured in a wavelength range of ultraviolet and visible light. In some embodiments, the method may comprise exposing the liquid phase stream to light of wavelengths in the ultraviolet and visible light ranges prior to measurement. The absorbance may be measured in the wavelength range of visible light and measured in the wavelength range of 170 nm to 280 nm. In particular, the absorbance is measured in a specific wavelength range so that all major odorous substances designated by the Ministry can be analyzed. In addition, the analysis efficiency can be improved because analysis in all ultraviolet regions is unnecessary.
In an embodiment of the present disclosure, the method may further comprise analyzing the odor-causing substances based on the measured absorbance as described above. Through the analysis, analyzing the types and concentrations of the odor-causing substances may be performed. Each of the odor-causing substances may have an inherent absorbance peak in the wavelength range described above. Depending on the absorbance peaks, the types of odor-causing substances may be specified. In addition, the area under the absorbance curve of a specific substance in the absorbance graph is proportional to the concentration of the corresponding substance. Hence, the types and concentrations of the odor-causing substances in the liquid-phase stream may be analyzed by comparing the absorbance data of a specific substance registered in a known database and measured absorbance data.
In the method of the present disclosure, the analysis of the remaining odor-causing substances is performed on the flue gas containing the reduced number of the odor-causing substances after passing through the odor removal unit. Except for quite exceptional cases, such as air pollution caused by accidents of unknown causes, fires, natural disasters, and the like, the main composition of the flue gas generated from a particular emission source is predictable by reactions performed in the emission source, reactants, products, by-products, and the like. Thus, analyzing the composition of the odor-causing substances in such flue gas in upstream processes of the odor removal unit is ineffective. In the present disclosure, the odor-causing substances remaining in the flue gas where the number of the odor-causing substances is expected to be reduced by allowing the flue gas to pass through the odor removal unit may be analyzed. Accordingly, the number of operating conditions may be increased or decreased according to the remaining amount of the predictable odor-causing substances. Alternatively, an additional process may be performed according to the presence of the un-predictable odor-causing substances.
Through the absorbance measurement method used herein, not only the analysis of a single odor-causing substance but also the analysis of a plurality of odor-causing substances may be simultaneously performed. However, as the number of the odor-causing substances increases, the accuracy and speed of the analysis inevitably deteriorate. Thus, the measurement is performed in downstream processes of the odor removal unit as described above, so that the method of the present disclosure can provide an advantage of further improving the accuracy and speed of the analysis by reducing the number of the odor-causing substances to be analyzed.
Additionally, in the method of the present disclosure, the analysis of the odor-causing substances in a liquid state, not a gas state, in which the flue gas is dissolved in the solvent is performed. Compared to measuring the absorbance directly on the gas-phase stream discharged from the odor removal unit, measuring the absorbance in the liquid-phase stream by dissolving the portion of the gas-phase stream has the following advantages:
In the present disclosure, the odor-causing substances may be analyzed based on the measured absorbance as described, and the operating conditions in the odor removal unit then may be controlled based on the analysis results. Alternatively, an additional process may be performed on the gas-phase stream in the downstream processes of the odor-removal unit through a separate unit.
For example, from the measurement results of the absorbance of the liquid-phase stream and the analysis results thereof,
According to an embodiment of the present disclosure when using the scrubber as the odor removal unit, the method of the present disclosure may further include measuring the absorbance of the water stream. The water stream contains the odor-causing substances removed from the flue gas. Thus, when the above-measured absorbance and the absorbance measured from the liquid-phase stream are compared and analyzed, the operating conditions in the odor removal unit may be modified for further optimization. In addition, through the analysis of the absorbance measured from the liquid-phase stream, the concentrations of odor-causing substances dissolved in the water stream may be considered to determine whether to recirculate the water stream to the scrubber. This reduces the usage of fresh water required in the scrubber, which is advantageous in terms of costs. Furthermore, in the process in which the scrubber wastewater is constantly recirculated, when measuring the absorbance of the water stream, the concentration of the odor-causing substances in scrubber circulating water can be monitored in real time, and thus can be used as an indicator to determine the time to replace scrubber water, which is advantageous.
While some embodiments of the present disclosure are described hereinafter with reference to the accompanying drawings, it is to be noted that the embodiments are disclosed only for illustrative purposes and should not be construed as limiting the scope of the present disclosure.
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Hereinafter, embodiments will be presented to aid understanding of the present disclosure. However, the following examples are provided to more easily understand the present disclosure, and the present disclosure is not limited thereto.
1. Measurement of Absorbance of Odor-Causing Substances
The absorbance of known odor-causing substances was measured. Specific odor-causing substances are shown in Tables 3 and 4 below. A spectrophotometer (Evolution 60S) manufactured by Thermo Fisher Scientific was used for absorbance measurement. Each of the substances specified in Tables 3 and 4 below was dissolved in water at a concentration of 1000 ppm (v/v), and then transferred to a quartz cuvette to measure the absorbance in a wavelength range of 190 nm to 270 nm. Due to solubility limitations, toluene and xylene were dissolved at concentrations of 520 ppm (v/v) and 200 ppm (v/v), respectively, and then measured in the same manner. The absorbance measurement results for each substance are also shown in Tables 3 and 4. In addition, a graph based on the data shown in Table 3 is shown in
As a result of measuring the absorbance of the odor-causing substances, it was seen that each of the odor-causing substances had an inherent absorbance at a specific wavelength in a wavelength band range of about 170 nm to 280 nm as seen from Tables 3 and 4, and
Although the embodiment of the present disclosure has been disclosed for illustrative purposes, the present disclosure is not limited to the above-described embodiment. In addition, those skilled in the art will appreciate that various modifications, additions, and substitutions are possible, without departing from the scope and spirit of the disclosure as disclosed in the accompanying claims. Furthermore, it is intended that such modifications are not to be interpreted independently from the technical idea or prospect of the disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0079206 | Jun 2022 | KR | national |
