Method for measuring content of phenolic organic matters in tar residue and phenol-containing wastewater

Abstract

The invention provides a method for determining the content of phenolic organic matters in tar residue and phenolic wastewater, which comprises the following steps: optimizing an MRM (Magnetic Resonance Modeling) method based on a GC-QQQ optimizer to obtain an optimized MRM method; detecting mixed standard solutions of phenol, o-methylphenol and p-methylphenol with different concentration gradients by using an optimized MRM method to obtain a linear regression equation corresponding to the characteristic ion flow peak area and the concentration of each compound, and taking the linear regression equation as a quantitative standard curve equation of each compound; the method comprises the following steps: extracting organic matters in a liquid phase and a solid content of coal tar and phenolic wastewater raw materials into an organic phase, and circularly washing the raw materials for multiple times by using an extraction solvent to obtain a to-be-detected organic phase; detecting a to-be-detected organic phase by using an optimized MRM method, and comparing and matching the quantitative ion pair and the qualitative ion pair with compounds in the standard solution to obtain a characteristic peak of the to-be-detected organic phase; and obtaining the content of each compound in the sample to be detected according to the peak area of the characteristic peak of each compound and the quantitative standard curve equation.

Description

Technical Field

[0001] The invention belongs to the field of energy chemical industry and analysis technology, and in particular belongs to a method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater. Background Art

[0002] In recent years, the coal chemical industry has developed rapidly. However, due to the limitation of process technology, a large amount of waste pollutants such as tar residue, coke powder, slag, liquefied residue, sludge and phenol-containing wastewater will be generated in the process. Tar residue is a viscous solid or semi-solid mixture produced by the coal chemical industry. Its main components are coal tar, coal powder, coke powder, resinous polymers and mechanical impurities. There are many phenolic organic pollutants in phenol-containing wastewater. After these pollutants enter the atmosphere, soil and water bodies, they will have ecotoxic effects on animals, plants and microorganisms. They can be absorbed and enriched by plants and enter the food chain, thus affecting human health. Among them, phenol, as a harmful substance, can cause acute or chronic damage to health. Long-term exposure to phenol may cause abnormal breathing, tremors, followed by coma and respiratory arrest. International regulatory agencies have also set strict standards for the emission of phenol into the environment. For example, the US Environmental Protection Agency stipulates that the concentration of phenol on the water surface must be less than 1 ppb.

[0003] Against the backdrop of increasing environmental protection requirements, the coal chemical industry is in urgent need of industrial and technological upgrades to reduce the impact of waste pollutants such as tar residue and phenol-containing wastewater on the environment, convert conventional industrial waste pollutants into products, further improve coal utilization efficiency, and thereby promote the optimization of the energy structure and move towards a green, low-carbon, high-quality and sustainable development path.

[0004] However, coal tar and phenol-containing wastewater have complex components, and the liquid phase contains inorganic and organic substances, as well as solids. The existing technology lacks a method that can extract phenolic organic substances without loss and detect their content. Therefore, a complete method is needed to accurately analyze the content of phenolic organic substances in waste before and after treatment. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater, so as to solve the technical problem that the content of phenolic organic matter in wastewater cannot be accurately measured in the prior related technology.

[0006] To achieve the above object, the present invention provides the following technical solutions: A method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater comprises the following steps: The MRM method was optimized based on the GC-QQQ optimizer, and the optimized MRM method suitable for phenol, o-cresol and p-cresol was obtained; Using the optimized MRM method to detect mixed standard solutions of phenol, o-cresol, and p-cresol with different concentration gradients, a linear regression equation corresponding to the characteristic ion current peak area of ​​each compound and its concentration is obtained, and the linear regression equation is used as the quantitative standard curve equation of each compound; Extracting organic matter from the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials into an organic phase, and using an extraction solvent to wash the raw materials through multiple cycles to obtain an organic phase to be tested; The optimized MRM method is used to detect the organic phase to be tested, and the characteristic peaks of the organic phase to be tested are obtained by comparing and matching the quantitative ion pairs and the qualitative ion pairs with the compounds in the standard solution; According to the peak area of ​​the characteristic peak of each compound and based on the quantitative standard curve equation, the specific content of each compound in the sample to be tested is obtained.

[0007] Further, the process of optimizing the MRM method based on the GC-QQQ optimizer to obtain the optimized MRM method suitable for phenol, o-methylphenol and p-methylphenol is: The precursor ions are fragmented at different collision energies, and the product ions with higher responses are selected; Selecting the ion pair with the highest response among the product ions with higher response as the quantitative ion pair; Two additional pairs of qualifier ion pairs were selected for each compound, the responses of which were just below the highest responding ion pair.

[0008] Further, based on the collision energy corresponding to the quantitative ion pair and the qualitative ion, the collision energy is optimized to obtain the collision energy with the highest response; When optimizing the collision energy, the collision energy is increased and decreased in equal proportion, and the collision energy with the highest response and the most optimized collision energy is selected under the increased and decreased collision energies.

[0009] Further, the mixed standard solutions of phenol, o-cresol and p-cresol with different concentration gradients are: The concentrations of phenol, o-cresol and p-cresol are all 5 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL and 100 μg / mL mixed standard solutions.

[0010] Furthermore, the instruments and equipment used in the optimized MRM method detection are: Agilent 8890-7000D gas chromatograph tandem triple quadrupole mass spectrometer, Dionex ASE 350 rapid solvent extractor and Gilson ASPEC XL liquid handling system.

[0011] Furthermore, the detection conditions of the optimized MRM method are: Chromatographic column: Agilent J&W HP-5, 30m; Carrier gas: helium, purity ≥ 99.999%.

[0012] Furthermore, the extraction process uses a rapid solvent extractor.

[0013] Furthermore, the extraction solvent used by the rapid solvent extractor is ethyl acetate.

[0014] Furthermore, the volume ratio of the ethyl acetate to the aqueous solution to be tested is 1:1.

[0015] Furthermore, the solvent extractor obtains the organic phase to be tested based on high performance liquid chromatography extraction.

[0016] Furthermore, the temperature during the extraction is 75-100° C., the pressure is 1500 psi, the heating time is 5 min, the static time is 5 min, the flushing volume is 60%, the purge time is 100 seconds; and the number of cycles is 3 times.

[0017] Compared with the prior art, the present invention has the following beneficial technical effects: The invention provides a method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater, comprising the following steps: optimizing an MRM method based on a GC-QQQ optimizer to obtain an optimized MRM method suitable for phenol, o-cresol and p-cresol; using the optimized MRM method to detect mixed standard solutions of phenol, o-cresol and p-cresol with different concentration gradients to obtain a linear regression equation corresponding to the characteristic ion flow peak area of ​​each compound and its concentration, and using the linear regression equation as a quantitative standard curve equation for each compound; extracting organic matter in the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials into an organic phase, and using the linear regression equation to obtain a linear regression equation corresponding to the characteristic ion flow peak area of ​​each compound and its concentration; extracting organic matter in the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials into an organic phase, and using the linear regression equation to obtain a linear regression equation corresponding to the characteristic ion flow peak area of ​​each compound and its concentration; and using the linear regression equation to obtain a linear regression equation corresponding to the characteristic ion flow peak area of ​​each compound and ... The raw material is washed with an extraction solvent through multiple cycles to obtain an organic phase to be tested; the organic phase to be tested is detected using the optimized MRM method, and the characteristic peaks of the organic phase to be tested are compared and matched with the compounds in the standard solution through quantitative ion pairs and qualitative ion pairs; the content of each specific compound in the sample to be tested is obtained according to the peak area of ​​the characteristic peak of each compound and based on the quantitative standard curve equation; the present application can completely separate the phenolic organic matter in the sample to be tested from other compounds with the same or similar retention time in gas chromatography, and remove the influence of background and impurities, so as to obtain more accurate qualitative and quantitative analysis results of the phenolic organic matter.

[0018] Furthermore, by finely controlling the fragmentation process of the precursor ions at different collision energies, this method can accurately screen out the product ions with the strongest response signals. These ions not only represent the characteristic fragments of the target compound, but also ensure the high sensitivity of the detection. Furthermore, the ion pairs with the highest response are selected from the many product ions with higher response as the quantitative ion pairs, which greatly improves the accuracy and stability of the quantitative analysis. To enhance the reliability of the results, two pairs of qualitative ion pairs with slightly lower responses but still significant are additionally selected for each compound. These ion pairs serve as auxiliary verification methods to effectively avoid the risk of misjudgment that may be caused by a single ion pair. This method not only optimizes the parameter settings of the MRM mode, improves the detection sensitivity and selectivity, but also enhances the credibility of data analysis through a multi-ion pair strategy.

[0019] Furthermore, this method maximizes the detection sensitivity of the target compound. During the optimization process, the strategy of increasing and decreasing the collision energy at equal intervals was adopted to systematically and comprehensively explore the changing laws of ion responses at different energy levels. This method not only ensures the accuracy of collision energy adjustment, but also significantly improves the efficiency of finding the optimal collision energy. Finally, the collision energy with the highest response was selected as the optimization result, so that the signal intensity of the target compound reached the best, further improving the accuracy and reliability of quantitative analysis.

[0020] Furthermore, this method uses mixed standard solutions of phenol, o-cresol and p-cresol with different concentration gradients (concentration range covers 5μg / mL to 100μg / mL), which provides a solid standard reference for the accurate determination of the content of these key phenolic organics in tar residue and phenol-containing wastewater. It not only covers a wide range from low concentration to high concentration, but also ensures the linearity and reliability of the experimental results. By comparing and analyzing the response signals of these standard solutions, the corresponding relationship between concentration and signal can be accurately established, thereby realizing the accurate determination of the content of phenolic organics in actual samples.

[0021] Furthermore, this method uses a high-end instrument combination of Agilent 8890-7000D gas chromatograph tandem triple quadrupole mass spectrometer, Dionex ASE 350 rapid solvent extractor and Gilson ASPEC XL liquid handling system, which has significant advantages in optimizing the MRM method for detecting the content of phenolic organic matter in tar residue and phenol-containing wastewater. It not only provides high-precision separation, extraction and quantitative analysis capabilities, but also ensures the automation and efficiency of the experimental process. Through integrated application, it can significantly improve the detection sensitivity, accuracy and reproducibility, while shortening the analysis cycle and reducing human errors.

[0022] Furthermore, this method uses an Agilent J&W HP-5 chromatographic column (30m) as a separation carrier, combined with high-purity (≥99.999%) helium as a carrier gas, to provide excellent chromatographic separation conditions for optimizing the MRM method for detecting the content of phenolic organic matter in tar residue and phenol-containing wastewater, ensuring efficient and accurate separation of target compounds, reducing sample matrix interference, and improving detection sensitivity and accuracy. High-purity helium as a carrier gas ensures the stability and reliability of the chromatographic system.

[0023] Furthermore, the method uses a rapid solvent extractor in combination with ethyl acetate as an extraction solvent, and sets the volume ratio of ethyl acetate to the aqueous solution to be tested to 1:1, thereby improving the extraction efficiency and purity of phenolic organic matter in tar residue and phenol-containing wastewater. The rapid solvent extraction technology, with its high efficiency and automation, effectively shortens the extraction time, improves the extraction rate and the repeatability of the extraction process, and eliminates errors that may be caused by manual operation. Ethyl acetate, as an extraction solvent, has good solubility and selectivity for phenolic organic matter, and can efficiently separate the target compound from a complex matrix.

[0024] Furthermore, the extraction conditions set by the present method, including a temperature of 75-100°C, a pressure of 1500psi, a heating time of 5 minutes, a static time of 5 minutes, a flushing volume of 60%, a purge time of 100 seconds, and a cycle number of 3 times, provide an ideal operating environment for the extraction process of phenolic organic matter in tar residue and phenol-containing wastewater. These conditions act together on the extraction system to effectively improve the penetration capacity of the solvent and the desorption efficiency of the target compound, thereby ensuring the adequacy and efficiency of the extraction process. The precisely controlled temperature, pressure, and time parameters help to reduce excessive decomposition of the solvent and degradation of the analyte, thereby ensuring the purity and stability of the extraction product. Multiple cycles of extraction further enhance the extraction effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The total ion current diagram of the MRM test method of the 100 μg / mL standard solution of the embodiment disclosed in the present invention; Figure 2 The standard curve diagram of quantitative analysis of phenol in the disclosed embodiment of the present invention; Figure 3 The standard curve diagram of the quantitative analysis of o-cresol in the disclosed embodiment of the present invention; Figure 4 The standard curve diagram of the quantitative analysis of p-methylphenol in the embodiment disclosed in the present invention; Figure 5 It is a total ion current diagram of the MRM test method of the phenol-containing wastewater raw material disclosed in the embodiment of the present invention; Figure 6This is the total ion current diagram of the MRM test method of the liquid after coal tar treatment according to the embodiment disclosed in the present invention. DETAILED DESCRIPTION

[0026] In the following, only some exemplary embodiments are briefly described. As those skilled in the art will appreciate, the described embodiments may be modified in various ways without departing from the spirit or scope of the present invention. Therefore, the drawings and descriptions are considered to be exemplary and non-restrictive in nature.

[0027] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0028] It should be understood that when used in this specification and the appended claims, the terms "include" and "comprises" indicate the presence of described features, integers, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or combinations thereof.

[0029] It should also be understood that the terms used in the present specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention. As used in the present specification and the appended claims, the singular forms "a", "an" and "the" are intended to include plural forms unless the context clearly indicates otherwise.

[0030] It should be further understood that the term "and / or" used in the present description and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

[0031] Various structural schematic diagrams of the embodiments disclosed in the present invention are shown in the accompanying drawings. These figures are not drawn to scale, and some details are magnified and some details may be omitted for the purpose of clear expression. The shapes of various regions and layers shown in the figures and the relative sizes and positional relationships therebetween are only exemplary, and may deviate in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may additionally design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0032] The embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0033] This embodiment discloses a method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater, comprising the following steps: The MRM method was optimized based on the GC-QQQ optimizer, and the optimized MRM method suitable for phenol, o-cresol and p-cresol was obtained; Using the optimized MRM method to detect mixed standard solutions of phenol, o-cresol, and p-cresol with different concentration gradients, a linear regression equation corresponding to the characteristic ion current peak area of ​​each compound and its concentration is obtained, and the linear regression equation is used as the quantitative standard curve equation of each compound; Extracting organic matter from the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials into an organic phase, and using an extraction solvent to wash the raw materials through multiple cycles to obtain an organic phase to be tested; The optimized MRM method is used to detect the organic phase to be tested, and the characteristic peaks of the organic phase to be tested are obtained by comparing and matching the quantitative ion pairs and the qualitative ion pairs with the compounds in the standard solution; According to the peak area of ​​the characteristic peak of each compound and based on the quantitative standard curve equation, the specific content of each compound in the sample to be tested is obtained.

[0034] Preferably, in the disclosed embodiment, the process of optimizing the MRM method based on the GC-QQQ optimizer to obtain the optimized MRM method suitable for phenol, o-cresol and p-cresol is: The precursor ions are fragmented at different collision energies, and the product ions with higher responses are selected; Selecting the ion pair with the highest response among the product ions with higher response as the quantitative ion pair; Two additional pairs of qualifier ion pairs were selected for each compound, the responses of which were just below the highest responding ion pair.

[0035] Further, based on the collision energy corresponding to the quantitative ion pair and the qualitative ion, the collision energy is optimized to obtain the collision energy with the highest response; When optimizing the collision energy, the collision energy is increased and decreased in equal proportion, and the collision energy with the highest response and the most optimized collision energy is selected under the increased and decreased collision energies.

[0036] Preferably, in the disclosed embodiment, the mixed standard solution of phenol, o-cresol and p-cresol with different concentration gradients is: The concentrations of phenol, o-cresol and p-cresol are all 5 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL and 100 μg / mL mixed standard solutions.

[0037] Preferably, in the embodiments of the present disclosure, the instruments and equipment used in the optimized MRM method detection are: Agilent 8890-7000D gas chromatograph tandem triple quadrupole mass spectrometer, Dionex ASE 350 rapid solvent extractor and Gilson ASPEC XL liquid handling system.

[0038] Preferably, in the disclosed embodiment, the detection conditions of the optimized MRM method are: Chromatographic column: Agilent J&W HP-5, 30m; Carrier gas: helium, purity ≥ 99.999%.

[0039] Preferably, in the embodiment of the present disclosure, the sample to be tested is extracted into an organic phase in a rapid solvent extractor; further, the extraction solvent used in the rapid solvent extractor is ethyl acetate, and the volume ratio of the ethyl acetate to the aqueous solution to be tested is 1:1.

[0040] The present invention provides an embodiment as follows: Preparation of instruments, reagents and materials: Agilent 8890-7000D gas chromatograph coupled with triple quadrupole mass spectrometer; Dionex ASE 350 Rapid Solvent Extractor - Gilson ASPEC XL Liquid Handling System; Phenol, o-cresol, and p-cresol were chemically pure and purchased from Sinopharm Chemical Reagent Co., Ltd.; Ethyl acetate, HPLC grade, was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0041] Sample preparation: The organic matter in the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials is extracted into the organic phase in a rapid solvent extractor. The extraction solvent is used to wash the raw materials through multiple cycles, and the organic matter extraction rate of more than 99% can be achieved. The volume of the extraction solvent is fixed, which avoids the concentration change of the organic matter to be tested caused by the volatilization of the solvent during the sample treatment process. The obtained organic phase is used for detection by gas chromatography tandem triple quadrupole mass spectrometry; Extraction solvent: ethyl acetate, HPLC grade; The extraction temperature was 75-100°C, the pressure was 1500 psi, the heating time was 5 min, the static time was 5 min, the flushing volume was 60%, the purge time was 100 sec, and the number of cycles was 3.

[0042] Table 1 shows the temperature effect of extracting petroleum hydrocarbons from soil in the embodiment of the present disclosure. Increasing the temperature not only increases the extraction recovery rate, but also improves the repeatability of the extraction. When the temperature is 75-100°C, the extraction recovery rate is about 100%, and the relative standard deviation is small, which meets the requirements of the present invention.

[0043] Table 1 Effect of extraction temperature on the recovery rate of petroleum hydrocarbons extracted from soil

[0044] Preparation of standard solution: Accurately weigh phenol, o-cresol, and p-cresol, dissolve them in ethyl acetate solvent, and prepare them into mixed standard solutions with the same concentration of each compound and 1000 μg / mL. Then dilute them into mixed standard solutions with concentrations of 5μg / mL, 10μg / mL, 20μg / mL, 50μg / mL, and 100μg / mL. The standard solutions should be prepared and used immediately, and usually stored in a sealed container at -20℃; Determine instrument analysis conditions, including chromatographic conditions and mass spectrometry conditions: Chromatographic column: Agilent J&W HP-5, 30m; Column box heating program: 50℃ for 1min, then increase the temperature to 260℃ at 3℃ / min, and maintain for 0min; then increase the temperature to 300℃ at 5℃ / min, and maintain for 0min; then run backflush for 2min; Carrier gas: helium, purity ≥99.999%; injection port temperature: 280℃; injection volume: 1μL; injection mode: splitless injection; electron bombardment source: 70eV; ion source temperature: 280℃; transfer line temperature: 280℃; solvent delay: 5min; The detection results of each compound in the 100 μg / mL standard solution obtained according to the analytical conditions are shown in Table 2.

[0045] Table 2 Organic substances detected in standard solutions and their retention times

[0046] The MRM method was established using the GC-QQQ optimizer: first, the precursor ions with higher responses and larger mass numbers were selected; then, the precursor ions were fragmented at different collision energies (5, 15, 25, 35) to select the product ions with higher responses. The ion pairs with the highest response were used as the quantitative ion pairs, and two pairs of qualitative ion pairs were selected for each compound; finally, the collision energy was optimized to obtain the collision energy with the highest response, thus obtaining a complete MRM analysis test method.

[0047] The total ion current of the 100 μg / mL standard solution obtained according to the established MRM analysis method is as follows: Figure 1 shown.

[0048] Table 3 Ion pairs and collision energy results selected for the established MRM analysis method

[0049] Establishment of quantitative method: The prepared mixed standard solutions of phenol, o-cresol and p-cresol with concentrations of 5 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL and 100 μg / mL were detected using the optimized MRM method to obtain the linear regression equation of the characteristic ion current peak area y of each compound and its concentration x (μg / mL), and the standard curve equation and its linear correlation coefficient R were obtained. 2 ; The obtained standard curves of phenol, o-cresol and p-cresol are as follows: Figure 2-4 The linear regression equations of the compounds are shown in Table 4: Table 4 Linear regression equation results of each compound

[0050] Testing of actual samples: After the phenol-containing wastewater raw material was diluted 250 times, and the liquid obtained by the thermal chemical conversion treatment of coal tar was diluted 50 times, the samples were pre-treated and detected using the established MRM method, and the characteristic peaks corresponding to the detected compounds were obtained through quantitative and qualitative ion pairs; The total ion flow chart of phenol-containing wastewater sample measured by MRM analysis method is as follows Figure 5 As shown, the total ion current of the liquid after coal tar treatment measured by MRM analysis method is as follows Figure 6 shown.

[0051] The test results are then used in the quantitative standard curve equation, and the content of each specific compound in the sample to be tested is obtained based on the characteristic ion current peak area of ​​each compound and the quantitative standard curve equation.

[0052] Table 5 Detection results of various compounds in phenol-containing wastewater raw materials

[0053] Table 6 Detection results of compounds detected in liquid after coal tar treatment

[0054] Table 7 Qualitative results of compounds detected in phenol-containing wastewater raw materials

[0055] Table 8 Qualitative results of compounds detected in liquid after coal tar treatment

[0056] The retention time of the detected compound in the sample to be tested is very close to the retention time of the corresponding compound in the standard solution. Combined with the determination of two pairs of qualifier ions, it shows that the qualitative results of the detected compounds are accurate and reliable.

[0057] The MRM (Multiple Reaction Monitoring) method in the present invention is a mass spectrometry technique, which is mainly used for qualitative and quantitative analysis of target compounds. This technique achieves high sensitivity and high selectivity detection of specific compounds by selectively monitoring the conversion of pre-set parent ions to daughter ions. In the analysis of complex samples, the MRM method is particularly effective because it can filter out interfering signals and focus on the signal measurement of the molecules to be tested, making the quantitative analysis more accurate.

[0058] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the attached claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention. Any figure mark in the claims should not be regarded as limiting the claims involved.

[0059] In addition, it should be understood that although this specification is described in accordance with the implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation modes that can be understood by those skilled in the art. The above content is only to illustrate the technical idea of ​​the present invention, and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution according to the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater, characterized in that: The following steps are involved: The MRM method was optimized based on the GC-QQQ optimizer, and the optimized MRM method suitable for phenol, o-cresol and p-cresol was obtained; Using the optimized MRM method to detect mixed standard solutions of phenol, o-cresol, and p-cresol with different concentration gradients, a linear regression equation corresponding to the characteristic ion current peak area of ​​each compound and its concentration is obtained, and the linear regression equation is used as the quantitative standard curve equation of each compound; Extracting organic matter from the liquid phase and solid content of coal tar and phenol-containing wastewater raw materials into an organic phase, and using an extraction solvent to wash the raw materials through multiple cycles to obtain an organic phase to be tested; The optimized MRM method is used to detect the organic phase to be tested, and the characteristic peaks of the organic phase to be tested are obtained by comparing and matching the quantitative ion pairs and the qualitative ion pairs with the compounds in the standard solution; According to the peak area of ​​the characteristic peak of each compound and based on the quantitative standard curve equation, the specific content of each compound in the sample to be tested is obtained.

2. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 1, characterized in that: The process of optimizing the MRM method based on the GC-QQQ optimizer to obtain the optimized MRM method suitable for phenol, o-cresol and p-cresol is as follows: The precursor ions are fragmented at different collision energies, and the product ions with higher responses are selected; Selecting the ion pair with the highest response among the product ions with higher response as the quantitative ion pair; Two additional pairs of qualifier ion pairs were selected for each compound, the responses of which were just below the highest responding ion pair.

3. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 2, characterized in that: Based on the collision energies corresponding to the quantitative ion pair and the qualitative ion, the collision energy is optimized to obtain the collision energy with the highest response; When optimizing the collision energy, the collision energy is increased and decreased in equal proportion, and the collision energy with the highest response and the most optimized collision energy is selected under the increased and decreased collision energies.

4. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 1, characterized in that: The mixed standard solutions of phenol, o-cresol and p-cresol with different concentration gradients are: The concentrations of phenol, o-cresol and p-cresol are all 5 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL and 100 μg / mL mixed standard solutions.

5. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 2, characterized in that: The instruments and equipment used in the optimized MRM method detection are: Agilent 8890-7000D gas chromatograph tandem triple quadrupole mass spectrometer, Dionex ASE 350 rapid solvent extractor and Gilson ASPEC XL liquid handling system.

6. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 2, characterized in that: The detection conditions of the optimized MRM method are: Chromatographic column: Agilent J&W HP-5, 30m; Carrier gas: helium, purity ≥ 99.999%.

7. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 1, characterized in that: The extraction process adopts a rapid solvent extractor.

8. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 7, characterized in that: The extraction solvent used by the rapid solvent extractor is ethyl acetate.

9. The method for measuring the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 8, characterized in that: The volume ratio of the ethyl acetate to the aqueous solution to be tested is 1:

1.

10. The method for determining the content of phenolic organic matter in tar residue and phenol-containing wastewater according to claim 7, characterized in that: The temperature during the extraction is 75-100° C., the pressure is 1500 psi, the heating time is 5 min, the static time is 5 min, the flushing volume is 60%, the purge time is 100 seconds; and the number of cycles is 3 times.

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