A method for identifying organic matters in coal chemical high-salinity wastewater based on ultra-high performance liquid chromatograph high-resolution mass spectrometry

Abstract

This application relates to a method for identifying organic matter in high-salt coal chemical wastewater based on ultra-high performance liquid chromatography and high-resolution mass spectrometry (UHPLC). Specifically, it provides a slime remover, the active ingredient of which is prepared by purifying coal pyrolysis wastewater. This active ingredient contains the first fraction of the coal pyrolysis wastewater, which is prepared by the following method: (1) the coal pyrolysis wastewater is purified and extracted using SPE to obtain a purified product of the coal pyrolysis wastewater; (2) the purified product of the coal pyrolysis wastewater from step (1) is separated using HPLC, and the first peak product is collected to obtain the first fraction of the coal pyrolysis wastewater. The slime remover of this application reduces the emissions from coal pyrolysis waste treatment and simultaneously realizes the comprehensive utilization of coal pyrolysis products.

Description

Technical Field

[0001] This invention belongs to the field of coal pyrolysis, specifically relating to a method for identifying organic matter in high-salt wastewater from coal chemical industry based on ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). Background Technology

[0002] Currently, there are obstacles in the treatment of coal pyrolysis wastewater. The high salinity of coal pyrolysis wastewater makes it extremely difficult to analyze the pollutants it contains, thus hindering its treatment and recycling, and causing significant environmental impact. Therefore, there is an urgent need in this field to analyze and identify the main pollutants in coal pyrolysis wastewater and to provide subsequent treatment methods to reduce the environmental impact of wastewater from the coal pyrolysis process. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this application aims to provide a method for preparing single-component samples of major pollutants by enriching wastewater using SPE, separating and purifying it using HPLC, obtaining the precise composition of the major pollutants through liquid chromatography-mass analysis, extrapolating the chemical formulas, identifying the compound structure by combining the physical properties of the target compounds, and providing an industrial application for the major pollutants.

[0004] Based on the above technical route, this application provides a slime remover, wherein the active ingredient of the slime remover is prepared by purifying coal pyrolysis wastewater, wherein the active ingredient of the slime remover contains the first fraction of coal pyrolysis wastewater, and the first fraction of coal pyrolysis wastewater is prepared by the following method: (1) coal pyrolysis wastewater is purified and extracted using SPE to obtain a purified product of coal pyrolysis wastewater; (2) the purified product of coal pyrolysis wastewater in step (1) is separated by HPLC, and the first peak product is collected to obtain the first fraction of coal pyrolysis wastewater.

[0005] As some embodiments of this application, the SPE purification and extraction conditions in step (1) are SPE normal phase extraction, the adsorbent includes at least one of silica adsorbent, alumina, and magnesium silicate adsorbent, and the eluting machine is methanol.

[0006] As some embodiments of this application, the HPLC separation and purification conditions in step (2) are as follows: C18 column, the ratio of methanol to acetonitrile in the mobile phase is 1:3, the system is first washed with the mobile phase, the column is balanced, and the baseline is stabilized. The first fraction of the coal pyrolysis wastewater is the first peak product of the HPLC separation and purification, with a retention time of 7.254 seconds.

[0007] As some embodiments of this application, the slime remover comprises 10-40 parts of an ethanol solution of zinc thiram, 10-40 parts of the first fraction of the coal pyrolysis wastewater, 5-20 parts of nonylphenol polyoxyethylene ether, 5-20 parts of triethanolamine, 5-20 parts of sodium dodecyl sulfate, 1-5 parts of calcium mercaptoacetate, and 150-300 parts of water, wherein the zinc thiram in the ethanol solution has a mass percentage concentration of 40-60 wt%.

[0008] As some embodiments of this application, the slime remover comprises 30 parts of an ethanol solution of zinc thiram, 30 parts of the first fraction of the coal pyrolysis wastewater, 15 parts of nonylphenol polyoxyethylene ether, 15 parts of triethanolamine, 15 parts of sodium dodecyl sulfate, 2 parts of calcium mercaptoacetate, and 200 parts of water, wherein the zinc thiram in the ethanol solution has a mass percentage concentration of 40-60 wt%.

[0009] This application also provides a method for preparing the active ingredient of a slime remover, the method comprising the following steps: (1) coal pyrolysis wastewater is purified and extracted using SPE to obtain a purified product of coal pyrolysis wastewater; (2) the purified product of the coal pyrolysis wastewater in step (1) is separated using HPLC and the first peak product is collected; (3) raw materials are added in the following order: nonylphenol polyoxyethylene ether, water, then zinc thiram solution, the first peak product of coal pyrolysis wastewater, then triethanolamine, sodium dodecyl sulfate, calcium mercaptoacetate, and finally all raw materials are stirred and mixed evenly.

[0010] As some embodiments of this application, the SPE purification and extraction conditions in step (1) are SPE normal phase extraction, the adsorbent includes at least one of silica adsorbent, alumina, and magnesium silicate adsorbent, and the eluting machine is methanol.

[0011] As some embodiments of this application, the HPLC separation and purification conditions for step (2) are as follows: C18 column, the ratio of methanol to acetonitrile in the mobile phase is 1:3, the system is first washed with the mobile phase, the column is balanced, and the baseline is stabilized. One fraction of the coal pyrolysis wastewater is the first peak product of the HPLC separation and purification, with a retention time of 7.254 seconds.

[0012] As some embodiments of this application, the slime remover comprises the following raw materials in parts by weight: 10-40 parts of an ethanol solution of zinc thiram, 10-40 parts of the first fraction of coal pyrolysis wastewater, 5-20 parts of nonylphenol polyoxyethylene ether, 5-20 parts of triethanolamine, 5-20 parts of sodium dodecyl sulfate, 1-5 parts of calcium mercaptoacetate, and 150-300 parts of water, wherein the zinc thiram in the ethanol solution has a mass percentage concentration of 40-60 wt%.

[0013] This application also provides the application of the described slime remover or the slime remover prepared by the described preparation method in industrial circulating cooling water.

[0014] As some embodiments of this application, the slime remover is used for slime removal and sterilization.

[0015] As described above, the identification and application of major pollutants in coal pyrolysis wastewater in this application have the following beneficial effects:

[0016] 1. This application overcomes the interference of high salinity in coal pyrolysis wastewater on the analysis of its main components by using SPE enrichment.

[0017] 2. This application has determined the chemical composition of the main pollutants in the first fraction of coal pyrolysis wastewater through analysis. This is the first time in the art that one of the main pollutants in coal pyrolysis wastewater has been identified.

[0018] 3. This application confirms that the main pollutant in the first fraction of the coal pyrolysis wastewater is isothiazolinone.

[0019] 4. This application uses the purified product of the first fraction of coal pyrolysis wastewater to prepare a slime remover, which reduces the emissions from coal pyrolysis waste treatment and realizes the comprehensive utilization of coal pyrolysis products.

[0020] 5. The slime remover of this application has better effects than isothiazolinone in terms of slime removal rate, heterotrophic bacteria sterilization rate and sulfate-reducing bacteria sterilization rate. It is speculated that the other unpurified components present in the primary purified component of this application have a synergistic effect on isothiazolinone, which promotes slime removal and sterilization effect. It can be applied to slime removal and sterilization in industrial circulating cooling water. Attached Figure Description

[0021] Figure 1 The ion chromatogram of fraction 4-1 extracted in positive ion mode is shown.

[0022] Figure 2 The 260 nm HPLC chromatogram of fraction 4-1 is shown.

[0023] Figure 3 The mass spectrum of fraction 4-1 in positive ion mode is shown.

[0024] Figure 4 The ion chromatogram of the 4-1 fraction extracted in positive ion mode is shown.

[0025] Figure 5 The mass spectrum of fraction 4-1 in positive ion mode is shown.

[0026] Figure 6 The chromatogram of the 4-1 fraction in negative ion mode is shown.

[0027] Figure 7 The mass spectrum of fraction 4-1 in negative ion mode is shown.

[0028] Figure 8 The gas chromatographic (GC) characterization results of the major components of the 4-1 fraction are shown. Detailed Implementation

[0029] To make the technical means, creative features, achieved objectives, and effects of this application readily understandable, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0030] [Experimental Materials]

[0031] The experimental reagents and consumables involved in this application are shown in Table 1.

[0032]

[0033] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0034] Example 1: Preliminary treatment of coal pyrolysis wastewater according to this application

[0035] This application utilizes SPE enrichment technology to overcome the adverse effects of high salt concentration in coal pyrolysis wastewater on the separation and identification of pollutants, thereby identifying the main pollutants in the wastewater and providing a technical basis for the clean treatment of coal pyrolysis wastewater. The specific treatment route is as follows: SPE enrichment of the coal pyrolysis wastewater, HPLC separation and purification, preparation of single-component samples of the main pollutants, obtaining the precise components of the main pollutants through liquid chromatography-mass spectrometry (LC-MS), extrapolating their chemical formulas, and combining the physical properties of the target compounds to conduct compound structure identification, thus determining the main pollutants.

[0036] 1.1 Wastewater SPE Concentration and Purification

[0037] Take 30 ml of water sample No. 4 (Yidong Group, Donghua Energy) and purify and extract it using SPE, which is the adsorbent used in normal phase extraction. Silica gel adsorbent can be used, but alumina or magnesium silicate adsorbent can also be used. Elute with 1 ml of methanol, evaporate to dryness, redissolve with 100 μl of methanol, and wait for HPLC to separate the fraction.

[0038] 1.2 Mass spectrometry-guided collection of single fractions

[0039] The purified and concentrated water sample from step 1.1 was analyzed using HPLC. A C18 column was selected, and the mobile phase consisted of methanol and acetonitrile in a 1:3 ratio. The system was first flushed with the mobile phase to equilibrate the column and ensure baseline stability. Next, the purified and concentrated water sample from step 1.1 was taken and filtered through a 0.45 μm filter membrane. Then, the detection wavelength and flow rate were set, and the sample was injected for analysis.

[0040] Fractions were collected according to their retention times, and the fractions and their respective retention times are shown in Table 3.

[0041]

[0042] Example 2: Separation and purification of major pollutants in fraction 4-1 of preliminary treatment of coal pyrolysis wastewater

[0043] The fractions collected in Table 3 were analyzed using UPLC-HRMS. Fraction 4-1 in Table 3 was analyzed.

[0044] Chromatographic conditions: The mobile phase was methanol (MS) and water (MS), and a BEH C18 column was used with gradient elution.

[0045] Acquity UPLC BEH C 18 Chromatographic column (100 mm × 2.1 mm, 1.7 μm); 1 mmol / L methanol-water mobile phase, gradient elution: 0–1 min, 10% A; 1–4 min, 10%–15% A; 4–18 min, 15%–30% A; 18–24 min, 30%–50% A; 24–28 min, 50%–100% A; 28–31 min, 100% A; 31–32 min, 100%–10% A; 32–35 min, 10% A; column temperature 30℃; flow rate 0.3 mL / min; injection volume 5 µL.

[0046] Mass spectrometry conditions: ESI source, positive / negative ion mode, full scan; scan time: 0-15 min; scan range: 100-600 Da.

[0047] 2.1 Different analytical methods were used to identify the main components of fraction 4-1.

[0048] 2.1.1 HPLC-MS analysis chromatogram

[0049] 4.1 The extract ion chromatogram, mass spectrum, and 260nm HPLC chromatogram corresponding to the fraction are shown in Figures 1-3, respectively.

[0050] The above three analytical results for fraction 4-1 are shown in the figure below. Figures 1-3 ,from Figures 1-3 visible, Figure 1 and Figure 2 The main peak marked by the middle arrow corresponds to Figure 3 The component labeled 231.0.

[0051] 2.1.2 UPLC-HRMS chromatogram analysis

[0052] The ion chromatograms and mass spectra of fraction 4.1 extracted in positive ion mode and fraction 4.1 extracted in negative ion mode are shown in Figures 4-7, respectively.

[0053] The main components of fraction 4-1 are the main peaks marked with arrows in each figure.

[0054] 2.4 Determination of Molecular Formula

[0055] Through mass spectrometry ( Figure 2 and Figure 4 Analysis revealed that the main component of fraction 4-1 exhibited a peak at m / z of 231.0230 in positive ion mode and a peak at m / z of 229.0189 in negative ion mode. Therefore, the relative molecular mass of the main component of fraction 4-1 should be 230.0152. The possible chemical formulas of the main components of fraction 4-1 are shown in Table 4.

[0056] Table 4.4-1 Possible chemical formulas of the main components of the fraction

[0057]

[0058] 2.6 Structural identification of major components

[0059] Since the compounds of the main component of fraction 4-1 have good absorption peaks at wavelengths of 260 nm and 280 nm, it indicates that the compound has a large conjugated system. Therefore, compounds with an unsaturation degree of less than 5 can be ruled out. The structural formulas of the above compounds were obtained from websites such as Pubchem. The main component of fraction 4-1 is presumed to be C9H2N4O4, and its structure is shown in Formula I:

[0060] Formula I

[0061] Table 6 Characterization of the main component compounds of fraction 4-1

[0062]

[0063] 2.7 Identification of the major component compounds of fraction 4-1

[0064] Gas chromatography (GC) was used to test the concentrated brine produced during the actual production process of Donghua Energy, a subsidiary of the Yidong Group, in coal chemical wastewater. The results are as follows: Figure 8 As shown.

[0065] Gas chromatography (GC) conditions: Column: DB-Wax (30m*0.25mm, 0.25um), Carrier gas: He, Injector temperature: 200℃, Initial column temperature: 50℃-3min-20℃ / min-120℃-3min, Interface temperature: 200℃, Constant flow mode: 30cm / sec, Split ratio: 70:1, Injection volume: 0.2uL

[0066] Analysis showed that the retention time was 6.77. Database comparison revealed that the main organic matter in the water was isothiazolinone (CAS No.: 26172-55-4).

[0067] from Figure 8 As can be seen, some characteristic peaks were not detected. Therefore, liquid chromatography was used to analyze the organic matter in the water, and the results are as follows. Figure 8 As shown.

[0068] Example 3 Application of the main components of fraction 4-1

[0069] Isothiazolinone is a bactericide and is commonly used in industry as a slime remover. This study explores the use of primary purified fraction 4-1 to reduce emissions from coal pyrolysis waste treatment to a certain extent, while simultaneously achieving comprehensive utilization of coal pyrolysis products.

[0070] 3.1 Preparation of fraction 4-1

[0071] According to Example 1, fraction 4-1 was collected and the process was repeated 3 times to obtain primary purified component samples 1-3.

[0072] 3.2 Evaluation of the slime-removing and bactericidal properties of the primary purified components

[0073] The method for evaluating the slime-removing and bactericidal properties in this application refers to the relevant method in CN112591905A, as follows:

[0074] (1) Add bacterial strains and nutrients to the culture tank to cultivate bacteria and algae;

[0075] (2) The culture is complete when the culture medium becomes slightly turbid. Connect the stainless steel test tube, which is 250 mm long and 10-15 mm in inner diameter. Circulate the tube dynamically until the stainless steel test tube grows sludge to the specified requirements. Remove the test tube and dry it at 40°C for 2 hours. Weigh it.

[0076] (3) Reconnect the weighed test tubes to the test chamber, add 300 mg / L of slime remover (primary purified component), run for 24 hours, then remove the test tubes, dry at 40℃ for 2 hours, and weigh. The overall dynamic control parameters are: pH value = 8.0~8.5, temperature 32±1℃, flow rate 1.0 m / h. Before adding the reagent and after 24 hours of operation, take samples of the culture medium to determine the sterilization rate of heterotrophic bacteria and sulfate-reducing bacteria.

[0077] The bactericidal performance evaluation refers to the standards "Determination of slime-forming bacteria in industrial circulating cooling water by plate counting method" (GB / T14643.1) and "Performance evaluation method of bactericides" (SY / T5890).

[0078] Isothiazolinone 300 mg / L was used as a control.

[0079] The measurement results are shown in Table 8.

[0080] Table 8

[0081]

[0082] As shown in Table 8, the primary purified components 1-3 of this application, as slime removers, have better effects than isothiazolinone in terms of slime removal rate, heterotrophic bacteria sterilization rate, and sulfate-reducing bacteria sterilization rate. It is speculated that the other unpurified components present in the primary purified components of this application have a synergistic effect on isothiazolinone, which promotes slime removal and sterilization effects, and can be applied to slime removal and sterilization in industrial circulating cooling water.

[0083] Example 4: Preparation of a slime remover containing the primary purified components of this application

[0084] This application uses the first fraction of coal pyrolysis wastewater to replace isothiazolinone in the preparation of a slime remover.

[0085] The slime remover comprises the following raw materials by weight: 10-40 parts of zinc thiram solution, 10-40 parts of the first fraction of coal pyrolysis wastewater, 5-20 parts of nonylphenol polyoxyethylene ether, 5-20 parts of triethanolamine, 5-20 parts of sodium dodecyl sulfate, 1-5 parts of calcium mercaptoacetate, and 150-300 parts of water. The zinc thiram solution has a mass percentage concentration of less than 70 wt%, and the solvent is ethanol.

[0086] The zinc thiram solution is a 40-60 wt% zinc thiram solution prepared with ethanol;

[0087] The preparation method of the slime remover includes the following steps:

[0088] Mix all ingredients thoroughly.

[0089] The order in which the raw materials are added is as follows:

[0090] Nonylphenol polyoxyethylene ether, water;

[0091] Zinc thiram solution, the first fraction of coal pyrolysis wastewater;

[0092] Triethanolamine, sodium lauryl sulfate, calcium mercaptoacetate;

[0093] Control the pH of the reaction products to 8-8.5.

[0094] The above description is merely a preferred embodiment of this application and is not intended to limit this application in any way. Although this application has disclosed the preferred embodiment as above, it is not intended to limit this application. Any person skilled in the art can make some modifications or alterations to the methods and techniques disclosed above to create equivalent embodiments without departing from the scope of the technical solution of this application. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of this application without departing from the content of the technical solution of this application shall still fall within the scope of the technical solution of this application.

Claims

1. A slime remover, characterized in that, The active ingredient of the slime remover is prepared by purifying coal pyrolysis wastewater. The active ingredient of the slime remover includes the first fraction of the coal pyrolysis wastewater, which is prepared by the following method: (1) The coal pyrolysis wastewater was purified and extracted using SPE to obtain the purified product of the coal pyrolysis wastewater; (2) Use HPLC to separate the purification products of the coal pyrolysis wastewater in step (1), collect the first peak product, and obtain the first fraction of the coal pyrolysis wastewater; The coal pyrolysis wastewater is a high-salt wastewater from coal chemical industry. The retention time of the first peak product in the first fraction was 7.254 seconds. The main component of the first fraction is isothiazolinone, with a precise molecular weight of 230.0152.

2. The slime remover according to claim 1, characterized in that, The SPE purification and extraction conditions in step (1) are SPE normal phase extraction, the adsorbent includes at least one of silica gel adsorbent, alumina, and magnesium silicate adsorbent, and the eluting machine is methanol.

3. The slime remover according to claim 1, characterized in that, The HPLC separation and purification conditions in step (2) are as follows: C18 column, the ratio of methanol to acetonitrile in the mobile phase is 1:3, the system is first washed with the mobile phase, the column is balanced, and the baseline is stabilized. The first fraction of the coal pyrolysis wastewater is the first peak product of the HPLC separation and purification, with a retention time of 7.254 seconds.

4. The slime remover according to claim 1, characterized in that, The slime remover comprises an ethanol solution of zinc thiram 10 40 portions, the first fraction of the coal pyrolysis wastewater, 10 40 parts, nonylphenol polyoxyethylene ether 5 20 portions, triethanolamine 5 20 parts, sodium dodecyl sulfate 5 20 portions, calcium thioglycolate 1 5 portions and 150 ml of water 300 parts, the ethanol solution of zinc thiram contains zinc thiram at a mass percentage concentration of 40-60 wt%.

5. The slime remover according to claim 1, characterized in that, The slime remover comprises 30 parts of an ethanol solution of zinc thiram, 30 parts of the first fraction of the coal pyrolysis wastewater, 15 parts of nonylphenol polyoxyethylene ether, 15 parts of triethanolamine, 15 parts of sodium dodecyl sulfate, 2 parts of calcium mercaptoacetate, and 200 parts of water. The zinc thiram in the ethanol solution has a mass percentage concentration of 40-60 wt%.

6. A method for preparing the active ingredient of the slime remover according to any one of claims 1-5, characterized in that, The method includes the following steps: (1) The coal pyrolysis wastewater was purified and extracted using SPE to obtain the purified product of the coal pyrolysis wastewater; (2) The purified products of the coal pyrolysis wastewater from step (1) were separated by HPLC, and the first peak product was collected; (3) Add the raw materials in the following order: nonylphenol polyoxyethylene ether, water, then add zinc thiram solution, the first fraction of coal pyrolysis wastewater, then add triethanolamine, sodium dodecyl sulfate, calcium mercaptoacetate, and finally stir and mix all the raw materials evenly.

7. The preparation method according to claim 6, characterized in that, The SPE purification and extraction conditions in step (1) are SPE normal phase extraction, the adsorbent includes at least one of silica gel adsorbent, alumina, and magnesium silicate adsorbent, and the eluting machine is methanol.

8. The preparation method according to claim 6, characterized in that, The HPLC separation and purification conditions in step (2) are as follows: C18 column, methanol and acetonitrile in the mobile phase in a ratio of 1:3, the system is first rinsed with the mobile phase, the column is balanced, and the baseline is stabilized. One fraction of the coal pyrolysis wastewater is the first peak product of the HPLC separation and purification, with a retention time of 7.254 seconds.

9. The preparation method according to claim 6, characterized in that, The slime remover comprises the following ingredients by weight: 10 parts of ethanol solution of zinc thiram. 40 samples, the first peak product of coal pyrolysis wastewater 10 40 parts, nonylphenol polyoxyethylene ether 5 20 portions, triethanolamine 5 20 parts, sodium dodecyl sulfate 5 20 portions, calcium thioglycolate 1 5 portions and 150 ml of water 300 parts, the ethanol solution of zinc thiram contains zinc thiram at a mass percentage concentration of 40-60 wt%.

10. The application of the slime remover according to any one of claims 1 to 5 or the slime remover prepared by the preparation method according to any one of claims 6 to 9 in slime removal and sterilization in industrial circulating cooling water.

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