Circulating water material leakage simulation device

Abstract

The circulating water material leakage simulation device comprises a water tank, a bottom port of the water tank is connected with an inlet of a circulating water pump, an outlet of the circulating water pump is connected with one end of a heater, the other end of the heater is connected with one end of a circulating water pipeline, and the other end of the circulating water pipeline is connected with a top port of the water tank; a labeling unit is arranged on the circulating water pipeline; a pretreatment unit is arranged on the circulating water pipeline between the labeling unit and the water tank; the water tank is connected with the cleaning unit. The device can simulate the real leakage condition of the circulating water material, enables the water flow to form dynamic circulating water, realizes the addition of the simulated leakage material in the circulating water through the standard adding unit, realizes the sampling of the circulating flowing water after the simulated leakage material is added through the pretreatment unit, and is combined with the gas chromatograph-mass spectrometer to carry out material analysis. Therefore, the problems that in the prior art, due to the fact that circulating flowing water cannot be simulated, sampling is uneven, representativeness is not achieved, analysis of feature information of leaked materials is inaccurate, and tracing is difficult are solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of circulating water material leakage, and particularly relates to a circulating water material leakage simulation device. BACKGROUND

[0002] The water-cooled heat exchanger in the circulating water system of the oil refinery, referred to as the water cooler, bears the heat exchange cooling of most production devices of the refinery. Due to long-period operation of the devices and deterioration of crude oil, the water cooler may leak due to corrosion and perforation.

[0003] Once the water cooler leaks, the water quality deteriorates, not only intensifying corrosion of the water cooler and shortening the service life of the water cooler, but also intensifying fouling of the water cooler, causing the heat exchange efficiency of the system to decrease, energy consumption to increase, and even causing the circulating water system to shut down and the production device to be out of planned shutdown, resulting in great economic losses.

[0004] The water cooler involved in the circulating water system has various materials and complex components, including heavy oil products (such as diesel and aviation coal) and light products (such as gasoline and naphtha), and it is necessary to trace the leaked material to determine the type of the leaked material and the water cooler with corrosion perforation, so the sampling and detection of the leaked material in the circulating water are particularly important.

[0005] In order to verify the feasibility of the sampling and detection technology, a material leakage simulation experiment is usually adopted, different types of leaked materials are configured in water, and then sampling and material leakage analysis are performed, and the feasibility of the sampling and analysis technology is verified by comparing the analysis results with the types of the leaked materials in the water. The pretreatment of the sample is performed at the same time as the simulation of the leakage of the circulating water, which not only saves the time for sample pretreatment after sampling, but also more truly simulates the real scene of stable circulating water flow rate and pressure, and the simulation data has reliability.

[0006] The commonly used sampling and analysis technology is solid-phase extraction technology. Solid-phase extraction (SPE) is a sample pretreatment technology, which combines liquid-solid extraction and liquid chromatography technology. SPE is mainly used for sample separation, purification and concentration, aiming to reduce sample matrix interference and improve detection sensitivity. The technology can more effectively separate the analyte from the interfering components and improve the recovery rate of the analyte by selective adsorption and selective elution.

[0007] Solid phase extraction method is divided into headspace solid phase microextraction (HS-SPME), under-liquid solid phase microextraction (SPME), stir bar sorptive extraction (SBSE). SPME technology is based on the principle of "like dissolves like". The extraction head is coated with a solid phase microextraction coating on a quartz fiber, which is protected by a thin stainless steel tube to prevent the quartz fiber from breaking. The fiber head can be extended and retracted in the steel tube. Dip the fiber head into the sample solution or headspace gas for a period of time, and stir the solution to speed up the equilibrium between the two phases. After the equilibrium is reached, the fiber head is inserted into the gas chromatography vaporization chamber, and the adsorbed substances on the coating are thermally desorbed. After desorption in the vaporization chamber, the extracted substances are introduced into the chromatographic column by the mobile phase, completing the whole process of extraction, separation and concentration. SPME has high selectivity for organic matter. Using SPME can quickly and effectively determine trace organic matter in water samples. SPME technology integrates sampling, extraction and concentration into one, does not require organic solvents, and avoids secondary pollution to the environment. This method is easy to operate, has high sensitivity, can realize ultra-trace analysis, and is fast and efficient. Stir bar sorptive extraction (Stir Bar Sorptive Extraction, SBSE) is a new sample pretreatment technology, which is a solvent-free extraction technology after solid phase microextraction (SPME). It can realize the separation and concentration of trace organic matter, and is mainly applied to the analysis of environmental pollutants and food analysis. Compared with SPME, the extraction phase has a larger volume and higher sensitivity. Combined with gas chromatography / mass spectrometry (GC / MS), it has more advantages in analyzing volatile and semi-volatile organic compounds.

[0008] The current method for artificially preparing, SPME extracting, simulating the real scene of circulating water material leakage and sampling in petrochemical devices is as follows: 1-2 microliters of material are extracted by a microsyringe and added to 2L of water. The mixed solution after stirring is used as the water sample to be tested. 10ml of the sample is taken by a pipette and placed in a sample bottle to fill it to the brim. The bottle cap is closed and placed in a CTC multifunctional automatic sampler. The SPME extraction head is inserted into the sample bottle for heating and shaking, and then enters the gas chromatography / mass spectrometry instrument for material leakage analysis.

[0009] However, the artificially prepared mixture is a static mixture, which is different from the real situation of circulating flow. Especially for diesel oil which is not easy to dissolve, the diesel oil is easy to float above the water surface in the static mixture, which may cause uneven sampling and escape of volatile components in gaseous form during sampling, resulting in non-representative sampling and inaccurate analysis results. It is difficult to trace the material leakage chromatogram.

[0010] Based on this, this application proposes a circulating water material leakage simulation device, which can simulate the real situation of circulating water material leakage, so that the water flow forms dynamic circulating water. The device uses a spiking unit to add simulated leaked materials to the circulating water, and a pretreatment unit to sample the circulating water after adding the simulated leaked materials. The device is then combined with a gas chromatography-mass spectrometry (GC-MS) instrument for material analysis. This solves the problems in the prior art that the inability to simulate circulating water leads to uneven and unrepresentative sampling, resulting in inaccurate analysis of the characteristic information of the leaked materials and difficulty in tracing the source. Summary of the Invention

[0011] The purpose of this invention is to overcome the shortcomings of the prior art and provide a circulating water material leakage simulation device.

[0012] To achieve the above objectives, the present invention adopts the following technical solution:

[0013] A circulating water material leakage simulation device includes a water tank, the bottom port of which is connected to the inlet of a circulating water pump, the outlet of which is connected to one end of a heater, the other end of which is connected to one end of a circulating water pipeline, and the other end of which is connected to the top port of the water tank.

[0014] The circulating water pipeline is equipped with a spiking unit for adding materials;

[0015] A pretreatment unit for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank.

[0016] The water tank is connected to the cleaning unit.

[0017] Preferably, a first valve is provided on the circulating water pipeline.

[0018] Preferably, the spiking unit includes spiking pipelines connected in parallel to both ends of the first valve, and the spiking pipelines are equipped with a second valve and a third valve;

[0019] The spiking line between the second valve and the second valve is connected to the material injection pump.

[0020] Preferably, a fourth valve is provided on the material addition pipeline between the material injection pump and the spiking pipeline.

[0021] Preferably, the preprocessing unit includes an SBSE module and an SPME module;

[0022] The SBSE module includes a hollowed-out mixing box fixed in the circulating water pipeline, and an SBSE stirring rod is installed inside the hollowed-out mixing box;

[0023] The SPME module includes an SPME extraction fiber needle inserted into the circulating water pipeline.

[0024] Preferably, the cleaning unit includes a detergent tank containing detergent, the outlet pipe of the detergent tank is connected to the inlet of a metering pump, and the outlet of the metering pump is connected to a water tank.

[0025] Preferably, a back pressure valve is installed on the circulating water pipeline between the pretreatment unit and the water tank.

[0026] Preferably, a sampling pipe is provided on the circulating water pipeline between the pretreatment unit and the back pressure valve, and a first ball valve is provided on the sampling pipe.

[0027] Preferably, a second pressure sensor is installed on the circulating water pipeline between the pretreatment unit and the sampling tube.

[0028] Preferably, a pipe damper is installed on the circulating water pipeline at the outlet end of the circulating water pump.

[0029] Preferably, a flow sensor, a first pressure sensor, and a first temperature sensor are installed on the circulating water pipeline between the pipe damper and the heater;

[0030] A second temperature sensor is installed on the circulating water pipe at the heater outlet.

[0031] Preferably, a bypass pipeline is connected in parallel at both ends of the circulating water pump, and a bypass valve is installed on the bypass pipeline.

[0032] Preferably, the water tank is equipped with a liquid level sensor for detecting the liquid level.

[0033] Preferably, the bottom of the water tank is provided with a drain pipe, and a drain valve is provided on the drain pipe.

[0034] The beneficial effects of this invention are:

[0035] The device proposed in this application can simulate the real situation of material leakage in circulating water, so that the water flow forms dynamic circulating water. The spiking unit realizes the addition of simulated leaked material to the circulating water, and the pretreatment unit realizes the sampling of the circulating water after adding simulated leaked material. Combined with gas chromatography-mass spectrometry (GC-MS) for material analysis, it solves the problems of uneven and unrepresentative sampling caused by the inability to simulate circulating water in the prior art, which leads to inaccurate characteristic information of leaked material analysis and difficulty in tracing the source. Attached Figure Description

[0036] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments of this application and their descriptions are used to explain this application and do not constitute an undue limitation of this application.

[0037] Figure 1 This is a schematic diagram of the circulating water material leakage simulation device of the present invention;

[0038] Figure 2 This is a schematic diagram of the SBSE module in this invention;

[0039] Figure 3 This is a schematic diagram of the SPME module in this invention;

[0040] Figure 4 This is the chromatogram of the diesel leak detection in Example 6;

[0041] Figure 5 This is the chromatogram of gasoline leak detection in Example 7;

[0042] Figure 6 This is the chromatogram of the detection of petroleum brain leakage in Example 8;

[0043] Figure 7 This is the chromatogram of diesel leak detection in Example 9;

[0044] Figure 8 This is the chromatogram of gasoline leak detection in Example 10;

[0045] Figure 9 This is the chromatogram of the detection of petroleum brain leakage in Example 11;

[0046] Figure 10 This is the chromatogram of the diesel leak detection in Comparative Example 1;

[0047] Figure 11 This is the chromatogram of the diesel leak detection in Comparative Example 2;

[0048] in:

[0049] 1-Water tank;

[0050] 11-Liquid level sensor;

[0051] 12- Drain valve;

[0052] 2- Circulating water pump;

[0053] 21-Bypass piping;

[0054] 22-Bypass valve;

[0055] 3-Heater;

[0056] 31 - Second temperature sensor;

[0057] 4- Circulating water pipeline;

[0058] 41-First valve;

[0059] 42 - Back pressure valve;

[0060] 43-First ball valve;

[0061] 44 - Pipeline damper;

[0062] 441 - Second ball valve;

[0063] 45 - Flow sensor;

[0064] 46 - First pressure sensor;

[0065] 47 - Temperature sensor;

[0066] 48 - Second pressure sensor;

[0067] 5-Stirring pipeline;

[0068] 51-Second valve;

[0069] 52-Third valve;

[0070] 53-Fourth valve;

[0071] 6-Detergent container;

[0072] 61-Metering pump;

[0073] 7-Pre-processing unit;

[0074] 71-SBSE module;

[0075] 711 - Hollowed-out mixing box;

[0076] 712-SBSE stirring rod;

[0077] 72-SPME module;

[0078] 721-SPME extracted fiber needles. Detailed Implementation

[0079] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0080] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0081] In this invention, terms such as "upper," "lower," "bottom," and "top" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are merely relational terms determined for the convenience of describing the structural relationship of the various components or elements of this invention, and do not specifically refer to any component or element in this invention, and should not be construed as limiting this invention.

[0082] In this invention, terms such as "connected" and "linked" should be interpreted broadly, indicating a fixed connection, an integral connection, or a detachable connection; a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can determine the specific meaning of these terms in this invention based on the specific circumstances, and they should not be construed as limitations on the invention.

[0083] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0084] Example 1:

[0085] like Figure 1 As shown, a circulating water material leakage simulation device includes a water tank 1. The bottom port of the water tank 1 is connected to the inlet of a circulating water pump 2, the outlet of the circulating water pump 2 is connected to one end of a heater 3, the other end of the heater 3 is connected to one end of a circulating water pipeline 4, and the other end of the circulating water pipeline 4 is connected to the top port of the water tank 1.

[0086] The circulating water pipeline 4 is equipped with a labeling unit for adding materials;

[0087] A pretreatment unit 7 for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank 1.

[0088] The water tank 1 is connected to the cleaning unit.

[0089] Example 2:

[0090] like Figure 1 As shown, a circulating water material leakage simulation device includes a water tank 1. The bottom port of the water tank 1 is connected to the inlet of a circulating water pump 2, the outlet of the circulating water pump 2 is connected to one end of a heater 3, the other end of the heater 3 is connected to one end of a circulating water pipeline 4, and the other end of the circulating water pipeline 4 is connected to the top port of the water tank 1.

[0091] The circulating water pipeline 4 is equipped with a labeling unit for adding materials;

[0092] A pretreatment unit 7 for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank 1.

[0093] The water tank 1 is connected to the cleaning unit.

[0094] Preferably, a first valve 41 is provided on the circulating water pipeline 4.

[0095] Preferably, the spiking unit includes a spiking pipeline 5 connected in parallel to both ends of the first valve 41, and the spiking pipeline 5 is provided with a second valve 51 and a third valve 52;

[0096] The spiking line 5 between the second valve 51 and the third valve 52 is connected to the material injection pump, which contains the material that needs to be simulated for leakage.

[0097] Preferably, a fourth valve 53 is provided on the material addition pipeline between the material injection pump and the spiking pipeline 5.

[0098] When no material needs to be added, the first valve 41 is open, and the second valve 51, the third valve 52, and the fourth valve 53 are all closed;

[0099] When materials need to be added, the first valve 41 is closed, and the second valve 51, the third valve 52, and the fourth valve 53 are all opened.

[0100] Example 3:

[0101] like Figure 1 As shown, a circulating water material leakage simulation device includes a water tank 1. The bottom port of the water tank 1 is connected to the inlet of a circulating water pump 2, the outlet of the circulating water pump 2 is connected to one end of a heater 3, the other end of the heater 3 is connected to one end of a circulating water pipeline 4, and the other end of the circulating water pipeline 4 is connected to the top port of the water tank 1.

[0102] The circulating water pipeline 4 is equipped with a labeling unit for adding materials;

[0103] A pretreatment unit 7 for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank 1.

[0104] The water tank 1 is connected to the cleaning unit.

[0105] Preferably, a first valve 41 is provided on the circulating water pipeline 4.

[0106] Preferably, the spiking unit includes a spiking pipeline 5 connected in parallel to both ends of the first valve 41, and the spiking pipeline 5 is provided with a second valve 51 and a third valve 52;

[0107] The spiking line 5 between the second valve 51 and the third valve 52 is connected to the material injection pump, which contains the material that needs to be simulated for leakage.

[0108] Preferably, a fourth valve 53 is provided on the material addition pipeline between the material injection pump and the spiking pipeline 5.

[0109] When no material needs to be added, the first valve 41 is open, and the second valve 51, the third valve 52, and the fourth valve 53 are all closed;

[0110] When materials need to be added, the first valve 41 is closed, and the second valve 51, the third valve 52, and the fourth valve 53 are all opened.

[0111] Preferably, the preprocessing unit includes an SBSE module 71 and an SPME module 72;

[0112] The SBSE module 71 includes a hollowed-out stirring box 711 fixed in the circulating water pipeline 4, and an SBSE stirring rod 712 is provided inside the hollowed-out stirring box 711.

[0113] The SPME module 72 includes an SPME extraction fiber needle 721 inserted into the circulating water line 4.

[0114] Example 4:

[0115] like Figure 1 As shown, a circulating water material leakage simulation device includes a water tank 1. The bottom port of the water tank 1 is connected to the inlet of a circulating water pump 2, the outlet of the circulating water pump 2 is connected to one end of a heater 3, the other end of the heater 3 is connected to one end of a circulating water pipeline 4, and the other end of the circulating water pipeline 4 is connected to the top port of the water tank 1.

[0116] The circulating water pipeline 4 is equipped with a labeling unit for adding materials;

[0117] A pretreatment unit 7 for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank 1.

[0118] The water tank 1 is connected to the cleaning unit.

[0119] Preferably, a first valve 41 is provided on the circulating water pipeline 4.

[0120] Preferably, the spiking unit includes a spiking pipeline 5 connected in parallel to both ends of the first valve 41, and the spiking pipeline 5 is provided with a second valve 51 and a third valve 52;

[0121] The spiking line 5 between the second valve 51 and the third valve 52 is connected to the material injection pump, which contains the material that needs to be simulated for leakage.

[0122] Preferably, a fourth valve 53 is provided on the material addition pipeline between the material injection pump and the spiking pipeline 5.

[0123] When no material needs to be added, the first valve 41 is open, and the second valve 51, the third valve 52, and the fourth valve 53 are all closed;

[0124] When materials need to be added, the first valve 41 is closed, and the second valve 51, the third valve 52, and the fourth valve 53 are all opened.

[0125] Preferably, the preprocessing unit includes an SBSE module 71 and an SPME module 72;

[0126] The SBSE module 71 includes a hollowed-out stirring box 711 fixed in the circulating water pipeline 4, and an SBSE stirring rod 712 is provided inside the hollowed-out stirring box 711.

[0127] The SPME module 72 includes an SPME extraction fiber needle 721 inserted into the circulating water line 4.

[0128] Preferably, the cleaning unit includes a cleaning agent tank 6 containing cleaning agent, the outlet pipe of the cleaning agent tank 6 is connected to the inlet of the metering pump 61, and the outlet of the metering pump 61 is connected to the water tank 6.

[0129] This application enables the cleaning of the device through the installation of a cleaning unit. During cleaning, the metering pump 61 injects the cleaning agent from the cleaning agent tank 6 into the water tank 1, and the water containing the cleaning agent is circulated within the device by the circulating water pump 2, thereby cleaning the device.

[0130] Example 5:

[0131] like Figure 1 As shown, a circulating water material leakage simulation device includes a water tank 1. The bottom port of the water tank 1 is connected to the inlet of a circulating water pump 2, the outlet of the circulating water pump 2 is connected to one end of a heater 3, the other end of the heater 3 is connected to one end of a circulating water pipeline 4, and the other end of the circulating water pipeline 4 is connected to the top port of the water tank 1.

[0132] The circulating water pipeline 4 is equipped with a labeling unit for adding materials;

[0133] A pretreatment unit 7 for sampling and adsorption is installed on the circulating water pipeline between the spiking unit and the water tank 1.

[0134] The water tank 1 is connected to the cleaning unit.

[0135] Preferably, a first valve 41 is provided on the circulating water pipeline 4.

[0136] Preferably, the spiking unit includes a spiking pipeline 5 connected in parallel to both ends of the first valve 41, and the spiking pipeline 5 is provided with a second valve 51 and a third valve 52;

[0137] The spiking line 5 between the second valve 51 and the third valve 52 is connected to the material injection pump, which contains the material that needs to be simulated for leakage.

[0138] Preferably, a fourth valve 53 is provided on the material addition pipeline between the material injection pump and the spiking pipeline 5.

[0139] When no material needs to be added, the first valve 41 is open, and the second valve 51, the third valve 52, and the fourth valve 53 are all closed;

[0140] When materials need to be added, the first valve 41 is closed, and the second valve 51, the third valve 52, and the fourth valve 53 are all opened.

[0141] Preferably, the preprocessing unit includes an SBSE module 71 and an SPME module 72;

[0142] The SBSE module 71 includes a hollowed-out stirring box 711 fixed in the circulating water pipeline 4, and an SBSE stirring rod 712 is provided inside the hollowed-out stirring box 711.

[0143] The SPME module 72 includes an SPME extraction fiber needle 721 inserted into the circulating water line 4.

[0144] Preferably, the cleaning unit includes a cleaning agent tank 6 containing cleaning agent, the outlet pipe of the cleaning agent tank 6 is connected to the inlet of the metering pump 61, and the outlet of the metering pump 61 is connected to the water tank 6.

[0145] This application enables the cleaning of the device through the installation of a cleaning unit. During cleaning, the metering pump 61 injects the cleaning agent from the cleaning agent tank 6 into the water tank 1, and the water containing the cleaning agent is circulated within the device by the circulating water pump 2, thereby cleaning the device.

[0146] Preferably, a back pressure valve 42 is provided on the circulating water pipeline 4 between the pretreatment unit and the water tank 1.

[0147] Preferably, a sampling pipe is provided on the circulating water pipeline 4 between the pretreatment unit and the back pressure valve 42, and a first ball valve 43 is provided on the sampling pipe.

[0148] Preferably, a second pressure sensor 48 is installed on the circulating water pipeline 4 between the pretreatment unit and the sampling tube.

[0149] Preferably, a pipe damper 44 is provided on the circulating water pipeline 4 at the outlet end of the circulating water pump 2. Specifically, a second ball valve 441 is provided on the pipeline connected to the circulating water pipeline 4.

[0150] The pipeline damper 44 reduces, delays, and dampens the water hammer generated instantaneously when the circulating water pump 2 starts, eliminating its peak value and turning it into a small fluctuation that is harmless to the instrument. This minimizes the harm of water hammer and greatly extends the service life of the instrument.

[0151] Preferably, a flow sensor 45, a first pressure sensor 46, and a first temperature sensor 47 are installed on the circulating water pipeline 4 between the pipeline damper 44 and the heater 3.

[0152] A second temperature sensor 31 is installed on the circulating water pipe 4 at the outlet of the heater 3.

[0153] Preferably, a bypass pipe 21 is connected in parallel at both ends of the circulating water pump 2, and a bypass valve 22 is provided on the bypass pipe 21.

[0154] Preferably, the water tank 1 is equipped with a liquid level sensor 11 for detecting the liquid level.

[0155] Preferably, a drain pipe is provided at the bottom of the water tank 1, and a drain valve 12 is provided on the drain pipe.

[0156] Specifically, the first valve 41, the second valve 51, the third valve 52, and the drain valve 12 are all solenoid valves. Example 6:

[0157] Using the circulating water material leakage simulation device in Example 5, diesel fuel is added to the circulating water to simulate diesel fuel leakage, and the diesel fuel leakage in the circulating water is detected by the SBSE module 71 in the pretreatment unit.

[0158] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water. 10μL of diesel fuel is added to the circulating water via the spiking unit. The heater 3 is set to 35℃. One SBSE stir bar 712 is placed in the perforated stirring box 711, immersing it in the circulating water for extraction. After 50 minutes, the mixture is cleaned and dried, then desorbed in a MARKES analytical tube and analyzed by gas chromatography-mass spectrometry (GC-MS). The resulting chromatogram of diesel fuel leakage in the circulating water is shown below. Figure 4 As shown.

[0159] MARKES parsing tube conditions:

[0160] Desorption temperature 260℃;

[0161] Analysis time: 5 minutes;

[0162] 50 ml / min shunt flow rate.

[0163] Chromatographic conditions:

[0164] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0165] The injection port temperature is 260℃;

[0166] The split ratio is 5:1;

[0167] Flow rate: 0.6 ml / min;

[0168] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0169] Mass spectrometry conditions:

[0170] EI source, electron energy 70eV, ion source temperature 230℃;

[0171] MS quadrupole 150C;

[0172] Transmission line temperature: 280℃;

[0173] Acquisition method: Full scan;

[0174] Scan quality range: (5~300) amu.

[0175] SBSE stir bar aging conditions: Aging at 290℃ for 30 minutes in a helium environment.

[0176] Example 7:

[0177] Using the circulating water material leakage simulation device in Example 5, gasoline is added to the circulating water to simulate diesel leakage, and the gasoline leakage in the circulating water is detected by the SBSE module 71 in the pretreatment unit.

[0178] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water. 10μL of gasoline is added to the circulating water via the spiking unit. The heater 3 is set to 35℃. One SBSE stir bar 712 is placed in the perforated stirring box 711, immersing it in the circulating water for extraction. After 50 minutes, the mixture is cleaned and dried, then desorbed in a MARKES analytical tube and analyzed by gas chromatography-mass spectrometry (GC-MS). The resulting chromatogram of gasoline leakage in the circulating water is shown below. Figure 5 As shown.

[0179] MARKES parsing tube conditions:

[0180] Desorption temperature 260℃;

[0181] Analysis time: 5 minutes;

[0182] 50 ml / min shunt flow rate.

[0183] Chromatographic conditions:

[0184] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0185] The injection port temperature is 260℃;

[0186] The split ratio is 5:1;

[0187] Flow rate: 0.6 ml / min;

[0188] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0189] Mass spectrometry conditions:

[0190] EI source, electron energy 70eV, ion source temperature 230℃;

[0191] MS quadrupole 150C;

[0192] Transmission line temperature: 280℃;

[0193] Acquisition method: Full scan;

[0194] Scan quality range: (5~300) amu.

[0195] SBSE stir bar aging conditions: Aging at 290℃ for 30 minutes in a helium environment.

[0196] Example 8:

[0197] Using the circulating water material leakage simulation device in Example 5, petroleum naphtha is added to the circulating water to simulate diesel leakage, and the petroleum naphtha leakage in the circulating water is detected by the SBSE module 71 in the pretreatment unit.

[0198] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water, and 10μL of gasoline is added to the circulating water via the spiking unit. The temperature of heater 3 is set to 35℃. One SBSE stir bar 712 is placed in the hollowed-out stirring box 711 and immersed in the circulating water for extraction. After 50 minutes, it is cleaned and dried, then placed in a MARKES analytical tube for desorption and analysis in a gas chromatography-mass spectrometry (GC-MS) instrument to obtain a chromatogram of petroleum naphtha leakage in the circulating water. Figure 6 As shown.

[0199] MARKES parsing tube conditions:

[0200] Desorption temperature 260℃;

[0201] Analysis time: 5 minutes;

[0202] 50 ml / min shunt flow rate.

[0203] Chromatographic conditions:

[0204] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0205] The injection port temperature is 260℃;

[0206] The split ratio is 5:1;

[0207] Flow rate: 0.6 ml / min;

[0208] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0209] Mass spectrometry conditions:

[0210] EI source, electron energy 70eV, ion source temperature 230℃;

[0211] MS quadrupole 150C;

[0212] Transmission line temperature: 280℃;

[0213] Acquisition method: Full scan;

[0214] Scan quality range: (5~300) amu.

[0215] SBSE stir bar aging conditions: Aging at 290℃ for 30 minutes in a helium environment.

[0216] Example 9:

[0217] Using the circulating water material leakage simulation device in Example 5, diesel fuel was added to the circulating water to simulate diesel fuel leakage, and the diesel fuel leakage in the circulating water was detected by the SPME module 72 in the pretreatment unit.

[0218] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water. 10μL of diesel fuel is added to the circulating water via the spiking unit. The heater 3 is set to 35℃. An SPME extraction fiber needle 721 is inserted into the SPME module 72 of the pretreatment unit and immersed in the circulating water for extraction for 40 minutes. The sample is then injected into the CTC inlet of a gas chromatography-mass spectrometry (GC-MS) instrument for analysis, yielding a chromatogram of the diesel fuel leakage in the circulating water. Figure 7 As shown.

[0219] CTC injection conditions:

[0220] SPME mode sample introduction;

[0221] Desorption temperature 250℃;

[0222] The parsing time is 3 minutes.

[0223] Chromatographic conditions:

[0224] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0225] The injection port temperature is 260℃;

[0226] The split ratio is 5:1;

[0227] Flow rate: 0.6 ml / min;

[0228] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0229] Mass spectrometry conditions:

[0230] EI source, electron energy 70eV, ion source temperature 230℃;

[0231] MS quadrupole 150C;

[0232] Transmission line temperature: 280℃;

[0233] Acquisition method: Full scan;

[0234] Scan quality range: (5~300) amu.

[0235] SPME extract fiber needles initial aging conditions: age at 260℃ for 30 minutes.

[0236] Example 10:

[0237] Using the circulating water material leakage simulation device in Example 5, gasoline was added to the circulating water to simulate diesel leakage, and the gasoline leakage in the circulating water was detected by the SPME module 72 in the pretreatment unit.

[0238] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water. 10μL of gasoline is added to the circulating water via the spiking unit. The heater 3 is set to 35℃. An SPME extraction fiber needle 721 is inserted into the SPME module 72 of the pretreatment unit and immersed in the circulating water for extraction for 40 minutes. The sample is then injected into the CTC inlet of the gas chromatography-mass spectrometry (GC-MS) instrument for analysis, obtaining a chromatogram for the detection of gasoline leakage in the circulating water. Figure 8 As shown.

[0239] CTC injection conditions:

[0240] SPME mode sample introduction;

[0241] Desorption temperature 250℃;

[0242] The parsing time is 3 minutes.

[0243] Chromatographic conditions:

[0244] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0245] The injection port temperature is 260℃;

[0246] The split ratio is 5:1;

[0247] Flow rate: 0.6 ml / min;

[0248] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0249] Mass spectrometry conditions:

[0250] EI source, electron energy 70eV, ion source temperature 230℃;

[0251] MS quadrupole 150C;

[0252] Transmission line temperature: 280℃;

[0253] Acquisition method: Full scan;

[0254] Scan quality range: (5~300) amu.

[0255] SPME extract fiber needles initial aging conditions: age at 260℃ for 30 minutes.

[0256] Example 11:

[0257] Using the circulating water material leakage simulation device in Example 5, petroleum naphtha is added to the circulating water to simulate diesel leakage, and the petroleum naphtha leakage in the circulating water is detected by the SPME module 72 in the pretreatment unit.

[0258] In the circulating water material leakage simulation device, water tank 1 is filled with 15L of water. 10μL of petroleum naphtha is added to the circulating water via the spiking unit. The heater 3 is set to 35℃. An SPME extraction fiber needle 721 is inserted into the SPME module 72 of the pretreatment unit and immersed in the circulating water for extraction for 40min. The sample is then injected into the CTC inlet of the gas chromatography-mass spectrometry (GC-MS) instrument for analysis, obtaining a chromatogram for detecting petroleum naphtha leakage in the circulating water. Figure 9 As shown.

[0259] CTC injection conditions:

[0260] SPME mode sample introduction;

[0261] Desorption temperature 250℃;

[0262] The parsing time is 3 minutes.

[0263] Chromatographic conditions:

[0264] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0265] The injection port temperature is 260℃;

[0266] The split ratio is 5:1;

[0267] Flow rate: 0.6 ml / min;

[0268] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0269] Mass spectrometry conditions:

[0270] EI source, electron energy 70eV, ion source temperature 230℃;

[0271] MS quadrupole 150C;

[0272] Transmission line temperature: 280℃;

[0273] Acquisition method: Full scan;

[0274] Scan quality range: (5~300) amu.

[0275] SPME extract fiber needles initial aging conditions: age at 260℃ for 30 minutes.

[0276] Comparative Example 1:

[0277] Chromatograms of diesel leaks in circulating water were determined using artificial preparation-SPME extraction-GC-MS.

[0278] 2 μL of diesel fuel was added to 3 L of circulating water containing no interfering substances. After thorough mixing, 19 mL of water sample was added to a 20 mL sample vial. The SPME extraction fiber needle 721 was immersed in the sample vial for extraction. After 40 min, desorption was performed at 250℃ for 3 min, and the sample was injected into the CTC inlet of a gas chromatography-mass spectrometry (GC-MS) instrument for analysis. The chromatogram for detecting diesel fuel leakage in water obtained using the manual preparation-SPME extraction-GC-MS method is shown below. Figure 10 As shown.

[0279] CTC injection conditions:

[0280] SPME mode sample introduction;

[0281] Desorption temperature 250℃;

[0282] The parsing time is 3 minutes.

[0283] Chromatographic conditions:

[0284] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0285] The injection port temperature is 260℃;

[0286] The split ratio is 5:1;

[0287] Flow rate: 0.6 ml / min;

[0288] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0289] Mass spectrometry conditions:

[0290] EI source, electron energy 70eV, ion source temperature 230℃;

[0291] MS quadrupole 150C;

[0292] Transmission line temperature: 280℃;

[0293] Acquisition method: Full scan;

[0294] Scan quality range: (5~300) amu.

[0295] SPME extract fiber needles initial aging conditions: age at 260℃ for 30 minutes.

[0296] Depend on Figure 7 and Figure 10 It can be seen that there is a significant difference between Comparative Example 1 and Example 5 in the detection results of diesel leakage in water of the same concentration. Because the artificially prepared diesel-containing water sample did not have sufficient circulation and contact with the water sample, it could not be completely dispersed and dissolved, which easily leads to large differences in the detection results of parallel samples from the same batch, making it difficult to obtain representative data.

[0297] Comparative Example 2:

[0298] Chromatograms of diesel leaks in circulating water were determined using a manual preparation-purge-trap-gas chromatography-mass spectrometry (GC-MS) method.

[0299] 1 μL of diesel fuel was added to 1.5 L of circulating water where no interfering substances were detected. After thorough mixing, 39 mL of water sample was added to a 40 mL sample bottle. The target compound was adsorbed into a collection tube after purging with high-purity nitrogen. The collection tube was heated and backflushed with high-purity nitrogen before being analyzed by gas chromatography-mass spectrometry (GC-MS). The chromatogram for detecting diesel fuel leaks in water using the artificial preparation-purging-collection-GC-MS method was obtained, as shown below. Figure 11 As shown.

[0300] Purge conditions:

[0301] The purging gas is nitrogen with a purity of 99.999%.

[0302] Inject 5ml;

[0303] Purging flow rate: 40 ml / min;

[0304] Purging time: 10 minutes;

[0305] Dry purging time: 1.0 min;

[0306] Flow rate 200 ml / min.

[0307] Chromatographic conditions:

[0308] HP-PONA capillary column (50m × 0.2mm × 0.25μm);

[0309] The injection port temperature is 260℃;

[0310] The split ratio is 5:1;

[0311] Flow rate: 0.6 ml / min;

[0312] Column temperature program: Initial column temperature 40℃, hold for 5 min, then increase to 320℃ at a rate of 5℃ / min.

[0313] Mass spectrometry conditions:

[0314] EI source, electron energy 70eV, ion source temperature 230℃;

[0315] MS quadrupole 150C;

[0316] Transmission line temperature: 280℃;

[0317] Acquisition method: Full scan;

[0318] Scan quality range: (5~300) amu.

[0319] Depend on Figure 7 and Figure 11 It can be seen that the detection results of diesel leakage in water of the same concentration differ significantly between Comparative Example 2 and Example 5. Figure 11 It is evident that, due to insufficient circulation and contact between the artificially prepared sample and the water sample, the diesel-containing water sample cannot be completely dispersed and dissolved, easily leading to significant differences in the test results of parallel samples from the same batch, making it difficult to obtain representative data. The purge-trap-gas chromatography-mass spectrometry (GC-MS) method for analyzing diesel leaks in circulating water exhibits weak signal response, low sensitivity, and incomplete component separation.

[0320] The device proposed in this application can simulate the real situation of material leakage in circulating water, so that the water flow forms dynamic circulating water. The spiking unit realizes the addition of simulated leaked material to the circulating water, and the pretreatment unit realizes the sampling of the circulating water after adding simulated leaked material. Combined with gas chromatography-mass spectrometry (GC-MS) for material analysis, it solves the problems of uneven and unrepresentative sampling caused by the inability to simulate circulating water in the prior art, which leads to inaccurate characteristic information of leaked material analysis and difficulty in tracing the source.

[0321] While the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, they are not intended to limit the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A circulating water material leakage simulation device characterized by, The water tank is connected with the inlet of the circulating water pump, the outlet of the circulating water pump is connected with one end of the heater, the other end of the heater is connected with one end of the circulating water pipeline, and the other end of the circulating water pipeline is connected with the top port of the water tank. The circulating water pipeline is provided with a labeling unit for adding materials. The circulating water pipeline between the labeling unit and the water tank is provided with a pretreatment unit for sampling and adsorption. The water tank is connected with a cleaning unit.

2. The circulating water material leak simulation apparatus according to claim 1, wherein The circulating water pipeline is provided with a first valve.

3. The circulating water material leak simulation apparatus according to claim 2, wherein The labeling unit comprises a labeling pipeline connected in parallel between the two ends of the first valve, and the labeling pipeline is provided with a second valve and a third valve. The second valve and the second valve are connected with a material injection pump.

4. The circulating water material leak simulation apparatus according to claim 3, wherein A material adding pipeline between the material injection pump and the labeling pipeline is provided with a fourth valve.

5. The circulating water material leak simulation apparatus according to claim 1, wherein The pretreatment unit comprises an SBSE module and an SPME module. The SBSE module comprises a hollow stirring box fixed in the circulating water pipeline, and an SBSE stirring rod is arranged in the hollow stirring box. The SPME module comprises an SPME extraction fiber needle inserted into the circulating water pipeline.

6. The circulating water material leak simulation apparatus according to claim 1, wherein The cleaning unit comprises a cleaning agent tank containing a cleaning agent, the outlet pipe of the cleaning agent tank is connected with the inlet of a metering pump, and the outlet of the metering pump is connected with the water tank.

7. The circulating water material leak simulation apparatus according to claim 1, wherein The circulating water pipeline between the pretreatment unit and the water tank is provided with a back pressure valve.

8. The circulating water material leak simulation apparatus according to claim 7, wherein The circulating water pipeline between the pretreatment unit and the back pressure valve is provided with a sampling pipe, and the sampling pipe is provided with a first ball valve.

9. The circulating water material leak simulation apparatus according to claim 8, wherein The circulating water pipeline between the pretreatment unit and the sampling pipe is provided with a second pressure sensor.

10. The circulating water material leak simulation apparatus according to claim 1, wherein The circulating water pipeline at the outlet end of the circulating water pump is provided with a pipeline damper.

11. The circulating water material leak simulation apparatus according to claim 10, wherein The circulating water pipeline between the pipeline damper and the heater is provided with a flow sensor, a first pressure sensor and a first temperature sensor. The circulating water pipeline at the outlet of the heater is provided with a second temperature sensor.

12. The circulating water material leak simulation apparatus of claim 1, wherein The circulating water pump is connected with a bypass pipeline in parallel at both ends, and the bypass pipeline is provided with a bypass valve.

13. The circulating water material leak simulation apparatus of claim 1, wherein The water tank is provided with a liquid level sensor for detecting the liquid level.

14. The circulating water material leak simulation apparatus of claim 1, wherein The bottom of the water tank is provided with a emptying pipe, and the emptying pipe is provided with an emptying valve.

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