Method for analyzing black blocky foreign matters in petroleum product treatment device

Abstract

The invention relates to the technical field of solid sample analysis, in particular to a method for analyzing black blocky foreign matters in a petroleum product treatment device. The analysis method provided by the invention at least comprises a Karl Fischer moisture meter, a headspace gas chromatograph-mass spectrometer (HSGCMS), a gas chromatograph-mass spectrometer (GCMS), a constant temperature drying box, a Fourier transform infrared spectrometer (FTIR), a pyrolysis gas chromatograph-mass spectrometer (PyGCMS), a thermogravimetric analyzer (TGA), an energy dispersive X-ray spectrometer (EDX), an X-ray diffractometer (XRD) and a muffle furnace. By analyzing and knowing the components and content of the black blocky foreign matters, oil product processing enterprises can conveniently analyze the generation reasons of the blocky foreign matters according to the components and content of the blocky foreign matters, optimize the processing technology, reduce or avoid the generation of the blocky foreign matters in oil product processing devices, reduce the maintenance frequency of the devices and improve the production benefits.

Description

Technical Field

[0001] The invention relates to the technical field of solid sample analysis, and in particular to an analysis method for black block foreign matter in a petroleum product processing device. Background Art

[0002] Petroleum is the world's most important industrial and power raw material. Numerous products are obtained from petroleum processing, which are widely used in daily life, industry, and agriculture. Key petroleum processing techniques include atmospheric and vacuum distillation, catalytic cracking, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, catalytic reforming, alkylation, isomerization, delayed coking, and gas treatment. Black solid deposits often appear on joints, filters, and internal walls of processing equipment such as catalytic cracking, hydrotreating, hydrocracking, and gas treatment. These deposits may be byproducts of the process or corrosion products of the equipment. The increase in black deposits in processing equipment seriously affects its efficiency and service life, shortening equipment maintenance and upgrade cycles and reducing production efficiency. Understanding the composition and content of solid deposits allows oil processing companies to analyze the causes of these deposits based on their composition and content, optimize processing techniques, reduce equipment maintenance, minimize or prevent corrosion, and improve production efficiency.

[0003] Most existing detection methods are aimed at detecting specific substances in samples, such as benzene series, sulfur compounds, VOC detection, element content detection, etc. These test results only reflect certain information of the sample and cannot fully reflect all the components and contents in the sample. Summary of the Invention

[0004] In response to the above problems, the present invention provides a method for analyzing the full composition of black block foreign matter, allowing enterprises to fully understand the composition and content of black block foreign matter, providing a basis for enterprises to improve process conditions, reduce or avoid the generation of foreign matter, and improve enterprise production efficiency.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A method for analyzing black block foreign matter in a petroleum product processing device comprises the following steps:

[0007] S1, Karl Fischer titrator analyzes the water content in the sample: first, perform a blank titration and calibration titration of the Karl Fischer titrator, then grind the bulk sample, accurately weigh the sample using a precision electronic balance, and place the weighed sample into the titration cell for titration to determine the water content in the sample;

[0008] S2, HSGCMS analysis of small molecules with low boiling points (less than 180°C) and volatile substances in the sample: the sample is placed in a sealed headspace vial for testing, and the collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are quantitatively or semi-quantitatively analyzed using the internal standard method;

[0009] S3, GCMS detection of substances with medium boiling points (less than 300°C) in the sample: organic components in the sample are extracted with an organic solvent, the extract is filtered through a nylon filter membrane with a pore size of 0.45 μm into a chromatographic vial for detection on the GCMS, the collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are quantitatively or semi-quantitatively analyzed using the internal standard method;

[0010] S4, test the volatile content of the sample in a constant temperature drying oven: place the sample on a watch glass and place it in a drying oven to constant weight, and calculate the approximate proportion of low-boiling-point substances in the sample;

[0011] S5, PyGCMS detection of macromolecular high-boiling point substances in dried samples: 0.1-2 mg of dried sample is placed in a pyrolysis cup for detection. The collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are semi-quantitatively analyzed;

[0012] S6, TGA analysis of the change in the mass of the dried sample with temperature to determine the proportion of organic matter, inorganic matter, and easily decomposable substances in the sample: 5-20 mg of sample was placed in a crucible for data collection;

[0013] S7, EDX detection of elemental composition in dried or ash samples: After the sample is gold-sprayed, it is fixed on the sample stage, and the area to be tested is scanned and tested. The characteristic peaks are identified to determine the element type and the element content is calculated;

[0014] S8, XRD detection of inorganic phases in oven-dried or ash-based samples, qualitative analysis of inorganic compounds in the sample: set the 2θ scanning range, grind the sample into a powder of 1-10 μm, evenly fill the sample holder, and ensure that the X-ray beam is aligned with the center of the sample for detection; export the diffraction data, identify the diffraction peaks, compare with the standard database, and determine the sample phase;

[0015] S9, test the ignition weight loss of the sample in a muffle furnace: set the temperature of the muffle furnace to 800℃ and keep it constant, weigh 3-8g of the sample and put it into a crucible, place the crucible in the muffle furnace and burn it to constant weight, and calculate the ignition weight loss of the sample.

[0016] As a preferred solution of the present invention, the following steps are also included:

[0017] S10, FTIR qualitative analysis of the main components in the dried sample: the sample after drying to constant weight is pressed with potassium bromide pellets for detection, the spectrum is viewed using software, the functional groups and chemical bonds in the sample are analyzed, and the spectrum is compared with the standard library to confirm the compound structure;

[0018] As a preferred embodiment of the present invention, in step S2, the heating temperature of the headspace sampler is set to 60-150°C, the equilibration time is 10-30 min, and the injection volume is 0.5-2 ml; the programmed temperature rise of the chromatographic column is an initial temperature of 40°C, maintained for 10 min, a heating rate of 20°C / min, heated to 200°C, maintained for 5 min, and then heated to 220°C, maintained for 16 min; the mass spectrometer selects an EI electron source, the ion source temperature is 200-250°C, the transmission line temperature is 250°C, the scan mode is full scan, and the mass-to-nuclear ratio (m / z) range is 35-500m / z.

[0019] As a preferred embodiment of the present invention, in step S3, the organic solvent for extracting the sample is acetone and / or chloroform, the injection port temperature of the gas chromatograph is 200-300°C, the heating program of the chromatographic column is an initial temperature of 60°C, maintained for 5 minutes, heated to 100°C at a heating rate of 3.5°C / min, maintained for 5 minutes, heated to 200°C at a heating rate of 8°C / min, maintained for 5 minutes, heated to 300°C at a heating rate of 15°C / min, maintained for 15 minutes, and the carrier gas flow rate is 1-2 ml / min; the mass spectrometer selects an EI electron source, the ion source temperature is 200-350°C, the transmission line temperature is 280°C, the scan mode is full scan, and the range is 10-1000 m / z.

[0020] As a preferred solution of the present invention, in step S10, the scanning range of FTIR is 400-4000 cm-1, the resolution is 4 cm-1, and the number of scans is 32 or 64.

[0021] As a preferred embodiment of the present invention, the cracking temperature of the cracker in step S5 is 300-800°C, the cracking time is 10-30S, and the programmed temperature rising conditions of the chromatographic column are as follows: the initial temperature is 50°C, maintained for 2min, heated to 200°C at a heating rate of 12°C / min, maintained for 0min, and then heated to 305°C at a heating rate of 20°C / min, maintained for 15min; the mass spectrometer uses an IE electron source, the ion source temperature is 200-350°C, the transmission line temperature is 280°C, the scanning mode is full scan, and the mass-to-nuclear ratio (m / z) range is 10-1000m / z.

[0022] As a preferred solution of the present invention, in step S6, nitrogen or air atmosphere is selected, the starting temperature is 45°C, the heating rate is 20°C / min, the ending temperature is 800°C, and it is maintained for 10 minutes; the material of the crucible used is one of alumina, platinum, quartz, and ceramic.

[0023] As a preferred solution of the present invention, in step S8, the scanning range of the 2θ angle is 5° to 80°, the scanning speed is 0.5° to 5° / min, and the step size is set to 0.02° to 0.05°.

[0024] As a preferred solution of the present invention, the temperature of the constant temperature drying oven in step S4 is from 105°C to a constant temperature.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] This method comprehensively detects the composition of black, lumpy foreign matter, including the composition and content of moisture, low-boiling-point volatile organic compounds, medium-boiling-point organic compounds, high-boiling-point organic compounds, and inorganic compounds. Based on the composition and content of the black, lumpy foreign matter, companies can infer the cause of the foreign matter and use this information to improve oil processing techniques, reduce or prevent foreign matter generation, extend the maintenance cycle and lifespan of oil processing equipment, and ultimately improve production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 HSGCMS spectrum of Example 1 of the present invention;

[0028] Figure 2 This is the GCMS spectrum of Example 1 of the present invention;

[0029] Figure 3 FTIR spectrum of Example 1 of the present invention is compared with the standard spectrum library;

[0030] Figure 4 This is the PyGCMS spectrum of Example 1 of the present invention;

[0031] Figure 5 This is the TGA spectrum of Example 1 of the present invention under air atmosphere;

[0032] Figure 6 This is the TGA spectrum of Example 1 of the present invention under a nitrogen atmosphere;

[0033] Figure 7 This is the EDX spectrum of Example 1 of the present invention;

[0034] Figure 8 is the XRD spectrum of Example 1 of the present invention;

[0035] Figure 9 HSGCMS spectrum of Example 2 of the present invention;

[0036] Figure 10 This is the GCMS spectrum of Example 2 of the present invention;

[0037] Figure 11 This is the PyGCMS spectrum of Example 2 of the present invention;

[0038] Figure 12 This is the TGA spectrum of Example 2 of the present invention under air atmosphere;

[0039] Figure 13 This is the EDX spectrum of Example 2 of the present invention;

[0040] Figure 14 This is the XRD spectrum of Example 2 of the present invention. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0042] The present invention provides a technical solution:

[0043] A method for analyzing black block foreign matter in a petroleum product processing device comprises the following steps: S1, analyzing the water content in a sample using a Karl Fischer titrator: first, performing a blank titration and a calibration titration of the Karl Fischer titrator, then crushing the block sample, accurately weighing the sample mass using a 1 / 10,000 precision electronic balance, placing the weighed sample into a titration cell for titration, and determining the water content in the sample; S2, analyzing the small molecule, low boiling point (approximately less than 180°C) volatile substances in the sample, such as small molecule alkanes, alkenes, alcohols, monocyclic aromatic hydrocarbons, and thiols, by high-pressure gas chromatography-mass spectrometry (HSGCMS): placing the sample into a sealed headspace bottle, setting the heating temperature, equilibration time, and injection volume of the headspace injector, the programmed temperature conditions of the gas chromatography column, the ion source temperature, transfer line temperature, scanning mode, and mass-to-nuclear ratio (m / z) range of the mass spectrometer, and comparing the mass spectrum with a standard library to confirm the structure of the target compound. Quantitative or semi-quantitative analysis of the components in the sample is performed using the internal standard method; S3, GCMS detection of substances with medium boiling points (approximately less than 300°C), medium- and long-chain alkanes, alkenes, aromatics, thiols, etc. in the sample: organic components in the sample are extracted with an organic solvent, and the extract is filtered into a chromatographic bottle using a nylon filter membrane with a pore size of 0.45 μm. The chromatographic bottle is placed on the sample tray, and the gas chromatograph injection port temperature, the programmed temperature conditions of the chromatographic column, the carrier gas flow rate, the ion source temperature, the transfer line temperature, the scanning mode and the mass-to-nuclear ratio (m / z) range of the mass spectrometer are set before detection. The mass spectrum is compared with the standard spectrum library to confirm the structure of the target compound. The components in the sample are quantitatively or semi-quantitatively analyzed by the internal standard method; S4, the content of volatile components in the sample is detected by a constant temperature drying oven: the temperature of the constant temperature drying oven is set to 105°C to a constant temperature, the sample is placed on a watch glass and placed in the drying oven to a constant weight, and the approximate proportion of low-boiling-point substances in the sample is calculated; S5, PyGCMS is used to detect large molecular high-boiling-point substances in the dried sample, such as long-chain alkanes, condensed-ring aromatic hydrocarbons, long-chain alkenes, etc.: the cracking temperature and cracking time of the cracker, the inlet temperature of the gas chromatograph, the programmed heating conditions of the chromatographic column, the ion source temperature, transfer line temperature, scanning mode and mass-to-nuclear ratio (m / z) range of the mass spectrometer are set, 0.1-2 mg of the dried sample is placed in the cracking cup for detection, the mass spectrum is compared with the standard spectrum library, and the structure of the target compound is confirmed.Through semi-quantitative analysis of the components in the sample; S6, TGA analysis of the change in the mass of the dried sample with temperature, determine the proportion of organic matter, inorganic matter, and easily decomposable substances in the sample: select a suitable atmosphere, set the starting temperature, heating rate, ending temperature and constant temperature time, and place 5-20 mg of sample in the crucible for data acquisition; S7, EDX detection of elemental composition in dried or ash samples: after gold spraying treatment, fix the sample on the sample stage, select the area to be tested for scanning and detection, identify the characteristic peak to determine the type of element, and calculate the element content; S8, XRD detection of inorganic phase in dried or ash samples, qualitative analysis of inorganic compounds in the sample: set the scanning range of 2θ angle, select the appropriate scanning speed, set the step size, grind the sample into 1-10 micron powder, evenly fill it into the sample holder, avoid gaps, and ensure that the X-ray beam is aligned with the center of the sample for detection. Export diffraction data, identify diffraction peaks, compare with the standard database, and determine the sample phase; S9, muffle furnace detection of sample loss on ignition: set the temperature of the muffle furnace to 800℃ and keep it constant, weigh 3-8g of sample and put it into a crucible, place the crucible in the muffle furnace and burn it to constant weight, and calculate the sample loss on ignition.

[0044] Next, in step S10, FTIR is used to qualitatively identify the main components of the dried sample: The FTIR scan range, resolution, and number of scans are set, and the dried sample, after constant weight, is pressed onto a potassium bromide pellet for detection. The spectra are then analyzed using software to analyze the functional groups and chemical bonds in the sample. The spectra are then compared with standard libraries (e.g., HR Spectra or NIST) to confirm the compound structure.

[0045] Further, in step S2, the heating temperature of the headspace sampler is set to 60-150°C, the equilibrium time is 10-30min, and the injection volume is 0.5-2ml; the temperature program of the chromatographic column is to maintain an initial temperature of 40°C for 10min, a heating rate of 20°C / min, and to be heated to 200°C for 5min, and then to be heated to 220°C for 16min; the mass spectrometer selects an EI electron source, an ion source temperature of 200-250°C, a transmission line temperature of 250°C, a scan mode of full scan, and a mass-to-nuclear ratio (m / z) range of 35-500m / z. Preferably, the heating temperature of the sampler is 100°C, the equilibrium time is 20min, the injection volume is 1ml, the ion source temperature of the mass spectrometer is 200°C, and the mass-to-nuclear ratio (m / z) range is 50-400m / z.

[0046] Furthermore, in step S3, the organic solvent for extracting the sample is acetone and / or chloroform, the gas chromatograph inlet temperature is 200-300°C, the chromatographic column temperature program is as follows: initial temperature is 60°C, maintained for 5 minutes, heated to 100°C at a heating rate of 3.5°C / min, maintained for 5 minutes, heated to 200°C at a heating rate of 8°C / min, maintained for 5 minutes, heated to 300°C at a heating rate of 15°C / min, maintained for 15 minutes, and the carrier gas flow rate is 1-2 ml / min. The mass spectrometer selects an EI electron source, the ion source temperature is 200-350°C, the transfer line temperature is 280°C, the scan mode is full scan, and the range is 10-1000 m / z. Preferably, the organic solvent for extracting the sample is acetone, the gas chromatograph inlet temperature is 280°C, the carrier gas flow rate is 1 ml / min, the mass spectrometer ion source temperature is 320°C, and the mass-to-nuclear ratio (m / z) range is 33-650m / z.

[0047] Furthermore, in step S10, the scanning range of FTIR is 400-4000 cm-1, the resolution is 4 cm-1, and the number of scans is 32 or 64.

[0048] Further, in step S5, the cracking temperature of the cracker is 300-800 DEG C, the cracking time is 10-30S, and the programmed temperature rising condition of the chromatographic column is that the initial temperature is 50 DEG C, holds 2min, is heated to 200 DEG C at a heating rate of 12 DEG C / min, holds 0min, is heated to 305 DEG C at a heating rate of 20 DEG C / min, holds 15min. The mass spectrometer uses an IE electron source, the ion source temperature is 200-350 DEG C, the transmission line temperature is 280 DEG C, the scanning mode is full scan, and the mass-to-nuclear ratio (m / z) ranges from 10 to 1000m / z. Preferably, the cracking temperature of the cracker is 500 DEG C, the cracking time is 12S, the ion source temperature is 320 DEG C, and the mass-to-nuclear ratio (m / z) ranges from 34 to 650m / z.

[0049] Furthermore, in step S6, nitrogen or air atmosphere is selected, the starting temperature is 45°C, the heating rate is 20°C / min, the ending temperature is 800°C, and the temperature is maintained for 10 minutes. The crucible is made of one of alumina, platinum, quartz, and ceramic.

[0050] Finally, in step S8, the scanning range of the 2θ angle is 5° to 80°, the scanning speed is 0.5° to 5° / min, and the step size is set to 0.02° to 0.05°. The preferred scanning speed is 5° / min, and the step size is set to 0.02°.

[0051] Implementation Case 1:

[0052] Provides an analysis scheme for black foreign matter in a hydrocracking unit:

[0053] Grind the block sample, use a 1 / 10,000 precision electronic balance to accurately weigh the sample mass, place the weighed sample into the titration cell of the Karl Fischer moisture analyzer for titration, and determine the water content in the sample.

[0054] like Figure 1 As shown, HSGCMS analysis: the sample was placed in a headspace bottle and sealed, the instrument parameters were set for detection, and the comparison of the mass spectrum with the standard library analysis showed that the low-boiling point volatile organic compounds in the sample mainly included 3-methylhexane, methylcyclohexane, n-heptane, 2-methylheptane, 3-methylheptane, n-octane, 3-ethylhexane, 2,5-dimethylheptane, 4-methyloctane, 1,2,4-trimethylcyclohexane, n-nonane, 2,5-dimethyloctane, 2-butyloctanol, ethylbenzene, p-xylene, 3-ethyl-2-methylheptane, 3-methylnonane, decane, 3-ethyltoluene, mesitylene, 1-methyl-3-propylbenzene, and 1,4-diethylbenzene.

[0055] like Figure 2 As shown, GCMS analysis: the organic matter in the sample was extracted with acetone and passed through a membrane for detection on the machine. Comparison of the mass spectrum with the standard library analysis showed that the medium-boiling point organic matter in the sample mainly contained methylcyclohexane, toluene, p-xylene, dodecane, tetradecane, biphenyl, n-pentadecane, 2,6,10-trimethyl-n-tetradecane, n-nonadecane, n-hexadecane, n-heptadecane, phytane, n-tetracosane, n-heneicosane, 3-ethyl-5-(2-ethylbutyl)octadecane, tridecane, tetratetradecane, n-heptacosane, 2-methyloctadecane, and 9-hexylheptadecane.

[0056] After the constant temperature drying oven is kept at 105℃, the sample is placed on a watch glass and placed in the drying oven to constant weight, and the approximate proportion of low-boiling-point substances in the sample is calculated;

[0057] like Figure 3 As shown, FTIR analysis was performed with a scan range of 400–4000 cm⁻¹, a resolution of 4 cm⁻¹, and 32 scans. The sample was dried in a constant temperature oven, ground, and then pressed into a potassium bromide pellet for detection. The spectrum was viewed using software and compared with a standard library. After matching the database, analysis revealed the presence of inorganic compounds.

[0058] like Figure 4 As shown in Figure 2, PyGCMS analysis: After setting the instrument parameters, a small amount of sample was taken and placed in a cracking cup for detection. The high-boiling-point organic compounds in the sample mainly contained m-xylene, p-xylene, undecane, naphthalene, tetradecane, 3-methylpentadecane, n-hexadecane, tetratetradecane, 3,5-dimethyloctane, 2,5-dimethylundecane, 4-methyldodecane, 4,6-dimethyldodecane, 2,6,10,15-tetramethylheptadecane, 2-methyltetradecane, n-nonadecane, n-heneicosane, etc.

[0059] like Figure 5-6 As shown, TGA analysis: After the sample is dried, a small amount of sample is taken and placed in an alumina crucible and a detection atmosphere is selected for detection. The analysis shows that the sample contains some organic matter, coke and substances that are easily decomposed at high temperature.

[0060] like Figure 7 As shown, EDX analysis: the sample was gold-sprayed and fixed on the sample stage, and the area to be tested was selected for scanning and detection. The analysis showed that the sample contained elements such as C, O, S, Si, Mn, and Fe.

[0061] like Figure 8 As shown, XRD analysis: the sample was dried and crushed and filled into the sample rack for testing. The original spectrum was opened using Search-Match and compared with the standard card. It was found that the sample contained silicon dioxide, ferrous oxide, iron oxide, ferrous sulfide, manganese dioxide and other components.

[0062] After the muffle furnace is kept at a constant temperature of 800℃, the sample is accurately weighed and placed in a crucible. The crucible is placed in the muffle furnace and burned to a constant weight. The ignition weight loss of the sample is calculated.

[0063] Example 2:

[0064] Provides a black scale analysis solution for residue hydrocracking units:

[0065] Grind the block sample, use a 1 / 10,000 precision electronic balance to accurately weigh the sample mass, place the weighed sample into the titration cell of the Karl Fischer moisture analyzer for titration, and determine the water content in the sample.

[0066] like Figure 9 As shown, HSGCMS analysis: the sample was placed in a headspace bottle and sealed, the instrument parameters were set for detection, and the comparison of the mass spectrum with the standard library analysis showed that the low-boiling point volatile organic compounds in the sample mainly included n-hexane, 2-methylhexane, benzene, ethylcyclopentane, 3-methyl-1-heptene, 2-methylheptane, toluene, ethylbenzene, p-xylene, 2,5-dimethylheptane, isobutylcyclopentane, ethylcyclohexane, 2-ethyl-p-xylene, 4-isopropyltoluene, n-propylcyclohexane, 4-methylnonane, 3-methylnonane, decane, 1-methyl-2-propylcyclohexane, and 1-isobutyl-3-methylcyclopentane.

[0067] like Figure 10As shown, GCMS analysis: the organic matter in the sample was extracted with acetone and passed through a membrane for detection on the machine. Comparison of the mass spectrum with the standard library analysis showed that the medium-boiling point organic matter in the sample mainly contained 3-methylpentane, ethylbenzene, 3-methyloctane, 1,2,4-trimethylcyclohexane, isopropylbenzene, n-propylbenzene, 1-ethyl-2-methylcyclohexane, 2,4,6-trimethylheptane, n-propylcyclohexane, 4-methylnonane, 1,2-dimethyl-4-ethylbenzene, 1,2,4,5-tetramethylbenzene, 3-methyldecane, undecane, 2,6,10-trimethyldodecane, 3-ethyl-2-methylheptane, 2-ethyloctane, and isodecane.

[0068] After the constant temperature drying oven is kept at 105℃, the sample is placed on a watch glass and placed in the drying oven to constant weight, and the approximate proportion of low-boiling-point substances in the sample is calculated;

[0069] like Figure 11 As shown in Figure 2, PyGCMS analysis: After setting the instrument parameters, a small amount of sample was taken and placed in a pyrolysis cup for detection. The high-boiling-point organic compounds in the sample mainly contained o-ethylmethylbenzene, mesitylene, 2,5-dimethylundecane, 2,6,7-trimethyldecane, 2,4,6-trimethyldecane, ethylbenzene, n-propylbenzene, undecane, dodecane, n-hexadecane, 1,4-diethylbenzene, 1,3-dimethyl-4-ethylbenzene, 1,2-dimethyl-4-ethylbenzene, n-nonadecane, n-heneicosane, n-tetracosane, etc.

[0070] like Figure 12 As shown, TGA analysis: After the sample is dried, a small amount of sample is taken and placed in an alumina crucible and a detection atmosphere is selected for detection. The analysis shows that the sample contains some organic matter and substances that are easily decomposed at high temperature.

[0071] like Figure 13 As shown, EDX analysis: the sample was gold-sprayed and fixed on the sample stage, and the area to be tested was selected for scanning and detection. The analysis showed that the sample contained elements such as C, O, S, and Fe.

[0072] like Figure 14 As shown, XRD analysis: the sample was dried and crushed and filled into the sample rack for testing. The original spectrum was opened using Search-Match and compared with the standard card. It was found that the sample contained components such as ferric oxyhydroxide, ferrosoferric oxide, and ferrous sulfide.

[0073] After the muffle furnace is kept at a constant temperature of 800℃, the sample is accurately weighed and placed in a crucible. The crucible is placed in the muffle furnace and burned to a constant weight. The ignition weight loss of the sample is calculated.

[0074] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for analyzing black block foreign matter in a petroleum product processing device, characterized in that: The following steps are involved: S1, Karl Fischer titrator analyzes the water content in the sample: first, perform a blank titration and calibration titration of the Karl Fischer titrator, then grind the bulk sample, accurately weigh the sample using a precision electronic balance, and place the weighed sample into the titration cell for titration to determine the water content in the sample; S2, HSGCMS analysis of small molecules with low boiling points (less than 180°C) and volatile substances in the sample: the sample is placed in a sealed headspace vial for testing, and the collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are quantitatively or semi-quantitatively analyzed using the internal standard method; S3, GCMS detection of substances with medium boiling points (less than 300°C) in the sample: organic components in the sample are extracted with an organic solvent, the extract is filtered through a nylon filter membrane with a pore size of 0.45 μm into a chromatographic vial for detection on the GCMS, the collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are quantitatively or semi-quantitatively analyzed using the internal standard method; S4, test the volatile content of the sample in a constant temperature drying oven: place the sample on a watch glass and place it in a drying oven to constant weight, and calculate the approximate proportion of low-boiling-point substances in the sample; S5, PyGCMS detection of macromolecular high-boiling point substances in dried samples: 0.1-2 mg of dried sample is placed in a pyrolysis cup for detection. The collected mass spectrum is searched using a spectral library to confirm the structure of the target compound; the components in the sample are semi-quantitatively analyzed; S6, TGA analysis of the change in the mass of the dried sample with temperature to determine the proportion of organic matter, inorganic matter, and easily decomposable substances in the sample: 5-20 mg of sample was placed in a crucible for data collection; S7, EDX detection of elemental composition in dried or ash samples: After the sample is gold-sprayed, it is fixed on the sample stage, and the area to be tested is scanned and tested. The characteristic peaks are identified to determine the element type and the element content is calculated; S8, XRD detection of inorganic phases in oven-dried or ash-based samples, qualitative analysis of inorganic compounds in the sample: set the 2θ scanning range, grind the sample into a powder of 1-10 μm, evenly fill the sample holder, and ensure that the X-ray beam is aligned with the center of the sample for detection; export the diffraction data, identify the diffraction peaks, compare with the standard database, and determine the sample phase; S9, test the ignition weight loss of the sample in a muffle furnace: set the temperature of the muffle furnace to 800℃ and keep it constant, weigh 3-8g of the sample and put it into a crucible, place the crucible in the muffle furnace and burn it to constant weight, and calculate the ignition weight loss of the sample.

2. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: The following steps are also included: S10, FTIR qualitative analysis of the main components in the dried sample: the sample after drying to constant weight is pressed with potassium bromide pellets for detection, the spectrum is viewed using software, the functional groups and chemical bonds in the sample are analyzed, and the spectrum is compared with the standard spectral library to confirm the compound structure.

3. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: In step S2, the heating temperature of the headspace sampler is set to 60-150°C, the equilibration time is 10-30 min, and the injection volume is 0.5-2 ml; the programmed temperature rise of the chromatographic column is to maintain the initial temperature at 40°C for 10 min, the heating rate is 20°C / min, the temperature is raised to 200°C and maintained for 5 min, and then the temperature is raised to 220°C and maintained for 16 min; the mass spectrometer selects the EI electron source, the ion source temperature is 200-250°C, the transmission line temperature is 250°C, the scan mode is full scan, and the mass-to-nuclear ratio (m / z) range is 35-500m / z.

4. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: In step S3, the organic solvent for extracting the sample is acetone and / or chloroform, the injection port temperature of the gas chromatograph is 200-300°C, the heating program of the chromatographic column is an initial temperature of 60°C, maintained for 5 minutes, heated to 100°C at a heating rate of 3.5°C / min, maintained for 5 minutes, heated to 200°C at a heating rate of 8°C / min, maintained for 5 minutes, heated to 300°C at a heating rate of 15°C / min, maintained for 15 minutes, and the carrier gas flow rate is 1-2 ml / min; the mass spectrometer selects an EI electron source, the ion source temperature is 200-350°C, the transmission line temperature is 280°C, the scan mode is full scan, and the range is 10-1000 m / z.

5. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 2, characterized in that: In step S10 , the scanning range of FTIR is 400-4000 cm-1, the resolution is 4 cm-1, and the number of scans is 32 or 64.

6. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: In step S5, the cracking temperature of the cracker is 300-800° C., the cracking time is 10-30 s, and the programmed temperature rising condition of the chromatographic column is as follows: the initial temperature is 50° C., maintained for 2 min, heated to 200° C. at a heating rate of 12° C. / min, maintained for 0 min, then heated to 305° C. at a heating rate of 20° C. / min, maintained for 15 min; the mass spectrometer uses an IE electron source, the ion source temperature is 200-350° C., the transmission line temperature is 280° C., the scan mode is full scan, and the mass-to-nuclear ratio (m / z) range is 10-1000 m / z.

7. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: In step S6, nitrogen or air atmosphere is selected, the starting temperature is 45°C, the heating rate is 20°C / min, the ending temperature is 800°C, and it is maintained for 10 minutes; the material of the crucible used is one of alumina, platinum, quartz, and ceramic.

8. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: In step S8 , the scanning range of the 2θ angle is 5° to 80°, the scanning speed is 0.5° to 5° / min, and the step size is set to 0.02° to 0.05°.

9. The method for analyzing black block foreign matter in a petroleum product processing device according to claim 1, characterized in that: The temperature of the constant temperature drying oven in step S4 is from 105°C to a constant temperature.

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