Method for evaluating content and property of volatile components in green coke

Abstract

The invention relates to a method for evaluating the content and property of volatile components in green coke. The method comprises the following steps: S1, extracting the volatile components; sS1, mixing the to-be-detected green coke sample with a first polar solvent, and carrying out first extraction to obtain a first insoluble substance; sS2, mixing the first insoluble substance with a second polar solvent, and carrying out second extraction to obtain a second insoluble substance; sS3, determining a weight difference between the first insoluble substance and the second insoluble substance, and when the weight difference between the first insoluble substance and the second insoluble substance is less than a threshold weight, performing a step SS4; or when the weight difference is larger than the threshold weight, the step SS2 and the step SS3 are repeated till the weight difference between the insoluble substances obtained through two adjacent times of extraction is smaller than the threshold weight, and the step SS4 is carried out; sS4, carrying out solid-liquid separation on the filtrate to obtain volatile components; and S2, analyzing the relative molecular mass and the like of volatile components. The method disclosed by the invention is simple and easy to implement, economical and efficient, and not only can obtain the content of the volatile components in the green coke, but also can further obtain the chemical properties of the volatile components.

Description

Technical Field

[0001] The present application relates to the field of chemical analysis, and in particular to a method for evaluating the content and properties of volatile matter in green coke. Background Art

[0002] Green coke is an important raw material for industries such as steelmaking and carbon production. Its quality directly affects the quality and production efficiency of downstream products in the industrial chain. The volatile matter in green coke refers to the hydrocarbons that evaporate during the heating process. The volatile matter content in green coke is a key factor affecting the production process and product quality. If the volatile matter content of green coke is too high, it can easily cause problems such as explosion and sintering during the coking process, resulting in a decrease in the quality of the finished coke, including excessive moisture, increased porosity, and weakened mechanical strength. Too low a volatile matter content can easily make it difficult to remove coke from the coking reactor. It can also easily cause problems such as carbon powder accumulation and pipe blockage during the coking reaction, leading to equipment failure and production stoppage, affecting production efficiency. Therefore, obtaining the volatile matter content and properties of the raw materials is of great significance for improving process conditions and plans.

[0003] As described in the GB / T 2001-2013 standard, the existing method for measuring volatile matter content involves weighing a coke sample, placing it in a covered porcelain crucible, and heating it at 900°C ± 10°C in an airtight state for 7 minutes. The volatile matter content of the coke is calculated as the mass fraction of the reduced mass relative to the mass of the coke sample, minus the air-dried moisture content of the coke sample. Patent 202111430689.8 discloses a method, apparatus, and electronic device for measuring coke volatile matter, which are used to calculate the residual volatile matter of high-temperature coke in a dry quenching coke oven. This method determines the residual volatile matter volume per unit mass of coke per unit time by taking the actual volatile matter and target temperature of the target coke, combined with a predetermined volatile matter content. Furthermore, combining the target coke mass and target time, the residual volatile matter released by the target coke at the target temperature and target time can be determined. Patent 200810143014.3 discloses a method for analyzing coal volatiles using a thermogravimetric analyzer and a differential scanning calorimeter. Patent 201910353915.3 discloses a method for measuring coal volatiles using a muffle furnace with segmented temperature control. Based on the type or physical properties of the coal sample to be measured, the sample is classified as low-volatile or high-volatile. Different heating control methods are used to prevent overheating and substandard testing.

[0004] The above methods or patents all involve dedicated instruments and equipment. These devices for detecting the volatile matter content in raw coke are expensive and have high maintenance costs. In addition, they cannot further obtain chemical information such as the molecular weight, elemental composition, chemical environment of carbon and hydrogen atoms, carbon number distribution, and distillation range distribution of the volatile matter. This is not conducive to providing sufficient information support for the formation rules of volatile matter and the improvement and optimization of process preparation conditions. Summary of the Invention

[0005] The purpose of the present disclosure is to provide a method for evaluating the content and properties of volatile matter in green coke, which is simple, easy to implement, economical and efficient, and can not only obtain the content of volatile matter in green coke, but also further obtain the chemical properties of the volatile matter.

[0006] To achieve the above objectives, the present disclosure provides a method for evaluating the volatile matter content and properties in green coke, the method comprising:

[0007] S1, extracting volatile matter;

[0008] SS1, mixing the green coke sample to be tested with a first polar solvent to perform a first extraction to obtain a first insoluble matter and a first filtrate;

[0009] SS2, mixing the first insoluble matter with a second polar solvent to perform a second extraction to obtain a second insoluble matter and a second filtrate;

[0010] SS3. Determine the weight difference between the first insoluble matter and the second insoluble matter. When the weight difference between the first insoluble matter and the second insoluble matter is less than a threshold weight, proceed to step SS4. Alternatively,

[0011] When the weight difference between the first insoluble matter and the second insoluble matter is greater than the threshold weight, repeating steps SS2 and SS3 until the weight difference between the insoluble matter obtained from two consecutive extractions is less than the threshold weight, and then proceeding to step SS4; wherein the threshold weight is 0.3-0.7 g;

[0012] SS4, performing solid-liquid separation on the first filtrate and the second filtrate to obtain a solvent and the volatile matter;

[0013] S2. Analyze one or more of the relative molecular mass, elemental composition, distillation range distribution, chemical environment of carbon and hydrogen atoms, and carbon number distribution of the volatile matter.

[0014] Optionally, the conditions for the first extraction and the second extraction each independently include: temperature of 100-200° C., time of 1-10 h; preferably, temperature of 140-190° C., time of 1-5 h.

[0015] Optionally, in step SS1, the amount of the first polar solvent used is 100-300 g, preferably 150-250 g, relative to 100 g of the coke sample to be tested; in step SS2, the amount of the second polar solvent used is 100-300 g, preferably 150-250 g, relative to 100 g of the first insoluble matter.

[0016] Optionally, the first polar solvent and the second polar solvent are each independently one or more of furfural, dimethyl sulfoxide, toluene, N-methylpyrrolidone and tetrahydrofuran.

[0017] Optionally, the green coke sample to be tested includes one or more of petroleum-based common coke, petroleum-based needle coke, petroleum-based isotropic coke, coal-based common coke, coal-based needle coke and coal-based isotropic coke; the average particle size of the green coke sample to be tested is 100-500 μm, preferably 100-200 μm.

[0018] Optionally, separating the second filtrate includes: distilling the second filtrate at the boiling point of the solvent.

[0019] Optionally, step S2 includes: using a VPO molecular weight meter to measure the relative molecular mass of the volatile matter;

[0020] Using an organic element analyzer and a trace sulfur and nitrogen analyzer to determine the elemental composition of the volatile matter;

[0021] Determining the distillation range distribution of the volatile matter using a gas chromatograph;

[0022] Using the Fourier transform ion cyclotron resonance mass spectrometer, the average carbon number and equivalent double bond number of pure aromatic hydrocarbons, as well as the average carbon number and equivalent double bond number of single heteroatom compounds, are determined according to field ionization time-of-flight mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry;

[0023] A nuclear magnetic resonance spectrometer is used to measure the hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum of the volatile matter.

[0024] Optionally, step S2 comprises: using a VPO molecular weight meter to measure the relative molecular mass of the volatile matter according to the SH / T 0583-1994 method;

[0025] The organic element analyzer is used to determine the mass fractions of C and H in the volatile matter according to the SH / T 0656-2017 method; the trace sulfur and nitrogen analyzer is used to determine the mass fraction of S according to the GB / T17040-2008 method; the mass fraction of N is determined according to the SH / T 0704-2010 method; and the mass fraction of O is calculated by the subtraction method;

[0026] The gas chromatograph is used to determine the distillation range distribution of the volatile matter according to the SH / T 0879-2014 method.

[0027] Optionally, step S2 includes: using the Fourier transform ion cyclotron resonance mass spectrometer, the ion source is an atmospheric pressure photoionization source, under the conditions of APPI positive ion mode, APPI source temperature of 350-500°C, collision voltage of 0-48V, mass-to-charge ratio detection range of 250-1200, and scanning 100-400 times, determining the average carbon number and equivalent double bond number of pure aromatic hydrocarbons in the volatile matter, as well as the average carbon number and equivalent double bond number of single heteroatom compounds.

[0028] Optionally, step S2 includes: using a nuclear magnetic resonance spectrometer, according to the SH / T 0793-2007 method, at 20-40° C., using a deuterated reagent CDCl 3 as a solution, using tetramethylsilane as a reference, with a pulse width of 1.0-3.0 μs, a spectral width of 3000-50000 Hz, a resonance frequency of the observation nucleus of 500-900 MHz, a sampling time of 0.5-2.0 s, and a magnetic field strength of 5-10 T, to measure the nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum of the volatile component, and obtain the distribution of H atoms and C atoms in the volatile component;

[0029] The chemical shift in the H NMR spectrum is 6.0-9.0 ppm, which is attributed to the hydrogen atom content H directly connected to the aromatic carbon. A The peak area with a chemical shift of 2.0-4.0 ppm is attributed to the hydrogen atom content H attached to the α-carbon of the aromatic ring. α The peak area with a chemical shift of 1.0-2.0 ppm is attributed to the hydrogen on the β carbon of the aromatic ring and the hydrogen atom content beyond β. β The peak area with a chemical shift of 0.5-1.0 ppm is attributed to the hydrogen atom content H at the γ position of the aromatic ring and the methyl group beyond the γ position. γ ;

[0030] The peak area of ​​the chemical shift 100-200 ppm in the carbon NMR spectrum is attributed to the aromatic carbon content C A The peak area of ​​chemical shift 24-60 ppm is attributed to the cycloalkane carbon content C N , alkane carbon content C P From formula C P =C A -C N Calculated.

[0031] The beneficial effects of the present invention are as follows:

[0032] (1) The present disclosure realizes a simple, economical and efficient method for quickly detecting the content of volatile matter in green coke. The method is easy to operate and has strong controllability, and can be adapted to various types of green coke.

[0033] (2) The disclosed method can further obtain chemical properties of the volatile matter in the raw coke, such as molecular weight, elemental composition, chemical environment of carbon and hydrogen atoms, carbon number distribution, distillation range distribution, and other chemical information. These property analyses not only provide sufficient information support for understanding the structure and formation patterns of the volatile matter, but also further provide ideas for optimizing process preparation conditions.

[0034] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following detailed description, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0036] Figure 1 is the H NMR spectrum of the volatile matter of the ordinary coke in Example 1 of the present disclosure;

[0037] Figure 2 is the NMR carbon spectrum of the volatile matter of the ordinary coke in Example 1 of the present disclosure;

[0038] Figure 3 is the H NMR spectrum of the needle coke volatile matter in Example 2 of the present disclosure;

[0039] Figure 4 is the NMR carbon spectrum of the needle coke volatile matter in Example 2 of the present disclosure;

[0040] Figure 5 is the H NMR spectrum of the volatile matter of the isotropic coke in Example 3 of the present disclosure;

[0041] Figure 6 is the NMR carbon spectrum of the volatile matter of the isotropic coke in Example 3 of the present disclosure;

[0042] Figure 7 is the H NMR spectrum of the volatile matter of the mixed coke of ordinary coke and needle coke in Example 4 of the present disclosure;

[0043] Figure 8 This is the NMR carbon spectrum of the volatile matter of the mixed coke of ordinary coke and needle coke in Example 4 of the present disclosure. DETAILED DESCRIPTION

[0044] The following describes the specific embodiments of the present disclosure in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure and are not intended to limit the present disclosure.

[0045] The present disclosure provides a method for evaluating the content and properties of volatile matter in green coke, the method comprising:

[0046] S1, extracting volatile matter;

[0047] SS1, mixing the green coke sample to be tested with a first polar solvent to perform a first extraction to obtain a first insoluble matter and a first filtrate;

[0048] SS2, mixing the first insoluble matter with a second polar solvent to perform a second extraction to obtain a second insoluble matter and a second filtrate;

[0049] SS3. Determine the weight difference between the first insoluble matter and the second insoluble matter. When the weight difference between the first insoluble matter and the second insoluble matter is less than a threshold weight, proceed to step SS4. Alternatively,

[0050] When the weight difference between the first insoluble matter and the second insoluble matter is greater than the threshold weight, repeating steps SS2 and SS3 until the weight difference between the insoluble matter obtained from two consecutive extractions is less than the threshold weight, and then proceeding to step SS4; wherein the threshold weight is 0.3-0.7 g;

[0051] SS4, performing solid-liquid separation on the first filtrate and the second filtrate to obtain a solvent and the volatile matter;

[0052] S2. Analyze one or more of the relative molecular mass, elemental composition, distillation range distribution, chemical environment of carbon and hydrogen atoms, and carbon number distribution of the volatile matter.

[0053] The method disclosed herein extracts volatile matter from green coke by extraction and then performs detection and analysis, which can not only obtain the content of volatile matter in the green coke, but also further obtain information such as the relative molecular mass, distillation range distribution and other chemical properties of the volatile matter. The method is simple, easy to implement, and economical and efficient.

[0054] According to the present disclosure, the content of volatile matter is obtained by dividing the mass of the volatile matter obtained in step SS4 by the mass of the green coke sample to be measured in step SS1.

[0055] According to the present disclosure, the weight difference between the first insoluble matter and the second insoluble matter refers to the difference in dry weight between the two. In a specific embodiment, the first insoluble matter in step SS1 and the second insoluble matter in step SS2 are dried. The drying can be carried out in an apparatus conventionally used by those skilled in the art, for example, a constant temperature drying oven. The present disclosure does not impose any specific restrictions on the drying conditions, as long as the liquid contained in the first insoluble matter and the second insoluble matter can be removed. For example, the drying temperature is set to the boiling point of the solvent and the drying time is 10-15 hours.

[0056] According to the present disclosure, the solid-liquid separation of the first filtrate and the second filtrate in step SS4 refers to the solid-liquid separation of all the filtrates obtained in step S1.

[0057] According to the present disclosure, the chemical environment of the carbon and hydrogen atoms includes the average carbon number and equivalent double bond number of pure aromatic hydrocarbons and single heteroatom compounds.

[0058] According to the present disclosure, extraction is well known to those skilled in the art and can be performed, for example, in an extraction separator. The conditions for the first extraction and the second extraction in the present disclosure may be the same or different. In one embodiment of the present disclosure, the conditions for the first extraction and the second extraction each independently include: a temperature of 100-200°C and a time of 1-10 hours; preferably, a temperature of 140-190°C and a time of 1-5 hours.

[0059] In one specific embodiment of the present disclosure, in step SS1, the amount of the first polar solvent used is 100-300 g, preferably 150-250 g, per 100 g of the green coke sample to be tested. In step SS2, the amount of the second polar solvent used is 100-300 g, preferably 150-250 g, per 100 g of the first insoluble matter. A suitable amount of polar solvent within this range allows for more effective extraction of volatile matter from the green coke.

[0060] According to the present disclosure, the types of solvents used in step SS1 and step SS2 may be the same or different, and this application does not impose any specific restrictions on this. In a preferred embodiment of the present disclosure, the first polar solvent and the second polar solvent are each independently one or more of furfural, dimethyl sulfoxide, toluene, N-methylpyrrolidone, and tetrahydrofuran.

[0061] According to the present disclosure, the green coke sample to be tested can be the green coke well known to those skilled in the art. In a specific embodiment of the present disclosure, the green coke sample to be tested can include but is not limited to one or more of petroleum-based common coke, petroleum-based needle coke, petroleum-based isotropic coke, coal-based common coke, coal-based needle coke and coal-based isotropic coke; the average particle size of the green coke sample to be tested is 100-500 μm, preferably 100-200 μm.

[0062] In a specific embodiment of the present disclosure, the solid-liquid separation of the first filtrate and the second filtrate includes: distilling the first filtrate and the second filtrate at the boiling point temperature of the solvent. According to the present disclosure, the distillation treatment can be carried out in a distillation apparatus, such as a distillation flask, and the distillate during the distillation treatment is the solvent, and the residue is the volatile matter. In the present disclosure, when the first filtrate and the second filtrate contain the same type of solvent, the boiling point temperature of the solvent refers to the boiling point temperature of the polar solvent contained. When the first filtrate and the second filtrate contain different types of solvents, the boiling point temperature of the solvent refers to the highest boiling point temperature among the polar solvents contained.

[0063] In a specific embodiment of the present disclosure, step S2 includes: using a VPO molecular weight meter to determine the relative molecular mass of the volatile matter; using an organic element analyzer and a trace sulfur and nitrogen analyzer to determine the elemental composition of the volatile matter; using a gas chromatograph to determine the distillation range distribution of the volatile matter; using a high-resolution mass spectrometer to determine the average carbon number and equivalent double bond number of pure aromatic hydrocarbons, as well as the average carbon number and equivalent double bond number of single heteroatom compounds according to field ionization time-of-flight mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry; and using a nuclear magnetic resonance spectroscopy to determine the nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum of the volatile matter.

[0064] In a specific embodiment of the present disclosure, step S2 includes: using a VPO molecular weight meter to measure the relative molecular mass of the volatile matter according to the SH / T0583-1994 method.

[0065] In a specific embodiment of the present disclosure, the organic element analyzer is used to determine the mass fractions of C and H in the volatile matter according to the SH / T0656-2017 method; the trace sulfur and nitrogen analyzer is used to determine the mass fraction of S according to the GB / T17040-2008 method; the mass fraction of N is determined according to the SH / T 0704-2010 method; and the mass fraction of O is calculated by subtraction.

[0066] In a specific embodiment of the present disclosure, the gas chromatograph is used to measure the distillation range distribution of the volatile matter according to the SH / T0879-2014 method.

[0067] In a specific embodiment of the present disclosure, step S2 includes: using the Fourier transform ion cyclotron resonance mass spectrometer, the ion source is an atmospheric pressure photoionization source (APPI), in APPI positive ion mode, APPI source temperature is 350-500 ° C, preferably 380-420 ° C, collision voltage is 0-48 V, mass-to-charge ratio detection range is 250-1200, scan times are 100-400 times, preferably 200-400 times, magnetic field strength is 5-10 T, preferably 8-10 T, the average carbon number and equivalent double bond number of pure aromatic hydrocarbons in the volatile matter, as well as the average carbon number and equivalent double bond number of single heteroatom compounds. Pure aromatic hydrocarbons refer to aromatic hydrocarbons composed only of carbon and hydrogen elements, represented by CH, and single heteroatoms include S, N, and O.

[0068] In a specific embodiment of the present disclosure, step S2 comprises: using a nuclear magnetic resonance spectrometer, according to the SH / T0793-2007 method, at 20-40° C., preferably 25-30° C., using a deuterated reagent CDCl3 as a solution, using tetramethylsilane (TMS) as a reference, with a pulse width of 1.0-3.0 μs, preferably 2.0-3.0 μs, a spectrum width of 30000-50000 Hz, preferably 40000-50000 Hz, an observation nuclear resonance frequency of 500-900 MHz, preferably 600-800 MHz, and a sampling time of 0.5-2.0 s, preferably 0.8-1.5 s, to measure the nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum of the volatile matter, and obtain the distribution of H atoms and C atoms in the volatile matter; wherein the chemical shift of 6.0-9.0 ppm in the nuclear magnetic resonance hydrogen spectrum is attributed to the hydrogen atom content H directly connected to the aromatic carbon. A The peak area with a chemical shift of 2.0-4.0 ppm is attributed to the hydrogen atom content H attached to the α-carbon of the aromatic ring. α The peak area with a chemical shift of 1.0-2.0 ppm is attributed to the hydrogen on the β carbon of the aromatic ring and the hydrogen atom content beyond β. β The peak area with a chemical shift of 0.5-1.0 ppm is attributed to the hydrogen atom content H at the γ position of the aromatic ring and the methyl group beyond the γ position. γ The peak area of ​​chemical shift 100-200ppm in the carbon NMR spectrum is attributed to the aromatic carbon content C A The peak area of ​​chemical shift 24-60 ppm is attributed to the cycloalkane carbon content C N , alkane carbon content C P From formula C P =C A -C N Calculated.

[0069] The present disclosure is further illustrated below by way of examples, but the present disclosure is not limited thereby.

[0070] Unless otherwise specified, the reagents used in the following examples and comparative examples were commercially available. The conventional coke, needle coke, and isotropic coke in the examples were provided by Sinopec Research Institute of Petroleum Processing Co., Ltd.

[0071] The relative molecular weight of the volatile matter in the examples was measured using a K-7000 vapor pressure osmometer produced by KNAUER, Germany, according to the SH / T 058-1994 method;

[0072] The atomic mass fractions of C and H in the volatile matter were determined using a vario EL organic element analyzer from Elementar (Germany) according to the SH / T 0656-2017 method. The atomic mass fraction of S was determined using a multiEA3100 trace sulfur and nitrogen analyzer from Jena (Germany) according to the GB / T 17040-2008 method. The atomic mass fraction of N was determined using the SH / T 0704-2010 method. The oxygen content was determined by subtraction of the carbon, hydrogen, sulfur, and nitrogen contents obtained by analysis.

[0073] The distillation range distribution of volatile matter was determined using an Agilent 7890A gas chromatograph according to the SH / T0879-2014 method;

[0074] The average carbon number and equivalent double bond number of pure aromatic hydrocarbons (HC) and single heteroatom compounds (S1, N1, O1) in the volatile matter of green coke were determined using an APEX-Qe Fourier transform ion cyclotron resonance mass spectrometer produced by Bruker Daltonics in the United States, according to the high-resolution mass spectrometry molecular recognition method described in Patent ZL201710995027.2. The specific test conditions were: atmospheric pressure photoionization (APPI) ion source, APPI positive ion mode, APPI source temperature of 400°C, collision voltage of 0-48V, mass-to-charge ratio detection range of 250-1200, 256 scans, and magnetic field strength of 9.4T.

[0075] The H and C nuclear magnetic resonance spectra of the volatile components, as well as the distribution of H and C atoms, were measured using an Agilent 700 MHz nuclear magnetic resonance spectrometer from Agilent, USA, according to the SH / T 0793-2007 method and in combination with the molecular structure characterization method for H and C atomic distribution and structural parameters of heavy oils introduced in the article "Characterization of Heavy Oil Structure by Nuclear Magnetic Resonance Method" by Yang Liqing et al. (Acta Petrolei Sinica (Petroleum Processing), 2016, 32(5): 1038-1044). The specific test conditions were: at 25°C, using deuterated reagent CDCl3 as the solution, tetramethylsilane (TMS) as the reference, a pulse width of 2.7 μs, a spectral width of 48,000 Hz, a resonance frequency of the observation nucleus of 700 MHz, and a sampling time of 1.0 s.

[0076] Example 1

[0077] S1. Extraction of volatile matter:

[0078] SS1. Place 100 g of green coke with a particle size of less than 300 μm in an extraction separator, add 200 g of furfural, raise the temperature to 140° C., maintain constant temperature and stirring for 2 hours, and filter to obtain the first furfural insoluble matter and the first filtrate.

[0079] SS2, the first furfural insoluble matter was dried and weighed, and then placed in an extraction separator, 200g of fresh furfural was added, the temperature was raised to 140°C, and the temperature was kept constant and stirred for 2h, and the second furfural insoluble matter and the second filtrate were obtained by filtration;

[0080] SS3. Dry and weigh the second furfural insoluble material. The weight difference between the dried first furfural insoluble material and the dried second furfural insoluble material is greater than the threshold weight. Therefore, step SS2 and step SS3 are repeated until the weight of the furfural insoluble material after two adjacent drying and recovery is less than the threshold weight, and step SS4 is performed; wherein the threshold weight is 0.5 g.

[0081] SS4. All filtrates from step S1 were placed in a distilling flask and heated to the boiling point of furfural to recover the solvent by distillation. The distillate was the recovered furfural, and the distilling flask residue was the volatile matter in the green coke, weighing 13.4 g. Therefore, the green coke had a volatile matter content of 13.4%.

[0082] S2. The volatile matter of the obtained raw coke was analyzed and characterized. Its chemical information such as distillation range distribution, elemental composition, carbon number distribution, etc. are shown in Table 1. The nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the volatile matter are shown in Table 1. Figure 1 and Figure 2 shown.

[0083] Table 1

[0084]

[0085]

[0086]

[0087] Note: HC in Table 1 represents pure aromatic hydrocarbons; S1 represents heteroatom compounds containing one S atom; N1 represents heteroatom compounds containing one N atom; O1 represents heteroatom compounds containing one O atom. The same applies to the following tables.

[0088] Example 2

[0089] S1. Extraction of volatile matter:

[0090] SS1. Place 100 g of green needle coke with a particle size of less than 400 μm in an extraction separator, add 200 g of dimethyl sulfoxide, raise the temperature to 160° C., maintain constant temperature and stirring for 4 hours, and filter to obtain the first dimethyl sulfoxide insoluble matter and filtrate.

[0091] SS2, after drying and weighing the first dimethyl sulfoxide insoluble matter, place it in an extraction separator, add 200g dimethyl sulfoxide, raise the temperature to 160°C, maintain constant temperature and stirring for 4h, and filter to obtain the second dimethyl sulfoxide insoluble matter and the second filtrate;

[0092] SS3 and the second dimethyl sulfoxide insoluble matter are dried and weighed. The weight difference between the dried first dimethyl sulfoxide insoluble matter and the second dimethyl sulfoxide insoluble matter is greater than the threshold weight. Therefore, step SS2 and step SS3 are repeated until the weight of the dimethyl sulfoxide insoluble matter after two adjacent drying and recovery is less than the threshold weight, and step SS4 is performed; wherein the threshold weight is 0.5 g.

[0093] SS4. The filtrate from step S1 was placed in a distillation flask and heated to the boiling point of dimethyl sulfoxide (DMSO) to recover the solvent by distillation. The distillate was recovered DMSO, and the residue in the distillation flask was the volatile matter from the green needle coke, weighing 11.3 g. Therefore, the volatile matter content of the green needle coke was 11.3%.

[0094] S2. The volatile matter of the obtained needle coke is analyzed and characterized. Its chemical information such as distillation range distribution, elemental composition, carbon number distribution, etc. are shown in Table 2. The nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the volatile matter are shown in Table 2. Figure 3 and Figure 4 shown.

[0095] Table 2

[0096]

[0097]

[0098] Example 3

[0099] S1. Extraction of volatile matter:

[0100] SS1. Place 100 g of isotropic green coke with a particle size of less than 300 μm in an extraction separator, add 200 g of toluene, raise the temperature to 140° C., maintain constant temperature and stirring for 2 hours, and filter to obtain a first toluene insoluble matter and a first filtrate.

[0101] SS2. Dry and weigh the first toluene-insoluble matter, then place it in an extraction separator, add 200 g of fresh toluene, raise the temperature to 140° C., maintain constant temperature and stirring for 2 h, and filter to obtain the second toluene-insoluble matter and the second filtrate.

[0102] SS3. Dry and weigh the second toluene-insoluble matter. The weight difference between the dried first toluene-insoluble matter and the dried second toluene-insoluble matter is greater than the threshold weight. Therefore, steps SS2 and SS3 are repeated until the weight of the toluene-insoluble matter after two adjacent drying and recovery steps is less than the threshold weight, and then step SS4 is performed; wherein the threshold weight is 0.5 g.

[0103] SS4. Place all of the filtrate from step S1 into a distillation flask and heat it to the boiling point of toluene to recover the solvent by distillation. The distillate is recovered toluene, and the residue in the distillation flask is the volatile matter from the isotropic coke green coke, weighing 15.4 g. Therefore, the volatile matter content of the isotropic coke green coke is 15.4%.

[0104] S2. The volatile matter of the obtained isotropic coke was analyzed and characterized. Its chemical information such as distillation range distribution, elemental composition, carbon number distribution, etc. are shown in Table 3. The nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the volatile matter are shown in Table 3. Figure 5 and Figure 6 shown.

[0105] Table 3

[0106]

[0107]

[0108] Example 4

[0109] S1. Extraction of volatile matter:

[0110] SS1. Place 100 g of mixed raw coke of general coke and needle coke with a particle size of less than 400 μm in an extraction separator in a mixing ratio of general coke to needle coke of 1:1, add 200 g of N-methylpyrrolidone, raise the temperature to 180°C, maintain constant temperature and stirring for 4 hours, and filter to obtain a first N-methylpyrrolidone insoluble matter and a first filtrate.

[0111] SS2, after drying and weighing the first N-methylpyrrolidone insoluble matter, place it in an extraction separator, add 200 g of fresh N-methylpyrrolidone, raise the temperature to 180 ° C, maintain constant temperature and stirring for 4 hours, and filter to obtain a second N-methylpyrrolidone insoluble matter and a second filtrate;

[0112] SS3. Dry and weigh the second N-methylpyrrolidone insoluble material. The weight difference between the dried first N-methylpyrrolidone insoluble material and the dried second N-methylpyrrolidone insoluble material is greater than the threshold weight. Therefore, step SS2 and step SS3 are repeated until the weight of the N-methylpyrrolidone recovered after two adjacent dryings is less than the threshold weight, and then step SS4 is performed; wherein the threshold weight is 0.5 g.

[0113] SS4. The filtrate from step S1 was placed in a distillation flask and heated to the boiling point of N-methylpyrrolidone to recover the solvent by distillation. The distillate was the recovered N-methylpyrrolidone, and the residue in the distillation flask was the volatile matter in the mixed green coke of general coke and needle coke, weighing 22.4 g. Therefore, the volatile matter content of the mixed green coke of general coke and needle coke was 22.4%.

[0114] S2. The volatile matter of the mixed raw coke of ordinary coke and needle coke was analyzed and characterized. Its chemical information such as distillation range distribution, elemental composition, carbon number distribution, etc. are shown in Table 4. The nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the volatile matter are shown in Table 4. Figure 7 and Figure 8 shown.

[0115] Table 4

[0116]

[0117]

[0118] Example 5

[0119] The volatile matter content and properties of the green coke were evaluated using the same method as in Example 1, except that in step SS1, the extraction temperature was 120° C. and the extraction time was 1 h.

[0120] The weight of the residue in the distillation flask in step SS4 is 11.2 g, so the volatile matter content of the above-mentioned ordinary coke green coke is 11.2%.

[0121] Example 6

[0122] The volatile matter content and properties of green coke were evaluated using the same method as in Example 1, except that in step SS1, 100 g of green coke with a particle size of less than 300 μm was placed in an extraction separator and 100 g of furfural was added. In step SS2, 100 g of fresh furfural was added.

[0123] The weight of the residue in the distillation flask in step SS4 is 10.8 g, so the volatile matter content of the above-mentioned ordinary coke green coke is 10.8%.

[0124] Comparative Example 1

[0125] 100 g of the same green coke as in Example 1 was taken and ground to a particle size of less than 300 μm. The volatile matter of the sample was tested according to the GB / T2001-2013 standard method, and the volatile matter content was found to be 15.17%.

[0126] From the above, it can be seen that the method disclosed in the present invention can well determine the content of volatile matter in green coke, and can further obtain the chemical properties of the volatile matter in the green coke.

[0127] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings. However, the present disclosure is not limited to the specific details of the above embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the scope of protection of the present disclosure.

[0128] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0129] In addition, the various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A method for evaluating the volatile matter content and properties of green coke, the method comprising: S1, extracting volatile matter; SS1, mixing the green coke sample to be tested with a first polar solvent to perform a first extraction to obtain a first insoluble matter and a first filtrate; SS2, mixing the first insoluble matter with a second polar solvent to perform a second extraction to obtain a second insoluble matter and a second filtrate; SS3. Determine the weight difference between the first insoluble matter and the second insoluble matter. When the weight difference between the first insoluble matter and the second insoluble matter is less than a threshold weight, proceed to step SS4. Alternatively, When the weight difference between the first insoluble matter and the second insoluble matter is greater than the threshold weight, repeating steps SS2 and SS3 until the weight difference between the insoluble matter obtained from two consecutive extractions is less than the threshold weight, and then proceeding to step SS4; wherein the threshold weight is 0.3-0.7 g; SS4, performing solid-liquid separation on the first filtrate and the second filtrate to obtain a solvent and the volatile matter; S2. Analyze one or more of the relative molecular mass, elemental composition, distillation range distribution, chemical environment of carbon and hydrogen atoms, and carbon number distribution of the volatile matter.

2. The method according to claim 1, wherein The conditions of the first extraction and the second extraction each independently include: The temperature is 100-200°C, and the time is 1-10 hours; preferably, the temperature is 140-190°C, and the time is 1-5 hours.

3. The method according to claim 1, wherein In step SS1, the amount of the first polar solvent used is 100-300 g, preferably 150-250 g, relative to 100 g of the coke sample to be tested; in step SS2, the amount of the second polar solvent used is 100-300 g, preferably 150-250 g, relative to 100 g of the first insoluble matter.

4. The method according to claim 1, wherein The first polar solvent and the second polar solvent are each independently one or more of furfural, dimethyl sulfoxide, toluene, N-methylpyrrolidone and tetrahydrofuran.

5. The method according to claim 1, wherein The green coke sample to be tested includes one or more of petroleum-based common coke, petroleum-based needle coke, petroleum-based isotropic coke, coal-based common coke, coal-based needle coke and coal-based isotropic coke; the average particle size of the green coke sample to be tested is 100-500 μm, preferably 100-200 μm.

6. The method according to claim 1, wherein The solid-liquid separation of the first filtrate and the second filtrate includes: distilling the first filtrate and the second filtrate at the boiling point of the solvent.

7. The method according to claim 1, wherein Step S2 comprises: using a VPO molecular weight meter to measure the relative molecular mass of the volatile matter; Using an organic element analyzer and a trace sulfur and nitrogen analyzer to determine the elemental composition of the volatile matter; Determining the distillation range distribution of the volatile matter using a gas chromatograph; The average carbon number and equivalent double bond number of pure aromatic hydrocarbons, as well as the average carbon number and equivalent double bond number of single heteroatom compounds, are determined by field ionization time-of-flight mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry using a Fourier transform ion cyclotron resonance mass spectrometer. A nuclear magnetic resonance spectrometer is used to measure the hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum of the volatile matter.

8. The method according to claim 7, wherein: Step S2 comprises: using a VPO molecular weight meter to measure the relative molecular mass of the volatile matter according to the SH / T0583-1994 method; The organic element analyzer is used to determine the mass fractions of C and H in the volatile matter according to the SH / T 0656-2017 method; the trace sulfur and nitrogen analyzer is used to determine the mass fraction of S according to the GB / T17040-2008 method; the mass fraction of N is determined according to the SH / T0704-2010 method; and the mass fraction of O is calculated by subtraction method; The gas chromatograph is used to determine the distillation range distribution of the volatile matter according to the SH / T 0879-2014 method.

9. The method according to claim 7, wherein: Step S2 includes: using the Fourier transform ion cyclotron resonance mass spectrometer, with an atmospheric pressure photoionization source as the ion source, in APPI positive ion mode, an APPI source temperature of 350-500°C, a collision voltage of 0-48V, a mass-to-charge ratio detection range of 250-1200, 100-400 scans, and a magnetic field strength of 5-10T, determining the average carbon number and equivalent double bond number of pure aromatic hydrocarbons in the volatile matter, as well as the average carbon number and equivalent double bond number of single heteroatom compounds.

10. The method according to claim 7, wherein: Step S2 comprises: using a nuclear magnetic resonance spectrometer, according to the SH / T0793-2007 method, at 20-40° C., using a deuterated reagent CDCl 3 as a solution, using tetramethylsilane as a reference, with a pulse width of 1.0-3.0 μs, a spectral width of 3000-50000 Hz, a resonance frequency of the observation nucleus of 500-900 MHz, and a sampling time of 0.5-2.0 s, measuring the nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum of the volatile component, and obtaining the distribution of H atoms and C atoms in the volatile component; The chemical shift in the H NMR spectrum is 6.0-9.0 ppm, which is attributed to the hydrogen atom content H directly connected to the aromatic carbon. A The peak area with a chemical shift of 2.0-4.0 ppm is attributed to the hydrogen atom content H attached to the α-carbon of the aromatic ring. α The peak area with a chemical shift of 1.0-2.0 ppm is attributed to the hydrogen on the β carbon of the aromatic ring and the hydrogen atom content beyond β. β The peak area with a chemical shift of 0.5-1.0 ppm is attributed to the hydrogen atom content H at the γ position of the aromatic ring and the methyl group beyond the γ position. γ ; The peak area of ​​the chemical shift 100-200 ppm in the carbon NMR spectrum is attributed to the aromatic carbon content C A The peak area of ​​chemical shift 24-60 ppm is attributed to the cycloalkane carbon content C N , alkane carbon content C P From formula C P =C A -C N Calculated.

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