CN112903621A - Coal molecule model building method based on multiple characterization means - Google Patents

Coal molecule model building method based on multiple characterization means Download PDF

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CN112903621A
CN112903621A CN202110080720.3A CN202110080720A CN112903621A CN 112903621 A CN112903621 A CN 112903621A CN 202110080720 A CN202110080720 A CN 202110080720A CN 112903621 A CN112903621 A CN 112903621A
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崔馨
赵培涛
严煌
杨锐
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China University of Mining and Technology CUMT
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Abstract

The invention provides a coal molecule model building method based on various characterization means, which comprises the steps of (1) carrying out industrial analysis, elemental analysis and analysis on a coal sample,13C-NMR analysis, FTIR absorption characteristic analysis, surface structure characteristic analysis, nuclear magnetic resonance analysis and infrared spectrum analysis; (2) establishing a connection between a skeleton structure and a surface functional group of the coal; (3) obtaining molecular structure parameters of a coal sample; (4) the invention uses ACD/ChemSketch10.0 software to construct a molecular structure model of a coal sample, obtains a combined analysis result of coal sample structure data by adopting various physicochemical analysis experiments, and uses the combined analysis result to analyze coal sample structure data13Research on coal samples with different metamorphism degrees by physical and chemical analysis methods such as C-NMR, FTIR and chemical experiment methodThe molecular composition structure and the establishment of the coal molecular structure model have milestone value for the development of coal chemical industry and have important reference significance for understanding the combustion characteristics of coal samples and improving the combustion efficiency.

Description

Coal molecule model building method based on multiple characterization means
Technical Field
The invention relates to a characterization technology of organic matter component structure and distribution of a coal sample, in particular to a coal molecule model building method based on multiple characterization means.
Background
Coal is a complex mixture formed by aggregating various substances, and the constituent substances are mainly organic substances. Wherein the organic matter mainly comprises C, H, O three elements, and simultaneously contains a small amount of S, N and other elements. Coal produces a large amount of pollutant-containing emissions such as soot, flue gas, and slag during combustion, wherein the soot contains particles of fly ash and carbon particles, and the flue gas contains CO in addition to CO2And SO in addition to CO2And NOXAnd the like, which causes serious damage to the natural environment and ecological balance. The emission of the pollutants is mainly formed by breaking chemical bonds in the molecular structure of coal due to a series of chemical reactions in the coal combustion process. Therefore, a coal molecular structure model is accurately constructed, the coal pyrolysis and combustion reaction mechanism is mined from a microscopic level, and the method has important theoretical and practical significance for efficient and clean utilization of coal.
For nearly half a century, researchers related to coal chemistry at home and abroad are dedicated to the systematic research on coal molecular structure, and the theoretical basis and modern physical analysis means are combined to obtain the molecular structure parameters of related coal, so that a feasible basis is provided for further research on a coal molecular structure model. Due to the non-uniqueness and complexity of the coal molecular composition, the interaction modes among the molecules in the coal structure are diversified, and the coal molecular structure still lacks a systematic and comprehensive explanation.
With the development of basic physics disciplines and precision instruments, the recognizable range and accuracy of modern physical analysis instruments are remarkably improved. Currently used in the field of coal molecular structure for characterizing chemical structural features and statistical structural resolution are13Physical instruments such as C-NMR, FTIR, X-ray (XRD) and HRTEM. The physical research method has the advantages of small damage degree to the chemical structure of coal and high sensitivity of quantitative analysis, and is widely used for the research of the molecular structure of coal. But no matter whether13C-NMR, FTIR, XRD and HRTEM, all have difficulty in directly analyzing the distribution pattern and the mutual combination mode of different organic components in a coal sample.
Disclosure of Invention
The invention provides a coal molecule model building method based on various characterization means for solving the problems of organic matter structure components and structure information of coal samples under different metamorphism degrees.
In order to solve the technical problems, the invention provides a coal molecule model building method based on various characterization means, which comprises the following steps: (1) performing industrial analysis, element analysis on the coal,13C-NMR analysis, FTIR absorption characteristic analysis, surface structure characteristic analysis, nuclear magnetic resonance analysis and infrared spectrum analysis are carried out to obtain basic data of the coal, and the basic data is utilized to obtain analysis data of the coal; (2) determining the percentage of the molecular structure composition and the ratio of protonated groups to unprotonated groups in the molecular structure composition; (3) determining the unsaturation degree of aliphatic carbon and the condensation degree of aromatic carbon in the coal, and determining the chemical structure and the molecular weight of coal molecules by counting the atomic numbers of nitrogen and sulfur in an integer; (4) the ACD/ChemSketch10.0 software was used to construct a model of the structure of the coal molecule using molecular simulation techniques.
Preferably, in step (2), the structural composition of the coal molecule comprises aromatic carbon, carbonyl carbon, aromatic ring carbon, protonated aromatic carbon, non-protonated aromatic carbon, phenolic hydroxyl or ether oxygen linked carbon, alkyl substituted aromatic carbon, aromatic bridged carbon, total aliphatic carbon, quaternary carbon, and-CH2One or more of group carbon, methyl and arylmethyl carbon, and oxygen connecting aliphatic carbon.
Preferably, in step (1), the basic data includes ash content, moisture content, volatile content, C, H, O, N content and S content data of coal in which13And C, chemical shift, sub-peak number, sub-peak area and coal surface structure characterization images.
Preferably, in the step (1), the analysis data includes the molecular structure composition, atomic ratio, surface functional group structure, surface functional group number, surface functional group vibration form and aromatic nucleus size data of the coal.
Preferably, use is made of13C-NMR chemical shift simulation method13C-NMR simulation spectrum according to the description in step (1)13Experimental pattern of C-NMR analysis by peak position ratioRather, on the premise that the total number of atoms is not changed, the13C-NMR simulation spectrum is adjusted.
Preferably, the chemical shift corresponding to the structural composition of the coal molecule is from 0 to 600 ppm. Preferably, an accurate fit is made to the peaks in the methylene region.
The invention has the beneficial effects that:
the coal molecule model building method adopts various physical and chemical analysis experiments to obtain the combined analysis result of the structural data of the coal sample, and the combined analysis result is obtained through13The molecular composition structures of the coal samples with different metamorphism degrees are researched by physical and chemical analysis methods such as C-NMR, FTIR and chemical experimental methods, and the method has important reference values for understanding the combustion characteristics of the coal samples and improving the combustion efficiency. The full understanding of the molecular structure characteristics of the coal sample is a breakthrough point of the development of the coal chemical industry, and the establishment of the coal molecular structure model has a milestone value for the development of the coal chemical industry.
Drawings
FIG. 1 is an SEM crystal structure image of a Nindong coal sample;
FIG. 2 is a sample of Nindong coal13C-NMR chemical shift vibration characteristic analysis results, wherein the first graph is a nuclear magnetic resonance spectrum fitting comparison result, the second graph is an aliphatic carbon region A peak-splitting spectrum, the third graph is an aliphatic carbon region B peak-splitting spectrum, the fourth graph is an aromatic carbon peak-splitting spectrum, and the fifth graph is a carbonyl carbon peak-splitting spectrum;
FIG. 3 shows FTIR vibrational absorption characteristic analysis results of Nindong coal samples, wherein the first graph is a baseline calibration graph of the infrared spectrum of Nindong coal, and the second graph is 3500cm of Nindong coal-1-3000cm-1An infrared spectrogram; the third graph is Ningdong coal 3000cm-1-2800cm-1An infrared spectrogram; the fourth graph shows that the Ningdong coal is 1800cm-1-1000cm-1An infrared spectrogram; the fifth graph shows Ningdong coal 900cm-1-700cm-1An infrared spectrogram;
FIG. 4 is a model of the molecular structure of a Nindong coal sample;
FIG. 5 is a molecular structure model of a coal sample13C-NMR prediction spectrogram;
FIG. 6 shows the molecular structure of Nindong coal sample13And comparing the C-NMR simulation spectrum with the experimental spectrum.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
A coal molecule model building method based on multiple characterization means comprises the following steps:
the first step, pretreatment and element and industrial analysis of coal samples: grinding the coal sample to enable the particle size of the coal sample to reach 200 meshes, removing moisture existing in the surface structure of the coal sample through vacuum drying, and performing industrial analysis and element analysis on the pretreated coal sample to obtain the contents of ash, moisture and volatile components in the coal and C, H, O, N and S elements.
And (4) performing element analysis and industrial analysis on the Ningdong coal sample according to the national standard GB/T476-2008. The results of the industrial and elemental analyses of the coal are shown in Table 1.
TABLE 1 Industrial and elemental analysis of Nindong coal
Figure BDA0002909171690000031
After obtaining the elemental analysis results of Nindong coal, the relative number of atoms in the coal can be obtained by dividing the mass fraction of each element by the relative atomic mass of each element. The atomic ratios of the various types in the coal structure can be determined using data from elemental analysis, which is used as the basis for a model of the structure of the coal molecule, see table 2.
TABLE 2 atomic ratio of coal molecular model
Figure BDA0002909171690000032
The surface structure characteristics of Nindong coal were characterized by scanning electron microscopy at representative magnification of 4 groups, and a, b, c and d in FIG. 1 are SEM representations at magnification of 500, 1000, 1500 and 4000, respectively. The observation shows that the coal particles present different sizes and surface morphologies, the size distribution of the coal particle morphology is extremely uneven, the reason for lightening part of the large particles is caused by the insecure adhesion between the conductive adhesive and the coal particles in the experimental process, the difference between the morphology and the size of the coal is more obvious after the image of the figure 1(b) is magnified by 1000 times compared with the image of the figure 1(a), and the detail structure of the coal particle morphology needs to be magnified by a larger magnification factor when the observation is required. Fig. 1(c) is an SEM image of the coal particles magnified 1500 times, and it is observed that the coal particles have extremely complicated surface morphology, flat and smooth portions, sharp and rough portions, smaller coal particles attached to a plurality of positions on the large particles, and a lamellar structure in a portion of the coal particles, and are layered. FIG. 1(d) shows more details of the coal particles, wherein the finer coal particles are attached to the surface of the particles, in a distribution similar to that of FIG. 1(a), and the coal layer structure is observed.
Second step, of coal sample13C-NMR and FTIR absorption characteristic analysis: by analysing coal samples13C-NMR spectrum to obtain13Chemical shift, number of sub-peaks, sub-peak area and the like of C.
Third step, by analysis13And obtaining 12 structural parameters of the coal sample by using a C-NMR (nuclear magnetic resonance) spectrum, and analyzing the surface functional group type and the vibration form of the molecular structure of the coal sample by combining an FTIR (infrared fluorescence spectroscopy) technology to establish the relation between the skeleton structure and the surface functional group of the coal. Quantitatively analyzing the functional group structure of the coal sample according to a chemical experiment method, and combining13And calculating the molecular structure parameters of the coal sample by physical and chemical analysis methods such as C-NMR, FTIR and chemical experiment methods.
Figure BDA0002909171690000041
Wherein f isaIn the molecular structure of the representative coal sampleAromatic carbon rateCorresponding chemical shifts of 90-240 ppm;
Figure BDA0002909171690000042
represents a carbonyl groupThe base carbon content, corresponding to a chemical shift of 165-240 ppm; f'aRepresentsAromatic ring carbonThe corresponding chemical shift is 90-165 ppm;
Figure BDA0002909171690000043
represents the content of protonated aromatic carbon, corresponding to a chemical shift of 100-129 ppm;
Figure BDA0002909171690000044
represents the content of non-protonated aromatic carbon;
Figure BDA0002909171690000045
representsPhenol and its saltsHydroxy orEther oxygen with carbonCorresponding to a chemical shift of 160-165 ppm;
Figure BDA0002909171690000046
represents an alkyl groupSubstituted aryl Of carbonContent, corresponding to a chemical shift of 137-150 ppm;
Figure BDA0002909171690000047
representsOf aromatic bridged carbonsThe content, corresponding to a chemical shift, was 129-137 ppm. f. ofalRepresents the total fatty carbon content, corresponding to a chemical shift of 0-90 ppm;
Figure BDA0002909171690000048
represents quaternary carbon, -CH and-CH2The content of group carbon, corresponding to chemical shift, is 23-50 ppm;
Figure BDA0002909171690000049
represents an aliphatic methyl group andarylmethyl groupThe carbon content, corresponding to a chemical shift, is 0-23 ppm;
Figure BDA00029091716900000410
represents oxygenTo aliphatic carbonsThe content corresponds to a chemical shift of 50-90 ppm.
According to chemical shift converting aromatic carbon faIs divided intoAromatic ring carbonf′aAnd a carbonyl group
Figure BDA00029091716900000411
Two parts, i.e.
Figure BDA00029091716900000412
Obtained by dipolar dephasingProtonation in aromatic carbonIn proportion to the non-protonated aromatic carbonAromatic ring carbonf′aInto protonated aromatic carbons
Figure BDA00029091716900000413
And non-protonated aromatic carbons
Figure BDA00029091716900000414
Namely, it is
Figure BDA00029091716900000415
Non-protonated aromatic carbons
Figure BDA00029091716900000416
Is divided intoEther oxygen with carbon
Figure BDA00029091716900000417
Alkyl radicalSubstituted aromatic carbons
Figure BDA00029091716900000419
Andaromatic carbon bridge
Figure BDA00029091716900000420
Three parts, i.e.
Figure BDA00029091716900000421
Aliphatic carbon falIs divided into
Figure BDA00029091716900000422
(methylene group
Figure BDA00029091716900000423
Methine radical
Figure BDA00029091716900000424
Andquaternary carbon
Figure BDA00029091716900000425
)、
Figure BDA00029091716900000426
(aliphatic methyl andarylmethyl groupCarbon) to,
Figure BDA00029091716900000427
(oxygen bonded to carbon) three moieties, i.e.
Figure BDA00029091716900000428
Wherein
Figure BDA00029091716900000429
Calculating coal samples according to equation (1)Aromatic carbon ratefaCalculating the fragrance according to the formula (2)The bridge carbon and the peripheral carbonAnd (4) the ratio.
fa＝A300-60ppm/A300-140ppm＝(1-A60-0ppm)/A300-0ppm＝77.05 (1)
Figure BDA00029091716900000430
The data are collated and listed in Table 3.
TABLE 1 Nindong coal model structural parameter percentages
Figure BDA00029091716900000431
The fourth step, combining13The method comprises the following steps of identifying aromatic structures and fat structures in the coal sample structure by utilizing a molecular simulation technology through physical and chemical analysis methods such as C-NMR, FTIR and chemical experimental methods, and constructing and optimizing a coal sample molecular structure model: according to structural parameters such as aromatic structural units, aliphatic group structures and the existence forms of heteroatoms of coal sample molecules obtained by nuclear magnetic resonance, infrared spectroscopy and chemical experimental methods, ACD/ChemSketch10.0 software is used for constructing the coal sampleAnd the molecular structure model is constructed by continuous adjustment and optimization. According to the results of the elemental analysis, the relative proportions of C, H, O, N and S atoms in the molecular structure of the coal sample were obtained. Suppose a coal sampleArticle structureThe number of carbon atoms is a (a is a positive integer greater than 0), according to which H/C ═ n1，O/C＝n2，NC＝n3And S/C ═ n4Deducing the chemical structure of the coal sample molecule as CaHn1aOn2aNn3aSn4a. Molecular structural integrity, nitrogen andsulfur atomThe integer atoms are present in the structural model. According to the element composition and the proportion, the calculation process of the molecular weight of the coal sample is deduced as follows:
12a+0.581a+16×0.206a+14×0.007a+32×0.005a＝2700(3)
a＝167
therefore, according to a, 167, H, 97; o ═ 34; n is 1; 1 is S ═ 1
Calculating the number of protonated aromatic carbon atoms according to a formula
Figure BDA0002909171690000051
To aromatic carbon atom number
Figure BDA0002909171690000052
Number of aromatic carbon atoms in side branch
Figure BDA0002909171690000053
Number of oxygen-substituted aromatic carbon atoms
Figure BDA0002909171690000054
Aromatic ring carbonAtomic number F'aNumber of carbon atoms of carbonyl group
Figure BDA0002909171690000055
Number of aliphatic carbon atoms FalThe structural parameters and the respective atomic numbers above are listed in table 4.
Figure BDA0002909171690000056
Figure BDA0002909171690000057
Figure BDA0002909171690000058
Figure BDA0002909171690000059
Figure BDA00029091716900000510
Figure BDA00029091716900000511
Fal＝fal×a (10)
TABLE 4 structural parameters and atomic numbers of molecular structures
Figure BDA00029091716900000512
Bromination method for coal sample in aliphatic carbonIs not limited toDegree of saturation (Con)U) To obtain the molecular structure ofIs not limited toThe saturation C ═ C double bond concentration, and the chemical shift of alkenyl group in nuclear magnetic resonance spectrum and the shift range of aromatic carbon overlap. Therefore, considerTo Fat blue carbonThe presence of an alkenyl group in the side chain structure,aromatic ring carbonActual number of atoms: (
Figure BDA00029091716900000513
) It is calculated by the following formula:
Figure BDA00029091716900000514
wherein N isa＝ConU×M/12
Ratio of aromatic bridge carbon to peripheral carbon of coal XBPWith X of an aromatic compoundBPThe values are compared. Therefore, the aromatic carbon structure in the molecular structure model of the coal sample mainly comprises naphthalene with the condensation degree of 2 and takes benzene, anthracene and the like as auxiliaries. The average number of aromatic rings (Q) and the number of aromatic carbons of the basic unit of the molecular skeleton structure of the coal sample are determined by formulas (12) to (14). The type and number of aromatic structural units are assumed.
9+6X1+10X2+14X3+18X4+22X5＝123； (12)
2(Q-1)/(6+2(Q-1))＝XBP (13)
Wherein, X1、X2、X3、X4And X5The following equation is satisfied:
(4+X1+2X2+3X3+4X4+5X5)/(4+X1+X2+X3+X4+X5)＝Q (14)
can be deduced, the above two formulas can be solved: x1＝2；X2＝2；X3＝2；X4＝3；X5＝0。
Thus, the coal aromatic carbon faThe value of the content is calculated to obtain the aromatic ring carbon
Figure BDA0002909171690000061
The number, in combination with the degree of unsaturation Con _ U of the aliphatic carbon, gives the chemical formula of the molecular structure and the total molecular weight of the coal sample.
Specific number of aromatics in chemical Structure of Table 4-1
Figure BDA0002909171690000062
Through peak separation and attribution analysis of FTIR spectrogram of Nindong coal, quantitative analysis of nuclear magnetic spectrum, industrial analysis and element analysis data of Nindong coal, the molecular chemical formula of the coal is calculated, and classification and relative quantity of various types of functional groups are judged, on the basis, combination of molecular structure skeleton and functional groups is realized by using ACD/chemSktch10.0, and the result is shown in FIG. 4.
The fifth step is according to13And calculating the chemical shift of a carbon atom in the coal sample molecular structure model by using the C-NMR chemical shift simulation method, and verifying the molecular model. Calculating the molecular structure according to ACD/Labs C-NMR predictor software13C chemical shift to obtain13C-NMR simulation spectrum. By passing13C-NMR simulated spectrum and13and (3) comparing peak positions of the C-NMR experimental spectrogram, modifying the number of methyl, methylene, alcoholic hydroxyl, phenolic hydroxyl and carboxyl to form a new model on the premise of ensuring that the total number of the atoms is not changed, and comparing the new simulated diagram with the original diagram to ensure that the chemical shift value of the carbon atoms in the molecular structure model of the coal sample tends to the experimental value. Model construction by ACD/Labs and13predicting a C-NMR model to obtain atom detailed chemical shift data of the model, chemically positioning carbon atoms in NMR Simulation Program software developed by Copyrighy LvorySolf, simulating a nuclear magnetic resonance spectrogram by the number and the shift of the carbon atoms in the model, and adjusting a proper line width to obtain a molecular structure model of the coal sample13The predicted spectrum of C-NMR is shown in FIG. 5. Through the corrected model comparison curve, the trend of the curve and the position of the main peak are unified in the fitting spectrum and the experimental spectrum, the accuracy is good, and certain difference still exists only in partial wave bands.
In FIG. 5, it can be seen that the peaks in the methylene region around 30ppm fit accurately, but the methyl group content in the region 0-20ppm is still less, presumably because the methyl functionality is affected by the adjacent hydroxyl groups to make the chemical shift larger; the spectrogram obtained in the 70ppm-90ppm section is slightly higher than the experimental spectrogram, and the presumed reason is that the content of methine and quaternary carbon in the built molecular structure is slightly higher; the nuclear magnetic experiment process is influenced by the action of an external magnetic field and environmental factors, so that experimental data and simulation data have certain difference but are within a reasonable error range. In the wave band of 150ppm-190ppm, model spectrogram and trueThe difference between the test spectrograms is obvious, the peak of the model spectrogram shifts leftwards compared with the whole peak of the experiment, and the shift is larger because the carbonyl oxygen has a sideband effect, and the coal sample is carried out13The chemical shift of carbonyl carbon atoms is increased in the process of C-NMR experiments, so that the position of the center of a carbonyl or carbon region peak in an experimentally obtained nuclear magnetic spectrum is integrally shifted to the right.
Analyzed according to the method described above to13The C-NMR technology, the FTIR technology and the industrial analysis element analysis are combined, the molecular structure model of the Ningdong coal can be quantitatively analyzed, and the established molecular model can reflect the basic characteristics of the Ningdong coal.
The invention is realized by the following technical scheme: a coal molecule model building method based on multiple characterization means comprises the following steps: the first step, pretreatment and element and industrial analysis of coal samples: grinding coal samples with different metamorphism degrees to enable the particle size of the coal samples to reach 200 meshes, removing moisture in the surface structure of the coal samples through vacuum drying, and carrying out industrial analysis and element analysis on the pretreated coal samples to obtain the contents of ash, moisture and volatile matters in the coal and C, H, 0 and N, S elements. Second step, of coal sample13C-NMR and FTIR absorption characteristic analysis: by analysing coal samples13C-NMR spectrum to obtain13Chemical shift, number of sub-peaks, sub-peak area and the like of C. Third step, by analysis13And obtaining 12 structural parameters of the coal sample by using a C-NMR (nuclear magnetic resonance) spectrum, and analyzing the surface functional group type and the vibration form of the molecular structure of the coal sample by combining an FTIR (infrared fluorescence spectroscopy) technology to establish the relation between the skeleton structure and the surface functional group of the coal. Quantitatively analyzing the functional group structure of the coal sample according to a chemical experiment method, and combining13And calculating the molecular structure parameters of the coal sample by physical and chemical analysis methods such as C-NMR, FTIR and chemical experiment methods.
Figure BDA0002909171690000071
Wherein f isaRepresenting the molecular structure of a coal sampleContent of aromatic carbon inCorresponding chemical shifts of 90-240 ppm;
Figure BDA0002909171690000072
representing the carbonyl carbon content, corresponding to a chemical shift of 165-240 ppm; f'aRepresentsAromatic ring carbonThe corresponding chemical shift is 90-165 ppm;
Figure BDA0002909171690000073
represents the content of protonated aromatic carbon, corresponding to a chemical shift of 100-129 ppm;
Figure BDA0002909171690000074
represents the content of non-protonated aromatic carbon;
Figure BDA0002909171690000075
representsPhenol and its saltsHydroxy orEther oxygen with carbonCorresponding to a chemical shift of 160-165 ppm;
Figure BDA0002909171690000076
represents an alkyl groupSubstituted aryl Of carbonContent, corresponding to a chemical shift of 137-150 ppm;
Figure BDA0002909171690000077
representsOf aromatic bridged carbonsThe content, corresponding to a chemical shift, was 129-137 ppm. f. ofalRepresents the total fatty carbon content, corresponding to a chemical shift of 0-90 ppm;
Figure BDA0002909171690000078
represents quaternary carbon, -CH and-CH2The content of group carbon, corresponding to chemical shift, is 23-50 ppm;
Figure BDA0002909171690000079
represents an aliphatic methyl group andarylmethyl groupThe carbon content, corresponding to a chemical shift, is 0-23 ppm;
Figure BDA00029091716900000710
represents the content of oxygen-linked aliphatic carbon, corresponding to a chemical shift of 50-90 ppm.
According to chemical shift converting aromatic carbonfaIs divided intoAromatic ring carbonf′aAnd a carbonyl group
Figure BDA0002909171690000081
Two parts, i.e.
Figure BDA0002909171690000082
Obtained by dipolar dephasingProtonation in aromatic carbonIn proportion to the non-protonated aromatic carbonAromatic ring carbonf′aInto protonated aromatic carbons
Figure BDA0002909171690000083
And non-protonated aromatic carbons
Figure BDA0002909171690000084
Namely, it is
Figure BDA0002909171690000085
Non-protonated aromatic carbons
Figure BDA0002909171690000086
Is divided intoEther oxygen with carbon
Figure BDA0002909171690000087
Alkyl radicalSubstituted aromatic carbons
Figure BDA0002909171690000088
Andaromatic carbon bridge
Figure BDA0002909171690000089
Three parts, i.e.
Figure BDA00029091716900000810
Aliphatic carbon falIs divided into
Figure BDA00029091716900000811
(methylene group
Figure BDA00029091716900000812
Methine radical
Figure BDA00029091716900000813
Andquaternary carbon
Figure BDA00029091716900000814
)、
Figure BDA00029091716900000815
(aliphatic methyl andarylmethyl groupCarbon) to,
Figure BDA00029091716900000816
(oxygen bonded to carbon) three moieties, i.e.
Figure BDA00029091716900000817
Wherein
Figure BDA00029091716900000818
Calculating coal samples according to equation (1)Aromatic carbon ratefaCalculating the fragrance according to the formula (2)The bridge carbon and the peripheral carbonAnd (4) the ratio. f. ofa＝A300-60ppm/A300-140ppm＝(1-A60-0ppm)/A300-0ppm (1)
Figure BDA00029091716900000819
The fourth step, combining13The method comprises the following steps of identifying aromatic structures and fat structures in the coal sample structure by utilizing a molecular simulation technology through physical and chemical analysis methods such as C-NMR, FTIR and chemical experimental methods, and constructing and optimizing a coal sample molecular structure model: according to structural parameters such as aromatic structural units, aliphatic group structures and the shapes of heteroatoms of coal sample molecules obtained by nuclear magnetic resonance, infrared spectroscopy and chemical experimental methods, ACD/ChemSketch10.0 software is used for constructing a molecular structure model of the coal sample, and the molecular structure model of the coal sample is constructed through continuous adjustment and optimization. According to the results of the elemental analysis, the relative proportions of C, H, O, N and S atoms in the molecular structure of the coal sample were obtained. Suppose a coal sampleArticle structureThe number of carbon atoms is (a is a positive integer greater than 0), based onH/C＝n1，O/C＝n2，N/C＝n3And S/C ═ n4Deducing the chemical structure of the coal sample molecule as CaHn1aOn2aNn3aSn4a. Considering the molecular structural integrity of the coal sample, nitrogen andsulfur atomThe integer atoms are present in the structural model. According to the element composition and the proportion, the calculation process of the molecular weight of the coal sample is deduced as follows:
12.01a+n1a+16×n2a+14×n3a+32×n4a＝M (3)
therefore, according to a, H is derived; o; n; the relative atomic ratio of S atoms in coal. Calculating the number of protonated aromatic carbon atoms according to a formula
Figure BDA00029091716900000820
To aromatic carbon atom number
Figure BDA00029091716900000821
Number of aromatic carbon atoms in side branch
Figure BDA00029091716900000822
Number of oxygen-substituted aromatic carbon atoms
Figure BDA00029091716900000823
Aromatic ring carbonAtomic number
Figure BDA00029091716900000824
Number of carbon atoms of carbonyl group
Figure BDA00029091716900000825
Number of aliphatic carbon atoms Fal。
Figure BDA00029091716900000826
Figure BDA00029091716900000827
Figure BDA00029091716900000828
Figure BDA00029091716900000829
Figure BDA00029091716900000830
Figure BDA00029091716900000831
Fal＝fal×a (10)
Bromination of unsaturation (Con) in the fatty carbons of coal samplesu) The concentration of C ═ C double bonds of the unsaturation in the molecular structure was obtained, and the chemical shift of the alkenyl group and the shift range of the aromatic carbon overlapped in the nuclear magnetic resonance spectrum. Thus, the actual number of aromatic ring carbon atoms (F) is considered in consideration of the presence of an alkenyl group in the aliphatic carbon side chain structurea u) It is calculated by the following formula:
Figure BDA0002909171690000091
wherein N isa＝ConU×M/12
Ratio of aromatic bridge carbon to peripheral carbon of coal XBPWith X of an aromatic compoundBPThe values are compared. Therefore, the aromatic carbon structure in the molecular structure model of the coal sample mainly comprises naphthalene with the condensation degree of 2 and takes benzene, anthracene and the like as auxiliaries. The average number of aromatic rings (Q) and the number of aromatic carbons of the basic unit of the molecular skeleton structure of the coal sample are determined by formulas (12) to (14). The type and number of aromatic structural units are assumed.
Figure BDA0002909171690000092
Wherein P represents C element in aromatic heterocycle of N, S atoms in aromatic structure of coal sample
2(Q-1)/(6+2(Q-1))＝XBP (13)
Wherein, X1、X2、X3、X4And X5The following equation is satisfied:
(4+X1+2X2+3X3+4X4+5X5)/(4+X1+X2+X3+X4+X5)＝Q (14)
can be pushed out, X1、X2、X3、X4And X5；
Thus, the value of the fa content of the coal aromatic carbon was calculated to give an aromatic ring carbon Fa uThe number, in combination with the degree of unsaturation Con _ U of the aliphatic carbon, gives the chemical formula of the molecular structure and the total molecular weight of the coal sample.
The fifth step is according to13And calculating the chemical shift of a carbon atom in the coal sample molecular structure model by using the C-NMR chemical shift simulation method, and verifying the molecular model. Calculating the molecular structure according to ACD/Labs C-NMR predictor software13C chemical shift to obtain13C-NMR simulation spectrum. By passing13C-NMR simulated spectrum and13and (3) comparing peak positions of the C-NMR experiment spectrogram, and continuously adjusting and optimizing the model structure to ensure that the chemical shift value of carbon atoms in the molecular structure model of the coal sample tends to the experiment value. Model construction by ACD/Labs and13predicting a C-NMR model to obtain atom detailed chemical shift data of the model, chemically positioning carbon atoms in NMR Simulation Program software developed by Copyrighy LvorySolf, simulating a nuclear magnetic resonance spectrogram by the number and the shift of the carbon atoms in the model, and adjusting a proper line width to obtain a molecular structure model of the coal sample13C-NMR prediction spectrum.
In the first step, the coal sample is pretreated, and the content of elements such as ash, moisture, volatile matters and C, H, O, N, S in the coal is obtained through industrial analysis. The organic matter atomic ratio and the chemical formula in the coal sample are obtained according to the results of element analysis and industrial analysis calculation. The experimental means is a common experimental method for coal quality analysis in the field of coal chemical industry.
Of coal samples in the second step13C-NMR and FTIR absorption characteristic analysis by analyzing coal samples13C-NMR and FTIR spectra13And C, carrying out qualitative and quantitative analysis on the carbon atom space structure and the functional group structure in the coal sample structure by using the parameters such as chemical shift, sub-peak number, sub-peak area and the like.
In the third step, 12 structural parameters of the coal sample are introduced according to13The C-NMR spectrum is combined with FTIR technology to analyze the surface functional group type and the vibration form of the molecular structure of the coal sample, and the connection between the skeleton structure and the surface functional group of the coal is established. Quantitatively analyzing the functional group structure of the coal sample according to a chemical experiment method, and combining13And calculating the molecular structure parameters of the coal sample by physical and chemical analysis methods such as C-NMR, FTIR and chemical experiment methods.
In the fourth step, the molecular structure model of the coal sample is combined13C-NMR, FTIR, chemical experiment and other physical and chemical analysis methods, and molecular simulation technology is used to construct and optimize the aromatic structure and the fatty structure in the coal sample structure. According to structural parameters such as aromatic structural units, aliphatic group structures and the shapes of heteroatoms of coal sample molecules obtained by nuclear magnetic resonance, infrared spectroscopy and chemical experimental methods, ACD/ChemSketch10.0 software is used for constructing a molecular structure model of the coal sample, and the model is constructed through continuous adjustment and optimization.
The molecular model of the coal sample in the fifth step is verified according to13The C-NMR chemical shift simulation method calculates the chemical shift of the carbon atom in the molecular structure model of the coal sample. By calculating the molecular structure according to ACD/Labs C-NMR predictor software13C chemical shift to obtain13C-NMR simulation spectrum. Comparative analysis13C-NMR simulated spectrum and13C-NMR experiment spectrogram, finds the difference between the structural components in the molecular model and the actual components, continuously adjusts and optimizes the model structure, and leads the carbon in the molecular structure model of the coal sample to be atomizedThe chemical shift values tend to be experimental values, and a reliable coal sample molecular model is obtained in the optimization calculation process.
A coal molecule model building method based on multiple characterization means comprises the following steps: the first step, pretreatment and element and industrial analysis of coal samples: grinding the coal sample to enable the particle size of the coal sample to reach 200 meshes, removing moisture existing in the surface structure of the coal sample through vacuum drying, and performing industrial analysis and element analysis on the pretreated coal sample to obtain the contents of ash, moisture, volatile matters and C, H, O, N, S elements in the coal.
Second step, of coal sample13C-NMR and FTIR absorption characteristic analysis: by analysing coal samples13C-NMR spectrum to obtain13Chemical shift, number of sub-peaks, sub-peak area and the like of C.
Third step, by analysis13And obtaining 12 structural parameters of the coal sample by using a C-NMR (nuclear magnetic resonance) spectrum, and analyzing the surface functional group type and the vibration form of the molecular structure of the coal sample by combining an FTIR (infrared fluorescence spectroscopy) technology to establish the relation between the skeleton structure and the surface functional group of the coal. Quantitatively analyzing the functional group structure of the coal sample according to a chemical experiment method, and combining13And calculating the parameters of the molecular structure and the composition of the coal sample by physical and chemical analysis methods such as C-NMR, FTIR and chemical experiment methods.
Figure BDA0002909171690000101
Wherein f isaIn the molecular structure of the representative coal sampleAromatic carbon rateCorresponding chemical shifts of 90-240 ppm;
Figure BDA0002909171690000102
representing the carbonyl carbon content, corresponding to a chemical shift of 165-240 ppm; f'aRepresentsAromatic ring carbonThe corresponding chemical shift is 90-165 ppm;
Figure BDA0002909171690000103
represents the content of protonated aromatic carbon, corresponding to a chemical shift of 100-129 ppm;
Figure BDA0002909171690000104
represents the content of non-protonated aromatic carbon;
Figure BDA0002909171690000105
representsPhenol and its saltsHydroxy orEther oxygen with carbonCorresponding to a chemical shift of 160-165 ppm;
Figure BDA0002909171690000106
represents an alkyl groupOf substituted aromatic carbonsContent, corresponding to a chemical shift of 137-150 ppm;
Figure BDA0002909171690000111
representsOf aromatic bridged carbonsThe content, corresponding to a chemical shift, was 129-137 ppm. f. ofalRepresents the total fatty carbon content, corresponding to a chemical shift of 0-90 ppm;
Figure BDA0002909171690000112
represents quaternary carbon, -CH and-CH2The content of group carbon, corresponding to chemical shift, is 23-50 ppm;
Figure BDA0002909171690000113
represents an aliphatic methyl group andarylmethyl groupThe carbon content, corresponding to a chemical shift, is 0-23 ppm;
Figure BDA0002909171690000114
represents oxygenTo aliphatic carbonsThe content corresponds to a chemical shift of 50-90 ppm.
According to chemical shift converting aromatic carbon faIs divided intoAromatic ring carbonf′aAnd a carbonyl group
Figure BDA0002909171690000115
Two parts, i.e.
Figure BDA0002909171690000116
Obtained by dipolar dephasingProtonation in aromatic carbonIn proportion to the non-protonated aromatic carbonAromatic ring carbonf′aCharacterised by protonated aromasCarbon (C)
Figure BDA0002909171690000117
And non-protonated aromatic carbons
Figure BDA0002909171690000118
Namely, it is
Figure BDA0002909171690000119
Non-protonated aromatic carbons
Figure BDA00029091716900001110
Is divided intoEther oxygen with carbon
Figure BDA00029091716900001111
Alkyl radicalSubstituted aromatic carbons
Figure BDA00029091716900001112
Andaromatic carbon bridge
Figure BDA00029091716900001113
Three parts, i.e.
Figure BDA00029091716900001114
Aliphatic carbon falIs divided into
Figure BDA00029091716900001115
(methylene group
Figure BDA00029091716900001116
Methine radical
Figure BDA00029091716900001117
Andquaternary carbon
Figure BDA00029091716900001118
)、
Figure BDA00029091716900001119
(aliphatic methyl andarylmethyl groupCarbon) to,
Figure BDA00029091716900001120
(oxygen bonded to carbon) three moieties, i.e.
Figure BDA00029091716900001121
Wherein
Figure BDA00029091716900001122
Calculating coal samples according to equation (1)Aromatic carbon rate f aCalculating the fragrance according to the formula (2)The bridge carbon and the peripheral carbonThe ratio is obtained from the formula (3)Average number of aromatic nucleiDimension Xb
fa＝A300-60ppm/A300-140ppm＝(1-A60-0ppm)/A300-0ppm (1)
Figure BDA00029091716900001123
The fourth step, combining13The method comprises the following steps of identifying aromatic structures and fat structures in the coal sample structure by utilizing a molecular simulation technology through physical and chemical analysis methods such as C-NMR, FTIR and chemical experimental methods, and constructing and optimizing a coal sample molecular structure model: according to structural parameters such as aromatic structural units, aliphatic group structures and the shapes of heteroatoms of coal sample molecules obtained by nuclear magnetic resonance, infrared spectroscopy and chemical experimental methods, ACD/ChemSketch10.0 software is used for constructing a molecular structure model of the coal sample, and the molecular structure model of the coal sample is constructed through continuous adjustment and optimization. According to the results of the elemental analysis, the relative proportions of C, H, O, N and S atoms in the molecular structure of the coal sample were obtained. Assuming that the number of carbon atoms in the structure of a coal sample is (a is a positive integer greater than 0), according to H/C ═ n1，O/C＝n2，N/C＝n3And S/C ═ n4Deducing the chemical structure of the coal sample molecule as CaHnlaOn2aNn3aSn4a. The nitrogen and sulfur atoms are present as integer atoms in the structural model, taking into account the molecular structural integrity of the coal sample. According to the element composition and the proportion, the calculation process of the molecular weight of the coal sample is deduced as follows:
12.01a+n1a+16×n2a+14×n3a+32×n4a＝M (4)
therefore, according to a, H is derived; o; n; the relative atomic ratio of S atoms in coal. Calculating the number of protonated aromatic carbon atoms according to a formula
Figure BDA00029091716900001124
To aromatic carbon atom number
Figure BDA00029091716900001125
Number of aromatic carbon atoms in side branch
Figure BDA00029091716900001126
Number of oxygen-substituted aromatic carbon atoms
Figure BDA00029091716900001127
Aromatic ring carbonAtomic number
Figure BDA00029091716900001128
Number of carbon atoms of carbonyl group
Figure BDA00029091716900001129
Number of aliphatic carbon atoms Fal。
Figure BDA00029091716900001130
Figure BDA00029091716900001131
Figure BDA00029091716900001132
Figure BDA0002909171690000121
Figure BDA0002909171690000122
Figure BDA0002909171690000123
Fal＝fal×a (11)
Bromination method for coal sample in aliphatic carbonIs not limited toDegree of saturation (Con)U) To obtain the molecular structure ofIs not limited toThe saturation C ═ C double bond concentration, and the chemical shift of alkenyl group in nuclear magnetic resonance spectrum and the shift range of aromatic carbon overlap. Therefore, considerTo Aliphatic carbonThe presence of an alkenyl group in the side chain structure,aromatic ring carbonActual number of atoms: (
Figure BDA0002909171690000124
) It is calculated by the following formula:
Figure BDA0002909171690000125
wherein N isa＝CcnU×M/12
Ratio of aromatic bridge carbon to peripheral carbon of coal XBPWith X of an aromatic compoundBPThe values are compared. Therefore, the aromatic carbon structure in the molecular structure model of the coal sample mainly comprises naphthalene with the condensation degree of 2 and takes benzene, anthracene and the like as auxiliaries. The average number of aromatic rings (Q) and the number of aromatic carbons of the basic unit of the molecular skeleton structure of the coal sample are determined by formulas (13) to (15). The type and number of aromatic structural units are assumed.
P+6X1+10X2+14X3+18X4+22X5＝Fa u (13)
Wherein P represents C element in aromatic heterocycle of N, S atoms in aromatic structure of coal sample
2(Q-1)/(6+2(Q-1))＝XBP (14)
Wherein the content of the first and second substances,X1、X2、X3、X4and X5The following equation is satisfied:
(4+X1+2X2+3X3+4X4+5X5)/(4+X1+X2+X3+X4+X5)＝Q (15)
can be pushed out, X1、X2、X3、X4And X5；
Thus, the value of the fa content of the coal aromatic carbon was calculated to give an aromatic ring carbon Fa uThe number, in combination with the degree of unsaturation Con _ U of the aliphatic carbon, gives the chemical formula of the molecular structure and the total molecular weight of the coal sample.
The fifth step is according to13And calculating the chemical shift of a carbon atom in the coal sample molecular structure model by using the C-NMR chemical shift simulation method, and verifying the molecular model. Calculating the molecular structure according to ACD/Labs C-NMR predictor software13C chemical shift to obtain13C-NMR simulation spectrum. By passing13C-NMR simulated spectrum and13and (3) comparing peak positions of the C-NMR experiment spectrogram, and continuously adjusting and optimizing the model structure to ensure that the chemical shift value of carbon atoms in the molecular structure model of the coal sample tends to the experiment value. Model construction by ACD/Labs and13predicting a C-NMR model to obtain atom detailed chemical shift data of the model, chemically positioning carbon atoms in NMR Simulation Program software developed by Copyrighy LvorySolf, simulating a nuclear magnetic resonance spectrogram by the number and the shift of the carbon atoms in the model, and adjusting a proper line width to obtain a molecular structure model of the coal sample13C-NMR prediction spectrum.
The invention relates to a characterization technology of organic matter component structure and distribution in coal, in particular to a molecular model construction method of coal. A coal molecule model building method based on multiple characterization means comprises the following steps: firstly, sampling a coal sample, grinding the particle size and drying moisture; second step, of coal sample13C-NMR and FTIR absorption characteristic analysis; third step, bonding13Calculation of coal samples by physicochemical analysis methods such as C-NMR, FTIR and chemical experimentsA molecular structure parameter; the fourth step of combining13Performing qualitative and quantitative analysis on the composition of aromatic structures and fat structures in the coal sample structure by using a molecular simulation technology through physical and chemical analysis methods such as C-NMR, FTIR and chemical experimental methods to construct a coal sample molecular structure model; the fifth step is according to13The C-NMR chemical shift simulation method calculates the chemical shift of carbon atoms in the molecular structure model of the coal sample. Obtained by following molecular simulation techniques13C-NMR simulated spectrum, comparative analysis13C-NMR simulated spectrum and13and C-NMR experiment spectrograms are used for continuously adjusting and optimizing the model structure, so that a reliable coal sample molecular model is obtained in the optimization calculation process, and the molecular characterization of the distribution form of organic components in the coal sample is realized. The molecular model adopted by the invention can be used for mining the coal pyrolysis and combustion reaction mechanism from a microscopic level and can be used for representing coal sample molecular models with different metamorphism degrees.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

Claims (7)

1. A coal molecule model building method based on various characterization means is characterized in that: the method comprises the following steps:
(1) performing industrial analysis, element analysis on the coal,13C-NMR analysis, FTIR absorption characteristic analysis, surface structure characteristic analysis, nuclear magnetic resonance analysis and infrared spectrum analysis are carried out to obtain basic data of the coal, and the basic data is utilized to obtain analysis data of the coal;
(2) determining the percentage of the molecular structure composition and the ratio of protonated groups to unprotonated groups in the molecular structure composition;
(3) determining the unsaturation degree of aliphatic carbon and the condensation degree of aromatic carbon in the coal, and determining the chemical structure and the molecular weight of coal molecules by counting the atomic numbers of nitrogen and sulfur in an integer;
(4) the ACD/ChemSketch10.0 software was used to construct a model of the structure of the coal molecule using molecular simulation techniques.
2. The method for modeling coal molecules based on multiple characterization means of claim 1, wherein: in the step (2), the coal molecular structure comprises aromatic carbon, carbonyl carbon, aromatic ring carbon, protonated aromatic carbon, non-protonated aromatic carbon, phenolic hydroxyl or etheric oxygen connected carbon, alkyl substituted aromatic carbon, aromatic bridge carbon, total aliphatic carbon, quaternary carbon, and-CH2One or more of group carbon, methyl and arylmethyl carbon, and oxygen connecting aliphatic carbon.
3. The method for modeling coal molecules based on multiple characterization means of claim 1, wherein: in the step (1), the basic data comprises the content data of ash, moisture, volatile components, C, H, O, N and S elements of the coal13And C, chemical shift, sub-peak number, sub-peak area and coal surface structure characterization images.
4. The method for modeling coal molecules based on multiple characterization means of claim 1, wherein: in the step (1), the analysis data includes the molecular structure composition, atomic ratio, surface functional group structure, surface functional group number, surface functional group vibration form, and aromatic nucleus size data of the coal.
5. The method for modeling coal molecules based on multiple characterization means of claim 1, wherein: by using13C-NMR chemical shift simulation method13C-NMR simulation spectrum according to the description in step (1)13The experimental chart of C-NMR analysis is compared with the peak position, and the total amount of each atomic number is unchanged13C-NMR simulation spectrum is adjusted.
6. The method for modeling coal molecules based on multiple characterization means of claim 2, wherein: the chemical shift corresponding to the coal molecular structure composition is 0-600 ppm.
7. The method for modeling coal molecules based on multiple characterization means of claim 5, wherein: an accurate fit was made to the peaks in the methylene region.
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