CN109540828A - The infrared structure parametric method of coal analysis - Google Patents
The infrared structure parametric method of coal analysis Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 218
- 238000004458 analytical method Methods 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 51
- 230000003595 spectral effect Effects 0.000 claims abstract description 43
- 238000012512 characterization method Methods 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 71
- 239000001257 hydrogen Substances 0.000 claims description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 67
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000002734 clay mineral Substances 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 238000005315 distribution function Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 241000208340 Araliaceae Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 abstract description 7
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 238000000921 elemental analysis Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002802 bituminous coal Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 241001515806 Stictis Species 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002864 coal component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000003696 structure analysis method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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Abstract
The present invention relates to the infrared structure parametric methods of coal analysis, mainly solve current conventional coal analysis method can not macromolecular bonding structure to coal carry out Efficient Characterization, therefore it cannot be effectively predicted and is evaluated reactive problem of coal during thermochemical study, be a kind of convenience, stabilization, reasonable, comprehensive and the pervasive true coal macromolecule bonding structure of characterization coal analysis method；First by 4000~400cm of coal sample‑1The original infrared spectrum of wave-number range is divided into six wave bands, then the baseline of each wave band is defined, and it carries out curve fitting processing to the original spectral line of each wave band, it decomposites several and is fitted sub- peak, the area at each sub- peak of fitting is calculated later, and determine its ownership, it finally constructs and calculates the specific infrared structure parameter of a series of scientific and reasonable and symbolical meanings, by comparing the opposite height of the above-mentioned infrared structure parameter value of different coal samples, Synthetical Analysis and Appraising is carried out to the Coal Characteristics of each coal sample from the level of molecular structure.
Description
Technical field
The invention belongs to energy and environment technical field, be related to the supplement of the coal analysis method being widely used at present and
Innovation, concretely relates to the infrared structure parametric method of coal analysis.
Background technique
Key problem of the relationship as coal chemistry research field between coal texture and reactivity, is not only chemical section
Learn the important extension of related basic research, even more numerous coal machining and transform technologies, such as gasification, coking, liquefaction technology develop into
The theoretical foundation of step.The relationship between coal texture and reactivity is explored, it is basic on condition that realizing the Efficient Characterization to the two.So
And due to the complexity of coal component and the diversity of coal, there is presently no one kind effectively to parse very in molecular level
The method of real texture of coal.For a long time, the coal analysis technology such as Industrial Analysis, elemental analysis and lithofacies analysis constitutes science
The conventional method system of research and industrial application characterization texture of coal.Although these coal analysis technology and methods are being with coal
The technological process of production and reactor design of raw material, process system and the guidance of equipment operating parameter etc. have played important work
With, but there is also apparent defect and deficiencies.
What Industrial Analysis obtained is moisture, volatile matter, fixed carbon and the content of ashes of coal entirety under test condition, and not
There are the valid data provided about coal chemistry structure, said on stricti jurise, belong to reactive test scope, to characterization coal knot
The meaning of structure is extremely limited.Elemental analysis provides the content of five kinds of elements of C, H, O, N, S of group coal-forming, and seeming is to coal chemistry
The quantitatively characterizing of composition, however its result is only macroscopical average value of several atom contents of heterogeneous coal, and it is each to have ignored decision
The chemical key information of combination between kind of atom, thus can not effecting reaction coal macromolecular structure.Lithofacies analysis is based on
In coal between different component optical characteristics difference, coal is divided into several organic and mineral subgroup and provides respective content, show
So it can not provide any specific chemical information.In conclusion the coal analysis technology and methods being widely used at present are equal
It is certain surfaces, average properties or macroscopic property based on coal, and lacks the characterization to coal macromolecule bonding structure.
The essence of any chemical reaction is all the fracture and recombination of chemical bond.Therefore, the reactive fundamental factor of coal is determined
It is the distribution characteristics of the chemical bond between the various atoms of group coal-forming.So being to the Efficient Characterization of coal macromolecule bonding structure
The final purpose and ideal of the reactive basic premise and coal analysis of prediction and evaluation coal during thermochemical study
Target.Particularly, the thermal transition technology for DCL/Direct coal liquefaction, indirect liquefaction, coking etc. based on pyrolytic reaction, Efficient Characterization
With the distribution characteristics of evaluation feed coal macromolecular chemistry key, can be provided for the quality prediction of chemical products and byproduct most directly
Scientific basis.
Infrared spectroscopy is just almost applied as a kind of test and analysis technology from the forties in last century once exploitation immediately
In the characterization of coal chemistry composition.Infrared spectrum can be to the structural information of a variety of functional groups in producing coal, and these information are to coal
The direct description of macromolecular chemistry key distribution characteristics.Although this analytical technology has been provided about coal extracting, curing, oxygen
The abundant information of change, liquefaction and carbonisation, but for a long time, the defect in terms of certain methods opinion limits it in characterization coal quality
The reasonability and popularity applied in terms of characteristic.Specifically, the following aspects can be divided into:
1, lack all-wave piecewise analysis to coal infrared spectrum, therefore the characterization to coal characteristic and insufficient and complete.Mesh
Before, in worldwide, all analyses that coal macromolecule chemical structure is carried out using infrared spectroscopy, only for coal
Infrared spectrum in a certain local wave band expansion, and not yet occur based on 4000~400cm-1Full band range INFRARED SPECTRUM
The analysis of figure.Therefore, infrared spectrum analysis all at present can not achieve the complete characterization to coal characteristic.
2, to the characterizing method existing defects of coal characteristic.In some infrared spectrum analysis using KBr pressed disc method, one
The height or area of a little absorption peaks are used directly to characterize abundance of the corresponding structure of functional groups in coal.According to Beer-
Lambert principle, if each KBr tabletting contains the coal sample of same concentrations, and thickness having the same, then absorption peak is strong
Degree (i.e. height or area) is directly proportional to the content of the functional group absorbed is caused herein.However, being prepared in actual KBr tabletting
Cheng Zhong, due to weighing link error, grinding link it is non-be sufficiently mixed and tabletting link it is non-absolutely it is smooth, it is above-mentioned
The precondition of Beer-Lambert principle application becomes that it is almost impossible.Therefore, the suction of directly more different coal samples
The meaning for receiving peak intensity is extremely limited.
3, the generality of method application and convenience are insufficient.It is some using infrared spectroscopy in coal certain component carry out
In quantitative analysis, staff has used some standard substances.However, the selection for suitable standard substance, there is no bright
True criterion, and many times standard substance and its spectrogram are very unobtainable.In addition, infrared quantitative analysis process equally by
The influence of each link error is prepared to KBr tabletting, while also needing additional chemical analysis means as auxiliary.Factors above is equal
Weaken the generality and convenience that these analytical IR methods are applied in coal analysis field.
4, used infrared structure parameter is not abundant enough, it would be highly desirable to supplement.Utilize specific suctions certain in the infrared spectrum of coal
The ratio between the area/height at peak is received to construct infrared structure parameter, for characterizing coal characteristic, can effectively avoid KBr
Tabletting prepares influence of each link error to analysis result.Although staff has used in some infrared spectrum analysis
Some infrared structure parameters are (such as fatty hydrogen ratio, fragrant hydrogen ratio, fatty hydrogen/fragrance hydrogen ratio, fat hydrogen+fragrance hydrogen ratios
Rate etc.) carry out this work, but these parameters are not enough for the macromolecular structure for characterizing coal comprehensively.For example, fatty hydrogen
And fragrant hydrogen ratio is the description of the allocation proportion between fatty structure and armaticity structure to hydrogen content of coal atom, however, not
With the aliphatic chain of length and branch degree, and different condensation levels aromatic ring system have dramatically different thermal stability and
Thermolytic reactivity.Therefore, some parameters for capableing of Efficient Characterization fatty and armaticity inside configuration feature are supplemented, for coal quality
Comprehensive characterization of characteristic is very necessary.
5, the building of some infrared structure parameters is not reasonable.Coal characteristic is carried out using infrared structure parameter most of
In the work of analysis, 1600cm in infrared spectrum-1The most strong absworption peak of left and right is regarded as most stable of peak, height/face
Product is used as denominator to construct infrared structure parameter, to characterize the relative amount of certain functional groups.However, in some cases,
The intensity of this absorption peak will will receive the influence of other structure of functional groups and change.For example, be connected with aromatic ring structure
Phenolic hydroxyl group, methylene bridge and ehter bond can be such that the intensity at this peak increases, and the number of rings increase for being condensed aroma system will make the strong of this peak
Degree reduces.Therefore, using this peak intensity as infrared structure parameter constructed by denominator, it may be subjected to the interference of some errors and make
Its symbolical meanings weakens.
In conclusion so far, worldwide there are no form a kind of reasonable, effective, comprehensive and pervasive table
The method for levying true coal macromolecule bonding structure.Develop it is a kind of can the distribution characteristics to chemical bond in true coal carry out effectively,
Comprehensive characterization and description, and the coal analysis method with universality, have very not only for basic scientific research field
Important theory significance, and there is realistic meaning very outstanding for practical engineering application field.
Summary of the invention
The technical issues of in order to solve proposed in background technique, the present invention provides one kind with Fourier transform infrared light
Spectrometer is test equipment, can facilitate, is reasonable, is effective, coal quality that is comprehensive and pervasively characterizing true coal macromolecule bonding structure
Analysis method.
In order to achieve the above object, it the present invention provides the infrared structure parametric method of coal analysis, is characterized in that: tool
Steps are as follows for gymnastics work:
(1) coal sample for meeting examination of infrared spectrum condition is produced, while Fourier Transform Infrared Spectrometer being adjusted to completely
The parameter tested enough finally obtains 4000~400cm of coal sample-1The original infrared spectrum of the high s/n ratio of wave-number range.
(2) according to the specific wave-number range of different functional groups difference vibration mode, with the minimum of the corresponding trough of original spectral line
Point is separation, and original infrared spectrum is divided into 3720~3581cm-1, 3099~2800cm-1, 1874~1365cm-1、
1334~950cm-1, 950~671cm-1, 622~439cm-1Six wave bands.According to the concrete condition of different coal samples, above-mentioned boundary
The position of point is slightly displaced from.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band respectively, to define the baseline of each wave band.
Select basic point with principle according to the following steps: a. selectes the separation at wave band both ends；B. the feature on the original spectral line of wave band is selected
The minimum point (if any) of trough, and guarantee to make similar all coal samples in the close positions of original spectral line
Selection；C. each pair of adjacent basic point is connected with line segment, then all line segments constitute the baseline of the wave band；D. if it is original
Occur being located at the trough minimum point (i.e. trough negative value point) under baseline on spectral line, then basic point is chosen to be, then according to step
Rapid c redefines baseline；If occurring being located at the non-trough point (i.e. common negative value point) under baseline on original spectral line, by it
Value zero.
(4) original for the wave crest hidden in the corresponding original spectral line of each trough of original spectral line second dervative is followed
Then, it carries out curve fitting processing to the original spectral line of each wave band.Using the side of Voigt distribution function and stator peak peak position
Formula separates the lap between each peak, decomposites several and is fitted sub- peak.
(5) each area for being fitted sub- peak is calculated, and determines its ownership.
(6) it on the basis of the sum of the area at all sub- peaks of fitting of whole wave bands, constructs and calculates a series of certain one kind of characterizations
The infrared structure parameter of structure of functional groups relative amount, while constructing and calculating two and characterizing fatty and fragrance component respectively
The infrared structure parameter of internal feature.Above-mentioned infrared structure parameter includes:
Ia1--- inorganic mineral vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AInorganic mineral/
AAlways, characterize the relative amount of inorganic mineral in coal；
Ia2--- clay minerals matter vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AClay minerals matter/AAlways, characterize the relative amount of clay minerals matter in coal；
Ib1--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFatty hydrogen/AAlways, characterization
The relative amount of fatty structure in coal；
Ib2--- the ratio of the sum of fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFragrant hydrogen/AAlways, characterization
The relative amount of armaticity structure in coal；
Ib3--- the ratio of the sum of fatty hydrogen and fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. Ib1+
Ib2, characterize the relative amount of total hydrogen in coal；
Ib4--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of fragrant hydrogen vibration peak area, i.e. Ib1/Ib2, characterization
The relative prevalence of hydrogen content of coal atom allocation proportion between fatty and armaticity structure；
Ic1--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AC—O/
AAlways, characterize the relative amount of carbon content in coal oxygen single key structure；
Ic2--- C=O bond C=O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AC=O/
AAlways, characterize the relative amount of carbon content in coal oxygen double bond structure；
Ic3--- carboxylic acid group COOH vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. ACOOH/
AAlways, characterize the relative amount of carboxylic acid group in coal；
Ic4--- the sum of the sum of carbon oxygen singly-bound C-O and C=O bond C=O vibration peak area and all sub- peak areas of fitting
Ratio, i.e. Ic1+Ic2, characterize the relative amount of total oxygen in coal；
Ic5--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and C=O bond C=O vibration peak area, i.e.,
Ic1/Ic2, characterize the relative prevalence of oxygen content of coal atom allocation proportion between carbon oxygen singly-bound C-O and C=O bond C=O structure；
Id1--- CH in fatty structure2Vibrate peak area and CH3Vibrate the ratio of peak area, i.e. ACH2/ACH3, characterize coal
Middle aliphatic side chains and bridge key length or branch degree, this parameter value is bigger, shows aliphatic side chains and bridged bond is longer or branch's journey
It spends lower；
Id2--- it is isolated in armaticity structure or two adjacent hydrogen vibrates the sum of peak areas and fragrant hydrogen stretching vibration peak area
Ratio, i.e. A1H+2H/AFragrant hydrogen is flexible, characterize the relative scale of the ring of high substitution or condensation level in aromatic ring system.
(7) the opposite height of the above-mentioned infrared structure parameter value of more different coal samples, according to the symbolical meanings of parameters,
Synthetical Analysis and Appraising is carried out to the Coal Characteristics of each coal sample.
Compared with prior art, the invention has the following beneficial effects:
1, can be realized at present conventional coal analysis method irrealizable have to true coal macromolecule bonding structure
Effect characterization, to provide direct basis to predict and evaluating reactivity of coal during thermochemical study.Particularly, for coal
The thermal transition technology based on pyrolytic reaction such as direct liquefaction, indirect liquefaction, coking can be the product of chemical products and byproduct
Matter prediction provides most direct scientific basis.
2, it can be realized to 4000~400cm of coal infrared spectrum-1The all-wave piecewise analysis of range, to realize to coal characteristic
It is abundant and completely characterize.
3, infrared structure parameter is constructed with ratio between specific absorption peak area in the infrared spectrum of coal sample, is used for table
Coal characteristic is levied, coal sample KBr tabletting can effectively be avoided to prepare influence of each link error to analysis result.
4, without using standard substance and additional chemical analysis means, to ensure that the application of this coal analysis method
Generality and convenience.
5, the sum of area of all absorption peaks constructs infrared structure parameter, Neng Gouyou as benchmark using in coal infrared spectrum
Effect is avoided with separate peak (such as 1600cm-1Locate vibration peak) when constructing infrared structure parameter on the basis of area, it is steady due to separate peak
Qualitative not good enough and the interference and error that may introduce.
6, infrared structure parameter abundant is introduced, can be realized comprehensive characterization to coal characteristic.
7, for the infrared spectrum of identical coal sample, the repeatability of infrared structure parameter calculated result obtained is excellent, really
The stability and science of this coal analysis method are protected.
8, for the infrared spectrum of different coal samples, the fitting sub- peak obtained for representing the identical vibration mode of same functional group
Peak position deviation very little, ensure that the reasonability and universality of this coal analysis method.
Detailed description of the invention
Fig. 1 is the original infrared spectrum of the embodiment of the present invention one；
Fig. 2 is each wave band swarming fitting result of the embodiment of the present invention one；
Fig. 3 is the original infrared spectrum of the embodiment of the present invention two；
Fig. 4 is each wave band swarming fitting result of the embodiment of the present invention two；
Fig. 5 is the original infrared spectrum of the embodiment of the present invention three；
Fig. 6 is each wave band swarming fitting result of the embodiment of the present invention three；
Fig. 7 is the original infrared spectrum of the embodiment of the present invention four；
Fig. 8 is each wave band swarming fitting result of the embodiment of the present invention four；
Fig. 9 is the original infrared spectrum of the embodiment of the present invention five；
Figure 10 is each wave band swarming fitting result of the embodiment of the present invention five；
Figure 11 is the original infrared spectrum of the embodiment of the present invention six；
Figure 12 is each wave band swarming fitting result of the embodiment of the present invention six；
Figure 13 is the original infrared spectrum of the embodiment of the present invention seven；
Figure 14 is each wave band swarming fitting result of the embodiment of the present invention seven；
Figure 15 is the I of the embodiment of the present invention one to sevena1Value and the drying base ash value A in Industrial AnalysisdBetween correlation；
Figure 16 is the I of the embodiment of the present invention one to sevenb3Value and the drying base hydrogen content H in elemental analysisdBetween correlation；
Figure 17 is the I of the embodiment of the present invention one to sevenc4Value and the drying base oxygen content O in elemental analysisdBetween correlation.
Above-described embodiment by one to seven be respectively the 7 kinds of coal samples of coal rank from low to high infrared structure parameter analysis process,
The present invention can be represented --- the infrared structure parametric method of coal analysis is applied to the case where different types of coal, specific data processing
And analytical procedure will be described in greater detail below.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
As shown in Fig. 1~17, the present invention provides the infrared structure parametric methods of coal analysis, specific steps are as follows:
(1) suitable method for making sample is used, produces the coal sample for meeting examination of infrared spectrum condition, while by Fourier transformation
Infrared spectrometer is adjusted to suitable test parameter, finally obtains the original infrared spectrum of coal sample of high s/n ratio.
(2) according to the specific wave-number range of different functional groups difference vibration mode, with the minimum of the corresponding trough of original spectral line
Point is separation, and original infrared spectrum is divided into six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band respectively, to define the baseline of each wave band.
(4) original for the wave crest hidden in the corresponding original spectral line of each trough of original spectral line second dervative is followed
Then, it carries out curve fitting processing to the original spectral line of each wave band, the lap between each peak is separated, several are decomposited
It is fitted sub- peak.
(5) each area for being fitted sub- peak is calculated, and determines its ownership.
(6) it on the basis of the sum of the area at all sub- peaks of fitting of whole wave bands, constructs and calculates a series of certain one kind of characterizations
The infrared structure parameter of structure of functional groups relative amount；It constructs simultaneously and calculates two and characterize fatty and fragrance component respectively
The infrared structure parameter of internal feature.
(7) the opposite height of the above-mentioned infrared structure parameter value of more different coal samples, according to the symbolical meanings of parameters,
Synthetical Analysis and Appraising is carried out to the Coal Characteristics of each coal sample.
The wave-number range of the original infrared spectrum of the coal sample is 4000~400cm-1。
Six wave bands are respectively 3720~3581cm-1, 3099~2800cm-1, 1874~1365cm-1, 1334~
950cm-1, 950~671cm-1, 622~439cm-1；According to the concrete condition of different coal samples, the position of above-mentioned wave band separation is omited
It offsets.
The basic point is selected with principle according to the following steps: a. selectes the separation at wave band both ends；B. it is former to select wave band
The minimum point (if any) of feature trough on beginning spectral line, and guarantee the phase for all coal samples, in original spectral line
Near position makes similar selection.
The baseline is determined with principle according to the following steps: a. connects each pair of adjacent basic point with line segment, then
All line segments constitute the baseline of the wave band；B. if appearance is located at the trough under the baseline most on original spectral line
Low spot (i.e. trough negative value point), then be chosen to be basic point, then redefine baseline according to step a；If on original spectral line
Occur being located at the non-trough point (i.e. common negative value point) under the baseline, then its value is zeroed.
The curve fit process is carried out by the way of Voigt distribution function and stator peak peak position.
The infrared structure parameter includes:
Ia1--- inorganic mineral vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AInorganic mineral/AAlways, characterize the relative amount of inorganic mineral in coal；
Ia2--- clay minerals matter vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AClay minerals matter/AAlways, characterize the relative amount of clay minerals matter in coal；
Ib1--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFatty hydrogen/AAlways,
Characterize the relative amount of fatty structure in coal；
Ib2--- the ratio of the sum of fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFragrant hydrogen/AAlways,
Characterize the relative amount of armaticity structure in coal；
Ib3--- the ratio of the sum of fatty hydrogen and fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e.,
Ib1+Ib2, characterize the relative amount of total hydrogen in coal；
Ib4--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of fragrant hydrogen vibration peak area, i.e. Ib1/Ib2, characterization
The relative prevalence of hydrogen content of coal atom allocation proportion between fatty and armaticity structure；
Ic1--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AC—O/AAlways, characterize the relative amount of carbon content in coal oxygen single key structure；
Ic2--- C=O bond C=O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AC=O/AAlways, characterize the relative amount of carbon content in coal oxygen double bond structure；
Ic3--- carboxylic acid group COOH vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
ACOOH/AAlways, characterize the relative amount of carboxylic acid group in coal；
Ic4--- the sum of carbon oxygen singly-bound C-O and C=O bond C=O vibration peak area and all sub- peak areas of fitting
The sum of ratio, i.e. Ic1+Ic2, characterize the relative amount of total oxygen in coal；
Ic5--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and C=O bond C=O vibration peak area, i.e.,
Ic1/Ic2, characterize the relative prevalence of oxygen content of coal atom allocation proportion between carbon oxygen singly-bound C-O and C=O bond C=O structure；
Id1--- CH in fatty structure2Vibrate peak area and CH3Vibrate the ratio of peak area, i.e. ACH2/ACH3, characterize coal
Middle aliphatic side chains and bridge key length or branch degree, this parameter value is bigger, shows aliphatic side chains and bridged bond is longer or branch's journey
It spends lower；
Id2--- it is isolated in armaticity structure or two adjacent hydrogen vibrates the sum of peak areas and fragrant hydrogen stretching vibration peak area
Ratio, i.e. A1H+2H/AFragrant hydrogen is flexible, characterize the relative scale of the ring of high substitution or condensation level in aromatic ring system.
Embodiment 1
Certain lignite sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 1.
The drying base Industrial Analysis of 1 embodiment of table, 1 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:200 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in Figure 1.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2809cm-1, 1874~1365cm-1、
1334~952cm-1, 950~673cm-1, 617~439cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3681-3663-3586；
B.3099~2809cm-1Wave band: 3099-2995-2809；
C.1874~1365cm-1Wave band:
1874—1805—1787—1777—1764—1744—1669—1483—1387—1365；
D.1334~952cm-1Wave band: 1334-952；
E.950~673cm-1Wave band: 950-892-849-716-673；
F.617~439cm-1Wave band: 617-439.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in Figure 2.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, the results are shown in Table 2.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A3+A12+A13+A14+A15+A16+A17+A18+A19+A20+A55+
A56+A57+A58+A59+A60+A61+A62+A63+A64+A65+A66+A67+
A68)/A1~68；
Ia2=AClay minerals matter/AAlways
=(A3+A12+A13+A14+A15+A16+A17+A20+A55+A56+A57+A58+A59+
A60+A61+A62+A63+A64+A65+A66+A67+A68)/A1~68；
Ib1=AFatty hydrogen/AAlways=(A49+A50+A51+A52+A53)/A1~68；
Ib2=AFragrant hydrogen/AAlways=(A9+A10+A11+A54)/A1~68；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A23+A24+A25+A26)/A1~68；
Ic2=AC=O/AAlways
=(A37+A38+A39+A40+A41+A42+A43+A44+A45+A46+A47+
A48)/A1~68；
Ic3=ACOOH/AAlways=A39/A1~68；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A52/A53；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A9+A10+A11)/A54。
The calculated result of each infrared structure parameter is as shown in table 3.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
2 embodiment 1 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 3 embodiment of table 1
Embodiment 2
Certain ub-bituminous coal sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 4.
The drying base Industrial Analysis of 4 embodiment of table, 2 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:200 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in Figure 3.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2809cm-1, 1874~1365cm-1、
1334~950cm-1, 950~682cm-1, 622~453cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3681-3663-3586；
B.3099~2809cm-1Wave band: 3099-2991-2809；
C.1874~1365cm-1Wave band:
1874—1805—1787—1777—1669—1483—1387—1365；
D.1334~950cm-1Wave band: 1334-950；
E.950~682cm-1Wave band: 950-932-682；
F.622~453cm-1Wave band: 622-453.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in Figure 4.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, the results are shown in Table 5.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A12+A13+A14+A15+A16+A17+A18+A19+A54+A55+A56+
A57+A58+A59+A60+A61+A62+A63+A64+A65+A66+A67)/A1~67；
Ia2=AClay minerals matter/AAlways
=(A2+A12+A13+A14+A15+A16+A19+A54+A55+A56+A57+A58+A59+
A60+A61+A62+A63+A64+A65+A66+A67)/A1~67；
Ib1=AFatty hydrogen/AAlways=(A48+A49+A50+A51+A52)/A1~67；
Ib2=AFragrant hydrogen/AAlways=(A9+A10+A11+A53)/A1~67；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A22+A23+A24+A25)/A1~67；
Ic2=AC=O/AAlways
=(A36+A37+A38+A39+A40+A41+A42+A43+A44+A45+A46+
A47)/A1~67；
Ic3=ACOOH/AAlways=A38/A1~67；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A51/A52；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A9+A10+A11)/A53。
The calculated result of each infrared structure parameter is as shown in table 6.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
5 embodiment 2 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 6 embodiment of table 2
Embodiment 3
Certain para bituminous coal sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 7.
The drying base Industrial Analysis of 7 embodiment of table, 3 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:200 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in Figure 5.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2809cm-1, 1874~1365cm-1、
1334~950cm-1, 950~671cm-1, 619~441cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3681-3663-3586；
B.3099~2809cm-1Wave band: 3099-2993-2809；
C.1874~1365cm-1Wave band:
1874—1805—1787—1777—1764—1744—1669—1483—1387—1365；
D.1334~950cm-1Wave band: 1334-950；
E.950~671cm-1Wave band: 950-930-671；
F.619~441cm-1Wave band: 619-441.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in Figure 6.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, the results are shown in Table 8.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A12+A13+A14+A15+A16+A17+A18+A19+A54+A55+A56+
A57+A58+A59+A60+A61+A62+A63+A64+A65+A66+A67)/A1~67；
Ia2=AClay minerals matter/AAlways
=(A2+A12+A13+A14+A15+A16+A19+A54+A55+A56+A57+A58+A59+
A60+A61+A62+A63+A64+A65+A66+A67)/A1~67；
Ib1=AFatty hydrogen/AAlways=(A48+A49+A50+A51+A52)/A1~67；
Ib2=AFragrant hydrogen/AAlways=(A8+A9+A10+A11+A53)/A1~67；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A22+A23+A24+A25)/A1~67；
Ic2=AC=O/AAlways
=(A36+A37+A38+A39+A40+A41+A42+A43+A44+A45+A46+
A47)/A1~67；
Ic3=ACOOH/AAlways=A38/A1~67；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A51/A52；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A8+A9+A10+A11)/A53。
The calculated result of each infrared structure parameter is as shown in table 9.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
8 embodiment 3 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 9 embodiment of table 3
Embodiment 4
Certain bituminous coal sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 10.
The drying base Industrial Analysis of 10 embodiment of table, 4 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:200 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in Figure 7.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2800cm-1, 1874~1365cm-1、
1334~950cm-1, 950~671cm-1, 595~439cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3663-3629-3586；
B.3099~2800cm-1Wave band: 3099-2991-2800；
C.1874~1365cm-1Wave band:
1874—1833—1814—1787—1777—1764—1754—1744—1669—1529—1365；
D.1334~950cm-1Wave band: 1334-950；
E.950~671cm-1Wave band: 950-930-903-671；
F.595~439cm-1Wave band: 595-439.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in Figure 8.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, as a result as shown in table 11.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A3+A15+A16+A17+A18+A19+A20+A21+A22+A57+A58
+A59+A60+A61+A62+A63+A64+A65+A66+A67+A68+A69+
A70)/A1~70；
Ia2=AClay minerals matter/AAlways
=(A3+A15+A16+A17+A18+A19+A22+A57+A58+A59+A60+A61+
A62+A63+A64+A65+A66+A67+A68+A69+A70)/A1~70；
Ib1=AFatty hydrogen/AAlways=(A51+A52+A53+A54+A55)/A1~70；
Ib2=AFragrant hydrogen/AAlways=(A11+A12+A13+A14+A56)/A1~70；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A25+A26+A27+A28)/A1~70；
Ic2=AC=O/AAlways
=(A39+A40+A41+A42+A43+A44+A45+A46+A47+A48+A49+
A50)/A1~70；
Ic3=ACOOH/AAlways=A41/A1~70；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A54/A55；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A11+A12+A13+A14)/A56。
The calculated result of each infrared structure parameter is as shown in table 12.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
11 embodiment 4 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 12 embodiment of table 4
Embodiment 5
Certain bituminous coal sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 13.
The drying base Industrial Analysis of 13 embodiment of table, 5 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:200 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in Figure 9.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2800cm-1, 1874~1365cm-1、
1334~950cm-1, 950~671cm-1, 619~441cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3682-3663-3586；
B.3099~2800cm-1Wave band: 3099-2991-2800；
C.1874~1365cm-1Wave band:
1874—1805—1787—1777—1764—1744—1669—1365；
D.1334~950cm-1Wave band: 1334-950；
E.950~671cm-1Wave band: 950-928-671；
F.619~441cm-1Wave band: 619-441.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
The results are shown in Figure 10.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, as a result as shown in table 14.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A3+A14+A15+A16+A17+A18+A19+A20+A55+A56+A57+
A58+A59+A60+A61+A62+A63+A64+A65+A66+A67+A68+
A69)/A1~69；
Ia2=AClay minerals matter/AAlways
=(A3+A14+A15+A16+A17+A18+A55+A56+A57+A58+A59+A60+
A61+A62+A63+A64+A65+A66+A67+A68+A69)/A1~69；
Ib1=AFatty hydrogen/AAlways=(A49+A50+A51+A52+A53)/A1~69；
Ib2=AFragrant hydrogen/AAlways=(A10+A11+A12+A13+A54)/A1~69；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A23+A24+A25+A26)/A1~69；
Ic2=AC=O/AAlways
=(A37+A38+A39+A40+A41+A42+A43+A44+A45+A46+A47+
A48)/A1~69；
Ic3=ACOOH/AAlways=A39/A1~69；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A52/A53；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A10+A11+A12+A13)/A54。
The calculated result of each infrared structure parameter is as shown in Table 15.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
14 embodiment 5 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 15 embodiment of table 5
Embodiment 6
Certain meta bituminous coal sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 16.
The drying base Industrial Analysis of 16 embodiment of table, 6 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:250 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in figure 11.
(2) original infrared spectrum is divided into 3716~3586cm-1, 3099~2800cm-1, 1874~1365cm-1、
1334~950cm-1, 950~671cm-1, 619~441cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3716~3586cm-1Wave band: 3716-3586；
B.3099~2800cm-1Wave band: 3099-2988-2800；
C.1874~1365cm-1Wave band:
1874—1805—1787—1777—1764—1755—1744—1726—1690—1681—1669—
1514—1502—1492—1483—1389—1365；
D.1334~950cm-1Wave band: 1334-950；
E.950~671cm-1Wave band: 950-712-671；
F.619~441cm-1Wave band: 619-441.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in figure 12.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, as a result as shown in table 17.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A3+A13+A14+A15+A16+A17+A18+A19+A20+A27+A57+
A58+A59+A60+A61+A62+A63+A64+A65+A66+A67+A68+A69+
A70)/A1~70；
Ia2=AClay minerals matter/AAlways
=(A3+A13+A14+A15+A16+A17+A20+A57+A58+A59+A60+A61+
A62+A63+A64+A65+A66+A67+A68+A69+A70)/A1~70；
Ib1=AFatty hydrogen/AAlways=(A51+A52+A53+A54+A55)/A1~70；
Ib2=AFragrant hydrogen/AAlways=(A9+A10+A11+A12+A56)/A1~70；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=(A23+A24+A25)/A1~70；
Ic2=AC=O/AAlways
=(A37+A38+A39+A40+A41+A42+A43+A44+A45+A46+A47+A48+
A49+A50)/A1~70；
Ic3=ACOOH/AAlways=(A39+A40+A41)/A1~70；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A54/A55；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A9+A10+A11+A12)/A56。
The calculated result of each infrared structure parameter is as shown in table 18.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
17 embodiment 6 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 18 embodiment of table 6
Embodiment 7
Certain anthracite sample, dries base Industrial Analysis and Elemental analysis data is as shown in table 19.
The drying base Industrial Analysis of 19 embodiment of table, 7 coal sample and Elemental analysis data
aIt is calculated by minusing
Concrete operation step (1)~(7) of the foregoing description according to the present invention, in conjunction with the concrete condition of this coal sample, according to
Lower method completes the infrared structure Parameter analysis of this coal sample:
(1) examination of infrared spectrum coal sample is prepared using KBr pressed disc method.Sample is abundant with the mass ratio of 1:300 first with KBr
Mixing, is made infrared tabletting for the mixture of 200mg later under the pressure of 10~12MPa, tabletting is finally placed in 50 DEG C
It is at least 48 hours dry in insulating box, in case test.The test wave-number range of Fourier Transform Infrared Spectrometer be 4000~
400cm-1, resolution ratio 4cm-1, scanning times 32.The finally obtained original infrared spectrum of coal sample is as shown in figure 13.
(2) original infrared spectrum is divided into 3720~3581cm-1, 3097~2807cm-1, 1658~1365cm-1、
1334~958cm-1, 958~671cm-1, 622~445cm-1Six wave bands.
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band, to define the baseline of each wave band.Baseline
Definition result it is as follows:
A.3720~3581cm-1Wave band: 3720-3581；
B.3097~2807cm-1Wave band: 3097-3088-2988-2926-2807；
C.1658~1365cm-1Wave band: 1658-1630-1483-1365；
D.1334~958cm-1Wave band: 1334-958；
E.958~671cm-1Wave band: 958-888-844-722-671；
F.622~445cm-1Wave band: 622-445.
(4) it carries out curve fitting processing to the original spectral line of each wave band, decomposites several and be fitted sub- peak, swarming fitting
As a result as shown in figure 14.
(5) area at each sub- peak of fitting is calculated, and determines its ownership, as a result as shown in table 20.
(6) it constructs and calculates following infrared structure parameter:
Ia1=AInorganic mineral/AAlways
=(A1+A2+A11+A12+A13+A14+A15+A16+A17+A18+A39+A40+A41+
A42+A43+A44+A45+A46+A47+A48+A49)/A1~49；
Ia2=AClay minerals matter/AAlways
=(A2+A11+A12+A13+A14+A15+A18+A39+A40+A41+A42+A43+A44+
A45+A46+A47+A48+A49)/A1~49；
Ib1=AFatty hydrogen/AAlways=(A33+A34+A35+A36+A37)/A1~49；
Ib2=AFragrant hydrogen/AAlways=(A8+A9+A10+A38)/A1~49；
Ib3=Ib1+Ib2；
Ib4=Ib1/Ib2；
Ic1=AC—O/AAlways=0；
Ic2=AC=O/AAlways
=(A30+A31+A32)/A1~49；
Ic3=ACOOH/AAlways=0；
Ic4=Ic1+Ic2；
Ic5=Ic1/Ic2；
Id1=ACH2/ACH3=A36/A37；
Id2=A1H+2H/AFragrant hydrogen is flexible=(A8+A9+A10)/A38。
The calculated result of each infrared structure parameter is as shown in table 21.
(7) the opposite height for comparing this coal sample and the above-mentioned infrared structure parameter value of other coal samples, according to parameters
Symbolical meanings carry out Synthetical Analysis and Appraising to the Coal Characteristics of this coal sample.
20 embodiment 7 of table is respectively fitted the area and ownership at sub- peak
Each infrared structure parameter calculated value of 21 embodiment of table 7
The I of the embodiment of the present invention one to sevena1Value and dry base ash content Ad、Ib3Value and dry base hydrogen content HdAnd Ic4Value
With dry base oxygen content OdBetween correlation, it is as shown in Figure 15, Figure 16 and Figure 17 respectively.It can be seen that the present invention is introduced
Infrared structure parameter calculated value, it is above-mentioned there is significant positive correlation between current conventional coal analysis data
The linearly dependent coefficient r of three groups of data20.9651,0.9648 and 0.9202 has been respectively reached, has been adopted to demonstrate the present invention
The reasonability and accuracy of curve-fit data processing method and the sub- peak ownership of identified fitting.
The above-mentioned purpose to embodiment description, which is easy for those skilled in the art, can fully understand and have
Effect uses the present invention.Person skilled in the art obviously can easily various be repaired by what is made to these embodiments
Change, general principle described herein is applied in other embodiments without having to go through creative labor.Therefore, of the invention
It is not limited to the above embodiments, those skilled in the art's enlightenment according to the present invention does not depart from the modification that scope is made
It all should be within protection scope of the present invention.
Claims (6)
1. a kind of infrared structure parametric method of coal analysis, steps are as follows:
(1) coal sample for meeting examination of infrared spectrum condition is produced, while Fourier Transform Infrared Spectrometer is adjusted to satisfaction and is surveyed
The parameter of examination finally obtains the original infrared spectrum of coal sample of high s/n ratio；
(2) according to the specific wave-number range of different functional groups difference vibration mode, the minimum point with the corresponding trough of original spectral line is
Original infrared spectrum is divided into six wave bands by separation；
(3) a series of basic points are selected on the original spectral line of above-mentioned each wave band respectively, to define the baseline of each wave band；
(4) principle for the wave crest hidden in the corresponding original spectral line of each trough of original spectral line second dervative is followed, it is right
The original spectral line of each wave band carries out curve fitting processing, and the lap between each peak is separated, several fittings are decomposited
Sub- peak；
(5) each area for being fitted sub- peak is calculated, and determines its ownership；
(6) it on the basis of the sum of the area at all sub- peaks of fitting of whole wave bands, constructs and calculates a series of certain a kind of function of characterizations
The infrared structure parameter of unity structure relative amount；It constructs simultaneously and calculates two and characterize inside fatty and fragrance component respectively
The infrared structure parameter of feature；
(7) the opposite height of the above-mentioned infrared structure parameter value of more different coal samples, according to the symbolical meanings of parameters, to every
The Coal Characteristics of a coal sample carry out Synthetical Analysis and Appraising.
2. the infrared structure parametric method of coal analysis according to claim 1, it is characterised in that: the coal sample is original red
The wave-number range of outer spectrogram is 4000~400cm-1；Six wave bands are respectively 3720~3581cm-1, 3099~
2800cm-1, 1874~1365cm-1, 1334~950cm-1, 950~671cm-1, 622~439cm-1。
3. the infrared structure parametric method of coal analysis according to claim 2, it is characterised in that: the basic point according to
Lower step and principle are selected: a. selectes the separation at wave band both ends；B. most if there is the feature trough on the original spectral line of wave band
Low spot is selected the minimum point of the feature trough on the original spectral line of wave band, and is guaranteed for all coal samples, in original spectral line
Close positions make similar selection.
4. the infrared structure parametric method of coal analysis according to claim 3, it is characterised in that: the baseline according to
Lower step is determined with principle: a. connects each pair of adjacent basic point with line segment, then all line segments constitute the wave
The baseline of section；B. if occurring being located at the trough minimum point under the baseline on original spectral line, it is chosen to be basic point, so
Baseline is redefined according to step a afterwards；If occurring being located at the non-trough point under the baseline on original spectral line, by its value
Zero.
5. the infrared structure parametric method of coal analysis according to claim 4, it is characterised in that: the curve fit process
It is carried out by the way of Voigt distribution function and stator peak peak position.
6. the infrared structure parametric method of coal analysis according to claim 5, it is characterised in that: the infrared structure ginseng
Number includes:
Ia1--- inorganic mineral vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AInorganic mineral/
AAlways, characterize the relative amount of inorganic mineral in coal；
Ia2--- clay minerals matter vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e.,
AClay minerals matter/AAlways, characterize the relative amount of clay minerals matter in coal；
Ib1--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFatty hydrogen/AAlways, characterization
The relative amount of fatty structure in coal；
Ib2--- the ratio of the sum of fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. AFragrant hydrogen/AAlways, characterization
The relative amount of armaticity structure in coal；
Ib3--- the ratio of the sum of fatty hydrogen and fragrant hydrogen vibration peak area and the sum of all sub- peak areas of fitting, i.e. Ib1+
Ib2, characterize the relative amount of total hydrogen in coal；
Ib4--- the ratio of the sum of fatty hydrogen vibration peak area and the sum of fragrant hydrogen vibration peak area, i.e. Ib1/Ib2, characterize in coal
The relative prevalence of hydrogen atom allocation proportion between fatty and armaticity structure；
Ic1--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AC—O/
AAlways, characterize the relative amount of carbon content in coal oxygen single key structure；
Ic2--- C=O bond C=O vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. AC=O/
AAlways, characterize the relative amount of carbon content in coal oxygen double bond structure；
Ic3--- carboxylic acid group COOH vibrates the ratio of the sum of the sum of peak area and all sub- peak areas of fitting, i.e. ACOOH/
AAlways, characterize the relative amount of carboxylic acid group in coal；
Ic4--- the sum of the sum of carbon oxygen singly-bound C-O and C=O bond C=O vibration peak area and all sub- peak areas of fitting
Ratio, i.e. Ic1+Ic2, characterize the relative amount of total oxygen in coal；
Ic5--- carbon oxygen singly-bound C-O vibrates the ratio of the sum of the sum of peak area and C=O bond C=O vibration peak area, i.e. Ic1/
Ic2, characterize the relative prevalence of oxygen content of coal atom allocation proportion between carbon oxygen singly-bound C-O and C=O bond C=O structure；
Id1--- CH in fatty structure2Vibrate peak area and CH3Vibrate the ratio of peak area, i.e. ACH2/ACH3, characterize rouge in coal
Fat side chain and bridge key length or branch degree, this parameter value is bigger, shows aliphatic side chains and bridged bond is longer or branch degree is got over
It is low；
Id2--- the ratio of the sum of isolated in armaticity structure or two adjacent hydrogen vibration peak areas and fragrant hydrogen stretching vibration peak area
Value, i.e. A1H+2H/AFragrant hydrogen is flexible, characterize the relative scale of the ring of high substitution or condensation level in aromatic ring system.
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