CN103472083A - Method for detecting influence of electron beam irradiation on free radical concentration of coal by virtue of electron paramagnetic resonance - Google Patents
Method for detecting influence of electron beam irradiation on free radical concentration of coal by virtue of electron paramagnetic resonance Download PDFInfo
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Abstract
The invention relates to a method for detecting the influence of electron beam irradiation on free radical concentration of coal by virtue of electron paramagnetic resonance. The method comprises the following experiment steps: (1) carrying out pretreatment on a coal sample; (2) irradiating the coal sample by electron beams of different doses; and (3) carrying out ESR (electron spin resonance) analysis on the coal sample before and after electron beam irradiation. By carrying out electron beam irradiation on the coal sample subjected to pretreatment, the coal sample with different irradiation doses can be obtained by controlling an electron accelerator. Then, analysis on Lande g factor, free radical concentration Ng, peak width delta H and peak height Hpp is carried out on the coal sample before and after electron beam irradiation so as to research the change of a coal structure. The method has the advantages that the operation is relatively simple and easy to master, the change of the free radical concentration of the coal can be measured in short time, and a good dose effect relation can be achieved, thereby laying a foundation for further research on a coal macromolecular structure.
Description
Technical field
The present invention relates to a kind of method of electron paramagnetic resonance detected electrons bundle irradiation on the impact of coal number of free radical of utilizing, contribute to further to study the macromolecular structure of coal, and coal is processed, improve productive rate.
Background technology
It is current science that continuous differentiation interpenetrates again, and particularly the distinguishing feature of chemistry subject development, produced many emerging cross disciplines thus.Radiation Chemistry of Polymer is the crossing domain of high polymer chemistry and radiation chemistry.High polymer chemistry is studied high molecular formation, structure and transformation; The various chemical changes that radiation chemistry research ionising radiation and matter interaction cause.Therefore Radiation Chemistry of Polymer is the research ionising radiation and chemical change and the effect thereof of monomer and interpolymer interaction, comprises the various polymerizations of ionising radiation initiation, crosslinked, grafting and cracking etc.
Along with the fast development of peaceful use of nuclear energy, the research of Polymer Irradiation Effect comes into one's own day by day with application.The variation of the performances such as the physical chemistry that when polymkeric substance is subject to irradiation, the absorption median dose is brought out and machinery is very remarkable.
And coal is the compositions of mixtures of different by molecular weight, that molecular structure is similar but incomplete same one group " analogue compounds ".The structure of coal is very complicated, it is generally acknowledged that it has the structure of high molecular polymer, but is different from general polymkeric substance, and it does not have unified polymerization single polymerization monomer.The large molecule of coal is formed by connecting by bridged bond by a plurality of structural similarities " basic structural unit ".This basic structural unit can be divided into: rule part and irregular part.Rule part is to be formed by several or tens phenyl ring, alicyclic ring, hydroaromatic ring and heterocycles (elements such as nitrogenous, oxygen, sulphur) polycondensation, is called aromatic proton, and irregular part is mainly some alkyl side chains, functional group etc.Because coal has the architectural feature that is similar to high molecular polymer, so being carried out to irradiation-induced degradation, coal becomes possibility.
After the 90's, the report of irradiation coal increased gradually, Vastola in 1984, F.J utilizes laser irradiation to carry out selective splitting to the maceral in coal, Ram in 1997, the people such as L.C utilize the gamma-rays of various dose to carry out irradiation to soft coal and the brown coal that are dissolved in different medium, inquire into the variation of the solubleness in different organic substances.Day in 2001 disclosure By Thermal Neutron Irradiation device, the irradiation coal and under High Temperature High Pressure liquefaction irradiated coal sample, a kind of safe, efficient liquefaction process is provided.These all illustrate that irradiation technique is applied in coal and more and more come into one's own, but the radiation source of above report is not all electron accelerator, is not electron beam irradiation.
The paramagnetic center concentration (number of free radical) of coal is the sensitive indexes of Coal Pore Structure destructive characteristics.And be unusual effective method with the free radical of ESR Study on Coal, four kinds of parameters that obtain with it (spin concentration, g value, live width and linear) are significant for structure, the origin cause of formation and the hot-working conversion process of understanding coal.Up to now, about the paramagnetic resonance research of coal, the purpose of author's research both at home and abroad is mainly the relation of inquiring between paramagnetic resonance characteristic and degree of coalification or maturity of organic matter, the coal sample changes of free radicals after irradiation is not carried out to systematic research.
Electron paramagnetic resonance (Electron Paramagnetic Resonance, write a Chinese character in simplified form EPR) or be called the effective means that electron spin resonance (Electron Spin Resonance, write a Chinese character in simplified form ESR) is direct-detection and the research paramagnet that contains unpaired electron (free radical).These means physics, chemistry, life science, environmental science, medical science, materialogy, ore deposit learn and a lot of fields such as chronology obtain widespread use.Usually, modern ESR spectrometer record be that a differential of absorption signal is linear, i.e. a differential spectral line.Analysis according to the spectrum parameters such as live width, line style, the g factor, hyperfine coupling and spin concentration to ESR experiment spectrogram, can obtain unpaired electron and molecular structure information in sample.The ESR spectrum of different paramagnetic samples takes on a different character, and can characterize with spectrum parameters such as live width, line style, the g factor, hyperfine coupling and spin concentrations, and wherein most important, the most basic spectrum parameter is the g factor.The g factor is an important physical amount relevant with atom internal motion and magnetic moment, and it has important impact to the magnetic of atom and the performance in outside magnetic field etc.
Summary of the invention
The object of the invention is to study the impact that irradiation changes the coal number of free radical, contribute to further to understand the coal macromolecular structure, and coal is processed to processing, raise the efficiency.
Characteristics of the present invention are at first coal sample to be carried out to electron beam irradiation, and then the coal sample after predose are carried out to the research of each parameter of free radical, while finding that dosage is 30 kGy, and the number of free radical maximum.The method operation is comparatively simple, easily grasps, and the variation that can record in a short period of time the coal number of free radical, there is dose-effect relationship preferably, make place mat for further studying the coal macromolecular structure.
For achieving the above object, the present invention adopts following technical scheme:
The pre-service of a, coal sample: at first coal particle is ground to below 20 μ m, then uses the NaOH solution washing of 1 M, filter, to remove original oil in coal; After coal sample after washing is dried to constant weight under vacuum 393 K, obtain dry coal dust, the sealing pack;
B, coal sample is carried out to electron beam irradiation: the GJ-2-II high frequency high voltage electron accelerator coal sample pretreated to step a that adopts ray applications research institute of Shanghai University to provide carried out irradiation, obtain dosage and be respectively 10 kGy, 20 kGy, 30 kGy, 40 kGy, the coal sample of 50 kGy;
C, the coal sample before and after electron beam irradiation is carried out to the ESR test: accurately take the sample of 15 mg, the sample hose of packing into, test by ESR spectrum parameters such as obtaining live width, line style, the g factor, hyperfine coupling and spin concentration.The ESR experiment is all carried out in Bruker EMX-8/ 2.7 type electronic paramagnetic resonance spectrometers; Central magnetic field: 3520.8 G; Field sweep width: 500 G; Microwave frequency: 9.871 GHz; Enlargement factor: 2.24e002; Modulation amplitude: 1 G; Modulating frequency: 100 KHz; Time constant: 163.84 ms; The field sweep time: 41.943 s;
D, can calculate out the relative concentration of free radical in coal according to following formula; Formula is: Ng ∝ (△ H)
2* Hpp; It is the product that free radical relative concentration Ng is proportional to the quadratic sum peak height Hpp of peak width △ H; When peak width changes when little, peak height Hpp is the relative concentration of the paramagnetic center of representative sample (free radical).
Compared with prior art, the present invention has following outstanding feature:
Because coal has the architectural feature that is similar to high molecular polymer, coal is carried out to electron beam irradiation and can realize the degraded to the coal macromolecule structure, contribute to the processing of coal, as coal direct liquefaction, indirect liquefaction.Utilize the ESR technology can understand coal architectural feature and destructiveness, the method is quick, efficient, directly, accurately, has dose-effect relationship preferably.
The accompanying drawing explanation
Fig. 1 is that the present invention obtains Shengli coal, and the g factor of shenfu coal is with the variation of irradiation dose.
Fig. 2 is Shengli coal, and the free radical of shenfu coal absorbs the variation of peak height with irradiation dose.
Embodiment
After now embodiments of the present invention specifically being described in.
Embodiment
?the step of the present embodiment is as follows:
(1) pre-service of coal sample: at first coal particle is ground to below 20 μ m, then uses the NaOH solution washing of 1 M, filter, to remove original oil in coal.After coal sample after washing is dried to constant weight under vacuum 393 K, obtain dry coal dust, the sealing pack.
(2) coal sample is carried out to electron beam irradiation: the GJ-2-II high frequency high voltage electron accelerator coal sample pretreated to step a that adopts ray applications research institute of Shanghai University to provide carried out irradiation, obtain dosage and be respectively 10 kGy, 20 kGy, 30 kGy, 40 kGy, the coal sample of 50 kGy.
(3) coal sample before and after electron beam irradiation is carried out to the ESR test: accurately take the sample of 15 mg, the sample hose of packing into, test by ESR spectrum parameters such as obtaining live width, line style, the g factor, hyperfine coupling and spin concentration.The ESR experiment is all carried out in Bruker EMX-8/ 2.7 type electronic paramagnetic resonance spectrometers.Central magnetic field: 3520.8 G, field sweep width: 500 G, microwave frequency: 9.871 GHz, enlargement factor: 2.24e002, modulation amplitude: 1 G, modulating frequency: 100 KHz, time constant: 163.84 ms, field sweep time: 41.943 s.
(4) impact of the different irradiation doses of the present embodiment gained on coal ESR characteristic parameter, in Table 1.Area in figure below sample paramagnetic resonance spectral line has represented the concentration of free radical in the sample; But, when the line style of spectral line is identical, its free radical relative concentration Ng is proportional to the product of the quadratic sum peak height Hpp of peak width Δ H.?
Ng∝(△H)
2×Hpp
When peak width changes when little, peak height Hpp is the relative concentration of the paramagnetic center of representative sample (free radical).
As shown in Table 1, the ESR spectrogram peak width of the Shengli coal after predose and shenfu coal does not all have to change, so the relative concentration of peak height Hpp stands for freedom base for the present invention.
Gained Shengli coal in the present embodiment, the g factor of shenfu coal, with the variation of irradiation dose, is shown in Fig. 1.Curve a means Shengli coal, and curve b means shenfu coal.As shown in Figure 1, the g factor of two kinds of coals is larger than single electron (2.0023), and changes between 2.004 and 2.005.After irradiation, the g factor of two kinds of coals all increases to some extent, g value by the S atom > the g value of O and N atom > the g value of C atom infers, coal has mainly generated low-molecular-weight hydrocarbons in the process of irradiation, the heteroatomss such as O, N, S are difficult for removing, and this may be relevant with the huge cross-linked network of coal.Along with the coal rank increase, it is the increase of degree of coalification, the g factor values of shenfu coal is less than Shengli coal, this is consistent with previous report, at the metamorphic process of coal, owing to constantly taking off alkyl, removing impurities atom and dehydrogenation, the carbon content of coal constantly increases, single electron comes from the π track that forwards purer hydro carbons containing heteroatomic π track to, causes the g factor to reduce.
The present embodiment gained Shengli coal, the free radical of shenfu coal absorbs the variation of peak height with irradiation dose, sees Fig. 2.Curve a means Shengli coal, and curve b means shenfu coal.As shown in Figure 2, with the increase of irradiation dose, the peak height of coal sample free radical absorption peak increases gradually, and when irradiation dose is greater than 30 kGy, peak height reduces.Illustrate that coal has all produced free radical after irradiation, and the concentration of free radical is all first increases and then decreases, when irradiation dose is 30 kGy, maximal value appears in number of free radical; When irradiation dose surpasses 30 kGy, number of free radical reduces.We infer, electron beam irradiation can weaken the bond energy in coal macromolecule, and causes the fracture of part key, produces free radical, and number of free radical is increased.But when irradiation dose is excessive, produce a large amount of free radicals, each other more easily pairing; Produced powerful sterically hinderedly due to the cross-linked network of the huge complexity of coal again, free radical has been played to the effect that cage closes, made part free radical generation polymerization generate molecule, finally caused number of free radical to descend.In sum, when dosage is 30 kGy, coal number of free radical maximum, be conducive to the coal cracking most.
Claims (1)
1. one kind is utilized the method for electron paramagnetic resonance detected electrons bundle irradiation on the impact of coal number of free radical, comprises following several step:
The pre-service of a, coal sample: at first coal particle is ground to below 20 μ m, then uses the NaOH solution washing of 1 M, filter, to remove original oil in coal; After coal sample after washing is dried to constant weight under vacuum 393 K, obtain dry coal dust, the sealing pack;
B, coal sample is carried out to electron beam irradiation: the GJ-2-II high frequency high voltage electron accelerator coal sample pretreated to step a that adopts ray applications research institute of Shanghai University to provide carried out irradiation, obtain dosage and be respectively 10 kGy, 20 kGy, 30 kGy, 40 kGy, the coal sample of 50 kGy;
C, the coal sample before and after electron beam irradiation is carried out to electron paramagnetic resonance (ESR) test: the sample that accurately takes 15 mg, the sample hose of packing into, test by ESR spectrum parameters such as obtaining live width, line style, the g factor, hyperfine coupling and spin concentration; The ESR experiment is all carried out in Bruker EMX-8/ 2.7 type electronic paramagnetic resonance spectrometers; Central magnetic field: 3520.8 G; Field sweep width: 500 G; Microwave frequency: 9.871 GHz; Enlargement factor: 2.24e002; Modulation amplitude: 1 G; Modulating frequency: 100 KHz; Time constant: 163.84 ms; The field sweep time: 41.943 s;
D, can calculate out the relative concentration of free radical in coal according to following formula; Formula is: Ng ∝ (△ H)
2* Hpp; It is the product that free radical relative concentration Ng is proportional to the quadratic sum peak height Hpp of peak width △ H; When peak width changes when little, peak height Hpp is the relative concentration of the paramagnetic center of representative sample (free radical).
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Cited By (7)
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| CN105676265A (en) * | 2014-11-18 | 2016-06-15 | 中国辐射防护研究院 | Sample preparation method of nail electron paramagnetic resonance technical detection for radiation dose estimation |
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| CN106404819A (en) * | 2016-08-30 | 2017-02-15 | 大连工业大学 | Method for detecting quality change during sea cucumber processing process based on electron spin resonance spectrum technology |
| CN106546621A (en) * | 2015-09-16 | 2017-03-29 | 中国辐射防护研究院 | External source induces low detection sensitivity electron paramagnetic resonance signal quantitative detecting method |
| CN108508056A (en) * | 2018-02-05 | 2018-09-07 | 华中科技大学 | A kind of method of accurate quantification trace solid free-radical contents |
| CN109813584A (en) * | 2018-10-08 | 2019-05-28 | 西安科技大学 | A method of coal spontaneous combustion is studied based on ultrasonic extraction |
| WO2023197691A1 (en) * | 2022-04-14 | 2023-10-19 | 国仪量子(合肥)技术有限公司 | Method for obtaining absolute spin number of unpaired electrons of sample |
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| CN106546621A (en) * | 2015-09-16 | 2017-03-29 | 中国辐射防护研究院 | External source induces low detection sensitivity electron paramagnetic resonance signal quantitative detecting method |
| CN106404819A (en) * | 2016-08-30 | 2017-02-15 | 大连工业大学 | Method for detecting quality change during sea cucumber processing process based on electron spin resonance spectrum technology |
| CN106404819B (en) * | 2016-08-30 | 2017-12-05 | 大连工业大学 | Method based on quality comparison during Electron Spin Resonance Spectra technology for detection Holothurian machining |
| CN108508056A (en) * | 2018-02-05 | 2018-09-07 | 华中科技大学 | A kind of method of accurate quantification trace solid free-radical contents |
| CN109813584A (en) * | 2018-10-08 | 2019-05-28 | 西安科技大学 | A method of coal spontaneous combustion is studied based on ultrasonic extraction |
| WO2023197691A1 (en) * | 2022-04-14 | 2023-10-19 | 国仪量子(合肥)技术有限公司 | Method for obtaining absolute spin number of unpaired electrons of sample |
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