CN102135508A - Method for testing chemical constituents in coal or coke ash by X-ray fluorescence spectrum analysis method - Google Patents
Method for testing chemical constituents in coal or coke ash by X-ray fluorescence spectrum analysis method Download PDFInfo
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- CN102135508A CN102135508A CN 201110026222 CN201110026222A CN102135508A CN 102135508 A CN102135508 A CN 102135508A CN 201110026222 CN201110026222 CN 201110026222 CN 201110026222 A CN201110026222 A CN 201110026222A CN 102135508 A CN102135508 A CN 102135508A
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Abstract
The invention relates to a method for testing chemical constituents in coal or coke ash by an X-ray fluorescence spectrum analysis method. The method comprises the following process steps: ashing coals or cokes; fluxing by using a mixed solvent of lithium metaborate and lithium tetraborate to obtain a glass sheet, and directly scanning by using an X-ray fluorescence spectrum analyzer; and testing the content of the chemical constitutes in the coal or coke ash. A sample is made by a glass flux sheet method, the method is easy to operate and high in analysis speed, and the constitutes such as Fe2O3, CaO, MgO, SiO2, Al2O3, TiO2, K2O, Na2O, P2O5, MnO and the like in the coal or coke ash can be analyzed at the same time. The method has the advantages that: the repetitiveness and the reproducibility are higher than those of the national standard method for testing the chemical constituents in the coal or coke ash; and the method has the characteristics of scientificity, advancement, applicability, popularization, short analysis time, high accuracy and repetitiveness, pollution absence and the like.
Description
Technical field
The present invention relates to the method for a kind of steel, belong to metallurgical chemistry analytical test technical field with chemical constitution in X-ray fluorescence spectra assay coal, the charred ashes.
Background technology
In iron and steel enterprise, coke is an indispensable furnace charge in the blast furnace ironmaking, mainly plays effects such as heat, reductive agent, stock column skeleton are provided, and the quality of coke directly has influence on the quality and the output of blast furnace ironmaking; In process of coking, the ash content in the coal almost all changes among the coke, and the pit ash height will inevitably make the ash content of coke also high, because the principal ingredient of coal ash is SiO
2, Al
2O
3Deng acidic oxide, fusing point is higher, in the process of ironmaking, can only could discharge by blast furnace with the slag form with the low-melting compound of their reaction generations by adding flux such as lime stone, thereby slag amount is increased, when coke is heated to above the coking temperature in blast furnace, because coke is different with the thermal expansivity of ash content, coke produces and the diffusion crackle around ash particles, makes the cracked or efflorescence of coke.Put down in writing the every rising 1% of general coke ash according to data, blast furnace flux consumption increases by 4% approximately, slag amount increases by 3% approximately, the pig iron per ton consumes amount of coke increases (1.7-2.0) %, pig iron output reduces (2.2-3.0) % approximately, and for coal for coking, ash content should hang down as far as possible, and principal ingredient in definite ash, just help instructing ironmaking.Therefore main chemical compositions and the content thereof that determines in the coal ash has certain directive significance to coking, also has certain effect thereby blast furnace is reduced coke ratio.The traditional chemical analytical approach can only the individual element analysis, the sample pre-treatments complexity, and link is many, and operation easier is big, length consuming time (single sample needs week age), consumes many, the poor repeatability of reagent.
Summary of the invention
The purpose of this invention is to provide a kind of method with chemical constitution in X-ray fluorescence spectra assay coal, the charred ashes, short in analysis time, there is not chemical contamination, accuracy height, good reproducibility solve the problems referred to above that background technology exists.
Technical scheme of the present invention is:
Method with chemical constitution in X-ray fluorescence spectra assay coal, the charred ashes, comprise following processing step: after coal, Jiao are carried out ashing treatment, with lithium metaborate with after the lithium tetraborate mixed flux is founded into glass sheet, directly, measure the wherein content of chemical constitution with the scanning of X-ray fluorescence spectra analyser.
The present invention has determined the ashing condition of coal, burnt sample, the condition of founding of ash sample glass sheet, the analysis condition of instrument; By standard sample of photo is scanned, the drawing curve, and then measure chemical constitution in coal, the charred ashes.
The present invention adopts the sample preparation of glass fuse piece method, and this method is simple to operate, and analysis speed is fast, can analyze Fe in coal, the charred ashes simultaneously
2O
3, CaO, MgO, SiO
2, Al
2O
3, TiO
2, K
2O, Na
2O, P
2O
5, composition such as MnO, by characteristics such as confirm that this method has science, advance, applicability, analysis time is short, accuracy is high, good reproducibility, pollution are few.Repeatability and Reproducibility all is better than GB/T 1574-2007 standard-required.
Good effect of the present invention is: the present invention is better than the assay method of chemical constitution in the coal, charred ashes of national standard, but this method has science, advance, applicability generalization, analysis time is short, accuracy is high, good reproducibility, characteristics such as pollution-free, by the correctness checking, show that the method has high accuracy and precision.
Embodiment
The present invention will be further described below by embodiment.
Method with chemical constitution in X-ray fluorescence spectra assay coal, the charred ashes, comprise following processing step: after coal, Jiao are carried out ashing treatment, with lithium metaborate with after the lithium tetraborate mixed flux is founded into glass sheet, directly, measure the wherein content of chemical constitution with the scanning of X-ray fluorescence spectra analyser.
Embodiment more specifically:
1, major equipment:
A), wavelength dispersion X fluorescent x ray spectroscopy x instrument:
Detecting device is sweep type gas proportional counter and scintillation counter;
Peak power: 4kW;
B), sample making apparatus:
High frequency fusion stove or infrared sample-melting stove.
2, chemical reagent:
A), oxygenant LiNO
3: 220mg/ml;
B), remover LiBr:30mg/ml.
C), flux LiB
4O
7+ LiBO
2: 67%+33%
Annotate: above reagent is analyzes pure above rank.
3, the ashing of sample:
Take by weighing the 1g granularity less than the coal of 1mm, burnt sample in cupel (the general analysis coal sample makes its every square centimeter and is no more than 0.15g), cupel sent in 100 ℃ the muffle furnace, leave under the condition in slit, the 15mm left and right sides in natural ventilation and fire door, slowly rise to 500 ℃, after keeping 30min under this temperature with 30min, rise under (815 ± 10) ℃, calcination 2h again, take out cooling after, calcination 30min again, be no more than up to its mass change till the per mille of ash sample quality, be constant mass.Take out, in air, place about 5min, change in the exsiccator.As untimely title sample, then need before claiming sample in, (815 ± 10) are calcination 30min ℃ again.
The high coal of sulfur content must not be placed on calcination in the same stove with the low coal of sulfur content; Its sulfur content should be roughly close during a plurality of sample of every stove calcination, and be with a kind of coal; Cupel in the muffle furnace must not stack multilayer, in order to avoid calcination is incomplete; The muffle furnace that uses should have an air hole (about 20mm) on the fire door, chimney (25-30mm) should be arranged on the stove rear wall.
4, the preparation of glass print
Take by weighing 8.0000g flux, the 0.8000g sample adds the LiNO3 of 1ml 220mg/ml, the LiBr of 1ml 30mg/ml, and at first, at 600 ℃ of following pre-oxidation 3min, at 1100 ℃ of following fusion 7min, back 4min waves, and after the fusion fully, it is standby that print is cooled to room temperature.
Coal, charred ashes are in preparation process, though passed through high temperature sintering, most elements all exists with the form of oxide, for guaranteeing the safe in utilization of platinum crucible, add oxygenant.
5, drawing curve
A), the selection of standard model
According to the content of daily test sample, select suitable a series of standard specimens, by 4 fusion cast glass sheets.
Table 1: standard model
B), scan conventional print, determine analysis condition
Select the higher conventional sample of chemical constitution to scan, general glitch-free k α 1 line is as analysis spectral line, and maximum peak position is the actual detected peak position; The general selection principle of analyzing crystal is that LiF is fit to the most elements in Ni ~ Te scope, and PET is suitable for the element in Al ~ Cl scope, and OVO-55 is suitable for the element in O ~ Mg scope; Factors such as light pipe voltage, electric current, collimator slit will be taken all factors into consideration, and guarantee that the photon intensity that detecting device receives is not higher than 500kcps; The PHA window analysis is all in and strengthens window when not introducing other spectral line signal as far as possible; Select single-point as a setting during the general both sides of background symmetries,, can ignore background intensity, to shorten sweep time when measured signal is higher than background signal by force more than 10 times the time; Analysis time in the sweep signal deviation less than 0.3% o'clock as analyzing the concluding time.Final definite optimum analysis condition is as follows:
Table 2: analysis condition
C), scanning standard specimen intensity, make and also optimize working curve
Under fixed analysis condition, scanning standard sample, data processor are made working curve automatically, because the known component content of standard model can not be all in 95 ~ 105% scopes, so can only adopt fixedly side reaction coefficient correction in this experiment; Sample adopts fusion method to make glass sheet, and matrix effect is little, noiseless element.It is as follows to optimize back working curve information:
Table 3: working curve information
| Test item | Slope/(%/kcps) | Intercept/% | The range of linearity/% | SD% |
| Fe 2O 3 | 0.08111 | 0.6216 | 2.81~39.61 | 0.167 |
| MnO | 0.03608 | 0.035 | 0.04~0.44 | 0.00354 |
| TiO 2 | 0.1337 | 0.00965 | 0.26~1.52 | 0.0459 |
| CaO | 0.1351 | -0.1647 | 3.27~18.37 | 0.185 |
| K 2O | 0.1273 | 0.02042 | 0.20~1.41 | 0.027 |
| P 2O 5 | 0.807 | -0.01258 | 0.09~1.44 | 0.0278 |
| SiO 2 | 1.4350 | -0.0233 | 15.66~48.02 | 0.109 |
| Al 2O 3 | 1.462 | -0.4656 | 7.34~33.72 | 0.341 |
| MgO | 0.7474 | 0.1360 | 0.69~6.05 | 0.0541 |
| Na 2O | 1.787 | 0.00893 | 0.28~1.75 | 0.035 |
6, correctness experiment
A), accuracy experiment
According to above sample melting method and analysis condition existing sample is analyzed, data are as follows:
B), precision experiment
Same sample is founded 10 prints respectively and is analyzed that can to get data as follows:
Above data show that this analytical approach has higher accuracy and precision, and Repeatability and Reproducibility all is better than national standard.
STRENGTH ON COKE is carried out the sample preparation analysis, carries out the sample ashing, and the fusion cast glass sheet adopts above analysis condition and working curve to analyze, and it is as follows to record data:
| The place of production | Numbering | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | P 2O 5 | K 2O | Na 2O | TiO 2 | MnO |
| The Zhangjiagang coke | 20100827 | 45.12 | 35.73 | 5.94 | 4.44 | 1.16 | 0.363 | 0.497 | 0.58 | 1.949 | 0.038 |
Claims (6)
1. method with chemical constitution in X-ray fluorescence spectra assay coal, the charred ashes, it is characterized in that comprising following processing step: coal, Jiao are carried out ashing treatment, with lithium metaborate with after the lithium tetraborate mixed flux is founded into glass sheet, directly, measure the wherein content of chemical constitution with the scanning of X-ray fluorescence spectra analyser.
2. according to the method for chemical constitution in the described usefulness X-ray fluorescence spectra assay coal of claim 1, the charred ashes, it is characterized in that the preparation process of glass print, the ratio of flux and sample is 10:1.
3. according to the method for chemical constitution in claim 1 or 2 described usefulness X-ray fluorescence spectra assay coals, the charred ashes, it is characterized in that the preparation process of glass print, lithium metaborate in the flux and lithium tetraborate proportion are 33% and 67%.
4. according to the method for chemical constitution in claim 1 or 2 described usefulness X-ray fluorescence spectra assay coals, the charred ashes, it is characterized in that the preparation process of glass print, also add oxygenant and remover.
5. according to the method for chemical constitution in the described usefulness X-ray fluorescence spectra assay coal of claim 4, the charred ashes, the preparation process that it is characterized in that the glass print is 600 ℃ of following pre-oxidation, and 4min is waved in 1100 ℃ of following fusions at least.
6. according to the method for chemical constitution in the described usefulness X-ray fluorescence spectra assay coal of claim 1, the charred ashes, it is characterized in that sample is sent into calcination in the muffle furnace, the per mille that is no more than sample mass until mass change is taken out, and behind the natural cooling, changes exsiccator over to.
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Cited By (13)
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|---|---|---|---|---|
| CN102980902A (en) * | 2012-12-03 | 2013-03-20 | 山西大学 | Visualization quantitative CT (Captive Test) characterization method for component distribution and physical structure of coal sample |
| CN103063462A (en) * | 2012-12-29 | 2013-04-24 | 上海华碧检测技术有限公司 | Identification method of burning through reasons of ferrosilicon heat furnace body |
| CN103278520A (en) * | 2013-06-11 | 2013-09-04 | 鞍钢股份有限公司 | X-ray fluorescence spectrum analysis method of siliceous slag conglomeration agent |
| CN103472080A (en) * | 2013-09-02 | 2013-12-25 | 贵州天义电器有限责任公司 | Non-cyanide analytic determination method for copper-nickel-zinc alloy |
| CN104280368A (en) * | 2013-10-31 | 2015-01-14 | 东旭集团有限公司 | Method for efficiently and accurately detecting main content of industrial magnesium oxide |
| CN104297272A (en) * | 2014-11-11 | 2015-01-21 | 山西大学 | CT characterization method for direct coal liquefaction residue sample |
| CN105928963A (en) * | 2016-04-14 | 2016-09-07 | 梧州市产品质量检验所 | Method for detecting quality of raw coal |
| CN106153657A (en) * | 2016-09-19 | 2016-11-23 | 长沙开元仪器股份有限公司 | Ature of coal on-line measuring device and method |
| CN107356618A (en) * | 2017-06-30 | 2017-11-17 | 马鞍山钢铁股份有限公司 | A kind of method of covering agent component content in x-ray fluorescence spectrometry |
| CN108982563A (en) * | 2018-08-03 | 2018-12-11 | 武汉科技大学 | Method for preparing glass sheet for XRF analysis of release aid effect |
| CN110274924A (en) * | 2019-05-28 | 2019-09-24 | 中国地质调查局西安地质调查中心 | A kind of sample-pretreating method suitable for x-ray fluorescence analysis glass flux sheet method |
| CN111239172A (en) * | 2020-02-24 | 2020-06-05 | 河北龙凤山铸业有限公司 | Method for determining phosphorus content in coal |
| CN114166880A (en) * | 2021-11-17 | 2022-03-11 | 酒泉钢铁(集团)有限责任公司 | Method for detecting primary and secondary elements in coal or coke |
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| CN102980902A (en) * | 2012-12-03 | 2013-03-20 | 山西大学 | Visualization quantitative CT (Captive Test) characterization method for component distribution and physical structure of coal sample |
| CN102980902B (en) * | 2012-12-03 | 2013-09-04 | 山西大学 | Visualization quantitative CT (Captive Test) characterization method for component distribution and physical structure of coal sample |
| CN103063462A (en) * | 2012-12-29 | 2013-04-24 | 上海华碧检测技术有限公司 | Identification method of burning through reasons of ferrosilicon heat furnace body |
| CN103278520A (en) * | 2013-06-11 | 2013-09-04 | 鞍钢股份有限公司 | X-ray fluorescence spectrum analysis method of siliceous slag conglomeration agent |
| CN103472080A (en) * | 2013-09-02 | 2013-12-25 | 贵州天义电器有限责任公司 | Non-cyanide analytic determination method for copper-nickel-zinc alloy |
| CN104280368A (en) * | 2013-10-31 | 2015-01-14 | 东旭集团有限公司 | Method for efficiently and accurately detecting main content of industrial magnesium oxide |
| CN104297272A (en) * | 2014-11-11 | 2015-01-21 | 山西大学 | CT characterization method for direct coal liquefaction residue sample |
| CN105928963A (en) * | 2016-04-14 | 2016-09-07 | 梧州市产品质量检验所 | Method for detecting quality of raw coal |
| CN106153657A (en) * | 2016-09-19 | 2016-11-23 | 长沙开元仪器股份有限公司 | Ature of coal on-line measuring device and method |
| CN107356618A (en) * | 2017-06-30 | 2017-11-17 | 马鞍山钢铁股份有限公司 | A kind of method of covering agent component content in x-ray fluorescence spectrometry |
| CN108982563A (en) * | 2018-08-03 | 2018-12-11 | 武汉科技大学 | Method for preparing glass sheet for XRF analysis of release aid effect |
| CN108982563B (en) * | 2018-08-03 | 2021-02-19 | 武汉科技大学 | Method for preparing glass sheet for XRF analysis of release aid effect |
| CN110274924A (en) * | 2019-05-28 | 2019-09-24 | 中国地质调查局西安地质调查中心 | A kind of sample-pretreating method suitable for x-ray fluorescence analysis glass flux sheet method |
| CN110274924B (en) * | 2019-05-28 | 2022-04-08 | 中国地质调查局西安地质调查中心 | Sample pretreatment method suitable for X-ray fluorescence analysis glass fuse method |
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Application publication date: 20110727 |