CN110672785B - Detection method for trace metal elements in coke and application thereof - Google Patents
Detection method for trace metal elements in coke and application thereof Download PDFInfo
- Publication number
- CN110672785B CN110672785B CN201911072364.XA CN201911072364A CN110672785B CN 110672785 B CN110672785 B CN 110672785B CN 201911072364 A CN201911072364 A CN 201911072364A CN 110672785 B CN110672785 B CN 110672785B
- Authority
- CN
- China
- Prior art keywords
- coke
- sample
- solution
- metal elements
- detected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000571 coke Substances 0.000 title claims abstract description 83
- 229910021654 trace metal Inorganic materials 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 24
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 230000003595 spectral effect Effects 0.000 claims description 12
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000011088 calibration curve Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000009616 inductively coupled plasma Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 230000029087 digestion Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004380 ashing Methods 0.000 abstract description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 37
- 239000011734 sodium Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000000184 acid digestion Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012482 calibration solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses an extraction method and application of trace metal elements in coke, wherein the extraction method comprises the following steps: taking coke to prepare a sample, uniformly stirring the sample, weighing the sample, placing the sample in a beaker, adding deionized water, uniformly stirring, and standing for a plurality of hours; filtering the soaked coke soak solution to ensure that no visible particulate matters exist in the filtrate; taking the filtrate into a volumetric flask, fixing the volume, adding a nitric acid solution, and uniformly mixing to obtain a first solution to be detected; and drying the filter residue, ashing, digesting with mixed acid to obtain a second solution to be detected, and finally, measuring the content of the target metal element by respectively adopting an EDTA method and an inductively coupled plasma atomic emission spectrometry. The method can extract the metal elements in the coke, has the advantages of simple steps, short time consumption and high extraction efficiency, and can eliminate experimental interference by adopting deionized water.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a method for detecting trace metal elements in coke and application thereof.
Background
Most of domestic long-process steel and iron combination enterprises are provided with coking plants, generally use coke produced by themselves in large proportion or even completely, have relatively stable and controllable quality, basically stay on the traditional quality inspection project when paying attention to the quality of the coke purchased, and do not pay enough attention to the problem of trace metal elements in the coke. In the industry, a method for detecting trace metal elements in the coke is also lacked, and in a coking plant, because desulfurization waste liquid, residual ammonia water in a coking process, denitration waste liquid, power generation boiler scaling washing water, biochemical dephenolization water and the like directly enter a coke quenching tank to participate in water coke quenching operation, a complex process causes that the finally obtained coke contains various metal elements, so that the quality of the coke is influenced. Most of the detection technologies aiming at the coke in the prior art only detect the soluble metal ions on the surface of the coke, and do not provide a detection technology for accurately quantifying the total content of specific trace metal elements in the coke.
The coke containing a plurality of trace metal elements such as k, Na, Ca, Mg and Zn is used as a smelting fuel in a great amount in metallurgical enterprises, after metal ions are vaporized after the upper part of a blast furnace is heated, the coke has a forward catalytic effect on the carbon dissolution loss reaction of the coke, namely the gasification reaction of the coke is promoted, so that the strength of the coke is reduced, the skeleton effect of the coke in the blast furnace is weakened, and the other part of metal ions are enriched in the blast furnace to aggravate the catastrophic expansion of pellets, the medium-temperature reduction pulverization of most sintered ores, the soft melting temperature of iron ore and the like, so that the air permeability of the blast furnace is poor, the pressure difference is increased, the furnace condition fluctuates and even the furnace condition is abnormal. Therefore, when the outsourcing coke is used by the steel and iron integrated enterprise, the trace metal elements k, Na, Ca, Mg and Zn in the outsourcing coke need to be accurately quantified, and the content of specific metal elements is estimated to possibly influence the blast furnace production.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention firstly provides a sample pretreatment method for determining trace metal elements in coke, a determination method and application thereof.
The detection method of the coke provided by the invention mainly comprises the steps of thoroughly dissolving trace metal elements in the coke in deionized water by combining a soaking method and a mixed acid digestion method, and determining the content of the trace metal elements in the coke for blast furnace smelting by adopting an EDTA titration method, thereby providing data support for coke quality acceptance, blast furnace condition trend analysis and the like.
The detection method mainly comprises the steps of completely dissolving trace metal elements in the coke in deionized water by combining a soaking method and a mixed acid digestion method, and measuring the trace metal content in the coke for blast furnace smelting by adopting an inductively coupled plasma atomic emission spectrometer, so as to provide data support for coke quality acceptance, blast furnace condition trend analysis and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a sample pretreatment method for determining trace metal elements in coke comprises the following steps:
(1) taking a coke sample entering a factory, crushing and sieving the coke sample step by step, taking 2kg of sieved coke bubble water to prepare a coke sample, uniformly stirring the sample, weighing 750-850 g of the sample, placing the sample in a 3000ml beaker, adding deionized water, uniformly stirring, and standing for at least 3 hours;
(2) filtering the soaked coke soak solution;
(3) and (3) taking the filtrate into a 50mL volumetric flask, fixing the volume, adding 1mL of nitric acid solution with the concentration of 50%, and uniformly mixing to obtain a first mixed solution, namely the part of metal ion solution on the surface of the coke to be detected.
Based on the technical scheme, the metal elements contained in the coke can be thoroughly extracted, evidence is provided for whether the coke is polluted by desulfurization waste liquid, residual ammonia water in the coking process, denitration waste liquid, power generation boiler scaling washing water, biochemical dephenolization water and the like in the coking enterprise, and a feasible extraction method is provided for accurately detecting the metal content in the coke.
Preferably, the step (3) is followed by the following step (4): drying 1.0g of filter residue at a low temperature, placing the filter residue in a porcelain crucible, placing the porcelain crucible in a muffle furnace, firing for a plurality of hours according to a set temperature-raising program, taking out the porcelain crucible after the temperature-raising program is finished, placing the porcelain crucible to the normal temperature, transferring a small amount of water into a tetrafluoroethylene beaker, adding mixed acid, placing the mixture on a heating plate for digestion, evaporating the mixture to be nearly dry after complete digestion, quantitatively transferring the mixture into a 50mL volumetric flask for constant volume, and adding 1mL of nitric acid solution with the concentration of 50% to obtain a second mixed solution.
Preferably, the temperature-raising program sequentially comprises: burning at 400 deg.C for 1.5h, at 480 deg.C for 2h, and at 550 deg.C for 1.5 h.
Preferably, the method for adding the mixed acid comprises the following steps: adding 10mL of hydrofluoric acid, 5.0mL of aqua regia and 1.5mL of perchloric acid in sequence, slowly raising the temperature to 280 ℃ on an electric hot plate, reducing the temperature after the perchloric acid is exhausted, adding 1mL of nitric acid solution with the concentration of 50% to extract a sample, cooling to room temperature, transferring the solution into a 50mL polytetrafluoroethylene volumetric flask, diluting with water to the scale, and shaking up.
Preferably, in the step (2), the soaked coke soak solution is filtered by adopting slow quantitative filter paper, and the coke soak solution is stirred and uniformly mixed before filtering.
A method for detecting trace metal elements in coke comprises the steps of obtaining a first mixed solution to be detected and a second mixed solution to be detected, detecting the content of the metal elements in the solutions to be detected by adopting an EDTA titration method respectively, and adding the detection results in proportion to obtain a final detection result.
A method for detecting trace metal elements in coke comprises the following steps:
s1, obtaining a first mixed solution to be detected and a second mixed solution to be detected by adopting the sample pretreatment method;
s2, measuring the spectral line intensity of metal elements in the first mixed solution and the second mixed solution respectively by using an inductively coupled plasma atomic emission spectrometer;
s3, calculating the content of metal elements in the coke to be detected; drawing an analysis element standard curve, and measuring the spectral intensity of the sample to be measured under the same condition with the standard curve; and (4) checking the content of the measured element on the calibration curve through the spectral intensity value, and adding the measurement results in proportion to obtain a final measurement result.
Preferably, in step S3, the step of plotting the standard curve of the analysis element includes plotting standard curves of species elements such as potassium, sodium, calcium, magnesium, zinc, and the like.
Preferably, in step S3, in the measurement process of the sample to be measured, if the mass concentration of the element to be measured in the sample to be measured exceeds the range of the calibration curve, the sample to be measured needs to be diluted and then measured again; replacing a water sample with deionized water, and determining a blank sample according to the same conditions as the determination of the sample; the calculation process is as follows:
calculated according to the following format: ρ ═ p (ρ)1-ρ2)×f；
Wherein rho represents the mass concentration of components in the sample to be detected, mg/L; rho1Represents the mass concentration of the components in the sample, mg/L; rho2mg/L as the mass concentration of the component in the blank sample, f as the conversion factor, and f as the dilution factor ×, wherein rho is the weight of the component1、ρ2Searching through a standard curve;
the coke gram refers to a sample amount of 750-850 g.
Compared with the prior art, the invention has the beneficial effects that: 1. the invention overcomes the technical prejudice, finds that the target metal in the coke can not be completely extracted only by a deionized water soaking method, and improves the detection accuracy by adopting the technical means of ashing the filter residue and then digesting and extracting the filter residue by using the mixed acid; 2. the invention provides a special heating program for coke filter residue and a selection ratio of mixed acid, and the method is initiated by the applicant; 3. the invention is also applicable to detecting other metal elements possibly existing in the coke; 4. the detection data of the invention has high precision, good accuracy, simple operation, low labor intensity and strong operability; 5. the method of the invention also has the characteristics of quick measurement, high efficiency, high flux, environmental protection and the like; 6. the method is suitable for accurately analyzing the content of potassium, sodium, calcium and magnesium in the coke soaking solution to be more than or equal to 1mg/L, and meets the quality acceptance requirement of coke entering a factory.
Detailed Description
Example 1
A sample pretreatment method for determining trace metal elements in coke comprises the following steps:
(1) taking a coke sample in a factory, crushing the coke sample step by step, sieving the crushed coke sample by a 13mm sieve, and taking 2kg of sieved coke bubble water to prepare a coke sample; uniformly stirring the samples, weighing the samples according to the table 1, placing the samples in 3000ml beakers, adding 1000ml of deionized water, uniformly stirring, and standing for more than 3 hours;
(2) uniformly stirring and mixing the coke soak solution, and filtering the soaked coke soak solution by adopting slow quantitative filter paper to ensure that no visible particulate matters exist in the filtrate;
(3) and (3) putting the filtrate into a 50ml volumetric flask, fixing the volume, adding 1ml of 50% nitric acid solution, and uniformly mixing to obtain a first mixed solution, namely a part of metal ion solution in the coke to be detected.
Example 2
A method for detecting the content of calcium and magnesium in coke comprises the following steps: steps (1) to (3) are the same as in example 1, and further include the following steps:
drying 1.0g of filter residue at low temperature, placing the filter residue in a porcelain crucible, placing the porcelain crucible in a muffle furnace, and firing for 1.5h at 400 ℃, 2h at 480 ℃ and finally 1.5h at 550 ℃ according to a set temperature raising program. After the temperature rise program is finished, taking out and placing to normal temperature, transferring a small amount of water to a tetrafluoroethylene beaker, sequentially adding 10mL of hydrofluoric acid, 5.0mL of aqua regia and 1.5mL of perchloric acid, slowly raising the temperature to 280 ℃ on an electric hot plate, reducing the temperature after the perchloric acid smokes, adding 1mL of nitric acid solution with the concentration of 50% to extract a sample, cooling to room temperature, transferring the solution to a 50mL polytetrafluoroethylene volumetric flask, diluting to a scale with water, and shaking uniformly to obtain a second mixed solution.
Example 3
And respectively detecting the contents of calcium ions and magnesium ions in the first mixed solution and the second mixed solution by adopting an EDTA titration method.
According to the technical scheme, the representative coke sample is prepared, deionized water is added for soaking for a plurality of hours to prepare the solution to be detected, and the contents of calcium and magnesium in the solution to be detected are determined by GB/T15452-2009 EDTA titration method for determining calcium and magnesium ions in industrial circulating cooling water, so that the technical problem that the contents of calcium and magnesium adsorbed in the coke cannot be detected at present is solved.
Example 4
A method for detecting potassium and sodium in trace metal elements in coke comprises the following steps:
s1, obtaining a first mixed solution and a second mixed solution to be detected by adopting the methods of the embodiment 1 and the embodiment 2;
s2, measuring the spectral line intensity of metal elements in the first mixed solution and the second mixed solution respectively by using an inductively coupled plasma atomic emission spectrometer;
s3, calculating the content of metal elements in the coke to be detected; drawing an analysis element standard curve, and measuring the spectral intensity of the sample to be measured under the same condition with the standard curve; and (4) checking the content of the measured element on the calibration curve through the spectral intensity value, and adding the measurement results in proportion to obtain a final measurement result.
In step S3, drawing an analysis element standard curve includes drawing a potassium standard curve and drawing a sodium standard curve;
the process of drawing the potassium standard curve is as follows: respectively transferring 0ml, 0.1 ml, 0.5 ml, 1.0 ml, 2.0 ml and 5.0ml of standard solution into corresponding 100ml volumetric flasks, adding 2ml of nitric acid solution with the concentration of 50% and a water sample, fixing the volume to scale, and uniformly mixing; obtaining 100ml of standard solution K2The O concentration is 0, 1.205, 6.025, 12.050, 24.100 and 60.250mg/l respectively; measuring the spectrum intensity of potassium in the calibration solution at 766.4nm wavelength by using inductively coupled plasma emission spectrometer, and measuring the spectrum intensity by K2Taking the concentration of O as an abscissa and the spectral line intensity as an ordinate, and drawing a potassium calibration curve;
the process of drawing the sodium standard curve is as follows: respectively transferring 0ml, 1.0 ml, 5.0ml, 10.0 ml, 20.0 ml and 50.0ml of standard solution into corresponding 100ml volumetric flasks, adding 2ml of nitric acid solution with the concentration of 50% and a water sample, fixing the volume to scale, and uniformly mixing; 100ml of standard solution Na is obtained2The O concentration is 0, 13.480, 67.400, 134.800, 269.600 and 674.000mg/l respectively; respectively measuring the spectral intensity of sodium in the calibration solution at the wavelength of 588.9nm by using an inductively coupled plasma emission spectrometer, and taking Na as the reference2And (4) drawing a sodium calibration curve by taking the O concentration as an abscissa and the spectral line intensity as an ordinate.
In the step S3, in the process of measuring the sample to be measured, if the mass concentration of the element to be measured in the sample to be measured exceeds the range of the calibration curve, the sample to be measured needs to be diluted and then is measured again; replacing a water sample with deionized water, and determining a blank sample according to the same conditions as the determination of the sample; the calculation process is as follows:
calculated according to the following format: ρ ═ p (ρ)1-ρ2)×f；
Wherein rho represents the mass concentration of components in the sample to be detected, mg/L; rho1Represents the mass concentration of the components in the sample, mg/L; rho2mg/L as the mass concentration of the component in the blank sample, f as the conversion factor, f as the dilution factor of × (1000 g/coke g), the dilution factor being generally 1, and ρ1、ρ2The coke grams refer to the sample weights in table 1, looked up by a standard curve.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (5)
1. A sample pretreatment method for determining trace metal elements in coke is characterized by comprising the following steps:
(1) taking a coke sample entering a factory, crushing and sieving the coke sample step by step, taking 2kg of sieved coke bubble water to prepare a coke sample, uniformly stirring the sample, weighing 750-850 g of the sample, placing the sample in a 3000ml beaker, adding deionized water, uniformly stirring, and standing for at least 3 hours;
(2) filtering the soaked coke soak solution;
(3) taking the filtrate to a 50mL volumetric flask, fixing the volume, adding 1mL of 50% nitric acid solution, and uniformly mixing to obtain a first mixed solution, namely a part of metal ion solution in the coke to be detected;
(4) drying 1.0g of filter residue at a low temperature, placing the filter residue in a porcelain crucible, placing the porcelain crucible in a muffle furnace, firing for a plurality of hours according to a set temperature-raising program, taking out the porcelain crucible after the temperature-raising program is finished, placing the porcelain crucible to the normal temperature, transferring a small amount of water into a tetrafluoroethylene beaker, adding mixed acid, placing the mixture on a heating plate for digestion, evaporating the mixture to be nearly dry after complete digestion, quantitatively transferring the mixture into a 50mL volumetric flask for constant volume, and adding 1mL of nitric acid solution with the concentration of 50% to obtain a second mixed solution;
the adding method of the mixed acid comprises the following steps: adding 10mL of hydrofluoric acid, 5.0mL of aqua regia and 1.5mL of perchloric acid in sequence, slowly raising the temperature to 280 ℃ on an electric hot plate, reducing the temperature after the perchloric acid is exhausted, adding 1mL of nitric acid solution with the concentration of 50% to extract a sample, cooling to room temperature, transferring the solution into a 50mL polytetrafluoroethylene volumetric flask, diluting with water to a scale, and shaking up;
and (3) filtering the soaked coke soak solution by adopting slow quantitative filter paper in the step (2), and stirring and uniformly mixing the coke soak solution before filtering.
2. The method of claim 1, wherein the temperature ramp sequence is: burning at 400 deg.C for 1.5h, at 480 deg.C for 2h, and at 550 deg.C for 1.5 h.
3. A method for detecting trace metal elements in coke is characterized in that a first mixed solution and a second mixed solution to be detected are obtained by the method of claim 2, the content of the metal elements in the solutions to be detected is detected by an EDTA titration method respectively, and the detection results are added in proportion to obtain a final detection result.
4. A method for detecting trace metal elements in coke is characterized by comprising the following steps:
s1, obtaining a first mixed solution to be detected and a second mixed solution by adopting the method of claim 1;
s2, measuring the spectral line intensity of metal elements in the first mixed solution and the second mixed solution respectively by using an inductively coupled plasma atomic emission spectrometer;
s3, calculating the content of metal elements in the coke to be detected; drawing an analysis element standard curve, and measuring the spectral intensity of the sample to be measured under the same condition with the standard curve; and (4) checking the content of the measured element on the calibration curve through the spectral intensity value, and adding the measurement results in proportion to obtain a final measurement result.
5. The method of claim 4, wherein the step of drawing a standard curve of the analysis elements in step S3 includes drawing a standard curve of five elements of K, Na, Ca, Mg and Zn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911072364.XA CN110672785B (en) | 2019-11-05 | 2019-11-05 | Detection method for trace metal elements in coke and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911072364.XA CN110672785B (en) | 2019-11-05 | 2019-11-05 | Detection method for trace metal elements in coke and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110672785A CN110672785A (en) | 2020-01-10 |
| CN110672785B true CN110672785B (en) | 2020-09-08 |
Family
ID=69086023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911072364.XA Active CN110672785B (en) | 2019-11-05 | 2019-11-05 | Detection method for trace metal elements in coke and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110672785B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111751357B (en) * | 2020-07-22 | 2022-05-24 | 攀钢集团研究院有限公司 | Determination of Fe in a polymorphic iron ion coexisting system in EDTA (ethylene diamine tetraacetic acid) complex denitration liquid2+With Fe3+Method of content |
| CN111751356B (en) * | 2020-07-22 | 2022-05-24 | 攀钢集团研究院有限公司 | Method for simultaneously determining concentration components of divalent and trivalent iron ions in Fe-EDTA (ethylene diamine tetraacetic acid) complex denitration solution |
| CN111751355B (en) * | 2020-07-22 | 2022-05-24 | 攀钢集团研究院有限公司 | Method for determining content of ferrous iron ions in Fe (II) -EDTA (ethylene diamine tetraacetic acid) complex denitration liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183477A (en) * | 2010-12-13 | 2011-09-14 | 河北省首钢迁安钢铁有限责任公司 | Method for simulation test of influence of alkali metal on coke degradation |
| CN208013083U (en) * | 2018-04-11 | 2018-10-26 | 安徽长江钢铁股份有限公司 | A kind of coke free elemental sulfur measurement system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106990055A (en) * | 2017-03-21 | 2017-07-28 | 南开大学 | The method for determining gold-palladium content in circuit board of mobile phone |
| CN108872200B (en) * | 2017-05-08 | 2021-06-08 | 上海梅山钢铁股份有限公司 | Detection method for sulfur content adsorbed on coke surface |
-
2019
- 2019-11-05 CN CN201911072364.XA patent/CN110672785B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183477A (en) * | 2010-12-13 | 2011-09-14 | 河北省首钢迁安钢铁有限责任公司 | Method for simulation test of influence of alkali metal on coke degradation |
| CN208013083U (en) * | 2018-04-11 | 2018-10-26 | 安徽长江钢铁股份有限公司 | A kind of coke free elemental sulfur measurement system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110672785A (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110672785B (en) | Detection method for trace metal elements in coke and application thereof | |
| CN102564973B (en) | Method for rapidly determining contents of phosphorus, lead and zinc in industrial iron-containing dust mud | |
| KR20120085296A (en) | Method for analyzing and detecting calcium element in ore | |
| CN102565176A (en) | Method for simultaneously determining harmful elements in iron ore | |
| CN102998303A (en) | Detection method for determining contents of niobium and tantalum in steel by applying microwave digestion-ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) | |
| Mketo et al. | An innovative microwave-assisted digestion method with diluted hydrogen peroxide for rapid extraction of trace elements in coal samples followed by inductively coupled plasma-mass spectrometry | |
| Sahuquillo et al. | Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments | |
| CN110487758B (en) | Method for measuring arsenic, selenium and lead in coal-fired power plant coal and combustion byproducts thereof | |
| CN103512911A (en) | Metallurgy miscellaneous material fast spectral analysis method | |
| CN102798644B (en) | Separating method and detection method for free carbon in vanadium carbide | |
| CN103018230A (en) | Method for synchronously measuring various elements in metallurgical sundries | |
| Ni et al. | Simultaneous determination of ultra-trace Pt, Pd, Rh and Ir in geochemical samples by inductively coupled plasma mass spectrometry following tin fire assay preconcentration and microwave digestion | |
| JP2013104848A (en) | Simple method for analyzing arsenic concentration in coal ash | |
| CN111650194A (en) | Method for determining phosphorus content in iron ore by bismuth-phosphorus-molybdenum blue | |
| CN108709882B (en) | Method for measuring contents of silicon element and phosphorus element in low-silicon nodulizer | |
| CN114414539B (en) | Method for measuring content of bismuth and antimony elements in roasted molybdenum concentrate | |
| CN100535637C (en) | Continuous detecting method for lead-cadmium in plastic sample | |
| CN108872200B (en) | Detection method for sulfur content adsorbed on coke surface | |
| CN111351779A (en) | Method for measuring content of heavy metal cobalt, manganese, nickel, strontium and vanadium in waste oil | |
| CN112098394A (en) | ICP-OES analysis method for determining content of metal elements in coal ash sample | |
| CN113533307A (en) | Method for measuring contents of calcium, magnesium, copper, aluminum, manganese, titanium, potassium, sodium, lead and zinc elements in blast furnace dust | |
| CN116380850B (en) | Method for detecting acid-forming elements from industrial hazardous waste | |
| CN115015224B (en) | Grading evaluation method for determining water body environment risk by using heavy metals contained in fly ash | |
| CN117413172A (en) | Method for detecting chromium content in laterite nickel ore | |
| Kessel | Recovery of Zinc from Municipal Solid Waste Fly Ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |