CN111289322A - Solid waste iron-containing sediment standard sample and preparation method thereof - Google Patents
Solid waste iron-containing sediment standard sample and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 69
- 239000013049 sediment Substances 0.000 title claims abstract description 30
- 239000002910 solid waste Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 9
- 229910052745 lead Inorganic materials 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 238000011156 evaluation Methods 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000010802 sludge Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 238000007689 inspection Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000009628 steelmaking Methods 0.000 claims description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 230000002159 abnormal effect Effects 0.000 description 12
- 238000004949 mass spectrometry Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910001349 ledeburite Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002279 physical standard Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- 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
- G01N1/34—Purifying; Cleaning
-
- 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
- G01N1/38—Diluting, dispersing or mixing samples
-
- 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
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- 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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
-
- 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
- G01N2001/2893—Preparing calibration standards
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a standard sample of solid waste iron-containing sediment, which comprises the following components in percentage by weight: CaO 0.3-55.0%, MgO 0.1-36%, SiO21.8‑8.0％、P2O50.05‑1.0％、TiO20.02‑0.5％、MnO 0.05‑8.0％、Al2O30.1-6.0 percent of iron-containing sediment standard sample, 1.5-65.0 percent of TFe, 0.03-16.0 percent of ZnO, 0.2-2.0 percent of S, 0.0001-0.003 percent of Pb, 0-0.0006 percent of As and 0.0001-0.004 percent of Sb. Focusing on As in the iron-containing sludgeHarmful elements to be detected in environmental evaluation such as Pb and F are subjected to fixed value, and the requirement of environmental detection is better met.
Description
Technical Field
The invention belongs to the technical field of standard samples, and relates to a solid waste iron-containing sediment standard sample and a preparation method thereof.
Background
The environmental problem and the resource problem are restrictive links for determining whether the steel industry in China can be further developed, the steel enterprise is one of the traditional industries with large energy consumption and serious pollution, and the recycling of solid wastes generated in the production process has important significance for protecting the environment and saving resources. The solid waste of iron and steel enterprises mainly comprises smelting waste residues and various iron-containing sludge, wherein the iron-containing sludge refers to the solid waste obtained by performing dry dust removal, wet dust removal and wastewater treatment on discharged smoke in the process of iron and steel production, and is called as iron-containing sludge due to high iron-containing content. Each ton of steel can generate 130kg of iron-containing settled sludge with the iron content of 30-70%, which causes a great deal of resource waste and environmental pollution.
Along with the annual increase of the yield of the iron-containing sludge in China, the utilization of the iron-containing sludge becomes an important industrial subject, particularly, the nation puts forward ecological civilized construction and energy-saving emission-reduction policies, enterprises pay more and more attention to the treatment and utilization of smelting solid wastes, the iron-containing sludge is generally returned to sintering or iron making at home and can be used as a cooling agent for converter steelmaking, but along with the development of circular economy, the treated iron-containing sludge is more widely applied, the chemical components and the performance of the treated iron-containing sludge conform to those of building materials and the like, and the treated iron-containing sludge is used for concrete, cement, mortar, bricks and the like.
The iron-containing sediment is a dust-like substance with light weight and tiny particles, the main chemical components in the iron-containing sediment comprise iron (TFe), calcium oxide, magnesium oxide, silicon dioxide, aluminum oxide, phosphorus pentoxide, zinc oxide, manganese oxide, alkali metal and the like, and the accurate determination of the content of various elements has great influence on the trade, utilization and the like of the iron-containing sediment. At present, the method for detecting the chemical components of the iron-containing sludge is widely applied to scientific research institutions, detection institutions and steel mill laboratories. But the standard product of the iron-containing sludge is lacked in the market, and the accurate detection of the content of each component cannot be guaranteed. Therefore, the iron-containing sediment standard sample is prepared, so that the detection of the iron-containing sediment is more standard, and the iron-containing sediment standard sample has great significance for promoting the reuse of the iron-containing sediment resources and promoting the national ecological civilization construction and energy conservation and emission reduction construction. A standard sample is a material or substance with sufficiently uniform and well-defined characteristic values that can be used to calibrate the apparatus, evaluate the measurement method, or assign a value to the material. Since the application of the iron-containing sludge is increased year by year as a metallurgical waste, the product inspection needs corresponding standard samples, and the demand of the iron-containing sludge is necessarily increased.
Therefore, the development of a standard sample containing iron sludge and a preparation method thereof are problems to be solved urgently by the people in the field.
Disclosure of Invention
In view of the above, the present invention provides a standard sample of iron-containing sludge and a preparation method thereof, and in order to achieve the above object, the present invention adopts the following technical scheme:
a standard sample of iron-containing sludge comprises the following components in percentage by weight: CaO 0.3-55.0%, MgO 0.1-36%, SiO21.8-8.0％、P2O50.05-1.0％、TiO20.02-0.5％、MnO 0.05-8.0％、Al2O30.1-6.0％、TFe 1.5-65.0％、ZnO 0.03-16.0％、S 0.2-2.0％、Pb 0.0001-0.003％、As 0-0.0006％、Sb 0.0001-0.004％。
The invention also provides a preparation method of the iron-containing sediment standard sample, which comprises the following steps:
(1) weighing each component according to the iron-containing sediment standard sample, placing the components into a ball mill for grinding, and sieving;
(2) uniformly mixing the sample sieved in the step (1) in a sample mixing machine;
(3) and (3) putting the uniformly mixed sample obtained in the step (2) into a glass bottle, sealing, and obtaining the iron-containing sediment standard sample after uniformity and stability inspection, method research, fixed value and uncertainty evaluation.
Further, the step (1) is carried out by sieving with a sieve of 160-180 meshes.
The adoption of the further beneficial effects is as follows: the granularity of the iron-containing sediment sample is less than or equal to 80 mu m, the granularity of the sample is fine enough, and the sample is more uniform;
further, the mixing speed of the sample mixing machine in the step (2) is 16-20 r/min.
The adoption of the further beneficial effects is as follows: the iron-containing sludge is repeatedly and fully mixed for many times.
The uniformity inspection method in the step (3) comprises the following steps: randomly extracting 20 bottles of samples, detecting, sending to a laboratory for detecting uniformity, measuring for three times in each bottle, counting 20 groups of analysis data of the detection result by adopting an variance analysis method, comprehensively analyzing the uniformity of the standard sample according to the statistic result of the variance analysis and the standard deviation value of original uniformity detection data, and evaluating the uniformity.
The stability testing method in the step (3) comprises the following steps: and (3) respectively carrying out stability test on the samples 24 months after subpackaging, wherein the conditions are in accordance with the general principle and statistical method for standard sample valuing of the standard sample work guide (3) of GB/T15000.3-2008:
in the formula xCRMRepresents a characteristic value, x, of a certified standard substancemeasFor measured observations uCRMDenotes the uncertainty, u, of the certified standardmeasRepresenting the uncertainty of the measurement, k is the inclusion factor, k is 2 at a confidence level of 95%, demonstrating that the sample is stable over 24 months.
The research of the method in the step (3) is as follows: for main element CaO, MgO and SiO2、P2O5、TiO2、MnO、Al2O3TFe and ZnO adopt a classical chemical wet analysis method, including a titration method, a gravimetric method and an inductively coupled plasma atomic emission spectrometry analysis, and the fixed values are reliable and accurate;
the method for determining the AS, Sb and Pb values adopts an inductively coupled plasma mass spectrometer ICP-MS for detection, and comprises the following specific steps: weighing iron-containing dust mud samples In a polytetrafluoroethylene beaker, decomposing the iron-containing dust mud samples by using hydrochloric acid, nitric acid and hydrofluoric acid, exhausting fluorine and silicon by using perchloric acid through smoke emission, supplementing the nitric acid, heating and dissolving soluble salts, carrying out volume determination by using a volumetric flask, carrying out a blank experiment along with the experiment, selecting Ge, In and Bi as internal standard elements by using an inductively coupled plasma mass spectrometer under the selected optimal instrument condition, correcting signal drift of the instrument and eliminating the influence of a matrix effect, and calculating the content of each element by measuring the strength of each element according to the selected proton number of arsenic, lead and antimony.
The value setting mode in the step (3) is as follows: 8 laboratories are adopted to carry out fixed value analysis on 8 samples, and more than two accurate and reliable analysis methods are selected for carrying out cooperative fixed value analysis after each laboratory passes national measurement and certification. Providing four data for each laboratory, checking whether abnormal values exist in the group according to the tolerance of the range difference of the method, and then calculating the average value of the data; the mean value of the mean values of the units is taken as the recommended standard value.
Checking whether the results of each group have equal precision by using a Cocklon criterion, checking whether abnormal values exist in each average value by using a Grabbs method, checking normality of all constant value analysis data and the average value of each group number by using a Charperot-Wilk method, regarding that the statistic is between a significance level α -0.01 and a significance level α -0.05, considering that the statistic is normal and reserved, and rejecting abnormal value data except the following cases:
1) normality abnormality, wherein the median value and the average value are basically consistent, the standard deviation can still meet the requirement, and the standard value is still calculated by the average value and reserved;
2) the Grabbs test is an abnormal value, and the standard deviation of the Grabbs test can meet the requirement of the precision of the test and analysis method and is reserved;
3) the Cocker test is an abnormal value, but the intra-group extreme difference is smaller than the allowable difference of the method, and the method is reserved;
after the abnormal values are processed, calculating the arithmetic mean value and the standard deviation of each group of data; the mean of the arithmetic mean of the 8 laboratory data is taken as the standard value and the standard deviation of the single determination counted by the quantitative analysis of the individual components is taken as the standard deviation.
The calculation method for uncertainty evaluation in the step (3) comprises the following steps: the uncertainty comprises uncertainty generated by fixed value statistics and uncertainty generated by bottle-to-bottle heterogeneity and instability of characteristic quantity values counted by uniformity tests, and the uncertainty calculation formula is as follows:
the extended uncertainty is: u-k UCRM(when the confidence probability is 95%, k is 2);
1)ucharto determine the degree of uncertainty caused:
2)ubbuncertainty introduced by inter-vial heterogeneity counted for homogeneity test:
3) The uncertainty counted by the stability test is:
us＝s(β1)·X
in the formula: u. ofsUncertainty introduced for stability s (β)1) Is β1(i.e., slope) standard deviation; x is a given shelf life, X ═ 24;
4) the synthesis uncertainty is:
the extended uncertainty is: u-k UCRM(when the confidence probability is 95%, k is 2);
in the formula, S is the standard deviation of single measurement of fixed value statistics, and p is the number of data groups; MS (Mass Spectrometry)amongIs the repeatability variance measured in the uniformity study between bottles; MS (Mass Spectrometry)withinIs the repeatability variance measured in the in-bottle homogeneity study; v is fromDegree, equal to m (n-1); sbbStandard deviation of the inter-vial non-uniformity was counted for uniformity test.
The invention has the beneficial effects that: the iron-containing sediment standard sample disclosed by the invention has the advantages that the main technical indexes of the iron-containing sediment are fixed, the element content gradient is wide, the iron-containing sediment standard sample can meet the requirements of various product analyses on the standard sample by solid wastes such As sintered iron-containing sediment, steelmaking iron-containing sediment and pellet iron-containing sediment, the harmful elements to be detected in environmental evaluations such As As, Pb, Sb and the like in the iron-containing sediment are accurately fixed, the requirements of customers are better met, the trace elements such As As, Sb, Pb and the like are detected by adopting an inductive plasma mass spectrometer (ICP-MS), and the detection method has high precision and accuracy.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the iron-containing sediment standard sample comprises the following steps:
(1) designing the composition and content of the standard sample of iron-containing sludge for chemical analysis, see table 1;
TABLE 1 composition and content of iron-containing sludge Standard sample
| Composition (I) | Content (wt%) |
| CaO | 0.3-55.0 |
| MgO | 0.1-36.0 |
| SiO2 | 1.8-8.0 |
| P2O5 | 0.05-1.0 |
| TiO2 | 0.02-0.5 |
| MnO | 0.05-8.0 |
| Al2O3 | 0.1-6.0 |
| TFe | 1.7-65.0 |
| ZnO | 0.03-16.0 |
| S | 0.2-1.6 |
| Pb | 0.0001-0.004 |
| As | 0-0.0006 |
| Sb | 0.0001-0.003 |
The invention provides 8 standard sample examples 1-8 of iron-containing sludge, see table 2:
table 2 examples 1-8 standard values and uncertainties for iron-containing sludge standards
Grinding the iron-containing sediment sample in accordance with the weight percentage in a ball mill, and sieving;
(2) uniformly mixing the sample sieved in the step (1) in a sample mixing machine;
(3) and (3) putting the uniformly mixed sample obtained in the step (2) into a glass bottle, sealing, and obtaining the iron-containing sediment standard sample after uniformity and stability inspection, method research, fixed value and uncertainty evaluation.
And (2) sieving the mixture with a sieve of 160-180 meshes.
In the step (2), the mixing speed of the sample mixing machine is 16-20 r/min.
The uniformity inspection method in the step (3) comprises the following steps: randomly extracting 20 bottles of samples, detecting, sending to a laboratory for detecting uniformity, measuring for three times in each bottle, counting 20 groups of analysis data of the detection result by adopting an variance analysis method, comprehensively analyzing the uniformity of the standard sample according to the statistic result of the variance analysis and the standard deviation value of original uniformity detection data, and evaluating the uniformity.
Numbering in sequence, and analyzing CaO, MgO and SiO with high precision2、P2O5、TiO2、MnO、Al2O3TFe, ZnO, S, As, Sb and Pb are analyzed under the same analysis conditions, uniformity test is carried out, measurement is carried out three times in each bottle, the test sequence is a first time sequence and a second time reverse sequence, measurement is carried out for the third time according to 1, 3, 5, …, 19, 2, 4, 6, … and 20, and the uniformity test analysis method and the sample weighing amount are shown in a table 3;
TABLE 3 homogeneity test analysis method and sample weighing
Uniformity test analysis data statistics:
according to the statistical result and the original data, the uniformity of the standard sample is good, and the requirement of the uniformity of the standard sample is met.
The stability testing method in the step (3) comprises the following steps:
and (3) respectively carrying out stability test on the samples 24 months after subpackaging, wherein the conditions are in accordance with the general principle and statistical method for standard sample valuing of the standard sample work guide (3) of GB/T15000.3-2008:
in the formula xCRMRepresents a characteristic value, x, of a certified standard substancemeasFor measured observations uCRMDenotes the uncertainty, u, of the certified standardmeasRepresenting the uncertainty of the measurement, k is the inclusion factor, k is 2 at a confidence level of 95%, demonstrating that the sample is stable over 24 months.
The research of the method in the step (3) is as follows: for main element CaO, MgO and SiO2、P2O5、TiO2、MnO、Al2O3TFe and ZnO adopt a classical chemical wet analysis method, including a titration method, a gravimetric method and an inductively coupled plasma atomic emission spectrometry analysis, and the fixed values are reliable and accurate;
the AS, Sb and Pb quantitative method in the step (3) can also adopt an inductively coupled plasma mass spectrometer ICP-MS for detection, and the specific steps are AS follows: weighing 0.2g of iron-containing dust mud sample In a polytetrafluoroethylene beaker, decomposing with 15mL of hydrochloric acid, 10mL of nitric acid and 1mL of hydrofluoric acid, smoking 2.5mL of perchloric acid to drive off fluorine and silicon, supplementing 5mL of nitric acid, heating to dissolve soluble salts, fixing the volume In a volumetric flask by 100mL, carrying out blank experiments along with the experiments, selecting Ge, In and Bi as internal standard elements by using an inductively coupled plasma mass spectrometer under the selected optimal instrument condition to correct the signal drift of the instrument and eliminate the influence of matrix effect, and calculating the content of each element by measuring the intensity of each element according to the proton number of the selected arsenic, lead and antimony and a working curve.
Through the comparative analysis among the detection result data of the standard substance, the test value of the national standard method and the test value of the experimental method, the difference between the test result and the standard value is within the standard tolerance range, the accuracy of the comparative result is high, the stability of the test result is good, and the analysis accuracy of the method meets the standard requirement.
The experimental results show that: in the test, samples are decomposed by nitric acid, hydrochloric acid, hydrofluoric acid and perchloric acid, and the elements of arsenic, antimony and lead in the iron-containing dust mud are determined by an ICP-MS method.
The value setting method in the step (3) comprises the following steps: setting values of 8 samples by 8 laboratories, measuring for 4 times in each bottle, taking the arithmetic mean value to represent one datum, providing four data for each laboratory, checking whether an abnormal value exists in the group by extreme difference according to the method allowance, and then calculating the mean value of the datum;
checking whether the results of each group have equal precision by using a Cocklon criterion, checking whether abnormal values exist in each average value by using a Grabbs method, checking normality of all constant value analysis data and the average value of each group number by using a Charperot-Wilk method, regarding that the statistic is between a significance level α -0.01 and a significance level α -0.05, considering that the statistic is normal and reserved, and rejecting abnormal value data except the following cases:
1) normality abnormality, wherein the median value and the average value are basically consistent, the standard deviation can still meet the requirement, and the standard value is still calculated by the average value and reserved;
2) the Grabbs test is an abnormal value, and the standard deviation of the Grabbs test can meet the requirement of the precision of the test and analysis method and is reserved;
3) the Cocker test is an abnormal value, but the intra-group extreme difference is smaller than the allowable difference of the method, and the method is reserved;
after the abnormal values are processed, calculating the arithmetic mean value and the standard deviation of each group of data; the mean of the arithmetic mean of the 8 laboratory data is taken as the standard value and the standard deviation of the single determination counted by the quantitative analysis of the individual components is taken as the standard deviation.
The calculation method for uncertainty evaluation in the step (3) comprises the following steps: the uncertainty comprises uncertainty generated by fixed value statistics and uncertainty generated by bottle-to-bottle heterogeneity and instability of characteristic quantity values counted by uniformity tests, and the uncertainty calculation formula is as follows:
the extended uncertainty is: u-k UCRM(when the confidence probability is 95%, k is 2);
1)ucharto determine the degree of uncertainty caused:
2)ubbuncertainty introduced by inter-vial heterogeneity counted for homogeneity test:
3) The uncertainty counted by the stability test is:
us＝s(β1)·X
in the formula: u. ofsUncertainty introduced for stability s (β)1) Is β1(i.e., slope) standard deviation; x is a given shelf life, X ═ 12;
4) the synthesis uncertainty is:
the extended uncertainty is: u-k UCRM(when the confidence probability is 95%, k is 2);
in the formula, S is the standard deviation of single measurement of fixed value statistics, and p is the number of data groups; MS (Mass Spectrometry)amongIs the repeatability variance measured in the uniformity study between bottles; MS (Mass Spectrometry)withinIs the repeatability variance measured in the in-bottle homogeneity study; v is a degree of freedom, equal to m (n-1); sbbStandard deviation of the inter-vial non-uniformity was counted for uniformity test.
The standard sample containing iron sludge is tried by a plurality of units such as sunshine steel, ledeburite and the like, the standard sample is consistently considered to have good uniformity, accurate quantity value and convenient use, the problem that the enterprise can determine the components of the iron sludge without standards is solved, a physical standard is particularly provided for environment detection and pollution element detection, and the determination accuracy is improved.
TABLE 4 use report of sunshine iron and steel group
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A standard sample of solid waste iron-containing sludge is characterized by comprising 8 powdery solid substances and comprising the following components in percentage by weight: CaO 0.3-55.0%, MgO 0.1-36%, SiO21.8-8.0％、P2O50.05-1.0％、TiO20.02-0.5％、MnO 0.05-8.0％、Al2O30.1-6.0％、TFe 1.5-65.0％、ZnO 0.03-16.0％、S0.2-2.0％、Pb 0.0001-0.003％、As 0-0.0006％、Sb 0.0001-0.004％。
2. The preparation method of the standard sample of the solid waste iron-containing sediment is characterized by comprising the following steps of:
(1) the standard sample of the iron-containing sludge as claimed in claim 1 is obtained from solid waste from steelmaking enterprises such as economic steel, mild steel and green steel;
(2) the standard sample of iron-containing sludge as claimed in claim 1, grinding in a ball mill, and sieving;
(3) uniformly mixing the sample sieved in the step (2) in a sample mixing machine;
(4) and (4) putting the uniformly mixed sample obtained in the step (3) into a glass bottle, sealing, and obtaining the iron-containing sediment standard sample after uniformity, stability inspection, fixed value and uncertainty evaluation.
3. The preparation method of the iron-containing sediment standard sample according to claim 2, wherein the step (1) is carried out by sieving with a sieve of 160-180 meshes.
4. The preparation method of the iron-containing sediment standard sample according to claim 2, wherein the mixing speed of the sample mixer in the step (2) is 16-20 r/min.
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