CN100456028C - Preparation method of cobalt oxide internal standard reagent used for measuring total iron content of iron ore - Google Patents

Preparation method of cobalt oxide internal standard reagent used for measuring total iron content of iron ore Download PDF

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Publication number
CN100456028C
CN100456028C CNB2003101089758A CN200310108975A CN100456028C CN 100456028 C CN100456028 C CN 100456028C CN B2003101089758 A CNB2003101089758 A CN B2003101089758A CN 200310108975 A CN200310108975 A CN 200310108975A CN 100456028 C CN100456028 C CN 100456028C
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cobalt oxide
iron content
iron ore
total iron
reagent
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CN1621820A (en
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黄港明
董凌鸣
王伟
张晓明
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The present invention relates to a preparing method of a cobalt oxide internal standard reagent used for measuring the total iron content of an iron ore, which comprises the following procedures: step A, a fluxing agent and cobalt oxide are used for being burnt for a plurality of hours at a first temperature; step B, the burnt cobalt oxide and the burnt fluxing agent are pulverized into 100 meshes; step C, the pulverized cobalt oxide and the pulverized fluxing agent are uniformly mixed for 20 to 30 minutes according to a certain proportion; step D, the uniform mixture is placed into a platinum crucible to be molten for 10 to 30 minutes at the temperature from 800 to 1200 DEG C; step E, the molten material is taken out to be pulverized and sieved by a 100-mesh sieve, and then the molten material is uniformly mixed for 30 to 60 minutes to obtain the cobalt oxide internal standard reagent used for measuring the total iron content of an iron ore. The cobalt oxide internal standard reagent manufactured by the method of the present invention can greatly increase the accuracy of using the X fluorescence method for analyzing the data of the total iron content, rapidly analyze the total iron content in the iron ores, and satisfy the requirements on manufacturing technology.

Description

Measure the interior manufacture method of marking reagent of cobalt oxide that the iron ore total iron content is used
Technical field
The present invention relates to the manufacture method of mark reagent in a kind of cobalt oxide, specifically, relate to a kind of interior manufacture method of marking reagent of cobalt oxide that the iron ore total iron content is used of measuring.
Background technology
Iron ore is the primary raw material of ironmaking, and total iron is the principal ingredient of iron ore, the height of its content not only directly influences the proportion scheme of sintering, and influences the procurement price of iron ore, and therefore the measurement to total iron content in the iron ore has crucial realistic meaning.The mensuration of total iron content adopts the wet chemical analysis mostly in the prior art, and it is loaded down with trivial details to handle sample, and analytical cycle is long, also can produce pollutant.It is to adopt the total iron content in the mark X fluorescence spectrometry iron ore in the cobalt that some bibliographical informations are also arranged, because production technology causes the content of commercial cobaltic oxide in every batch of product that certain difference is arranged, simultaneously loss amount is also different during heating and melting, the data precision influence that total iron content is analyzed is bigger, thereby is difficult to satisfy actual needs.But it is, also more and more higher to the requirement of the instrumental analysis of total iron content in the iron ore along with the development of iron-smelting process, correlation technique and the market demand.
The assay method of iron ore total iron content adopts the hydrochloric acid decomposition samples in the wet chemical analytical approach, after the ferric iron in the solution reduces with stannous chloride or sulfuretted hydrogen, with the ferrous calculating total iron content of potassium dichromate oxidation reductometry.(it tests indoor standard deviation: 0.0004X+0.0619 though this method data precision is higher, as total iron content in certain iron ore standard specimen is 61.97%, then its indoor standard deviation is 0.086), but owing to comprise sample decomposition, filtration, washing, ferric iron reduction, titration and blank test etc., cause complex operation step, be difficult for grasping, cycle while is long, and can contain Cr by the generation pollutant in operating process 6+Waste water.
Total iron content mainly contains and adopts fusion method not add direct analyzing total iron content of internal standard element and interpolation internal standard element employing internal standard method analyzing total iron content in the X fluorescence spectrum method for measuring iron ore.For the method for not adding the direct analyzing total iron content of internal standard element, owing to not only be subjected to the granularity effect influence different with crystalline state, also be subjected to the influence of absorption-enhancement effect between each element simultaneously, even adopt the matrix correction method, also be to be difficult to obtain desirable linear relationship, and data precision is not high, and (the laboratory internal standard deviation of stipulating in ISO9516 is: 0.0031X-0.0116, for example certain iron ore standard specimen total iron content is 61.97%, then its indoor standard deviation is 0.180%), thereby be difficult to satisfy the actual requirement of producing; Also there is bibliographical information to adopt cobalt internal standard method analyzing total iron content, can realize in theory, but cobaltic oxide and anhydrous lithium tetraborate itself very easily absorb water, sample weighting amount is few, and because the production technology of cobaltic oxide and anhydrous lithium tetraborate causes when between every batch of product certain difference and heating and melting being arranged loss amount different, the data precision influence of analyzing for total iron content is bigger.
Summary of the invention
The object of the present invention is to provide the manufacture method of mark reagent in a kind of cobalt oxide, mark reagent in the cobalt oxide by this method manufacturing, can increase substantially the precision of X fluorescence method analyzing total iron content data, and can analyze total iron content in the iron ore apace, satisfy the requirement of production technology.
For achieving the above object, mark the manufacture method of reagent in the cobalt oxide that measurement iron ore total iron content provided by the invention is used, it comprises the following step:
A. choose flux and cobalt oxide calcination some hrs under first temperature;
B. the cobalt oxide after the calcination is crushed to 100 orders with fluxing;
C. cobalt oxide after will pulverizing and flux carry out 20-30 minute mixing by a certain percentage;
D. homomixture is placed Platinum crucible at 800-1200 ℃ of following fusion 10-30 minute;
E. fused mass is taken out and pulverized 100 mesh sieves, carry out 30-60 minute mixing again, obtain measuring the interior mark of the cobalt oxide reagent that the iron ore total iron content is used.
Flux is lithium tetraborate or anhydrous lithium tetraborate;
In the steps A, first temperature is 500~600 ℃, and calcination time is approximately 4 hours;
Among the step C, cobalt oxide after the pulverizing and flux were in 1: 5~1: 10 ratio mixing;
At last, mark reagent is preferably bottled and is preserved in dry environment in the cobalt oxide that obtains.
Utilize method of the present invention, at high temperature fused state, cobalt oxide can be good at being dissolved in the flux, before fusion He after the fusion cobalt oxide and flux is carried out hybrid processing simultaneously, has so just guaranteed the uniformity of potpourri.Utilize the present invention to make the interior mark of the cobalt oxide reagent of production, can increase substantially the precision of X fluorescence method analyzing total iron content data, and can analyze total iron content in the iron ore apace, satisfy the requirement of production technology.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
Following according to Fig. 1, a better embodiment of the present invention is described.
As shown in Figure 1, be a kind of schematic flow sheet of measuring the manufacture method of mark reagent in the cobalt oxide that the iron ore total iron content uses provided by the invention.It comprises the following step: at first, choose flux lithium tetraborate or anhydrous lithium tetraborate and cobalt oxide 4 hours (step 11) of calcination under 500~600 ℃ of temperature environments; Next, the cobalt oxide after the calcination and flux lithium tetraborate or anhydrous lithium tetraborate are crushed to 100 order (step 12); Then, cobalt oxide and flux after pulverizing are carried out 20-30 minute mixing (step 13) in 1: 5~1: 10 ratio; Again homomixture is placed Platinum crucible 800-1200 ℃ of following fusion 10-30 minute (step 14); 100 mesh sieves were pulverized in the fused mass taking-up, carried out 30-60 minute mixing again, obtained measuring the interior mark of the cobalt oxide reagent (step 15) that the iron ore total iron content is used.At last, mark reagent in the cobalt oxide that obtains is packed in the bottle, place dry environment to preserve (step 16).
At present, mark reagent in the cobalt oxide that the method according to this invention is made, the examination of factory's iron ore into, the production control of engineering sample have been effectively applied to, use discovery through experiment, it has with wet chemical analyzes close precision, it for total iron content 61.97% and 65.75% standards for iron ore sample, it is tested indoor standard deviation and all is lower than 0.1000%, while and wet chemical have carried out check analysis, can prove between two kinds of analytical approachs not have system deviation, and less with the departure degree of chemical analysis value.And in use do not produce and contain Cr 6+Pollutant and other objectionable impurities.
Below, will be by some data, illustrate by mark reagent in the cobalt oxide of the inventive method manufacturing to be applied to measure useful technique effect behind the iron ore total iron content.
Accurately take by weighing the iron ore sample of 0.8000 gram, mark reagent in the lithium tetraborate flux of 7.000 grams and the 1.0000 gram cobalt oxides and place platinum crucible, add a certain amount of K1 as remover by the inventive method manufacturing.Platinum crucible is placed in 1085-1100 ℃ the melting furnace, heated while stirring automatically 18 minutes, wherein static heating 4 minutes, stove inclined 14 minutes, spinned 12 minutes, turned round 2 minutes.After heating finishes, platinum crucible is taken out cooling, make the glass sheet sample of even matter, wherein be close to platinum and simultaneously be measurement face.
Utilize said method, choose two standards for iron ore samples of GBW7220 and GBW7218 and make 32 disk samples continuously, carry out the standard specimen checking, data are shown in following table one:
The standard specimen numbering GBW7220 GBW7218
The standard specimen value 61.97 65.75
Measured value 1 61.96 65.80
Measured value 2 61.9 65.67
Measured value 3 61.97 65.61
Measured value 4 61.93 65.84
Measured value 5 61.89 65.82
Measured value 6 61.96 65.90
Measured value 7 62.06 65.64
Measured value 8 61.98 65.88
Measured value 9 61.96 65.71
Measured value 10 61.92 65.62
Measured value 11 62.09 65.82
Measured value 12 61.89 65.69
Measured value 13 62.01 65.77
Measured value 14 61.96 65.69
Measured value 15 61.98 65.63
Measured value 16 62.11 65.78
Measured value 17 61.99 65.72
Measured value 18 62.03 65.77
Measured value 19 62.11 65.59
Measured value 20 62.08 65.70
Measured value 21 62.04 65.83
Measured value 22 61.88 65.73
Measured value 23 61.89 65.87
Measured value 24 61.95 65.78
Measured value 25 61.94 65.73
Measured value 26 61.88 65.65
Measured value 27 62.03 65.79
Measured value 28 61.90 65.90
Measured value 29 61.91 65.66
Measured value 30 61.92 65.75
Measured value 31 61.96 65.74
Measured value 32 61.90 65.62
Measure average 61.97 65.74
Standard deviation 0.071 0.089
Table one
Can obtain from last table data, mark reagent in the cobalt oxide by method manufacturing of the present invention, it is applied to measure the total iron content of iron ore, standard deviation is lower than 0.100%, well below 0.260% of 0.180% and general bibliographical information of required standard, very near utilizing wet chemical to measure the standard deviation of iron ore total iron content.And its measuring speed is 7-8 times of wet chemical, illustrate in the cobalt oxide that adopts method of the present invention to make and mark in the process of reagent total iron content in measuring iron ore, no matter on data precision, still aspect measuring speed, can be applied in the actual production.And in measuring process, can not produce poisonous and harmful substance.
Below, respectively by table two, table three, table four, table five, choose imported iron ore stone, homemade Hainan iron ore, engineering sintering deposit iron ore, engineering iron ore, mark reagent in the cobalt oxide of method manufacturing of the present invention is applied in the total iron content process in the fluorescence spectrometry iron ore, and and wet chemical contrast, carry out the resulting data of check t time, illustrate by the beneficial effect of mark reagent in the total iron content process that is applied to measure in the iron ore in the cobalt oxide of the inventive method manufacturing:
Sequence number Fluorescent value Chemical score Difference
1 58.48 58.24 0.24
2 63.26 63.45 -0.19
3 62.40 62.42 -0.02
4 63.71 63.62 0.09
5 59.38 59.40 -0.02
6 67.55 67.48 0.07
d 0.03
s 0.14
T 0.40
T. 2.57
Table two. imported iron ore stone
Sequence number Fluorescent value Chemical score Difference
1 54.48 54.35 0.13
2 53.26 53.47 -0.21
3 54.80 54.97 -0.17
4 53.67 53.69 -0.02
5 55.09 55.00 0.09
6 54.53 54.30 0.23
d 0.01
s 0.17
T 0.10
T. 2.57
Table three. homemade Hainan Island iron ore
Sequence number Fluorescent value Chemical score Difference
1 58.20 58.22 -0.02
2 58.20 58.02 0.18
3 58.20 58.24 -0.04
4 58.19 57.92 0.27
5 58.15 58.40 -0.25
6 58.30 58.24 0.06
d 0.03
s 0.18
T 0.45
T. 2.57
Table four, engineering sintering deposit
Sequence number Fluorescent value Chemical score Difference
1 51.75 51.69 0.06
2 52.07 52.08 -0.01
3 52.38 52.48 -0.10
4 50.86 50.91 -0.05
5 51.35 51.30 0.05
6 52.60 52.48 0.12
d 0.0117
s 0.0804
T 0.3556
T. 2.57
Table five. the engineering iron ore
(in the above table, d represents the mean difference of two kinds of analytical approachs from above-mentioned t inspection statistics data form; S represents the standard deviation of difference; T represents the value of t inspection statistics statistics gained; T.Expression t check degree of confidence is 95% standard value) as can be seen, mark reagent in the cobalt oxide that adopts method of the present invention to make, be applied to the X fluorescence method and measure total iron content in the iron ore, can reach and the akin precision of wet chemical.And adopt mark reagent in the cobalt oxide that method of the present invention makes, be applied to the X fluorescence method and measure total iron content in the iron ore, measuring speed is fast, can be widely used in measuring in the analysis of iron ore total iron content of multiple class.

Claims (4)

1, a kind of manufacture method of measuring mark reagent in the cobalt oxide that the iron ore total iron content uses, it comprises the following step:
A. choose flux and cobalt oxide calcination some hrs under first temperature;
B. the cobalt oxide after the calcination is crushed to 100 orders with fluxing;
C. cobalt oxide after will pulverizing and flux carry out 20-30 minute mixing in 1: 5~1: 10 ratio;
D. homomixture is placed Platinum crucible at 800-1200 ℃ of following fusion 10-30 minute;
E. fused mass is taken out and pulverized 100 mesh sieves, carry out 30-60 minute mixing again, obtain measuring the interior mark of the cobalt oxide reagent that the iron ore total iron content is used.
2, mark the manufacture method of reagent in the cobalt oxide that measurement iron ore total iron content as claimed in claim 1 is used, it is characterized in that described flux is lithium tetraborate or anhydrous lithium tetraborate.
3, mark the manufacture method of reagent in the cobalt oxide that measurement iron ore total iron content as claimed in claim 1 or 2 is used, it is characterized in that in the steps A, first temperature is 500~600 ℃, calcination time is approximately 4 hours.
4, mark the manufacture method of reagent in the cobalt oxide that measurement iron ore total iron content as claimed in claim 1 or 2 is used, it is characterized in that, also comprise step: mark reagent in the cobalt oxide that obtains is bottled in dry environment, preserve.
CNB2003101089758A 2003-11-28 2003-11-28 Preparation method of cobalt oxide internal standard reagent used for measuring total iron content of iron ore Expired - Fee Related CN100456028C (en)

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CN108982562B (en) * 2018-08-03 2021-02-19 武汉科技大学 Preparation method of cobalt internal standard XRF (X-ray fluorescence) analysis glass sheet based on release assisting agent

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN101825588A (en) * 2010-04-30 2010-09-08 衡阳华菱连轧管有限公司 Method for measuring contents of As and Sn elements in iron ore by adopting X-ray fluorescence spectrum melting method
CN101825588B (en) * 2010-04-30 2013-05-22 衡阳华菱连轧管有限公司 Method for measuring contents of As and Sn elements in iron ore by adopting X-ray fluorescence spectrum melting method
CN102539207A (en) * 2011-12-27 2012-07-04 攀钢集团攀枝花钢铁研究院有限公司 Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components
CN102539207B (en) * 2011-12-27 2013-11-06 攀钢集团攀枝花钢铁研究院有限公司 Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components

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