CN108469423A - The detection method of micro sulfur content in a kind of cobalt carbonate, cobalt oxalate - Google Patents
The detection method of micro sulfur content in a kind of cobalt carbonate, cobalt oxalate Download PDFInfo
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- CN108469423A CN108469423A CN201810199588.6A CN201810199588A CN108469423A CN 108469423 A CN108469423 A CN 108469423A CN 201810199588 A CN201810199588 A CN 201810199588A CN 108469423 A CN108469423 A CN 108469423A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 29
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000001514 detection method Methods 0.000 title claims abstract description 29
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 title claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000005864 Sulphur Substances 0.000 claims abstract description 54
- 239000010941 cobalt Substances 0.000 claims abstract description 44
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 239000003708 ampul Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000000717 retained effect Effects 0.000 abstract description 6
- 238000011946 reduction process Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000012937 correction Methods 0.000 description 7
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910020343 SiS2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
- G01N2021/3572—Preparation of samples, e.g. salt matrices
Abstract
The invention discloses a kind of detection methods of micro sulfur content in cobalt carbonate, cobalt oxalate comprising following steps：(1) cobalt raw material will be contained and cobalt powder is made；(2) cobalt powder and fluxing agent are burnt, generates sulfur dioxide and carbon dioxide；The concentration that sulfur dioxide is measured by infrared absorption method, obtains the mass percent of sulphur in cobalt powder, carbon, to obtain the mass percent containing element sulphur in cobalt raw material.It is cobalt-containing material to be reduced into cobalt powder in reduction furnace first, then detect the content of element sulphur in this method, it in reduction process, is retained in cobalt powder containing the element sulphur in cobalt raw material, does not have consumption, since element sulphur to be retained in cobalt powder to the maximum extent, the detection precision of element sulphur is improved.
Description
Technical field
Present invention relates particularly to a kind of detection methods of micro sulfur content in cobalt carbonate, cobalt oxalate.
Background technology
In Powder Metallurgy Industry, sulfur content has the quality of hard alloy more important influence：In sintering process,
Silicon and sulphur are with SiS2Compound evaporation is lost while causing silicon with sulphur, or is formed CaS with calcium and be retained in the viscous of hard alloy
It ties in phase, to generate different influences to the quality of hard alloy.
Sulphur in hard alloy is mainly derived from raw material：Such as tungsten carbide, cobalt powder or carbon black.To ensure the matter of hard alloy
Amount, needs to accurately control the sulfur content in hardmetall binder cobalt powder.The preparation of cobalt powder at present is mainly with cobalt carbonate or grass
Sour cobalt is that raw material is prepared through hydrogen reducing, and chemical equation is：
2CoC2O4·2H2O+3H2=2Co+3CO+CO2+7H2O；
CoCO3+H2=Co+H2O+CO2。
In reduction process, the element sulphur in cobalt carbonate, cobalt oxalate is retained in cobalt powder, therefore the sulfur content in cobalt powder takes
The certainly sulfur content in cobalt carbonate, cobalt oxalate, in order to accurately control the sulfur content in cobalt powder, it is necessary to its oxide spinel cobalt, grass
The sulfur content of sour cobalt carries out analysis detection.
According to GB/T26285-2010《Super-fine cobalt powder》Requirement in standard：The content requirement of element sulphur in cobalt powder is：
1, the trade mark is S element≤0.005% in FCo999 cobalt powders；2, the trade mark is S element≤0.010% in FCo997 cobalt powders；3、
The trade mark is S element≤0.02% in FCo995 cobalt powders；Above-mentioned content is mass percent.
In cobalt carbonate and cobalt oxalate element sulphur at two, when sulfate radical before synthesis contained by cobalt chloride solution from
Son, second is that element sulphur contained in the preceding ammonium bicarbonate soln of synthesis and ammonium oxalate solution, since the burning point of sulphur is 246~266 DEG C,
When material being made to be calcined in Muffle furnace, sub-fraction elemental sulfur can be lost.
Currently, what is usually constrained in cobalt carbonate, cobalt oxalate technical target of the product is the content of sulfate radical, generally use chemistry
Cobalt carbonate, cobalt oxalate as gravimetric method, spectrocolorimetry are detected, or are first converted to cobalt oxide and so use chemistry afterwards again by method
Method-iodimetric titration surveys sulfate radical content, or directly surveys sulfur content with infrared absorption method, since above-mentioned detection method is required to use
Muffle furnace is calcined, and is aoxidized and be usually in opening-wide state in atmosphere again, is caused the loss of part element sulphur, is caused to detect
Data have certain deviation, to influence the accuracy of detection of hard alloy sulfur content in high-purity cobalt powder product.
Invention content
To solve the above problems, the present invention proposes a kind of detection method, it can more accurately using the detection method
Detect that the micro element sulphur in cobalt carbonate or cobalt oxalate, specific technical solution are as follows：
A kind of detection method of micro sulfur content in cobalt carbonate, cobalt oxalate comprising following steps：
(1) cobalt raw material will be contained and carries out reduction reaction in reducibility gas, cobalt powder is made；
(2) cobalt powder and fluxing agent being placed in closed coreless induction furnace and is burnt, element sulphur is oxidized to sulfur dioxide,
Carbon is oxidized to carbon dioxide；
The concentration that sulfur dioxide is measured by infrared absorption method, obtains the quality percentage of element sulphur and carbon in cobalt powder
Number, the mass percent containing element sulphur in cobalt raw material is calculated by public formula (I)；
In public formula (I)：
ω1% is the mass percent containing element sulphur in cobalt raw material；
ω2% is the mass percent of element sulphur in cobalt powder；
m1For the quality of cobalt powder；
m2For the quality containing cobalt raw material；
The cobalt raw material that contains is cobalt carbonate or cobalt oxalate.
It is cobalt-containing material to be reduced into cobalt powder in reduction furnace first, then detect the content of element sulphur in this method, also
It during original, is retained in cobalt powder containing the element sulphur in cobalt raw material, does not have consumption, compared with prior art, this method avoids
It is oxidized to sulfur dioxide gas at high temperature containing sulphur simple substance or compound micro in cobalt raw material and is lost in, in high temperature reduction
Reaction condition under, sulphur or sulfide are thoroughly changed into sulphur simple substance, are stable in the presence of in cobalt powder, then in closed coreless induction furnace
Logical oxygen combustion generates sulfur dioxide and is precipitated, by the method for infrared ray absorbing, measures the concentration of sulfur dioxide, calculate sulphur
Constituent content.Since element sulphur to be retained in cobalt powder to the maximum extent, the detection precision of element sulphur is improved.
Further, in step (1), the reduction reaction containing cobalt raw material is carried out using sliding rail tube furnace, specially：Containing cobalt raw material
It is placed in the quartz ampoule of sliding rail tube furnace, protective gas is first passed through in quartz ampoule, empty the air in quartz ampoule, then be passed through
The reducibility gas, the protective gas use nitrogen, and originality gas uses hydrogen, using electrical heating, at 300-600 DEG C
At a temperature of, make to carry out reduction reaction containing cobalt raw material；The purity of the hydrogen is >=99.5%, and the purity of nitrogen is >=99%, hydrogen
The purity of gas and nitrogen is volume ratio.Sliding rail tube furnace preferably uses the sliding rail tube furnace of model MXGH.MXGH sliding rail tubes
The quartz ampoule of formula stove has closed reaction compartment, can fully ensure that element sulphur can retain in cobalt powder to the maximum extent,
It will not cause damages because of volatilization.
Further, in step (1), the in-furnace temperature of sliding rail tube furnace includes the first heating section, the first constant temperature zone, the successively
Two warming-up sections, the second constant temperature zone and temperature descending section；In the first heating section, in-furnace temperature rises to 300 ± 10 DEG C by room temperature；Second
In warming-up section, in-furnace temperature rises to 600 ± 10 DEG C；In temperature descending section, in-furnace temperature is down to room temperature.
Within the scope of above-mentioned parameter, experiment can be effectively prevented from and material spray phenomenon occur in the process, and influence test data.
Above-mentioned parameter can ensure 2 crystallizations water in free moisture and cobalt oxalate in efficient removal cobalt carbonate and cobalt oxalate, together
When ensure that material cracks thoroughly in protective gas nitrogen, form sub- cobalt compound and be reduced into high-purity cobalt powder.
Preferably, the heating rate of the first heating section is 4-5 DEG C/min；The heating rate of second warming-up section is 4.5-5.5
DEG C/min.
The rate of temperature fall of temperature descending section is 2-3 DEG C/min.
The time of first constant temperature zone is 50-70 minutes；The time of second constant temperature zone is 90-110 minutes.
Under the control of above-mentioned response parameter, it is ensured that the reduction reaction containing cobalt raw material is smoothed out.In first segment perseverance
In the warm period, it can remove completely containing the various forms of moisture in cobalt raw material, and successfully proceed by cracking reaction,
In second segment constant temperature time section, it is ensured that be properly completed reduction reaction after completing to crack containing cobalt raw material.
Preferably, the flow velocity that hydrogen is passed through is 1-1.5L/ minutes, and the flow velocity that nitrogen is passed through is 2-3L/ minutes.
Within the scope of above-mentioned parameter, gas consumption can be not only saved, experimentation cost is saved, it may also be ensured that restoring
The consistent high-purity cobalt powder of Cheng Shengcheng forms.
Preferably, the pressure in quartz ampoule is controlled in 0.015-0.03MPa.
In above-mentioned pressure limit, it is ensured that dehydration, cracking and reduction reaction containing cobalt raw material are smoothed out.
Description of the drawings
Fig. 1 is temperature profile when to being restored containing cobalt raw material in the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 1 in, by linearization process and standard sample correction after, integral area and sample
The relationship of middle sulfur content.
Specific implementation mode
Embodiment 1：
To being detected containing the micro sulfur content in cobalt raw material, steps are as follows：
(1) preparation of cobalt powder：
(1.1) cobalt powder is prepared using cobalt carbonate：
Appropriate cobalt carbonate is weighed, is put into the quartz ampoule of MXGH sliding rail tube furnaces, stone is put into containing cobalt raw material with crucible tongs handle
The middle position of English pipe, installs flange；
Nitrogen flow is adjusted first, and the nitrogen that purity is >=99% is passed into the flow velocity of 2-3L/min in quartz ampoule,
Until nitrogen charge is up to 99.9% or more in pipe；
Hydrogen flowing quantity is adjusted again, and the hydrogen that purity is >=99.5% is passed into the flow velocity of 2-3L/min in quartz ampoule；
Air bleeding valve is adjusted, the pressure in quartz ampoule is controlled in 0.015-0.03MPa；
Temperature curve as shown in Figure 1 adjusts in-furnace temperature, and cobalt powder is made in cobalt carbonate.
In-furnace temperature includes the first heating section S10, the first constant temperature zone S20, the second warming-up section S30, the second constant temperature zone successively
Label S100 in S40 and temperature descending section S50, Fig. 1 indicates whole temperature curve.
In the first heating section S10, in-furnace temperature rises to 300 DEG C by room temperature, and temperature fluctuation controls within the scope of ± 10 DEG C,
Heating rate is 4-5 DEG C/min.In the second warming-up section S30, in-furnace temperature rises to 600 DEG C, and temperature fluctuation is controlled at ± 10 DEG C
In range, heating rate is 4.5-5.5 DEG C/min.In temperature descending section S50, in-furnace temperature is down to room temperature, and rate of temperature fall is 2-3 DEG C/
Minute.The constant temperature time of first constant temperature zone S20 is 60 minutes, and the constant temperature time of the second constant temperature zone S40 is 120 minutes.
(1.2) cobalt powder is prepared using cobalt oxalate：
Cobalt carbonate prepares the preparation process of cobalt powder in the same step of preparation method (1.1).
(2) the carbon sulphur instrument of model CS2008 is used to carry out the content of the element sulphur in the cobalt powder obtained by step (1)
Detection, the carbon sulphur instrument have closed coreless induction furnace for burning to cobalt powder and fluxing agent, and are surveyed using infrared absorption method
Determine the concentration of sulfur dioxide；It is as follows to the specific detecting step of element sulphur in cobalt powder using carbon sulphur instrument：
(2.1) start carbon sulphur instrument, and preheated；
(2.2) parameter setting：9.99 volts of the switching voltage of carbon；9.99 volts of the switching voltage of sulphur；Heating time：20-25s；
Smooth points：45s；Sampling time：40-45s；Washing time：15-25s；Power atmospheric pressure nitrogen：0.20-0.30mpa；Analysis
Gas oxygen pressure：0.15-0.25mpa；Select low-sulfur channel；
(2.3) baseline is adjusted, the special tungsten fluxing agent of analysis of carbon and sulfur of 1.5g, carbon sulphur content are added in pretreated crucible
The parameter for analysing special tungsten fluxing agent is：20-40 mesh, L-type, blank value sulphur, carbon are respectively less than 3ppm.
Crucible added with the special tungsten fluxing agent of analysis of carbon and sulfur is placed into progress stability of instrument measurement on crucible tray, it is empty
It is white to measure 3 times, the measurement background value that crucible and fluxing agent are brought is eliminated, that is, eliminates blank value；
(2.4) standard specimen measures：
The detection of sulphur in (2.4.1) standard specimen：
Low-sulfur standard specimen specifically uses the GBW01148a pure iron low-sulfur marks that Iron and Steel Research Geueral Inst analysis testing research is produced
Sample assert sulfur content 0.0016%；Low-sulfur standard specimen is weighed, pure iron fluxing agent (L-type, purity ＞ 99.9%, granularity 20-40 is added
Mesh, blank value carbon, sulphur content be less than 5ppm) 0.25g, tungsten particle fluxing agent (L-type, purity ＞ 99.9%, the granularity 20- of 1.5g
40 mesh, blank value carbon, sulphur content be less than 3ppm), uniform fold surface measures successively, pending data come out after, carry out three
Point calibration, specific detection data such as table 1：
Table 1
| Standard specimen serial number | Sulfur content % | Weigh quality/g of low-sulfur standard specimen | The integral area of sulphur |
| Standard specimen 1# | 0.00158 | 0.2041 | 0.1 |
| Standard specimen 2# | 0.00159 | 0.3022 | 0.2 |
| Standard specimen 3# | 0.00159 | 0.4064 | 0.3 |
| After correction | 0.00160 | 0.3053 | 0.2 |
The output signal obtained due to the infrared detector of carbon sulphur instrument is for the concentration of carbon dioxide and sulfur dioxide, right and wrong
Linear, when analysis, needs to carry out Linearized correction, i.e., to the advanced row Linearized correction of each obtained output signal, integral
Summation, obtains integral area corresponding with carbon, sulphur in sample, participates in calculating the sulfur content and carbon content in sample, in table 1
Data after correction are the obtained data after linearization process.After linearization process and standard sample correction,
The relationship of sulfur content is as shown in Fig. 2, in Fig. 2 in integral area and sample, and abscissa is integral area (VS), and ordinate is
The quality (mg) of contained element sulphur in sample.
The detection of carbon in (2.4.2) standard specimen：
Carbon standard specimen specifically uses the DT4 electrical pure iron carbon standard specimen of Shanghai Inst. of Materials's production (to assert carbon content
0.023%) it, weighs carbon standard specimen, pure iron fluxing agent (L-type, purity ＞ 99.9%, granularity 20-40 mesh, blank value carbon, sulphur is added
Content is less than 5ppm) 0.25g, tungsten particle fluxing agent (L-type, purity ＞ 99.9%, granularity 20-40 mesh, blank value carbon, the sulphur of 1.5g
Content be less than 3ppm), uniform fold surface measures successively, after pending data comes out, carries out three point calibrations, specific to detect
Data such as table 2：
Determination data such as table 2：
Table 2
| Standard specimen serial number | Carbon content % | Weigh quality/g of carbon standard specimen | The integral area of carbon |
| Standard specimen 4# | 0.02320 | 0.3256 | 21.8 |
| Standard specimen 5# | 0.02296 | 0.3010 | 19.9 |
| Standard specimen 6# | 0.02294 | 0.3138 | 20.7 |
| After correction | 0.02301 | 0.3153 | 21.2 |
(2.5) sample detection：8 standard specimens, each standard specimen are respectively taken from cobalt powder prepared in step (1.1) and (1.2)
Middle addition pure iron fluxing agent (L-type, purity ＞ 99.9%, granularity 20-40 mesh, blank value carbon, sulphur content be less than 5ppm)
0.25g, 1.5g tungsten particle fluxing agent (L-type, purity ＞ 99.9%, granularity 20-40 mesh, blank value carbon, sulphur content be less than
3ppm), uniform fold surface, the detecting step of the sulphur in the same step of detecting step (2.4.1), detection data such as table 3.
Table 3
In table 3, cobalt powder sample 1-8# is the cobalt powder restored using cobalt oxalate, cobalt powder sample 9-16# be using cobalt carbonate also
Former cobalt powder.
(2.6) data calculating and stability analysis：
A/ can be seen that by the above detection data：The carbon content of 16 groups of samples is below within 100PPm
0.01%, illustrate that reduction process is very thorough, meets the quality standard of Processes of Cobalt Powders For Hard Alloys.
B/ restores the relative standard deviation RSD of cobalt powder using formula (II) calculating oxalate cobalt or cobalt carbonate,
The relative average debiation RAD of cobalt powder is restored using formula (III) calculating oxalate cobalt or cobalt carbonate：
The relative standard deviation of the analysis of sulfur content data of 8 groups of cobalt oxalate reduction cobalt powder samples is RSD=0.539%；RAD
Relative average debiation is 0.323%；
The relative standard deviation of the analysis of sulfur content data of 8 groups of cobalt carbonate reduction cobalt powder samples is RSD=0.403%；RAD
Relative average debiation is 0.346%.
After restoring cobalt powder sample and the multiple Parallel testing of cobalt carbonate reduction cobalt powder sample progress to cobalt oxalate, detection
The relative standard deviation of data is respectively less than 1.0%, and relative average debiation is respectively less than 0.50%, it is seen that this method excellent stability.
C/ data accuracies are tested：
Further to verify the accuracy of detection method in the application, sample is carried out according to the above test method for surveying sulphur
Mark-on reclaims are tested, as a result such as table 4.
4 (unit of table：μg)
| Test serial number | Sample sulfur content | Sulfur content is added | Measure sulfur content | Rate of recovery % |
| 1# | 0.851 | 1.550 | 2.400 | 99.96 |
| 2# | 1.206 | 1.200 | 2.406 | 100.00 |
| 3# | 2.107 | 4.500 | 6.606 | 99.99 |
| 4# | 2.548 | 7.250 | 9.799 | 100.01 |
As shown in Table 4, the recovery of standard addition of sample is 99.96%~100.01%, illustrates the detection method in the present invention
Accuracy is reliable.
(2.3) result calculates, and detailed process is as follows：
The content of element sulphur is calculated by formula (I) in cobalt carbonate or cobalt oxalate：
In formula 1, ω1% is that the mass percent containing element sulphur in cobalt raw material is specifically in the present embodiment containing cobalt raw material
Cobalt carbonate or cobalt oxalate；
ω2% is the mass percent of element sulphur in cobalt powder；
m1For the quality of cobalt powder；
m2For the quality containing cobalt raw material.
It is calculated according to formula (I), as a result such as table 5.
Table 5
Cobalt material in table 5 is the abbreviation containing cobalt raw material, is as cobalt carbonate or cobalt oxalate.
In table 5, the corresponding cobalt material of cobalt powder sample 1-8# are cobalt oxalate；The corresponding cobalt material of cobalt powder sample 9-16# are cobalt carbonate.
Claims (8)
1. the detection method of micro sulfur content in a kind of cobalt carbonate, cobalt oxalate, which is characterized in that include the following steps：
(1) cobalt raw material will be contained and carries out reduction reaction in reducibility gas, cobalt powder is made；
(2) cobalt powder and fluxing agent are placed in closed coreless induction furnace and are burnt, element sulphur is oxidized to sulfur dioxide, carbon quilt
It is oxidized to carbon dioxide；
The concentration that sulfur dioxide is measured by infrared absorption method, obtains the mass percent of element sulphur and carbon in cobalt powder,
The mass percent containing element sulphur in cobalt raw material is calculated by public formula (I)；
In public formula (I)：
ω1% is the mass percent containing element sulphur in cobalt raw material；
ω2% is the mass percent of element sulphur in cobalt powder；
m1For the quality of cobalt powder；
m2For the quality containing cobalt raw material；
The cobalt raw material that contains is cobalt carbonate or cobalt oxalate.
2. detection method according to claim 1, which is characterized in that
In step (1), the reduction reaction containing cobalt raw material is carried out using sliding rail tube furnace, specially：It is placed on sliding rail containing cobalt raw material
In the quartz ampoule of tube furnace, it is first passed through protective gas in quartz ampoule, empties the air in quartz ampoule, then be passed through the reproducibility
Gas, the protective gas use nitrogen, and reducibility gas uses hydrogen, using electrical heating, at a temperature of 300-600 DEG C,
Make to carry out reduction reaction containing cobalt raw material；
The purity of the hydrogen is >=99.5%, and the purity of nitrogen is >=99%, and the purity of hydrogen and nitrogen is volume ratio.
3. detection method according to claim 2, which is characterized in that
In step (1), the in-furnace temperature of sliding rail tube furnace includes the first heating section, the first constant temperature zone, the second warming-up section, the successively
Two constant temperature zones and temperature descending section；
In the first heating section, in-furnace temperature rises to 300 ± 10 DEG C by room temperature；
In the second warming-up section, in-furnace temperature rises to 600 ± 10 DEG C；
In temperature descending section, in-furnace temperature is down to room temperature.
4. detection method according to claim 3, which is characterized in that
The heating rate of the first heating section is 4-5 DEG C/min；
The heating rate of second warming-up section is 4.5-5.5 DEG C/min.
5. detection method according to claim 3, which is characterized in that
The rate of temperature fall of temperature descending section is 2-3 DEG C/min.
6. detection method according to claim 3, which is characterized in that
The time of first constant temperature zone is 50-70 minutes；
The time of second constant temperature zone is 90-110 minutes.
7. detection method according to claim 2, which is characterized in that the flow velocity that hydrogen is passed through is 1-1.5L/ minutes, nitrogen
The flow velocity being passed through is 2-3L/ minutes.
8. detection method according to claim 2, which is characterized in that the pressure in quartz ampoule is controlled in 0.015-
0.03MPa。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817517A (en) * | 2004-12-06 | 2006-08-16 | 深圳市格林美高新技术有限公司 | Production and producing apparatus for super fine cobalt powder by circulating technology |
| CN101745644A (en) * | 2010-03-09 | 2010-06-23 | 南京寒锐钴业有限公司 | Method for preparing cobalt powder |
| CN106346021A (en) * | 2016-09-27 | 2017-01-25 | 南京寒锐钴业股份有限公司 | Method for preparing cobalt powder through high-pressure hydrogen reduction |
| CN107570723A (en) * | 2017-08-10 | 2018-01-12 | 湖南工业大学 | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof |
-
2018
- 2018-03-12 CN CN201810199588.6A patent/CN108469423A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817517A (en) * | 2004-12-06 | 2006-08-16 | 深圳市格林美高新技术有限公司 | Production and producing apparatus for super fine cobalt powder by circulating technology |
| CN101745644A (en) * | 2010-03-09 | 2010-06-23 | 南京寒锐钴业有限公司 | Method for preparing cobalt powder |
| CN106346021A (en) * | 2016-09-27 | 2017-01-25 | 南京寒锐钴业股份有限公司 | Method for preparing cobalt powder through high-pressure hydrogen reduction |
| CN107570723A (en) * | 2017-08-10 | 2018-01-12 | 湖南工业大学 | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof |
Non-Patent Citations (1)
| Title |
|---|
| 国家发展和改革委员会: "《中华人民共和国有色金属工业行业标准 YS/T 673-2008 还原钴粉》", 30 September 2008 * |
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