CN105467068A - Method for detecting copper, iron and calcium in flash converting furnace slag - Google Patents
Method for detecting copper, iron and calcium in flash converting furnace slag Download PDFInfo
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Abstract
The invention provides a method for detecting copper, iron and calcium in flash converting furnace slag. The method comprises the following steps: (A) dissolving a flash converting furnace slag test sample with acid to obtain a first solution containing copper ions, iron ions and calcium ions, performing reaction on the first solution, sodium sulfide and sodium hydroxide, and filtering to obtain precipitates and filtrate; (B) dissolving the obtained precipitates with acid to obtain a second solution containing bivalent copper ions and iron ions, masking iron with ammonium bifluoride in the second solution, detecting copper by adopting an iodometry method to obtain the copper content, releasing iron in the solution subjected to copper detection with aluminium trichloride, and detecting iron by adopting the iodometry method to obtain the iron content; (C) titrating the filtrate obtained in the step (A) with edetic acid, thus obtaining the calcium content. The procedures of the detection method provided by the invention are simple, one-step sample weighing is realized, and the contents of three key elements, copper, iron and calcium, in the flash converting furnace slag can be quickly, accurately and continuously measured.
Description
Technical field
The present invention relates to copper ashes detection technique field, particularly relate to the detection method of copper, iron and calcium in a kind of flash blowing slag.
Background technology
Containing a large amount of available resource in copper ashes, the analysis of the composition such as copper, iron in copper smelting slag is detected, this to smelting process and resource reutilization significant.At present, the analytical approach of copper and iron in copper ashes concentrate is mainly contained.Cupper determination comprises following two kinds: in copper ashes concentrate, the mensuration of copper amount of more than 10% can use short iodimetric titration, concrete grammar is, sample is after hydrochloric acid, nitric acid, perchloric acid, sulfuric acid dissolution decompose, the pH value regulating solution with ammonium acetate solution is 3.0 ~ 4.0, iron is sheltered with ammonium bifluoride, add potassium iodide and cupric effect, the iodine of precipitation take starch as indicator, with the titration of sodium thiosulfate standard titration solution.In copper concentrate, the mensuration of copper amount of more than 13% can use short iodimetric titration and long iodimetric titration, long iodimetric titration operating process is, sample is through hydrochloric acid, nitric acid and sulfuric acid decomposition, use hypo solution cement copper, isolated by filtration, precipitation nitration mixture dissolves, the pH value regulating solution is 3.0 ~ 4.0, iron is sheltered with ammonium bifluoride, add potassium iodide and cupric effect, the iodine of separating out take starch as indicator, and with the titration of sodium thiosulfate standard titration solution, filtrate is with the in addition correction of aas determination copper amount.
In copper ashes concentrate, the mensuration of iron of more than 20% can use dichromate method, test portion adopts hydrochloric acid, nitric acid, sulfuric acid dissolution, ammoniacal liquor monochlor(in)ate ammonium precipitated iron is separated with matrix copper, in hydrochloric acid medium, with Reduction with Stannous Chloride major part iron, remaining a small amount of iron to make indicator titanium trichloride by sodium tungstate and reduce, take diphenylamine sulfonic acid sodium salt as indicator, with the titration of potassium dichromate standard titration solution.
For flash blowing slag, also there is no the analytical approach of standard at present.Flash blowing is exactly by the matte melt shrend of smelting furnace (Flash Smelting Furnace, Isa furnace, noranda furnace etc., FCF) output, utilizes industrial oxygen or oxygen-enriched air to blow, produce blister copper continuously, thermally after levigate in Outokumpu Flash Smelting Furnace.Flash blowing slag be powdery copper matte regulus in flash converting furnace, through strong oxidation of sulfureted reaction produce into blister copper while discharge alkaline calcium ferrite type slag, principal ingredient has Cu, Fe, S, CaO, SiO
2deng.The vermicularizing control parameter such as Copper in Slag, CaO/Fe ratio can be understood by analyzing each component content of FCF flash blowing slag, for ensureing that stable normal operation of the working of a furnace has vital role, therefore, the quick on-the-spot sample analysis of flash blowing slag seems particularly important aborning.
Flash converting furnace vermicularizing control analyzes the mass content that one of most important index is exactly copper, iron and calcium in flash blowing slag.In flash blowing slag, the roughly content range of copper, iron, calcium is: copper 10% ~ 30%, iron 30% ~ 40%, calcium 5% ~ 18%.General rapid analysis mainly x ray fluorescence spectrometry, but need various basic valued methods as support.In copper concentrate and copper ashes concentrate, the analytical approach of copper amount and iron relates to iodimetric titration, titrimetry, spectrophotometric method, flame atomic absorption spectrometry, ICP-OES method etc., but these analytical approachs all can not directly apply in the analysis of flash blowing slag.Flash blowing calcium in furnace and content of magnesium higher, also there is significant limitation in conventional short iodometric determination copper amount; Though long iodimetric titration accuracy is high, longer for flow process single element measures, analysis speed is slower.Further, these analytical approachs are all the independent analytical approachs of each element of dispersion, and analysis process is longer, and the time is slow, can not meet the requirement of express-analysis.Although ICP-OES method analysis speed is very fast, be not suitable for the analysis of the copper of high-load, iron and calcium.
So, work out a set of specially for the rapid analysis of copper, iron and calcium in flash blowing slag, emergent fast alternative method during to break down as the basis of valuation of X-ray fluorescence spectra on-the-spot sample analysis method or instrument, significant.
Summary of the invention
In view of this, the detection method that the application provides a kind of flash to blow copper, iron and calcium in slag, detection method flow process provided by the invention is simple, can fast, accurately, METHOD FOR CONTINUOUS DETERMINATION flash blows the content of copper, iron and calcium in slag.
The invention provides the detection method of copper, iron and calcium in a kind of flash blowing slag, comprise the following steps:
A) by flash converting furnace slag sample acid dissolve, the first solution of copper ions, ferric ion and calcium ion is obtained; Described first solution and sodium sulphide and NaOH are reacted, filters, be precipitated and filtrate;
B) by steps A) the precipitation acid dissolve that obtains, obtain the second solution containing bivalent cupric ion and ferric ion; Described second solution ammonium bifluoride is sheltered iron, and adopts iodimetric titration to detect copper, obtain copper content; To the solution aluminium choride Iron Release after copper be detected, and adopt iodimetric titration to detect iron, obtain iron content;
C) by steps A) filtrate that obtains uses ethylenediamine tetraacetic acid titration, obtains calcium content.
Preferably, in described flash blowing slag, the mass content of copper is 10% ~ 30%, and the mass content of iron is 30% ~ 40%, and the mass content of calcium is 5% ~ 18%.
Preferably, steps A) in, be 2 ~ 3 by described first solution sulfuric acid adjust ph, add sodium sulfide solution successively and sodium hydroxide solution reacts, filter, be precipitated and filtrate.
Preferably, step B) in, with hydrochloric acid and nitric acid, heating for dissolving steps A) precipitation that obtains, continues heating, adds water, obtain the second solution containing bivalent cupric ion and ferric ion.
Preferably, step B) in, be 3 ~ 4 by described second solution adjust ph, then add ammonium bifluoride saturated solution and shelter iron;
Add liquor kalii iodide to sheltering in the solution after iron, the iodine of precipitation take starch as indicator, with sodium thiosulfate standard solution titration copper, obtains copper content.
Preferably, step B) in, the solution after titration copper adds aluminum trichloride solution and liquor kalii iodide, and adjust ph is 1 ~ 2, uses sodium thiosulfate standard solution titration of iron, obtains iron content.
Preferably, step C) in, to steps A) filtrate that obtains adds TEPA, and use ethylenediamine tetraacetic acid titration, obtain calcium content.
Preferably, step C) in, to steps A) filtrate that obtains adds triethanolamine, and use ethylenediamine tetraacetic acid titration, obtain calcium content.
Preferably, step C) in, to steps A) add TEPA and triethanolamine in the filtrate that obtains, more than adjust ph to 12, use ethylenediamine tetraacetic acid titration, obtain calcium content.
Preferably, by step B) detect iron after solution detect calcium amount, carry out calcium content correction;
By step C) solution after titration detects copper amount, carries out the correction of copper content;
By step C) solution after titration detects iron, carries out iron content correction.
Compared with prior art, the main flow of detection method provided by the invention is: after acid dissolve flash converting furnace slag sample, and utilize sodium sulphide and sodium hydroxide pellets separating copper and iron, gained precipitation titrimetry substep measures copper and iron; Gained filtrate uses titration measuring calcium.The present invention achieves first and once samples, and gets final product the content of these the three kinds of important elements of copper, iron and calcium in METHOD FOR CONTINUOUS DETERMINATION flash blowing slag.The flash blowing g of slag sample that the present invention is directed to calcium-magnesium-containing higher detects, and method flow is simple, and fast, easily operate, measurement result meets the requirement of production control completely.
Accompanying drawing explanation
The testing process of copper, iron and calcium in the flash blowing slag that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides the detection method of copper, iron and calcium in a kind of flash blowing slag, comprise the following steps:
A) by flash converting furnace slag sample acid dissolve, the first solution of copper ions, ferric ion and calcium ion is obtained; Described first solution and sodium sulphide and NaOH are reacted, filters, be precipitated and filtrate;
B) by steps A) the precipitation acid dissolve that obtains, obtain the second solution containing bivalent cupric ion and ferric ion; Described second solution ammonium bifluoride is sheltered iron, and adopts iodimetric titration to detect copper, obtain copper content; To the solution aluminium choride Iron Release after copper be detected, and adopt iodimetric titration to detect iron, obtain iron content;
C) by steps A) filtrate that obtains uses ethylenediamine tetraacetic acid titration, obtains calcium content.
Detection method provided by the invention can measure the content of copper, iron and calcium in flash blowing slag rapidly, continuously, and method flow is simple, easily operates, and detects preci-sion and accuracy all better, can meet the requirement that production control detects.
The testing process of copper, iron and calcium in the flash blowing slag provided for the embodiment of the present invention see Fig. 1, Fig. 1.First the embodiment of the present invention by flash converting furnace slag sample acid dissolve, obtains the first solution of copper ions, ferric ion and calcium ion.
In the present invention, flash blowing slag is the alkaline calcium ferrite type slag that powdery copper matte regulus is discharged in flash converting furnace while blister copper is produced in the reaction of strong oxidation of sulfureted, and principal ingredient has Cu, Fe, S, CaO and SiO
2deng.In an embodiment of the present invention, in described flash blowing slag, the mass content of copper is 10% ~ 30%, and the mass content of iron is 30% ~ 40%, and the mass content of calcium is 5% ~ 18%.In one embodiment of the invention, in described flash blowing slag, the mass content of copper is 15% ~ 20%, and the mass content of iron is 33% ~ 38%, and the mass content of calcium is 9% ~ 14%.
The embodiment of the present invention take a certain amount of (be designated as m) flash blowing g of slag sample, be placed in conical beaker, and add a small amount of water-soaked sample.Said sample nitration mixture can dissolve by the embodiment of the present invention, and described nitration mixture comprises hydrochloric acid, nitric acid and sulfuric acid; The addition sequence of described nitration mixture is not particularly limited, and first can add hydrochloric acid, add nitric acid and sulfuric acid again, and other also can be adopted to add form, makes the solution obtaining copper ions, ferric ion and calcium ion.In one embodiment of the invention, first add hydrochloric acid in the sample, low-temperature heat, micro-ly to boil 3 ~ 5 minutes, slightly cold, then add nitric acid and sulfuric acid, continue to be heated to evaporate to dryness, cooling, adds 35mL ~ 45mL water, obtains the first solution.In an embodiment of the present invention, hydrochloric acid, nitric acid can be 3:2:1 with the volumetric usage ratio of sulfuric acid.
After obtaining the first solution, the embodiment of the present invention adds sodium sulphide and NaOH wherein, reacts, and filters.Described first solution sulfuric acid adjust ph is preferably 2 ~ 3 by the present invention, adds sodium sulfide solution successively and sodium hydroxide solution reacts, and filters, is precipitated and filtrate.
In an embodiment of the present invention, add water in the first solution, slowly heat, add the sulfuric acid solution that mass concentration is 50%, until the pH value of the first solution is in 2 ~ 3 scopes.Then, the embodiment of the present invention is slightly cold, slowly adds sodium sulfide solution, micro-8min ~ 12min that boils; Slightly cold, stir and slowly drip sodium hydroxide solution, until red precipitate no longer increases in solution.In an embodiment of the present invention, the volume ratio of the reaction solution obtained, sodium sulfide solution and sodium hydroxide solution is preferably (45 ~ 50): 20:(3 ~ 5); The concentration of sodium sulfide solution can be 100g/L, and the mass concentration of sodium hydroxide solution can be 20%.The embodiment of the present invention is put slightly calm for the reaction solution obtained, and filters; The sediment that available hot wash obtains 3 times, gained filtrate retains stand-by.
The precipitation acid dissolve that the embodiment of the present invention will obtain, obtains the second solution containing bivalent cupric ion and ferric ion.The present invention preferably uses hydrochloric acid and nitric acid, the precipitation that heating for dissolving obtains, and continues heating, adds water, and obtains the second solution containing bivalent cupric ion and ferric ion.
The sediment that filtration obtains by the embodiment of the present invention and filter paper are put back in former conical beaker, and use nitration mixture dissolution precipitation, described nitration mixture comprises hydrochloric acid and nitric acid; The addition sequence of described nitration mixture is not particularly limited, and obtains the second solution containing bivalent cupric ion and ferric ion.In one embodiment of the invention, add hydrochloric acid and nitric acid, heating for dissolving precipitates, and steams near dry; Then add water in beaker, the salt making to obtain can be heated and dissolve, take off and be cooled to room temperature, obtain the second solution containing bivalent cupric ion and ferric ion.In an embodiment of the present invention, the usage ratio of hydrochloric acid, nitric acid and precipitation can be 15mL:5mL:(0.3 ~ 0.5) g.
After obtaining the second solution, the embodiment of the present invention adds ammonium bifluoride wherein and shelters iron, and adopts iodimetric titration to detect copper, obtains copper content.
Described second solution adjust ph is preferably 3 ~ 4 by the present invention, then adds ammonium bifluoride saturated solution and shelters iron.The embodiment of the present invention drips ammonium acetate saturated solution in the second solution, no longer deepens and excessive 3mL ~ 5mL to redness, makes solution ph be 3 ~ 4.Then, the embodiment of the present invention drips ammonium bifluoride saturated solution, disappears and excessive 1mL, shake up, can blow a small amount of water along wall of cup until red.Wherein, the consumption of described ammonium bifluoride saturated solution can be 5mL ~ 6mL.
After sheltering iron, the present invention adopts iodimetric titration to detect copper.In the present invention, iodimetric titration is using iodine as oxygenant, or carries out the method for titration using iodide (as potassium iodide) as reductive agent.Concrete, the embodiment of the present invention adds liquor kalii iodide to sheltering in the solution after iron, potassium iodide and cupric effect, and the iodine of precipitation take starch as indicator, with sodium thiosulfate standard solution titration copper, obtains copper content.
In one embodiment of the invention, adding liquor kalii iodide to sheltering in the solution after iron, shaking up, (concentration is designated as c to use rapidly sodium thiosulfate standard solution
1) be titrated to light yellow, add starch solution, continue to be titrated to light blue, add potassium thiocyanate solution, fierce shake is deepened to blue, continues to be titrated to blue just disappearance for terminal.Write down the volume of quota of expenditure solution, be designated as V
1, calculate the percentage composition of copper.
After detection obtains copper content, the solution aluminium choride Iron Release that the embodiment of the present invention will detect after copper, and adopt iodimetric titration to detect iron, obtain iron content.
The present invention preferably adds aluminum trichloride solution and liquor kalii iodide to the solution after titration copper, and adjust ph is 1 ~ 2, uses sodium thiosulfate standard solution titration of iron, obtains iron content.To in the solution after titration, the embodiment of the present invention adds excessive aluminum trichloride solution, and ferric iron is discharged; The concentration of described aluminum trichloride solution can be 500g/L, and consumption can be 18mL ~ 22mL.The embodiment of the present invention also adds liquor kalii iodide, and can add mass concentration be 50% hydrochloric acid solution regulate solution ph be 1 ~ 2; The iron (III) discharged and potassium iodide effect, separate out the iodine of equivalent, then be titrated to blueness with sodium thiosulfate standard solution and just disappear, and is terminal.Write down the volume consuming sodium thiosulfate standard solution, be designated as V
2, calculate the percentage composition of iron.
Retain stand-by filtrate before getting, embodiment of the present invention ethylenediamine tetraacetic acid titration, obtains calcium content.Wherein, ethylenediamine tetraacetic acid is called EDTA usually, and it is a kind of organic compound, is a kind of good metal ion chelation agent in chemical field.
The present invention preferably adds TEPA (TEPA) to the filtrate obtained, and shelters copper, zinc plasma.The present invention preferably adds triethanolamine to the filtrate obtained, and shelters iron, aluminium plasma.The present invention preferably adds TEPA and triethanolamine in the filtrate obtained, more than adjust ph to 12, by the calcium amount in EDTA volumetric soiutions.
In one embodiment of the invention, by the filtrate constant volume that obtains before in volumetric flask, leave standstill, divide again and take out a certain amount of filtrate, be placed in conical beaker, add TEPA, triethanolamine, NaOH and calcium carboxylate indicator, with EDTA standard solution, (concentration is designated as c
2) titration, become pure blue to redness and be terminal.Write down the volume of quota of expenditure solution, be designated as V
3, calculate the percentage composition of calcium.
The solution detected after iron is preferably detected calcium amount by the present invention, carries out calcium content correction; Solution after titration calcium is detected copper amount, carries out the correction of copper content; Solution after titration calcium is detected iron, carries out iron content correction.During correction, the solution after titration calcium can be placed in beaker by the embodiment of the present invention, adopts Atomic Absorption Spectrometer, and the copper amount measured wherein (is designated as k
1) and iron (be designated as k
2).The embodiment of the present invention by the solution constant volume after mensuration iron in volumetric flask, can leave standstill, adopt Atomic Absorption Spectrometer, measure calcium amount wherein, be designated as k
3.
The present invention can pass through previous experiments, gropes compensating value k
1, k
2and k
3content range, get its mean value using as constant.Due to k
1, k
2and k
3relative copper, iron and calcium content are all very low, and concerning also negligible analysis of production control, the result precision in such practical operation also can meet production control requirement completely, and significantly can accelerate finding speed.
The present invention can calculate Cu content by formula 1:
In formula 1, c
1the actual concentrations of the material of-sodium thiosulfate standard solution, mol/L;
V
1during-titration copper consume the volume of sodium thiosulfate standard titration solution, mL;
The molal weight of 63.54-copper, g/mol;
The quality of m-take sample, g;
R
1-point get ratio, 5/3;
K
1the compensating value of copper in-filtrate, %.
The present invention can calculate Fe content by formula 2:
In formula 2, c
1the molal weight of-sodium thiosulfate standard solution, mol/L;
V
2-titration of iron consumes the volume of sodium thiosulfate standard solution, mL;
Molal weight × 1000 of 55.85-iron;
M-take sample mass, g;
R
1-point get ratio, 5/3;
K
2the compensating value of iron in-filtrate, %.
The present invention can calculate Ca content by formula 3:
In formula 3, c
2the volumetric molar concentration of-standard solution, mol/L;
V
3-titration calcium amount consumes the volume of EDTA standard solution, mL;
The molal weight of 40.08-calcium oxide, g/moL;
The quality of m-take sample, g;
R
2-point get ratio, 10;
K
3the compensating value of calcium in-precipitation, %
It should be noted that, in practical operation, k
1, k
2and k
3in relative sample, copper, iron and calcium content are very low, as k
1=0.01 ~ 0.02%, k
2=0.01 ~ 0.03%, k
3=0.02 ~ 0.04%, substantially all in 0.01% ~ 0.04% scope, its mean value 0.025% desirable, also can ignore, and does not affect concerning vermicularizing control is analyzed.
In sum, detection method provided by the invention comprises: after acid dissolve flash converting furnace slag sample, and utilize sodium sulphide and sodium hydroxide pellets separating copper and iron, gained precipitation titrimetry substep measures copper and iron; Gained filtrate uses titration measuring calcium.The present invention achieves first and once samples, and gets final product the content of these the three kinds of important elements of copper, iron and calcium in METHOD FOR CONTINUOUS DETERMINATION flash blowing slag.Relative to the elemental analysis method of traditional dispersion, simplified operation step of the present invention, improve analysis speed, testing result meets the requirement of production control completely.
In order to understand the application further, in the flash converting furnace copper ashes provided the application below in conjunction with embodiment, the detection method of copper, iron and calcium describes particularly.
Embodiment 1 Precision Experiment
(1) Cupper determination:
With flash blowing slag for sample, take 0.4000g (m) sample and be placed in 250mL conical beaker, add a small amount of water, soak sample, add 15mL hydrochloric acid, low-temperature heat is micro-boils 3 ~ 5 minutes, slightly cold, add 10mL nitric acid and 5mL sulfuric acid again, continue to be heated to evaporate to dryness, cooling.
In above-mentioned conical beaker, add 40mL water, slowly heat, add the sulfuric acid solution that mass concentration is 50%, make the pH value of the first solution obtained be 2 ~ 3.Slightly cold, slowly add the sodium sulfide solution of 20mL100g/L, micro-10min that boils.Slightly cold, stirring and slowly dripping mass concentration is the sodium hydroxide solution of 20%, and to solution, red precipitate no longer increases.Slightly cold, leave standstill 5min, filter, with hot water washing sediment 3 times; Filtrate retains stand-by.
Precipitation and filter paper are put back in former conical beaker, add 15mL hydrochloric acid and 5mL nitric acid, heating for dissolving precipitates, and steams near dry.Then, in this beaker, blow 20mL water, heating makes salt dissolve, and takes off and is cooled to room temperature, obtains the second solution containing bivalent cupric ion and ferric ion.
In the second solution obtained, drip ammonium acetate saturated solution, no longer deepen and excessive 3 ~ 5mL to redness, then drip ammonium bifluoride saturated solution, disappear and excessive 1mL to red, shake up, blow a small amount of water along wall of cup.Adding 5mL400g/L liquor kalii iodide to sheltering in the solution after iron, shaking up, use rapidly sodium thiosulfate standard solution (c
1=0.0415mol/L) carry out being titrated to light yellow, add 2mL5g/L starch solution, continue to be titrated to light blue, add 3mL200g/L potassium thiocyanate solution, fierce shake is deepened to blue, continues to be titrated to blue just disappearance for terminal.Write down the volume (V of quota of expenditure solution
1), calculate the percentage composition of copper.
(2) mensuration of iron:
To in the solution after titration copper, add 20mL500g/L aluminum trichloride solution and 5mL400g/L liquor kalii iodide, add mass concentration be 50% hydrochloric acid solution regulate solution ph be 1 ~ 2, shake up, leave standstill 5min, be titrated to blueness with above-mentioned sodium thiosulfate standard solution just to disappear, be terminal, write down the volume (V consuming sodium thiosulfate standard solution
3), calculate the percentage composition of iron.
(3) calcium catalyst:
Stand-by filtrate constant volume will be retained in 250mL volumetric flask in (1), leave standstill, divide and get 25mL in 250mL conical beaker, add the triethanolamine of TEPA, 2mL30wt% of 2mL30wt%, 15mL200g/L NaOH and 0.1g calcium carboxylate indicator, with EDTA standard solution (c
2=0.0207mol/L) titration, become pure blue to redness and be terminal.Write down the volume (V of quota of expenditure solution
3), calculate the percentage composition of calcium.
(4) correction:
Pipette test solution in 150mL (3) in volumetric flask in 250mL beaker, Atomic Absorption Spectrometer measures copper amount (k wherein
1) and iron (k
2).By measuring the solution constant volume after iron in (2) in 250mL volumetric flask, leaving standstill, Atomic Absorption Spectrometer measures calcium amount (k wherein
3).Compensating value all gets its mean value 0.025%.
With said method to copper in flash converting furnace slag sample, iron and calcium amount replicate determination 6 times, carry out Precision Experiment.Wherein, calculate Cu content by above-mentioned formula 1, calculate Fe content by above-mentioned formula 2, calculate Ca content by above-mentioned formula 3.Then, the relative standard deviation of measurement result is calculated.Testing result is in table 1, and table 1 is the result of embodiment of the present invention Precision Experiment.
Precision refers under the same conditions repeatedly the degree that replication result is consistent each other, and the size of precision represents by deviation, and the less explanation precision of deviation is higher.According to table 1, experiment shows that the precision of detection method provided by the invention is better.
The result of table 1 embodiment of the present invention Precision Experiment
Embodiment 2 accuracy is tested
1, accuracy experiment is carried out to flash converting furnace slag sample, namely detect copper, iron and calcium amount in 3 flash converting furnace slag samples by the method in embodiment 1.Testing result in table 2, the result that table 2 is tested for embodiment of the present invention accuracy.
2, existing method is adopted to carry out Cupper determination: iodimetric titration
Take 0.3000g sample, be placed in 250mL conical beaker, use a small amount of water-wet, add 5mL nitric acid and 15mL hydrochloric acid, cover table ware, low-temperature heat is dissolved completely, steams near dry, takes off slightly cold.Add 50mL water and 10mL sulfuric acid, boil, under stirring, the hypo solution slowly dripping 25mL200g/L, to precipitating generation in a large number, filters while hot.Precipitate more than 3 times with hot wash, make solution be blue, leave standstill and occur supernatant to solution, continuing to drip mass concentration is that the sodium hydroxide solution of 50% is to no longer occurring precipitation.Washing lotion and filtrate are collected in 200mL volumetric flask, add 10mL chloroazotic acid, with water constant volume, shake up.
Sediment and filter paper are returned in former conical beaker, adds 5mL nitric acid and 15mL hydrochloric acid, heat resolve precipitation and filter paper, be heated near dry, cooling.With 30mL water purge table ware and wall of cup, cover table ware, be placed on electric hot plate and boil, dissolve solubility salt, take off cooling.Drip ammoniacal liquor to generate to sediment, then drip acetic acid and disappear to sediment, after amount 4mL, add 3mL ammonium bifluoride saturated solution, shake up.Add 2 ~ 3g potassium iodide, shake is dissolved, be titrated to light yellow with the sodium thiosulfate standard titration solution of 0.04mol/L immediately, add the starch solution of 2mL5g/L, continue to be titrated to light blue, add the potassium thiocyanate solution of 5mL100g/L, shake is deepened to blue, then is titrated to blueness and just disappears for terminal.Calculate the mass concentration C of copper
1(%).
Use Air-acetylene Flame, at Atomic Absorption Spectrometer wavelength 324.7nm place, measure copper series standard solution, return to zero with water simultaneously, the absorbance of filtrate in measuring capacity bottle, deducts the absorbance of the blank solution of test portion, finds the mass concentration C of corresponding copper from working curve
2(%).
The content (%) of copper is the difference of twice measurement result: C
1(%)-C
2(%).The results are shown in Table 2.
3, existing method is adopted to carry out the mensuration of iron: dichromate method
Take 0.2000g sample in 250mL beaker, add 10mL hydrochloric acid and 5mL nitric acid, heating for dissolving, steam near dry, take off cooling.Add 30mL water, add 5g ammonium chloride, heating for dissolving.Add water to 70mL, be heated to closely boil, add ammonia neutralization Kocide SD precipitation while stirring completely, excessive 10mL, boils.Filter with Medium speed filter paper, hot ammonia scrubbing beaker 3 times is to the blueness without copper.With hot water wash beaker and precipitate each 2 times.Ferric hydroxide precipitate be transferred in former beaker, rinse filter paper with hot hydrochloric acid yellow to nothing, thermal precipitation dissolves completely.
Drip 60g/L stannous chloride solution to light yellow, drip 3 5g/L copper-baths again, be stirred to colourless, add 15mL mixture of sulfuric phosphoric acid and 5 2g/L diphenylamine sulfonic acid sodium solutions immediately, being titrated to purple with 0.05mol/L potassium dichromate standard solution is terminal, calculates the content of iron.The results are shown in Table 2.
4, existing method is adopted to carry out calcium catalyst: EDTA titrimetry
Take 0.2000g sample, be placed in the platinum crucible filling 2g natrium carbonicum calcinatum and 1g boric acid, mixing.Be placed in the high temperature furnace melting 30min of 950 ~ 1000 DEG C.After decomposing completely, take out cooling.Crucible is put into the 250mL beaker filling 75mL hot water and 20mL hydrochloric acid, after leaching frit, wash out crucible with water.
Solution is steamed to 100mL, adds 1g ammonium chloride, regulate solution ph to 7 with (1+1) ammoniacal liquor, boil 5min.Take off, be filtered hot in 250mL volumetric flask, cooling, adds 2g cupferron, stirs, and places 15min, and constant volume mixes, and does and filters.
Pipette 50mL in 250mL beaker, heating water, to 100mL, adds 5mL (1+4) triethanolamine, 15mL200g/L NaOH and 0.1g calcon-carboxylic acid, is titrated to pure blue is terminal with 0.01mol/LEDTA standard solution, calculates the content of calcium.The results are shown in Table 2.
Contrasted by the inventive method in table 2 and existing method, experiment shows that the accuracy of detection method provided by the invention is better.
The result of table 2 embodiment of the present invention accuracy experiment
As seen from the above embodiment, measure copper, iron and calcium amount in flash converting furnace slag sample rapidly, continuously by this method, preci-sion and accuracy is all better, can meet the requirement that production control detects, have certain promotional value.
Claims (10)
1. the detection method of copper, iron and calcium in flash blowing slag, comprises the following steps:
A) by flash converting furnace slag sample acid dissolve, the first solution of copper ions, ferric ion and calcium ion is obtained; Described first solution and sodium sulphide and NaOH are reacted, filters, be precipitated and filtrate;
B) by steps A) the precipitation acid dissolve that obtains, obtain the second solution containing bivalent cupric ion and ferric ion; Described second solution ammonium bifluoride is sheltered iron, and adopts iodimetric titration to detect copper, obtain copper content; To the solution aluminium choride Iron Release after copper be detected, and adopt iodimetric titration to detect iron, obtain iron content;
C) by steps A) filtrate that obtains uses ethylenediamine tetraacetic acid titration, obtains calcium content.
2. detection method according to claim 1, is characterized in that, in described flash blowing slag, the mass content of copper is 10% ~ 30%, and the mass content of iron is 30% ~ 40%, and the mass content of calcium is 5% ~ 18%.
3. detection method according to claim 1 and 2, is characterized in that, steps A) in, be 2 ~ 3 by described first solution sulfuric acid adjust ph, add sodium sulfide solution successively and sodium hydroxide solution reacts, filter, be precipitated and filtrate.
4. detection method according to claim 1 and 2, is characterized in that, step B) in, with hydrochloric acid and nitric acid, heating for dissolving steps A) precipitation that obtains, continues heating, adds water, obtain the second solution containing bivalent cupric ion and ferric ion.
5. detection method according to claim 1 and 2, is characterized in that, step B) in, be 3 ~ 4 by described second solution adjust ph, then add ammonium bifluoride saturated solution and shelter iron;
Add liquor kalii iodide to sheltering in the solution after iron, the iodine of precipitation take starch as indicator, with sodium thiosulfate standard solution titration copper, obtains copper content.
6. detection method according to claim 5, is characterized in that, step B) in, the solution after titration copper adds aluminum trichloride solution and liquor kalii iodide, and adjust ph is 1 ~ 2, uses sodium thiosulfate standard solution titration of iron, obtains iron content.
7. detection method according to claim 1 and 2, is characterized in that, step C) in, to steps A) filtrate that obtains adds TEPA, and use ethylenediamine tetraacetic acid titration, obtain calcium content.
8. detection method according to claim 1 and 2, is characterized in that, step C) in, to steps A) filtrate that obtains adds triethanolamine, and use ethylenediamine tetraacetic acid titration, obtain calcium content.
9. detection method according to claim 1 and 2, is characterized in that, step C) in, to steps A) add TEPA and triethanolamine in the filtrate that obtains, more than adjust ph to 12, use ethylenediamine tetraacetic acid titration, obtain calcium content.
10. detection method according to claim 1 and 2, is characterized in that, by step B) detect iron after solution detect calcium amount, carry out calcium content correction;
By step C) solution after titration detects copper amount, carries out the correction of copper content;
By step C) solution after titration detects iron, carries out iron content correction.
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| CN106501238A (en) * | 2016-10-17 | 2017-03-15 | 阳谷祥光铜业有限公司 | The detection method of copper thing phase in a kind of flash smelting furnace copper ashes |
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| CN112415129A (en) * | 2020-10-26 | 2021-02-26 | 广东韶钢松山股份有限公司 | Method for detecting calcium and magnesium in sintered ore |
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