CN101839828A - Digestion method and detection method for iron ore - Google Patents
Digestion method and detection method for iron ore Download PDFInfo
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- CN101839828A CN101839828A CN 201010176617 CN201010176617A CN101839828A CN 101839828 A CN101839828 A CN 101839828A CN 201010176617 CN201010176617 CN 201010176617 CN 201010176617 A CN201010176617 A CN 201010176617A CN 101839828 A CN101839828 A CN 101839828A
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Abstract
The invention provides a digestion method and a detection method for iron ore. The digestion method comprises the following steps: adding an iron ore sample in which hydrofluoric acid and nitric acid (or sulfuric acid) are mixed, then carrying out high-pressure closed microwave digestion to obtain a suspension; and heating the suspension in an unclosed system to secure the second digestion with residual nitric acid (or residual sulfuric acid) and added perchloric acid and hydrogen peroxide, thereby obtaining a solution which is digested fully. The detection method comprises the following steps: preparing a solution with the digested solution, and detecting the prepared solution by inductive coupling plasma atomic emission spectrometry, thereby obtaining content of each element of the iron ore sample. The invention has the advantages of high efficiency, high accuracy, and simple and fast process. Especially, the invention realizes accurate detection of key element content in iron ore, such as As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and Mo which affect product quality of iron and steel smelting and vanadium/titanium extraction.
Description
Technical field
The present invention relates to the technical field of analysis and detection of compound, more particularly, relate to the iron ore classification, especially the digestion procedure of all kinds sefstromite and detection method.
Background technology
Sefstromite (comprises raw ore, concentrate, mine tailing, sintering deposit, pellet and the titanium dioxide iron ore etc. that contain vanadium, titanium, ferro element, hereinafter be also referred to as sefstromite class sample) be different from common iron ore, its composition and phase structure are all very complicated, and contain the TiO about 10 usually
2V with a few percent
2O
5For example, China's Panxi Diqu is composed has profuse vanadium titano-magnetite, these vanadium titano-magnetites are the multielement mineral intergrowth, composition and phase structure are all quite complicated, and the component difference of different ore deposit points is also bigger, except that containing main secondary elements such as Fe, V, Ti, Si, Al, Ca, Mg, O, also contain indissoluble rare elements such as Nb, Zr, Sc.These cause clearing up with the trace element detection of sefstromite sample all difficult more than common iron ore, can not indiscriminately imitate or continue to use the analyzing detecting method of common iron ore.Especially for sintering deposit or the pellet and the titanium dioxide iron ore of the sefstromite intermediate product that original sefstromite stone is obtained after production Technology such as oversintering, pelletizingization or oxidizing roasting are handled, because most TiO wherein
2Meet the generation crystal transfer and generate the extremely difficult rutile TiO that is dissolved in acid
2So clearing up with detection of these sintering deposits, pellet and iron titanium oxide sample ore product is difficult more.
At present, the mode of clearing up that is used for ore deposit class sample mainly contains following four kinds:
(1) molten the clearing up of acid: directly with HF-HCl-HNO
3-H
2SO
4(or HClO
4) in unlimited systems such as electric hot plate, clear up sample, these class methods can only be used in the occasion not high to the measurement result accuracy requirement.Even because do not contain vanadium titanium or the very low common iron ore of vanadium Ti content, owing to all have the SiO of high level in the common ore deposit
2, Al
2O
3Deng the indissoluble oxide, it is complete with Specimen eliminating to adopt the molten mode of electric hot plate acid to be difficult to, and sour undissolved residue easily wraps up, adsorbs element to be measured, causes testing result on the low side.If clear up the high sample of vanadium Ti content with this method, then residue is more, and the accuracy of follow-up testing result is poorer.
(2) pyrogenic process fusion: clear up sample with reagent high-temperature fusion in muffle furnace such as a large amount of boric acid-sodium carbonate, lithium borate, potassium pyrosulfates.Be used for the high-load ultimate analysis more, measure Fe in common iron ore or the sefstromite as volumetric method, gravimetric method or XRF
2O
3, SiO
2, Al
2O
3, TiO
2, main matter such as CaO, MgO.Though can clear up sefstromite fully, but a large amount of salts and alkali metal ion have been introduced, it is complicated to cause solution matrix to be measured to be formed, and blank background height is unwell to micro-exact instrument analytical approachs such as ICP-AES, atomic absorption spectrography (AAS).
(3) molten time slag of acid: first wet method is cleared up acid-soluble substance, with the pyrogenic process fusion method remaining undissolved residue is cleared up again.A kind of analytical approach with copper, cobalt, nickel, chromium, molybdenum, vanadium, titanium, manganese and aluminium in ICP-AES (ICP-AES) the mensuration iron ore is provided among foreign standard C MS 02 01 94 01-1999 as the analytical chemistry aspect, and this method adopts HF-HCl-HNO
3-H
2SO
4Come decomposition samples, filter the undissolved residue that obtains and return slag with the potassium pyrosulfate fusion.Acid molten time slag method be that wet process acid is molten clears up the defective of clearing up with the pyrogenic process fusion separately in order to overcome, and with both in conjunction with formed a kind of method.Yet, still there are many shortcomings in molten time slag method of acid, though reduced level of residue by acid dissolving earlier, reduced the alkaline reagent consumption with respect to direct fusion, to a certain degree alleviate adverse effect, but can't thoroughly solve alkali metal ion and salt and disturb a difficult problem, and increase and prolonged checking procedure, analysis process and cycle greatly.Especially, because TiO in the sefstromite
2Equal size is very high, and sour undissolved residue is a lot, must increase the consumption of potassium pyrosulfate when adopting molten time slag method of acid to measure sefstromite greatly, and matrix effect has a strong impact on measurement result, so these class methods are not suitable for the detection of sefstromite class sample.
(4) micro-wave digestion: under high-pressure sealed condition, adopt microwave heating to clear up sample with acid.Clearing up technology with tradition compares, penetrability and the activating reaction ability of micro-wave digestion by utilizing microwave heats reagent and sample in the closed container, can increase the pressure in the sample preparation container, improves temperature of reaction, thereby improved reaction rate greatly, shortened the time of specimen preparation.In addition, micro-wave digestion also can be controlled reaction conditions such as conditions such as pressure and temperature increasing schedules by control, thereby makes that the sample preparation precision is higher, and has reduced environmental pollution, improves operating personnel's working environment simultaneously.
As mentioned above, there is plurality of advantages in micro-wave digestion, yet, for adopting the micro-wave digestion vanadium titano-magnetite, still there is following shortcoming:
1. after passing through micro-wave digestion, can form suspension, in suspension, have more residue, make clear up thorough inadequately.These residues may adsorb, wrap up element to be measured, thereby cause the testing result of follow-up each element very large deviation to occur.If filter out the residue of failing by micro-wave digestion by the mode of filtering, then can cause analysis result bigger deviation to occur, can not reflect the content of each element in the ore faithfully.These residues mainly include titanium carbonitride, titanium carbide, vanadium carbide, titanium nitride, vanadium nitride, simple substance carbon and/or other insolubles etc.In addition, because sefstromite classification difference, there are very big-difference in its composition and phase composition, so also have difference for the composition of different types of sefstromite residue.All there is undissolved residue in various sefstromite class samples (comprising raw ore, concentrate, mine tailing, sintering deposit, pellet and titanium dioxide iron ore) behind micro-wave digestion, just there is some difference in how many meetings of level of residue.For example, sintering deposit, pellet and titanium dioxide iron ore are producing more residue through meeting behind the micro-wave digestion.Sintering deposit is that concentrate, fuel (as coke powder and anchracite duff) and flux (as unslaked lime and rauhkalk) are mixed by a certain percentage, operations such as drying, preheating, fuel sintering, fusing and condensation then, make the local fusion liquid phase thing that generates of raw material with the heat that utilizes fuel combustion to produce, utilize the fusion liquid phase thing that generates to make the bulk cargo particle cohere into block sintering deposit.Similarly, pellet is after breeze and flux etc. are mixed, to be pressed into or to be rolled into green-ball, makes it fixed through operations such as super-dry and roastings then, becomes " ripe ball ".Because in these two kinds of process treatment process, carbon in sefstromite and fuel, furnace charge, airborne nitrogen, the fire resistive material etc. all may react, thereby cause the increase of carbonide, nitride and carbonitride etc., and in sintering and pelletizing processing procedure, also crystal transfer can take place such as compositions such as titania in the sefstromite, these have all increased the amount of undissolved residue behind the micro-wave digestion.Have again, the titanium dioxide iron ore is in order to stop up production equipment for anatase titanium dioxide hydrolysis in avoiding because of ore forms precipitation when putting forward the titanium operation, and by a certain technology sefstromite is processed into the titanium dioxide iron ore in advance, anatase titanium dioxide is all changed into rutile titanium dioxide, and this technology has increased the undissolved residue amount of titanium dioxide iron ore micro-wave digestion equally.
2. influence the subsequent detection step.Be mainly reflected in 2 points: the one, micro-wave digestion need use hydrofluorite usually, however the hydrofluorite that remains in the digestion solution can the used detecting instrument of heavy corrosion subsequent detection step.If detecting instrument is used the particular component with antiseptic power instead, usually can reduce important technology performances such as transmission nebulization efficiency, and weaken the corrosive mode of hydrofluorite with the boric acid complexing, then increased the kind of the salt in the solution to be measured, make that the matrix of solution to be measured is complicated more, thereby cause the factor of Interference Detection to increase, influence the accuracy of testing result; The 2nd, because through behind the micro-wave digestion, the high content silicon in the sefstromite is not purged and is retained in the solution, causes the increase of matrix complicacy and salt density, thereby disturbed the accuracy that each element in the vanadium titano-magnetite class sample is detected.
3. for guaranteeing safety, when microwave airtight digestion sefstromite class sample, generally need avoid using the reagent such as perchloric acid, hydrogen peroxide and sulfuric acid of strong oxidizing property as far as possible, thereby cause the carboritride in the titanomagnetite class sample effectively not decompose, influence the accuracy of testing result.Micro-wave digestion generally is because its oxidisability is stronger without perchloric acid, with some substance reaction explosion danger is arranged; Without hydrogen peroxide mainly is to cause jar internal pressure too high because of decomposing to produce oxygen easily; Without sulfuric acid is because of its high density, high viscosity, can measure subsequent instrumentation and produce the matrix effect influence.
In order to realize the comprehensive utilization of sefstromite resource, be controlled at smelting iron and steel, vanadium extraction and propose the pollution of introducing impurity element in the production process such as titanium, improve the quality of steel product, vanadium goods and titanium article, need detect the content in the sefstromite class sample exactly such as impurity elements such as As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr, Mo.
In sum, need badly a kind of can be accurately and detect the analyzing detecting method of each micronutrient levels in the sefstromite class sample apace.
Summary of the invention
At above-mentioned problems, the present invention is by clearing up in conjunction with micro-wave digestion and wet chemistry, realized thoroughly the clearing up of iron ore (particularly sefstromite class sample), thereby can accurately detect in the iron ore (particularly sefstromite class sample) such as content of elements such as As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and Mo.
A kind of digestion procedure of iron ore is provided according to an aspect of the present invention, described digestion procedure comprises step: (1) places container with iron ore to be measured, adds hydrofluorite and nitric acid, airtight described container in described container, carry out clearing up the first time with microwave then, form suspension; (2) described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, the perchloric acid and the hydrogen peroxide of residual nitric acid and adding comes the residue in the suspension is carried out clearing up the second time in the suspension to utilize, thereby obtains clearing up solution completely.
The digestion procedure of iron ore according to an aspect of the present invention, when the addition of iron ore in the step (1) is 0.1000g to 0.5000g, the mass percent concentration of hydrofluorite and addition can be respectively 40%～47% and 0.5mL～1.5mL, the mass percent concentration of nitric acid and addition can be respectively 65%～68% and 2.0mL～5.0mL, in the step (2), the mass percent concentration of perchloric acid and addition can be respectively 70.0%～72.0% and 1.0mL～1.5mL, and the mass percent concentration of hydrogen peroxide and addition can be respectively 〉=and 30% and 0.5mL～1.0mL.
The digestion procedure of iron ore according to an aspect of the present invention, step (1) can adopt the slope heating mode, controlled being made as below the 800psi of pressure in the described container, the microwave heating program can be set to material in the described container is warming up to 160 ℃～190 ℃ with 2～5min, is incubated 8min～10min subsequently.
A kind of detection method of iron ore is provided in accordance with a further aspect of the present invention, described detection method comprises step: A, iron ore to be measured is placed container, add hydrofluorite and nitric acid, airtight described container in described container, carry out clearing up the first time with microwave then, form suspension; B, described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, come the residue in the suspension is carried out clearing up the second time with perchloric acid and the hydrogen peroxide that utilizes residual nitric acid in the suspension and adding, continue to heat to evaporate and clear up the solution that obtains for the second time, to drive the hydrofluorite in the solution, when treating that solution is the wet salt shape, stop heating, cooling adds the diluted hydrochloric acid dissolution salt then, and last constant volume obtains solution to be measured; C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore, described detection method comprises ICP-AES, inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry) and spectrophotometric method.
A kind of digestion procedure of iron ore is provided according to a further aspect in the invention, described digestion procedure comprises step: (1) places container with iron ore to be measured, adds hydrofluorite and sulfuric acid, airtight described container in described container, carry out clearing up the first time with microwave then, form suspension; (2) described suspension is transferred to another container, described another container of heating under the system of opening wide comes the residue in the suspension is carried out clearing up the second time to utilize sulfuric acid residual in the suspension, thereby obtains clearing up solution completely then.
The digestion procedure of iron ore according to a further aspect of the invention, when the addition of iron ore in the step (1) is 0.1000g to 0.2500g, the mass percent concentration of hydrofluorite and addition can be respectively 40%～47% and 0.5mL～1.5mL, and the mass percent concentration of sulfuric acid and addition can be respectively 95%～98% and 1.5mL～3.0mL.
The digestion procedure of iron ore according to a further aspect of the invention, step (1) can adopt the slope heating mode, controlled being made as below the 800psi of pressure in the described container, the microwave heating program can be set to material in the described container is warming up to 200 ℃～230 ℃ with 5～8min, is incubated 5min～8min subsequently.
A kind of detection method of iron ore is provided according to another aspect of the invention, described detection method comprises step: A, iron ore to be measured is placed container, add hydrofluorite and sulfuric acid, airtight described container in described container, carry out clearing up the first time with microwave then, form suspension; B, described suspension is transferred to another container, under the system of opening wide, heat described another container then, to utilize sulfuric acid residual in the suspension to come the residue in the suspension is carried out clearing up the second time, continue heating and evaporate,, treat that solution evaporation went out after the dense white smoke 5～10 minutes to drive the hydrofluorite in the solution through clearing up the solution that obtains for the second time, stop heating, cooling, the class that adds then that Water dissolve salt, last constant volume obtains solution to be measured; C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore, described detection method comprises ICP-AES, inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry) and spectrophotometric method.
Digestion procedure and detection method according to iron ore of the present invention, described iron ore can comprise common iron ore and the sefstromite that does not contain vanadium, titanium elements, and described sefstromite can comprise raw ore, concentrate, mine tailing, sintering deposit, pellet and the titanium dioxide iron ore that contains vanadium, titanium, ferro element.
According to the detection method of iron ore of the present invention, described element can comprise at least a among As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and the Mo.
Compared with prior art, beneficial effect of the present invention is as follows:
1. clear up thoroughly the accuracy in detection height.Carry out clearing up the first time reaction by microwave, contain in the sefstromite such as SiO
2, Al
2O
3, rutile TiO
2And the slightly solubility oxide of W, Sn etc. is all decomposed completely and is entered solution; Again by in opening wide system, utilizing in the solution original residual acid or additional reagent to carry out clearing up the second time reaction, the residue that may comprise carbonitride, titanium carbide, vanadium carbide, titanium nitride, vanadium nitride, simple substance carbon and/or other insolubles etc. has been cleared up in strong oxidation, clear up thoroughly, avoided residue self to the influence of testing result with because of the influence of the element to be measured in the residue parcel solution, so the accuracy height of the testing result of each element in the sefstromite to testing result.
2. the sample use amount is few, and reagent dosage is few.The minimum amount of clearing up with the required sample of detection method of the present invention is 0.1000g, and this has well reduced the testing sample quantitative limitation.Reduced the amount of agents useful for same in digestion process and the testing process simultaneously.In digestion procedure according to the present invention, the molten method of usefulness quantity not sufficient acid 30% of the acid amount of acid, effectively reduce of the influence of reagent blank background to determination of trace element, in other words, effectively reduced the systematic error of detection method, thereby improved the accuracy of testing result, particularly, helped measuring easy contaminated Ca, elements such as As, Pb.
3. detection speed is fast.Do not have characteristics such as volatilizing loss because microwave quickens to clear up with air-tight state reagent, the consumption of reagent and water seldom, the sample solution volume is also just very little, moreover need not to wait for the solution sub-cooled, promptly transferable about 90 ℃, evaporation; When particularly clearing up sample, thereby, can only control low temperature and increase reagent dosage, long-time slow molten sample for avoiding the too early volatilization loss influence of reagent to clear up effect owing to the molten method of conventional acid.The present invention has finished Specimen eliminating substantially when microwave is cleared up reaction for the first time, what clear up the reaction employing for the second time is high temperature heating rapid evaporation mode, not only saved the reaction time greatly, and high temperature also is more conducive to clear up carbonitride and decomposes remaining sulfuric acid, and drives hydrofluorite and silicon tetrafluoride etc.Therefore, compare with the molten method of acid, the present invention has shortened concentration and evaporation greatly and has driven the time of acid.Clear up the mode coupling and use though the present invention is two kinds, increased operation steps, the operating process refining, microwave is cleared up fast, liquor capacity is little and several big characteristics such as high temperature evaporation are guaranteed that whole sample is cleared up and can be finished with interior at 1 hour.With respect to needing 4-6 hour and sample still can not clear up sour completely molten method and 6-8 hour and to measuring sour molten time more slag method of disturbing effect factor, the present invention is with the obvious advantage, more can adapt to the requirement of modern industry to the analysis of sample fast detecting.
4. do not corrode detecting instrument.According to of the present invention clear up with detection method in, clear up in the course of reaction for the second time and can drive away SiF
4, HF (or F
-) and decompose and to have reduced remaining sulfuric acid in the solution, thereby eliminated when each constituent content of subsequent detection corrosive attack to analytical instrument.And catch up with sour step also to simplify solution matrix to be measured and form, reduced salt density, more help the detection of each quasi-instrument.
5. at micro-wave digestion with do not use hydrochloric acid (HCl) second time subsequently in the digestion process, when therefore in the system of opening wide, heating, cause testing result possibility on the low side thereby avoided elements such as As, Pb, Cr to combine the loss of formation effumability compound with chlorion or chlorine oxonium ion up hill and dale.And clear up in the scheme (that is, when micro-wave digestion, adding the scheme of hydrofluorite and sulfuric acid) at second cover of the present invention, only utilize higher boiling remaining in the micro-wave digestion solution for the first time, the H of strong oxidizing property
2SO
4When clearing up for the second time reaction, decompose carboritride, make Specimen eliminating more completely; And, removed the remaining H of part in the solution by the high temperature evaporation decomposition
2SO
4, reduced influence to subsequent measurements, overcome the shortcoming of former micro-wave digestion effectively.Simultaneously, still be retained in SO in the solution
4 2-With complexings such as Ti, W, Sn, Fe, guarantee that solution can hydrolysis under relatively low acidity yet, so the direct water dissolved salts and dilute constant volume of this scheme among the present invention, low acidity also helps reducing corrosive attack and the disturbing effect to measuring to detecting instrument more.
6. applied widely, the detectable element kind is many.The applicable sefstromite that results in all kinds, grade and vanadium Ti content of method of the present invention, and clear up thoroughly, any undissolved residue do not had; And by can directly determining the various micronutrient levelss of As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and Mo simultaneously in conjunction with multiple detection methods such as ICP-AES.
Embodiment
Embodiment 1
The digestion procedure of iron ore according to an aspect of the present invention comprises step: (1) places container with iron ore to be measured, adds hydrofluorite and nitric acid in described container, and airtight described container carries out clearing up the first time with microwave then, forms suspension; (2) described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, the perchloric acid and the hydrogen peroxide of residual nitric acid and adding comes the residue in the suspension is carried out clearing up the second time in the suspension to utilize, thereby obtains clearing up solution completely.
The digestion procedure of iron ore according to an aspect of the present invention, hydrofluorite and nitric acid dosage can be according to the SiO that contains in the quality of iron ore to be measured and the iron ore to be measured
2, Al
2O
3, TiO
2And the amount of indissoluble things such as carbonide, nitride and carbonitride and deciding.In addition, the low more required sour consumption of the concentration of hydrofluorite and nitric acid is many more, and the reaction time is also long more, and this is unfavorable for realizing detecting fast and efficiently, so hydrofluorite and sulfuric acid are all selected the concentrated acid of not diluted for use.More particularly, when the addition of iron ore in the step (1) is 0.1000g to 0.5000g, the mass percent concentration of hydrofluorite and addition can be respectively 40%～47% and 0.5mL～1.5mL, the mass percent concentration of nitric acid and addition can be respectively 65%～68% and 2.0mL～5.0mL, in the step (2), the mass percent concentration of perchloric acid and addition can be respectively 70.0%～72.0% and 1.0mL～1.5mL, and the mass percent concentration of hydrogen peroxide and addition can be respectively 〉=and 30% and 0.5mL～1.0mL.Here, add hydrogen peroxide and be in order to utilize its oxidisability to come oxidation to comprise residue, thereby make that clearing up of iron ore is more thorough such as carbonitride, carbonide and nitride.In addition; the perchloric acid that adds can be cleared up residue residual in the suspension on the one hand; utilize its higher boiling can drive hydrofluorite residual in the solution on the other hand, thereby reach the purpose of protection subsequent detection instrument, so the addition of perchloric acid is determined according to the consumption of hydrofluorite.When the large usage quantity of hydrofluorite, the consumption of perchloric acid is also bigger.Be to shorten round of visits, used perchloric acid is the concentrated acid of not diluted.Preferably, when the addition of iron ore in the step (1) was 0.1000g to 0.5000g, the adding mass percentage concentration was perchloric acid 1.0mL～1.5mL of 70.0%～72.0%, but is not limited thereto, and also usable concentration is lower than 70.0% perchloric acid.Clear up the time of reaction and concentration and evaporation for shortening, improve analysis speed, require the distilled water total amount of reagent and flushing tank skin to be no more than 15mL, so preferred concentrated acid that uses not diluted, be the hydrofluorite of 40%-47% and the nitric acid of 65%-68%, but the invention is not restricted to this, also can working concentration be lower than the hydrofluorite and the nitric acid of this scope.
The digestion procedure of iron ore according to an aspect of the present invention can adopt micro-wave digestion equipment commonly used to realize that closed microwave clears up.Preferably, in the digestion procedure of according to an aspect of the present invention iron ore, step (1) can adopt the slope heating mode, controlled being made as below the 800psi of pressure in the described container, the microwave heating program can be set to material in the described container is warming up to 160 ℃～190 ℃ with 2～5min, is incubated 8min～10min subsequently.
In all technical schemes of the present invention, because in the micro-wave digestion process, the pressure in the container is big more, helps more clearing up, so pressure is the bigger the better when micro-wave digestion.Yet bearing pressure for the safety of counteracting tank maximum of the present invention is 800psi, and therefore, for purposes of the invention, controlled being made as below the 800psi of pressure during micro-wave digestion in the container preferably, is 800psi.But, the invention is not restricted to this, that is, bear the situation of pressure greater than 800psi for the safety of counteracting tank, according to of the present invention clear up with detection method in micro-wave digestion the time pressure can correspondingly increase.
The detection method of iron ore according to a further aspect of the present invention comprises step: A, iron ore to be measured is placed container, add hydrofluorite and nitric acid in described container, airtight described container carries out clearing up first time with microwave then, the formation suspension; B, described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, come the residue in the suspension is carried out clearing up the second time with perchloric acid and the hydrogen peroxide that utilizes residual nitric acid in the suspension and adding, continue to heat to evaporate and clear up the solution that obtains for the second time, to drive the hydrofluorite in the solution, when treating that solution is the wet salt shape, stop heating, cooling adds the diluted hydrochloric acid dissolution salt then, and last constant volume obtains solution to be measured; C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore.Here, described detection method comprises ICP-AES (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), flame atomic absorption spectrometry (F-AAS), GFAAS (graphite furnace atomic absorption spectrometry) (GF-AAS) and spectrophotometric method.Described element comprises at least a among As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and the Mo.The described watery hydrochloric acid that is used for dissolved salts can be the watery hydrochloric acid by the ratio formulated (1+2) of the concentrated hydrochloric acid of 1 part of 36%-38% and 2 parts of water, and its addition can be 15.0mL～25.0mL.But the invention is not restricted to this, also can use the dilute hydrochloric acid solution of other ratio.In addition, the volume of constant volume is decided according to the detection limit of the detection method selected for use etc.
It is pointed out that for all technical schemes of the present invention, described iron ore can comprise common iron ore and the sefstromite that does not contain vanadium, titanium elements.Described sefstromite can comprise raw ore, concentrate, mine tailing, sintering deposit, pellet and the titanium dioxide iron ore etc. that contain vanadium, titanium, ferro element.Vanadium titano-magnetite is a kind of of sefstromite, and therefore, sefstromite of the present invention comprises various types of vanadium titano-magnetites, for example, and the raw ore of vanadium titano-magnetite, concentrate, mine tailing, sintering deposit, pellet and titanium dioxide iron ore etc.
At this, coming the purpose of dissolved salts with watery hydrochloric acid is to avoid hydrolysis in low acidity solution such as titanium, tungsten, tin to produce precipitation.
Though it should be noted that here according to top description method of the present invention to be divided into digestion procedure and detection method is described, it should be appreciated by those skilled in the art that the purpose of clearing up is for follow-up detection, clear up and detect to mutually combine.
Below in conjunction with example 1 to example 12 further describe according to an aspect of the present invention the iron ore digestion procedure and the detection method of iron ore according to a further aspect of the present invention.
The iron ore digestion procedure according to an aspect of the present invention and the detection method of iron ore according to a further aspect of the present invention specifically can may further comprise the steps: take by weighing the iron ore sample in container and add nitric acid and hydrofluorite, closed container carries out micro-wave digestion; Take advantage of heat to transfer in the polytetrafluoroethylene beaker gained suspension of micro-wave digestion, add perchloric acid, high temperature rapid evaporation to suspension emits dense white perchloric acid smog on electric hot plate, drip the strong oxygenolysis residue of hydrogen peroxide, continue to be evaporated to the nearly dried wet salt shape that is of solution, cooling adds the diluted hydrochloric acid dissolution salt, with water dilution constant volume, make detection solution.Here, the high temperature rapid evaporation is meant that the temperature of resistance wire in the electric hot plate is much higher than traditional temperature that only adopts the resistance wire of electric hot plate in the method that electric hot plate clears up, for example, high temperature can be meant that the temperature of the resistance wire of electric hot plate is more than 400 ℃, or electric hot plate is selected the above high temperature resistance silk of power 1200W for use, thereby can improve velocity of evaporation, shorten detection time greatly, and help clearing up of residue in the suspension more.
In the example below, use the ICP-AES method to detect solution and carry out check and analysis, thereby obtain As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, the Ni in the sefstromite, the content of impurity elements such as Cr, Mo clearing up sefstromite sample gained.Also can use ICP-MS, F-AAS, GF-AAS method to detect the element of suitable concentration scope.
Example 1
Used hydrofluorite, nitric acid, perchloric acid, hydrogen peroxide and the water of this example is the pure rank of top grade, used microwave digestion system is produced Mars5 by U.S. CE M company, and ICP-AES is the silent generation that iCAP6300 of the company type inductively coupled plasma atomic emission spectrometer that flies of U.S.'s match.
Clearing up of sefstromite
In this example, testing sample is sefstromite head sample (climbing steel group produces) (hereinafter being called sample No. 1), and its Main Ingredients and Appearance comprises: TiO
2=9.0%, V
2O
5=0.3%, Al
2O
3=10%, Fe=26%.
The sefstromite head sample that takes by weighing 0.2500g in micro-wave digestion jar in, dripping mass percent concentration along interior jar of tank skin earlier is that 40% dense hydrofluorite (HF) 1.0mL and mass percent concentration are 65% red fuming nitric acid (RFNA) (HNO
3) 3.5mL.Put outer jar then, build lid and tighten, to guarantee good seal with torque spanner.By the instrumentation step good seal outer canned gone into microwave and clear up in the stove, connect temperature, pressure transducer.Carry out micro-wave digestion by set micro-wave digestion heating schedule.The micro-wave digestion mode that present embodiment adopts the single stage Fast Heating to heat up heats up with the slope, and pressure control is at 800psi (1psi=6.895KPa), and the microwave heating program is set to material in the container is warming up to 160 ℃ with 2min, is incubated 10min subsequently.
After the micro-wave digestion EOP (end of program), for easy to operate, wait in the air cooling jar solution to 85 ℃, take out the counteracting tank and the nut of in fuming cupboard, slowly outwarding winding and discharge surplus pressure, with transferring in the polytetrafluoroethylene beaker through the resulting suspension of micro-wave digestion in the container, polytetrafluoroethylene beaker is placed on the electric hot plate heat again.Drip 0.5mL H
2O
2, clear up remaining residue in the suspension to assist.Add mass percent concentration then and be 70% dense perchloric acid (HClO
4) 1.0mL, and the solution in the use electric hot plate Fast Heating evaporation polytetrafluoroethylene beaker is to emitting dense white smog, continue evaporation until the nearly dried wet salt state that presents of solution, add 20.0mL (1+2) diluted hydrochloric acid dissolution salt after being cooled to room temperature, dilute constant volume in the 100mL volumetric flask with water at last, form solution to be measured.On inductively coupled plasma atomic emission spectrometer, described solution to be measured is measured.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
The detection of sefstromite
In this example, digestion solution as detection means, directly, simultaneously carries out analytical control to the elements such as Cu, Ni, Cr, Mo, W, As, Pb and Zn that contained in the sefstromite with ICP-AES.Determination step carries out basically in the usual way.
Example 2
In this example, testing sample is sefstromite head sample (climbing steel group produces) (hereinafter being called sample No. 2), and its Main Ingredients and Appearance comprises: TiO
2=11%, V
2O
5=0.5%, Al
2O
3=10%, Fe=33%.In addition, in this example, removing sample quality is 0.1000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 68% dense HNO
33.0mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
20.6mL (1+2) watery hydrochloric acid 15.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 5min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 3
In this example, testing sample is sefstromite concentrate sample (climbing steel group produces) (hereinafter being called sample No. 3), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=1.0%, Al
2O
3=4.5%, Fe=52%.In addition, in this example, removing sample quality is 0.5000g, and reagent dosage is respectively: mass percent concentration is that 45% dense HF 1.5mL, mass percent concentration are 67% dense HNO
35.0mL, mass percent concentration is 72% dense perchloric acid 1.5mL, H
2O
20.7mL (1+2) watery hydrochloric acid 25.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 3min, is incubated 10min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 4
In this example, testing sample is sefstromite concentrate sample (climbing steel group produces) (hereinafter being called sample No. 4), and its Main Ingredients and Appearance comprises: TiO
2=14%, V
2O
5=0.7%, Al
2O
3=3.5%, Fe=54%.In addition, in this example, removing sample quality is 0.2500g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 68% dense HNO
33.0mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
20.5mL (1+2) watery hydrochloric acid 20.0mL, the microwave heating program is set to material in the container is warming up to 170 ℃ with 5min, is incubated 7min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 5
In this example, testing sample is sefstromite sintering deposit sample (climbing steel group produces) (hereinafter being called sample No. 5), and its Main Ingredients and Appearance comprises: TiO
2=10%, V
2O
5=0.5%, Al
2O
3=4.5%, Fe=45%.In addition, in this example, removing sample quality is 0.2000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 0.5mL, mass percent concentration are 68% dense HNO
33.5mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
21.0mL (1+2) watery hydrochloric acid 20.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 5min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 6
In this example, testing sample is iron titanium oxide ore sample (climbing steel group produces) (hereinafter being called sample No. 6), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=0.5%, Al
2O
3=5.0%, Fe=48%.In addition, in this example, removing sample quality is 0.4000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.5mL, mass percent concentration are 68% dense HNO
34.0mL, mass percent concentration is 72% dense perchloric acid 1.5mL, H
2O
21.0mL (1+2) watery hydrochloric acid 25.0mL, the microwave heating program is set to material in the container is warming up to 160 ℃ with 3min, is incubated 10min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 7
In this example, testing sample is sefstromite pellet sample (climbing steel group produces) (hereinafter being called 7 samples), and its Main Ingredients and Appearance comprises: TiO
2=11%, V
2O
5=0.5%, Al
2O
3=4.5%, Fe=45%.In addition, in this example, removing sample quality is 0.2000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 68% dense HNO
33.0mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
20.5mL (1+2) watery hydrochloric acid 15.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 4min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 8
In this example, testing sample is sefstromite pellet sample (climbing steel group produces) (hereinafter being called sample No. 8), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=0.5%, Al
2O
3=5.0%, Fe=47%.In addition, in this example, removing sample quality is 0.4000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.5mL, mass percent concentration are 68% dense HNO
34.0mL, mass percent concentration is 72% dense perchloric acid 1.5mL, H
2O
20.5mL (1+2) watery hydrochloric acid 25.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 5min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 9
In this example, testing sample is sefstromite mine tailing sample (climbing steel group produces) (hereinafter being called sample No. 9), and its Main Ingredients and Appearance comprises: TiO
2=11%, V
2O
5=0.1%, Al
2O
3=12%, Fe=13%.In addition, in this example, removing sample quality is 0.1500g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 68% dense HNO
33.0mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
20.5mL (1+2) watery hydrochloric acid 25.0mL, the microwave heating program is set to material in the container is warming up to 190 ℃ with 5min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 10
In this example, testing sample is that (standard model of General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry Echen Iron ﹠ Steel Plant development GSBH30003-97) (hereinafter is called sample No. 10) to common iron ore sample, and its Main Ingredients and Appearance comprises: Al
2O
3=4.07%, Fe=54.05%.In addition, in this example, removing sample quality is 0.5000g, and reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 68% dense HNO
34.0mL, mass percent concentration is 72% dense perchloric acid 1.0mL, H
2O
20.5mL (1+2) watery hydrochloric acid 25.0mL, the microwave heating program is set to material in the container is warming up to 160 ℃ with 5min, is incubated 10min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 1.
Above-mentioned example 1 has been selected 9 sefstromite samples to example 10, and the sefstromite of having contained number of different types such as raw ore, concentrate, mine tailing, sintering deposit, pellet and titanium dioxide iron ore, also selected 1 common iron ore sample, can verify the performance of clearing up of the present invention by the actual effect of clearing up of these samples.Adopt method of the present invention to clear up common iron ore and various types of sefstromite when (comprising the sefstromite of handling through oversintering, pelletizing metallization processes), clear up completely, the noresidue sample, do not have insoluble residue, solution clarification.As seen, method of the present invention has good effect and the extensive applicability cleared up, and all has the good ability of clearing up for various dissimilar iron ores.
Example 11
Clear up, the test of the precision of detection method
3,5, No. 7 sefstromite samples are carried out respectively independently clearing up, adopt the ICP-AES assay determination 8 times, 8 measurement results are carried out statistical treatment, assess precision of the present invention according to relative standard deviation.Measurement result sees Table 1.
Table 1 sefstromite sample analysis result and precision
By in the table 1 as can be known, the relative standard deviation of each element testing result (RSD%) is all less than 5%, show the present invention actual clear up and detect respond well, precision height, favorable reproducibility.Can satisfy the needs of element determination in the various sefstromite.
Example 12
Clear up, detection method analytical standard sample result control test
Use the present invention that country-level standard model is tested, measurement result contrasts with the standard value that adopts the standard chemical analytical approach to determine, table 2 visible result unanimity shows that the present invention accurately and reliably.
The contrast of table 2 standard model measurement result
In the table, "/" expression calibration sample is not to this element definite value
Embodiment 2
The digestion procedure of iron ore according to a further aspect of the invention comprises step: (1) places container with iron ore to be measured, adds hydrofluorite and sulfuric acid in described container, and airtight described container carries out clearing up the first time with microwave then, forms suspension; (2) described suspension is transferred to another container, described another container of heating under the system of opening wide comes the residue in the suspension is carried out clearing up the second time to utilize sulfuric acid residual in the suspension, thereby obtains clearing up solution completely then.
The digestion procedure of iron ore according to a further aspect of the invention, hydrofluorite and nitric acid dosage can be according to the SiO that contains in the quality of iron ore to be measured and the iron ore to be measured
2, Al
2O
3, TiO
2, W, Sn and indissoluble things such as carbonide, nitride and carbonitride amount and decide.In addition, the low more required sour consumption of the concentration of hydrofluorite and sulfuric acid is many more, and the reaction time is also long more, and this is unfavorable for realizing detecting fast and efficiently, so hydrofluorite and sulfuric acid are all selected the concentrated acid of not diluted for use.More particularly, when the addition of iron ore in the step (1) is 0.1000g to 0.2500g, the mass percent concentration of hydrofluorite and addition can be respectively 40%～47% and 0.5mL～1.5mL, and the mass percent concentration of sulfuric acid and addition can be respectively 95%～98% and 1.5mL～3.0mL.Here, come further oxidation to clear up the residue that comprises such as carbonitride, carbonide and nitride by sulfuric acid residual behind the micro-wave digestion, thereby make that clearing up of iron ore is more thorough.In addition, also utilize the higher boiling of sulfuric acid to drive hydrofluorite residual in the solution, thereby arrive the purpose of protection subsequent detection instrument.Clear up the time of reaction and concentration and evaporation for shortening, improve analysis speed, require the distilled water total amount of reagent and flushing tank skin to be no more than 15mL, so preferred concentrated acid that uses not diluted, be the hydrofluorite of 40%-47% and the sulfuric acid of 95%-98%, but the invention is not restricted to this, also can working concentration be lower than the hydrofluorite and the sulfuric acid of this scope.
The digestion procedure of iron ore according to a further aspect of the invention can adopt micro-wave digestion equipment commonly used to realize that closed microwave clears up.Preferably, in the digestion procedure of according to a further aspect of the invention iron ore, step (1) can adopt the slope heating mode, controlled being made as below the 800psi of pressure in the described container, the microwave heating program can be set to material in the described container is warming up to 200 ℃～230 ℃ with 5～8min, is incubated 5min～8min subsequently.
Detection method according to the iron ore of another aspect of the invention, described detection method comprises step: A, iron ore to be measured is placed container, add hydrofluorite and sulfuric acid, airtight described container in described container, carry out clearing up the first time with microwave then, form suspension; B, described suspension is transferred to another container, under the system of opening wide, heat described another container then, to utilize sulfuric acid residual in the suspension to come the residue in the suspension is carried out clearing up the second time, continue heating and evaporate,, treat that solution evaporation went out after the dense white smoke 5～10 minutes to drive the hydrofluorite in the solution through clearing up the solution that obtains for the second time, stop heating, cooling, the class that adds then that Water dissolve salt, last constant volume obtains solution to be measured; C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore.Here, described detection method comprises ICP-AES (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), flame atomic absorption spectrometry (F-AAS), GFAAS (graphite furnace atomic absorption spectrometry) (GF-AAS) and spectrophotometric method.Described element comprises at least a among As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and the Mo.In addition, the volume of constant volume is decided according to the detection limit of the detection method selected for use etc.
In addition, in background technology, mention,, can measure subsequent instrumentation and produce the matrix effect influence, so micro-wave digestion should avoid using sulfuric acid as far as possible because sulfuric acid has high density, full-bodied character.Yet in the present embodiment, the sulfuric acid consumption is few, less than 3%, can eliminate its influence by the matrix matching method, and in the second time of present embodiment digestion process, sulfuric acid has also consumed a part because of decomposing.In addition, with respect to embodiment 1 because sulfuric acid has complexing, thus can be directly when clearing up for the second time with Water dissolve salt class and dilute constant volume.
Below in conjunction with example 13 to example 22 further describe according to a further aspect of the invention the iron ore digestion procedure and according to the detection method of the iron ore of another aspect of the invention.
Iron ore digestion procedure according to a further aspect of the invention and specifically can may further comprise the steps: take by weighing the iron ore sample in container according to the detection method of the iron ore of another aspect of the invention, in container, add hydrofluorite and sulfuric acid, clear up with microwave behind the closed container; Take advantage of heat to transfer in the polytetrafluoroethylene beaker solution of micro-wave digestion, utilize residual sulfuric acid in the suspension, directly in the system of opening wide, carry out clearing up the second time with electric hot plate heating suspension, high temperature heating rapid evaporation residual hydrogen fluoric acid, remaining sulfuric acid decomposes the dense white SO of generation in solution
3Smog is cooled to the class that adds that Water dissolve salt after the room temperature, with water dilution constant volume, makes solution to be measured at last.Here, the high temperature rapid evaporation is meant that the temperature of resistance wire in the electric hot plate is much higher than traditional temperature that only adopts the resistance wire of electric hot plate in the method that electric hot plate clears up, for example, high temperature can be meant that the temperature of the resistance wire of electric hot plate is more than 400 ℃, or electric hot plate is selected the above high temperature resistance silk of power 1200W for use, thereby can improve velocity of evaporation, shorten detection time greatly, and help clearing up of residue in the suspension more.
In the following embodiments, use ICP-AES to carry out check and analysis, thereby obtain the content of the impurity elements such as As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and Mo in the iron ore clearing up iron ore sample gained detection solution.Also can use ICP-MS, F-AAS, GF-AAS to detect the element of suitable concentration scope.
Example 13
Used hydrofluorite, sulfuric acid and the water of this example is the pure rank of top grade, and used microwave digestion system is produced Mars5 by U.S. CE M company, and ICP-AES is the silent generation that iCAP6300 of the company type inductively coupled plasma atomic emission spectrometer that flies of U.S.'s match.
Clearing up of sefstromite
In this example, testing sample is sefstromite head sample (No. 1 sample), and its Main Ingredients and Appearance comprises: TiO
2=9.0%, V
2O
5=0.3%, Al
2O
3=10%, Fe=26%.
The sefstromite head sample that takes by weighing 0.1000g in the jar, is earlier 47% dense hydrofluorite (HF) 0.5mL along interior jar of tank skin dropping mass percent concentration in micro-wave digestion, and mass percent concentration is 98% red fuming nitric acid (RFNA) (H
2SO
4) 1.5mL.Put outer jar then, build lid and tighten, to guarantee good seal with torque spanner.By the instrumentation step good seal outer canned gone into microwave and clear up in the stove, connect temperature, pressure transducer.Carry out micro-wave digestion by set micro-wave digestion heating schedule.The micro-wave digestion mode that this example adopts the single stage Fast Heating to heat up heats up with the slope, and pressure control is at 800psi, and the microwave heating program is set to material in the container is warming up to 200 ℃ with 5min, is incubated 8min subsequently.
After the micro-wave digestion EOP (end of program), for easy to operate, wait in the air cooling jar solution to 85 ℃, take out the counteracting tank and the nut of in fuming cupboard, slowly outwarding winding and discharge surplus pressure, to transfer in the polytetrafluoroethylene beaker through the resulting suspension of micro-wave digestion in the container again, polytetrafluoroethylene beaker placed heat rapid evaporation on the electric hot plate, residual sulfuric acid is decomposed and is produced SO in suspension
3Behind the dense white smog 5 minutes, be cooled to and add 30.0mL after the room temperature Water dissolve salt class, at last with water dilution constant volume in the 50mL volumetric flask, form solution to be measured.On inductively coupled plasma atomic emission spectrometer, described solution to be measured is measured.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
The detection of sefstromite
In this example, digestion solution as detection means, directly, simultaneously carries out analytical control to the elements such as Cu, Ni, Cr, Mo, W, As, Pb and Zn that contained in the sefstromite with ICP-AES.Determination step carries out basically in the usual way.
Example 14
In this example, testing sample is sefstromite head sample (No. 2 sample), and its Main Ingredients and Appearance comprises: TiO
2=11%, V
2O
5=0.5%, Al
2O
3=10%, Fe=33%.In addition, in this example, except sample quality is 0.2500g, reagent dosage is respectively: mass percent concentration is that 47% dense HF1.5mL, mass percent concentration are 98% dense H
2SO
43.0mL, decompose sulfuric acid and produce SO
3Dense white smog 10 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 230 ℃ with 8min, is incubated 5min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 15
In this example, testing sample is sefstromite concentrate sample (No. 3 sample), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=1.0%, Al
2O
3=4.5%, Fe=52%.In addition, in this example, except sample quality is 0.1500g, reagent dosage is respectively: mass percent concentration is that 47% dense HF1.0mL, mass percent concentration are 98% dense H
2SO
42.0mL, decompose sulfuric acid and produce SO
3Dense white smog 8 minutes, constant volume 50mL, the microwave heating program is set to material in the container is warming up to 200 ℃ with 8min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 16
In this example, testing sample is sefstromite concentrate sample (No. 4 sample), and its Main Ingredients and Appearance comprises: TiO
2=14%, V
2O
5=0.7%, Al
2O
3=3.5%, Fe=54%.In addition, in this example, except sample quality is 0.2000g, reagent dosage is respectively: mass percent concentration is that 47% dense HF1.0mL, mass percent concentration are 98% dense H
2SO
42.5mL, decompose sulfuric acid and produce SO
3Dense white smog 8 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 220 ℃ with 6min, is incubated 7min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 17
In this example, testing sample is iron titanium oxide ore sample (No. 6 sample), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=0.5%, Al
2O
3=5.0%, Fe=48%.In addition, in this example, except sample quality is 0.1500g, reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 98% dense H
2SO
42.0mL, decompose sulfuric acid and produce SO
3Dense white smog 5 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 220 ℃ with 6min, is incubated 7min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 18
In this example, testing sample is sefstromite stone pellet sample (No. 8 sample), and its Main Ingredients and Appearance comprises: TiO
2=12%, V
2O
5=0.5%, Al
2O
3=5.0%, Fe=47%.In addition, in this example, except sample quality is 0.2000g, reagent dosage is respectively: mass percent concentration is that 47% dense HF1.5mL, mass percent concentration are 98% dense H
2SO
42.5mL, decompose sulfuric acid and produce SO
3Dense white smog 10 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 220 ℃ with 6min, is incubated 7min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 19
In this example, testing sample is sefstromite mine tailing sample (No. 9 sample), and its Main Ingredients and Appearance comprises: TiO
2=11%, V
2O
5=0.1%, Al
2O
3=12%, Fe=13%.In addition, in this example, except sample quality is 0.1000g, reagent dosage is respectively: mass percent concentration is that 47% dense HF1.0mL, mass percent concentration are 98% dense H
2SO
42.0mL, decompose sulfuric acid and produce SO
3Dense white smog 5 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 220 ℃ with 6min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Example 20
In this example, testing sample is common iron ore sample (No. 10 sample), and its Main Ingredients and Appearance comprises: Al
2O
3=4.07%, Fe=54.05%.In addition, in this example, except sample quality is 0.2500g, reagent dosage is respectively: mass percent concentration is that 47% dense HF 1.0mL, mass percent concentration are 98% dense H
2SO
42.5mL, decompose sulfuric acid and produce SO
3Dense white smog 10 minutes, constant volume 100mL, the microwave heating program is set to material in the container is warming up to 220 ℃ with 5min, is incubated 8min subsequently, and corresponding step is identical with parameter in all the other steps and parameter and the example 13.By observation, find the clarification of gained digestion solution, do not have and do not allow residue the Specimen eliminating result.
Select 7 sefstromite stone samples among the example 13-20 respectively, these samples have been contained the sefstromite of number of different types such as raw ore, concentrate, titanium dioxide iron ore, pellet and mine tailing, also selected 1 common iron ore sample, verified the effect of clearing up of the present invention by the actual effect of clearing up of these samples.Adopt method of the present invention to clear up common iron ore and various types of sefstromite when (comprising the sefstromite of handling through peroxidating or pelletizing metallization processes), clear up completely, the noresidue sample, do not have insoluble residue, solution clarification.As seen, method of the present invention has good effect and the extensive applicability cleared up, and all has the good ability of clearing up for various dissimilar iron ores.
Example 21
Clear up, the test of the precision of detection method
4,6, No. 8 sefstromite stone samples are carried out respectively independently clearing up, adopt the ICP-AES assay determination 8 times, 8 measurement results are carried out statistical treatment, assess the level of accuracy of sample digestion of the present invention and detection according to relative standard deviation.Measurement result sees Table 3.
Table 3 sefstromite stone sample analysis result and precision
By in the table 3 as can be known, each element relative standard deviation (RSD%) is all less than 5%, show the present invention actual clear up and detect respond well, favorable reproducibility, the precision height, workable, can satisfy the needs of element determination in the various sefstromite.
Example 22
Clear up, detection method analytical standard sample result control test
Use the present invention that country-level standard model is tested, measurement result contrasts with the standard value that adopts the standard chemical analytical approach to determine, table 4 visible result unanimity shows that the present invention accurately and reliably.
The contrast of table 4 standard model measurement result
"/" expression calibration sample is not to this element definite value
Iron ore according to the present invention is cleared up and detection method, combining the unlimited system wet chemistry of modern microwave high pressure airtight digestion technology and traditional electrical hot plate clears up, maximize favourable factors and minimize unfavourable ones, embody a concentrated reflection of advantage separately and overcome original shortcoming, fast and efficiently all kinds sefstromite is cleared up fully, and the disturbing effect minimum that subsequent instrumentation is measured.
Iron ore according to the present invention is cleared up with detection method and has been realized efficient, simple and direct, fast, clear up completely to iron ore; Simultaneously by with the coupling of microelement analyzer device, realized influencing smelting iron and steel, vanadium extraction, proposing the accurate detection of the key element of handicraft product quality such as titanium in the iron ore such as As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and Mo etc., and improved the accuracy, work efficiency and the analysis speed that detect data, wide prospects for commercial application has been arranged.
Although above described exemplary embodiment of the present invention in detail, it will be understood by a person skilled in the art that in the spirit and scope that do not break away from claim of the present invention and limited, can carry out various changes and modifications.
Claims (10)
1. the digestion procedure of an iron ore is characterized in that described digestion procedure comprises step:
(1) iron ore to be measured is placed container, add hydrofluorite and nitric acid in described container, airtight described container carries out clearing up the first time with microwave then, forms suspension;
(2) described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, the perchloric acid and the hydrogen peroxide of residual nitric acid and adding comes the residue in the suspension is carried out clearing up the second time in the suspension to utilize, thereby obtains clearing up solution completely.
2. the digestion procedure of iron ore as claimed in claim 1, it is characterized in that, when the addition of iron ore in the step (1) is 0.1000g to 0.5000g, the mass percent concentration of hydrofluorite and addition are respectively 40%～47% and 0.5mL～1.5mL, the mass percent concentration of nitric acid and addition are respectively 65%～68% and 2.0mL～5.0mL, in the step (2), the mass percent concentration of perchloric acid and addition are respectively 70.0%～72.0% and 1.0mL～1.5mL, and the mass percent concentration and the addition of hydrogen peroxide be respectively 〉=and 30% and 0.5mL～1.0mL.
3. the digestion procedure of iron ore as claimed in claim 1, it is characterized in that step (1) adopts the slope heating mode, pressure control in the described container is below the 800psi, the microwave heating program is set to material in the described container is warming up to 160 ℃～190 ℃ with 2～5min, is incubated 8min～10min subsequently.
4. the detection method of an iron ore is characterized in that described detection method comprises step:
A, iron ore to be measured is placed container, add hydrofluorite and nitric acid in described container, airtight described container carries out clearing up first time with microwave then, the formation suspension;
B, described suspension is transferred to another container, in described another container, add perchloric acid, under the system of opening wide, heat described another container then, in described another container, add hydrogen peroxide again, come the residue in the suspension is carried out clearing up the second time with perchloric acid and the hydrogen peroxide that utilizes residual nitric acid in the suspension and adding, continue to heat to evaporate and clear up the solution that obtains for the second time, to drive the hydrofluorite in the solution, when treating that solution is the wet salt shape, stop heating, cooling adds the diluted hydrochloric acid dissolution salt then, and last constant volume obtains solution to be measured;
C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore, described detection method comprises ICP-AES, inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry) and spectrophotometric method.
5. the digestion procedure of an iron ore is characterized in that described digestion procedure comprises step:
(1) iron ore to be measured is placed container, add hydrofluorite and sulfuric acid in described container, airtight described container carries out clearing up the first time with microwave then, forms suspension;
(2) described suspension is transferred to another container, described another container of heating under the system of opening wide comes the residue in the suspension is carried out clearing up the second time to utilize sulfuric acid residual in the suspension, thereby obtains clearing up solution completely then.
6. the digestion procedure of iron ore as claimed in claim 5, it is characterized in that, when the addition of iron ore in the step (1) is 0.1000g to 0.2500g, the mass percent concentration of hydrofluorite and addition are respectively 40%～47% and 0.5mL～1.5mL, and the mass percent concentration of sulfuric acid and addition are respectively 95%～98% and 1.5mL～3.0mL.
7. the digestion procedure of iron ore as claimed in claim 5, it is characterized in that step (1) adopts the slope heating mode, pressure control in the described container is below the 800psi, the microwave heating program is set to material in the described container is warming up to 200 ℃～230 ℃ with 5～8min, is incubated 5min～8min subsequently.
8. the detection method of an iron ore is characterized in that described detection method comprises step:
A, iron ore to be measured is placed container, add hydrofluorite and sulfuric acid in described container, airtight described container carries out clearing up first time with microwave then, the formation suspension;
B, described suspension is transferred to another container, under the system of opening wide, heat described another container then, to utilize sulfuric acid residual in the suspension to come the residue in the suspension is carried out clearing up the second time, continue heating and evaporate,, treat that solution evaporation went out after the dense white smoke 5～10 minutes to drive the hydrofluorite in the solution through clearing up the solution that obtains for the second time, stop heating, cooling, the class that adds then that Water dissolve salt, last constant volume obtains solution to be measured;
C, adopt one or more detection method to detect described solution to be measured, thereby obtain the content of each element in the iron ore, described detection method comprises ICP-AES, inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry, GFAAS (graphite furnace atomic absorption spectrometry) and spectrophotometric method.
9. as the digestion procedure of any described iron ore in claim 1 to 3 and 5 to 7, it is characterized in that, described iron ore comprises common iron ore and the sefstromite that does not contain vanadium, titanium elements, and described sefstromite comprises raw ore, concentrate, mine tailing, sintering deposit, pellet and the titanium dioxide iron ore that contains vanadium, titanium, ferro element.
10. as the detection method of any described iron ore in claim 5 or 8, it is characterized in that described element comprises at least a among As, Pb, Zn, W, Sn, Ca, Mg, Cu, Co, Ni, Cr and the Mo.
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