CN104792647B - Copper in telluride copper, tellurium, gold and silver content assay method - Google Patents
Copper in telluride copper, tellurium, gold and silver content assay method Download PDFInfo
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Abstract
The present invention provides the assay method of copper in a kind of telluride copper, tellurium, gold and silver content, includes the following steps：By telluride copper sample, acid solution and the solution reaction containing chlorion, precipitation and the first reaction solution are obtained；The precipitation is subjected to ashing processing, obtains grey slugging；The grey slugging using Fire Assaying gravimetric method is measured, obtains the content of gold and silver in telluride copper；By first reaction solution and alkaline reaction, Kocide SD precipitation and the second reaction solution are obtained；The Kocide SD is precipitated and is measured using iodimetric titration, obtains the content of copper in telluride copper；Second reaction solution is made to form tellurium precipitation, by tellurium precipitation using gravimetric detemination, obtains the content of tellurium in telluride copper.The application in telluride copper is measured copper, tellurium, gold with silver content during, by once claiming sample, you can realize telluride copper sample in gold, silver, copper and tellurium continuous separation determination, simplify continuous mode, and accuracy is higher.
Description
Technical field
The present invention relates to the measure sides of copper in element determination technical field more particularly to telluride copper, tellurium, gold and silver content
Method.
Background technology
Tellurium is a kind of rare and scatter element, is crystallized for orthorhombic system silvery white.High purity tellurium improves the strength of materials, hard due to having
Degree improves the advantages of material wear-resistant and corrosion resisting property, is widely used in semiconductor devices, alloy, industrial chemicals, cast iron, rubber
Additive is made in the industry such as glue, glass.But the independent deposit of tellurium is considerably less at present, mainly has coloured gold from copper, lead and zinc etc.
Belong to association in the electrolysis anode sludge that wet smelting process generates.
Since the electrode potential of tellurium is higher than the electrode potential of copper, in electrolytic refining course of copper, tellurium will not be in cathode
It is precipitated and is mainly deposited in the earth of positive pole.Tellurium is in the earth of positive pole generally with Ag2Te、Au2Te、Cu2The forms such as Te exist, and usually exist
It handles in the techniques of noble metals such as copper anode mud production gold and silver, needs to leach the valuable elements such as selenium, tellurium in early period；And selenium, tellurium etc.
The leaching of valuable element is to make tellurium and other separation of metal ions using the various compounds of copper displacement tellurium in sulfuric acid solution,
Obtain telluride copper.
Telluride copper is the crystal powder of black, more stable in air under room temperature.Telluride copper is downstream tellurium Refining
Produce the important source material of pure tellurium.The chemical composition analysis of telluride copper is of great significance for Instructing manufacture and quality clearing.
Copper in telluride copper, tellurium, Jin Heyin substantially content range be：The copper of 25wt%~65wt%, 15wt%~
The tellurium of 40wt%, the gold of 10g/t~200g/t, the silver of 100g/t~5000g/t.Gold, silver, copper and tellurium de-termination mesh in telluride copper
It is preceding to refer to the analysis method of Copper in Concentrate amount without standard method of analysis, the analysis method of tellurium, Jin Heyin in the earth of positive pole
And analysis method of tellurium etc. in pure tellurium.But telluride copper has unique property in itself, works out a set of specifically for telluride
The assay method of important component is of great significance in copper.
For copper content the Copper in Concentrate of 13~50% ranges measure, generally using iodimetric titration.Sample through hydrochloric acid,
After nitric acid decomposes, ammonium acetate solution is used to adjust the pH value of solution as in the range of 3.0~4.0, iron, addition are sheltered with ammonium acid fluoride
Potassium iodide is acted on cupric, and the iodine of precipitation is titrated, according to drop using starch as indicator with sodium thiosulfate standard titration solution
Determine result and calculate amount of copper.For tellurium content, tellurium de-termination, generally use are heavy in the copper anode mud of 0.50%~10.00% range
Potassium chromate-iron ammonium sulfate back titration.Sample nitric acid, sulfuric acid dissolution in hydrochloric acid medium, are with stannous chloride reductive tellurium
Simple substance tellurium is detached with a large amount of impurity such as same, arsenic, antimony, bismuth, lead, precipitated after being dissolved with acid, adds in excessive potassium bichromate standard drop
Determine solution oxide tellurous acid, then the potassium bichromate with iron ammonium sulfate standard titration solution back titration excess.Gold and silver are contained
Gold and silver determination in 0.50g/t~40.00g/t and the copper concentrate of 50.0g/t~2500g/t ranges respectively are measured, it is general straight
It connects using Fire Assaying gravimetric method, sample forms lead through dispensing, high-temperature fusion, the noble metal melted in the metallic lead trapping sample of state
It detains, other substances in sample generate fusibility slag with flux, and lead button ash is blown, and obtain gold and silver and close grain, remove conjunction grain surface
The impurity of adherency, through nitric acid parting, with titration measuring silver content, gravimetric detemination gold amount.
The assay method of existing Copper in Concentrate, tellurium de-termination method in copper anode mud, tellurium de-termination method in pure tellurium
And gold and silver determination method comparative maturity in copper concentrate, and telluride copper and copper concentrate, copper anode mud and pure
The composition of tellurium has larger difference, and in the prior art and there is no gold, silver, copper and tellurium de-termination methods in telluride copper.
Invention content
Present invention solves the technical problem that it is to provide the assay method of copper in a kind of telluride copper, tellurium, gold and silver content, this
The assay method of application can realize the measure of copper in telluride copper, tellurium, gold and silver content, and accuracy is higher.
In view of this, this application provides the assay method of gold, silver, copper and tellurium content in a kind of telluride copper, including following
Step：
By telluride copper sample, acid solution and the solution reaction containing chlorion, precipitation and the first reaction solution are obtained；
The precipitation is subjected to ashing processing, obtains grey slugging；The grey slugging is surveyed using Fire Assaying gravimetric method
It is fixed, obtain the content of gold and silver in telluride copper；
By first reaction solution and alkaline reaction, Kocide SD precipitation and the second reaction solution are obtained；
The Kocide SD is precipitated and is measured using iodimetric titration, obtains the content of copper in telluride copper；
Second reaction solution is made to form tellurium precipitation, by tellurium precipitation using gravimetric detemination, obtains tellurium in telluride copper
Content.
Preferably, the telluride copper sample includes：The copper of 25wt%~65wt%, the tellurium of 15wt%~40wt%, 10g/t
The silver of the gold and 100g/t~5000g/t of~200g/t.
Preferably, the Kocide SD precipitation is further included before being measured using iodimetric titration：
Kocide SD precipitation is used into dissolving with hydrochloric acid, then constant volume, is then reacted with sodium hydroxide, it is then anti-with hydrochloric acid
Should, obtain reaction solution；
Adjust the pH to 3~4 of the reaction solution, then with the solution reaction of fluoride ion.
Preferably, the Fire Assaying gravimetric method is specially：
The grey slugging with dispensing is mixed, obtains mixture, mixing coverture is covered in the mix surface, obtains
Pre- fusant；
The pre- fusant is melted, is cooled down, obtains lead button and slag；
The lead button is heated to black film to slough, ash is blown, obtain close grain, by it is described conjunction grain reacted with glacial acetic acid after with heat
Nitric acid reaction is weighed after dry.
Preferably, it is (16~22) that the dispensing, which is mass ratio,:(8~10):(7~10):(3~4):(90~100)
Sodium carbonate, silica, borax, starch and lead oxide mixture；It is (3~5) that the mixing coverture, which is mass ratio,：(1~
3)：The mixture of the sodium carbonate of (1~2), silica and borax.
Preferably, it is sulfurous acid and hydrazine hydrochloride that second reaction solution is made, which to form the reagent that tellurium precipitates,.
Preferably, the acid solution is sulfuric acid, and the solution containing chlorion is sodium chloride solution.
Preferably, the lye is sodium hydroxide.
This application provides the assay method of copper in a kind of telluride copper, tellurium, gold and silver content, first by telluride copper sample
It is handled using acid solution and the solution containing chlorion, undissolved gold and silver chlorate is made to fully enter in precipitation, from
And the content of Fire Assaying gravimetric detemination gold and silver may be used；And the elements such as copper and tellurium enter in filtrate, filtrate is anti-with lye
Should, copper forms Kocide SD and enters precipitation, and tellurium does not react into reaction solution, by the content of iodometric determination copper, leads to
Cross the content of gravimetric detemination tellurium.According to the above process it is found that the application is during telluride copper is measured, by once claiming
Sample, each element can fractional precipitation, separation and realization measure.The experimental results showed that the assay method using the application measures
Gold, silver, copper and tellurium content relative standard deviation it is smaller, then the assay method precision of the application is higher.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only for the feature and advantage that further illustrate the present invention rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses the assay method of gold, silver, copper and tellurium content in a kind of telluride copper, including following step
Suddenly：
By telluride copper sample, acid solution and the solution reaction containing chlorion, precipitation and the first reaction solution are obtained；
The precipitation is subjected to ashing processing, obtains grey slugging；The grey slugging is surveyed using Fire Assaying gravimetric method
It is fixed, obtain the content of gold and silver in telluride copper；
By first reaction solution and alkaline reaction, Kocide SD precipitation and the second reaction solution are obtained；
The Kocide SD is precipitated and is measured using iodimetric titration, obtains the content of copper in telluride copper；
Second reaction solution is made to form tellurium precipitation, by tellurium precipitation using gravimetric detemination, obtains tellurium in telluride copper
Content.
The assay method that the application provides can not only measure the content of gold, silver, copper and tellurium each element in telluride copper, more
It is measured it is important that once claiming sample that each element fractional precipitation, separation, then substep can be realized；Wherein gold is used with silver determination
It is the method flow of Fire Assaying, Cupper determination uses iodimetric titration, and tellurium de-termination is using gravimetric method.
In telluride copper is measured during gold, silver, copper and tellurium content, the application is molten by telluride copper sample, acidity first
Liquid and the solution reaction containing chlorion, make the silver ion in telluride copper sample react in an acidic solution with chlorion,
Precipitation and the first reaction solution are obtained, precipitation includes silver nitride precipitation and the gold insoluble in acid solution, and in the first reaction solution
Including copper, tellurium and other impurities element.Herein described acid solution is preferably sulfuric acid, and the solution containing chlorion is excellent
It is selected as sodium chloride.Unless otherwise specified, the reagent that the application is added does not allow to introduce gold ion, silver ion, copper ion and tellurium
Ion, and influence the accuracy of its assay.This process occur reaction be：Cl-+Ag+=AgCl.
According to the present invention, in gold with money kind element with after copper and two kinds of element sepatations of tellurium, then dividing again respectively it
From.Precipitation containing gold and silver chlorate is carried out ashing processing by the application first, obtains grey slugging.Ashing processing refer to by
Described be deposited in high temperature furnace is heated, the process that moisture therein is sloughed.Then the grey slugging is used into Fire Assaying weight
Method is measured, and obtains the content of gold and silver in telluride copper.After gold and silver is detached with copper tellurium, the application uses Fire Assaying weight
Amount method measures the content of gold and silver.The Fire Assaying gravimetric method is specially：
The grey slugging with dispensing is mixed, obtains mixture, mixing coverture is covered on the batch mixing surface, is obtained pre-
Fusant；
The pre- fusant is melted, is cooled down, obtains lead button and slag；
The lead button is heated to black film to slough, ash is blown, obtain close grain, by it is described conjunction grain reacted with glacial acetic acid after with heat
Nitric acid reaction is weighed after dry.
In the above process, the dispensing is preferably that mass ratio is (16~22):(8~10):(7~10):(3~4):(90
~100) sodium carbonate, silica, borax, starch and lead oxide mixture, the mixing coverture is preferably mass ratio
For (3~5)：(1~3)：Sodium carbonate, silica and the borax of (1~2).The mixture and the mass ratio of the grey slugging
Preferably (20000~35000):1.Wherein sodium carbonate described in dispensing is strong basicity fluxing agent, decomposable metal oxide and
Silicate, and can sulphur removal；It is acidic flux again that the borax and silicate, which are combined in slag flux, reduces slag making fusing point, is increased
Big smelt flow；The lead oxide generates lead button in melting, and aggregation is flutterred collection gold and silver and is gathered in lead button when sinking；It is described
Silica is strong basicity flux, generates silicate with metal oxide during melting, is the main component of slag.The covering is mixed
Mixture is that grey slugging and dispensing are completely cut off air, prevents from being reduced substance reoxidizing.
According to the present invention, then the pre- fusant is melted.The temperature of the melting is preferably 1100~1200 DEG C,
The time of the melting is preferably 10~20min.The fusant that melting obtains preferably is poured into and is preheated and has applied oil by the application
Cast iron film in cooled down.Then lead button is detached with slag after cooling.The weight of lead button should be 30~45g, if lead button is too small,
Lead trapping gold and silver are incomplete, and the rate of recovery is low, and measurement result can be made relatively low, if lead button is too big, ash blows down lead overlong time, gold and silver
Loss is excessive, as a result also relatively low.Then lead button progress ash is blown, the process that the ash is blown is specially：The lead is buckled on
In the cupel of the Muffle furnace of the preheating at 900~1000 DEG C, after the black film on lead button surface is decorporated, muffle-furnace door is opened by stove
Temperature drop carries out ash to 850~900 DEG C and blows, and closes grain and occurs after glistening, then grey blowing beam.
After grey blowing beam, the application then carries out parting operation.The conjunction grain is used into glacial acetic acid first before parting
Lead in grain is closed with removal, then will close grain and hot nitric acid reaction, nitric acid dissolving is made to close the silver in grain, gold is obtained after finally cleaning
The particle of yellow, that is, weigh.In telluride copper is measured during the content of gold and silver, involved reaction is：Pb+2HAC
=PbAC2+H2；2Ag+2HNO3=2AgNO3+H2。
Gold and the computational methods of the content of silver can be obtained according to formula (1), (2) in telluride copper in the application：
Wherein, m0For sample size, g；
m1The quality of grain, ug are closed for gold and silver in lead oxide used；
m2For the quality of goldc grains in lead oxide used, ug；
m3The quality of grain, ug are closed for gold and silver in institute's test specimens；
m4For the quality of goldc grains in institute's test specimens, ug.
According to the present invention, then the application has carried out Cupper determination.First by above-mentioned reaction solution and contain hydroxide ion
Alkaline reaction, obtain Kocide SD precipitation with the second reaction solution.The Kocide SD precipitation is described for measuring the content of copper
Second reaction solution is used to measure the content of tellurium.The application further includes following step before being detected using Kocide SD precipitation
Suddenly：
Kocide SD precipitation is used into dissolving with hydrochloric acid, then constant volume, is then reacted with sodium hydroxide, it is then anti-with hydrochloric acid
Should, obtain reaction solution；
The pH to 3~4 of the reaction solution is adjusted, then using the solution reaction of the not fluoride ion of copper ions.
In the above process, using dissolving with hydrochloric acid, constant volume, then generation precipitation is reacted with sodium hydroxide, then hydrochloric acid is added dropwise to heavy
It forms sediment and disappears, be in order to detect in Kocide SD precipitation whether contain iron ion, because iron can generate brownish red wadding with sodium hydroxide
Shape precipitates, if containing iron ion, adjusts the pH to 3~4 of the reaction solution, then with the solution reaction of fluoride ion, treats palm fibre
After red is taken off completely, so that it may prove that iron ion is sheltered completely, it is dry to prevent iron and subsequent sodium thiosulfate from reacting
Disturb Cupper determination.After by iron ion removing, then using the content of iodometric determination copper, the iodimetric titration is specially：
Solution after reaction is reacted with liquor kalii iodide, then be titrated to using sodium thiosulfate it is light yellow, at this point, solution
In most of iodine react, add starch indicator, continue to be titrated to light blue, then add in thiocyanate ion
Solution shakes to blue and deepens, and is finally added dropwise to blue and disappears for terminal, you can calculates the content of copper.
The reaction occurred during this is specially：20% sodium hydroxide generation Kocide SD precipitation is added dropwise：Cu2++2OH-=
Cu(OH)2；Saturation ammonium acid fluoride shelters iron ion：Fe3++6F-=FeF6 3-；Liquor kalii iodide reacts with copper ion：4I-+
Cu2+=2CuI+I2；With iodine complex reaction occurs for sodium thiosulfate：I2+2S2O3 2-=S4O6 2-+2I-；Starch is indicator, meets iodine
Show bluish violet, potassium thiocyanate solution reacts with cuprous iodide, so as to discharge by the iodine SCN of its absorption-+ CuI=
CuSCN+I-.The above process can be calculated the mass fraction of copper by formula (3), and numerical value is represented with %：
Wherein：C1For the molal weight of sodium thiosulfate standard solution, mol/L；
V1The volume of sodium thiosulfate standard solution, mL are consumed for titration copper；
V0Standard liquid volume, ml are consumed for blank
Molal weights of the M for copper, g/mol；
m0To weigh sample mass, g；
r1Ratio is taken for constant volume point：1/40.
The application finally carries out the measure of tellurium content, and second reaction solution is made to form tellurium precipitation, and tellurium precipitation is adopted
With gravimetric detemination, the content of tellurium in telluride copper is obtained.Make the reagent that second reaction solution forms tellurium precipitation excellent in the application
It is selected as sulfurous acid and hydrazine hydrochloride.The application also there may be impurity during tellurium is measured, and Impurity Potential must influence tellurium
Measure, thus the tellurium de-termination preferably carry out in the following manner：
Second reaction solution, sulfurous acid with hydrazine hydrochloride are reacted, obtain third reaction solution；The third reaction solution is taken out
Filter obtains filtrate and precipitation；
By the filtrate using the concentration of ICP emission spectrometers detection tellurium ion；
It is dry after the precipitation is rinsed, it is repeated several times, dried precipitation of weighing；Salt is precipitated and dissolved in by dried
In acid and nitric acid, constant volume using the concentration of ICP detections wherein impurity, calculates the content of impurity.
In above process, the application uses sulfurous acid with hydrazine hydrochloride as precipitating reagent, and uses ICP emission spectrometers
The impurity content in the tellurium content and precipitation in filtrate is measured, impurity level in precipitation is subtracted, then add filtrate using precipitation capacity method
In content of the tellurium amount as final tellurium, improve accuracy.The reaction equation of the above process is as follows：2SO3 2-+Te4++
2H2O=2SO4 2-+Te+4H+, N2H6 2++Te4+=N2+Te+6H+.The mass fraction of tellurium, number are calculated in the above process by formula (4)
Value is represented with %：
Wherein：m0For sample weighting amount (g)；
m5Quality (g) for glass sand core crucible；
m6Add the quality (g) of sediment for glass sand core crucible after constant weight；
m7Total impurities (m) for precipitation recycling；
C2Concentration (g/mL) for tellurium in filtrate；
V2Total volume (mL) for filtrate；
r2Ratio is taken for constant volume point：1/10.
The detection process of the content of gold, silver, copper and tellurium is specially in the application telluride copper：Sample sulfuric acid dissolution, then use
Sodium chloride deposit silver, is separated by filtration copper and tellurium；It precipitates and your gold is trapped by dispensing, high-temperature fusion, metallic lead after ashed processing
Belong to and obtain suitable lead button, other impurity generate fusibility slag with flux, lead button ash is blown, and obtain gold and silver and close grain, remove its table
The impurity of face adherency, after nitric acid parting, with gravimetric detemination gold and silver content；Filtrate constant volume point takes back end hydrogenation sodium hydroxide solution to make
Copper becomes Kocide SD precipitation and is detached with solution containing tellurium；It is 3~4 to adjust pH value after Kocide SD precipitation dissolving, uses ammonium acid fluoride
Iron is sheltered, potassium iodide is added to be acted on cupric, the iodine of precipitation is titrated using starch as indicator with sodium thiosulfate standard solution；
In the range of filtrate adjusting acidity is 3~4, tellurium is precipitated with diammonium hydrochloride and sulfurous acid, deducts the impurity in precipitation, and calculate filter
Tellurium in liquid, it follows that the content of tellurium in sample.By the above process it is found that first step sulfuric acid and sodium chloride solution processing
Afterwards, undissolved gold and silver chlorate are fully entered in precipitation, can be used for measuring Jin Heyin；Other elements such as copper, tellurium all into
Enter filtrate, can be used for measuring copper and tellurium.After naoh treatment, copper forms Kocide SD and enters precipitation second step, can
To be used for measuring copper, filtrate is used for measuring tellurium.By the above process, it is found that each pacing timing will use previous step, treated
Precipitation or filtrate, it is the process that a whole set of each element separation and concentration and substep measure, this is sequentially that cannot upset or overturn
's.If sample first is detached copper with naoh treatment, the content of gold and silver is relatively very low in sample, it is impossible to ensure institute
Some silver forms silver hydroxide and silver oxide simultaneously can enter precipitation with gold, it is difficult to handle subsequent precipitation and solution, measure
Gold and silver also have large error.Therefore the separation determination sequence of this method cannot be changed.
For a further understanding of the present invention, with reference to embodiment to gold, silver, copper and tellurium in telluride copper provided by the invention
The assay method of content is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Weigh 5.0034g (m0) sample is placed in 500mL beakers in tall form, adds in a small amount of water, soak sample, a moment is boiled,
It removes slightly cold, adds in 15mL sulfuric acid (analysis is pure), cap upper surface ware is placed on electric hot plate and dissolves by heating, and solution is steamed white to emitting
Color dense smoke, removes and is cooled to room temperature, purges the salt on surface and wall of cup with water, to 300mL is added water in beaker, 10mLNaCl is molten
Liquid (20g/L), a small amount of filter paper pulp stir evenly, are placed on electric hot plate and boil 5min, remove it is slightly cold after, filtered with Medium speed filter paper.It will be heavy
Shallow lake is transferred completely on filter paper, and precipitation is washed till no blue with hot water, retains filtrate (1).By the filter paper of stick and wall of cup that cleans the windows
It is placed in clay pot together with the filter paper pulp for being loaded with precipitation (1), is put into 550 DEG C of assay furnace and is ashed completely, taking-up is cooled to room
Temperature.
Dispensing：Above-mentioned ashing filter residue after cooling is subjected to dispensing in clay crucible by 1 dosage of table and is stirred evenly, is covered
About 10mm thickness mixes coverture (sodium carbonate：Silica：Borax=4:2:1).Simultaneously by table 1 into line blank test, blank is tried
Test whether the reagent mainly tested and added in dispensing contains Jin Heyin, specific method is：Do not claim sample, directly in clay pot
The middle various reagents added in table 1, sample equally carries out melting below, ash is blown, the process of parting with normally doing after mixing,
Obtain the content of Jin Heyin.Since the reagent in table 1 substantially only has lead oxide that can contain a small amount of gold and silver, blank test
What is actually obtained is the amount of gold and silver in lead oxide, obtains the quality m that gold and silver in lead oxide closes grain1=80.5ug and lead oxide
The quality m of middle goldc grains2=0.5ug.
1 Fire Assaying gravimetric method dispensing component table of table
Melting：Crucible with honest material is placed in 900 DEG C of assay furnace, heated up 45min to 1150 DEG C, heat preservation 15min goes out
Stove.Crucible gently taps on iron plate to two, fusant is poured into the pig mold for being preheated and having applied oil after three times.Cooling
Lead button with slag is detached afterwards, lead button cube and is weighed hammer out.The quality of lead button is 34g.
Ash is blown：Lead button is put into the cupel for preheating 30min in 920 DEG C of Muffle furnaces, 2~5min of fire door is closed, treats
After lead liquid surface black film is sloughed, immediately slightly blow-on door knob furnace temperature be down to 880 DEG C carry out ashes blow.After conjunction grain glistens, ash
It blows and comes to an end.Cupel is moved into stove gate, slightly cold rear taking-up.
Parting：It is taken out from cupel with Medical hemostat by grain is closed, is boiled with glacial acetic acid (1+3) and wash away the impurity on surface simultaneously
Calcination.It weighs, closes grain weight (m3)19010.9ug.The thin slice hammer out on small riveting stake, is placed in 30ml porcelain crucibles, add in 10~
The nitric acid (1+7) of 15ml heat, is placed on low temperature electric hot plate, keeps nearly boiling, is evaporated to about 1ml, adds the nitric acid (1+ of 10ml heat
1) it, is further continued for after being evaporated to 5ml or so, removes, decantation discards supernatant liquid, distills water washing goldc grains and wall of cup 3~5 times, will
Porcelain crucible is placed on electric furnace plate first low temperature drying, and to golden yellow, goldc grains weight (m is weighed up after removing cooling by high temperature sintering 5min again4)
123.1ug, it follows that golden content is 24.5g/t, and silver-colored content is 3759g/t.
Filtrate (1) is collected in constant volume in 500mL volumetric flasks to shake up, takes 50mL.20% sodium hydroxide is added dropwise to a large amount of
Kocide SD precipitation (2) generates, and in blue.It stands to there is clear liquid, sodium hydroxide is added dropwise to no longer precipitating.Filtering,
Precipitation is washed with 5% sodium hydroxide 6-8 times, and filtrate (2) is collected in the volumetric flask of 250ml, adds in 10ml chloroazotic acid, and constant volume shakes
It is even.
Kocide SD is precipitated (2) to be dissolved in the volumetric flask of 200ml with HCl (1+1), constant volume shakes up.It is molten to pipette 50ml
Liquid is in the conical beaker of 250ml, in company with into line blank test (V0=0.01ml), 20% sodium hydroxide is added dropwise and extremely sinks
It forms sediment, then drops to precipitation with HCl (1+1) and disappear.The ethyl sodium buffer solution of 15mlpH=3.6 is added in, adds in the fluorine of saturation
Change hydrogen ammonium 5mL and add 5mL liquor kalii iodides, slightly shake up.Sodium thiosulfate standard (C is used rapidly1=0.0425mol/l) solution drop
It is fixed extremely light yellow, 2mL starch solutions are added in, continue to be titrated to light blue.Add 5mL potassium thiocyanate solutions, fierceness shaking to blue
Deepen, continue to be titrated to blue disappeared just for terminal (titration volumes V1=21.10ml).The content for calculating copper is 45.58%.
It pipettes in filtrate (2) to 500 milliliters of conical beakers, adds in 80 milliliters of sulfurous acid, 4g diammonium hydrochlorides are added in after shaking up,
Rock solution.Cap upper surface ware, low-temperature heat make solution keep slight boiling condition 20 minutes.Conical beaker is removed, is cooled down.With
Glass sand core crucible (m through constant weight5=16.4192g) it filters, tellurium black precipitate is rinsed repeatedly with water to neutrality, uses glass
Precipitation is compressed, the precipitation flushing glued on glass bar is lost no time with water, record filtrate volume (V2=200ml)；Filtrate is emitted with ICP
Tellurium ion concentration (C in spectrometer detection filtrate2=0.000012g/ml).Again tellurium black precipitate 1~2 is rinsed with absolute ethyl alcohol
It is secondary.Glass sand core crucible is removed and is put into constant temperature oven 105~110 DEG C of dryings 2 hours, drier is transferred into and cools down 20 points
Clock is weighed, and is again transferred in constant temperature oven 105~110 DEG C of dryings 1 hour, is transferred into drier and cools down 20 minutes, weigh
(m6=16.5419g), until constant weight mass difference is not more than 0.0005 gram twice.Sediment is transferred to 250 milliliter three as possible
In the beaker of angle, add 15 milliliters of hydrochloric acid and 5 milliliters of nitric acid, dissolve by heating, be settled in 100 milliliters of volumetric flasks with water transfer, use ICP
Detect the quality (m of impurity element in the solvent soln of sediment7=0.0025g).Examination is calculated by the tellurium amount in precipitation and filtrate
The content of tellurium is 24.74% in sample.
According to the following formula in telluride copper gold, silver, copper and tellurium content.
m0=5.0034, sample size, g；
m1=80.5, gold and silver closes the quality of grain, ug in lead oxide used；
m2=0.5, the quality of goldc grains, ug in lead oxide used；
m3=19010.9, gold and silver closes the quality of grain, ug in institute's test specimens；
m4=123.1, the quality of goldc grains, ug in institute's test specimens；
C1=0.0425, the molal weight of sodium thiosulfate standard solution, mol/L；
V1=21.10, the volume of titration copper consumption sodium thiosulfate standard solution, mL；
V0=0.01, blank consumption standard liquid volume, ml；
M=63.55, the molal weight of copper, g/mol；
m0=5.0034, weigh sample mass, g；
r1=1/40, constant volume point takes ratio：1/40；
m0=5.0034, sample weighting amount (g)；
m5=16.4192, the quality (g) of glass sand core crucible
m6=16.5419, glass sand core crucible adds the quality (g) of sediment after constant weight
m7=0.0025, precipitate the total impurities (m) of recycling
C2=0.000012, the concentration (g/mL) of tellurium in filtrate
V2=300, the total volume (mL) of filtrate
r2=1/10, constant volume point takes ratio：1/10.
Using the above method to same sample parallel determination 6 times, the relative standard deviation of measurement result, such as table are then calculated
Shown in 2.
2 precision test tables of data of table
Embodiment 2
The weight for the sample that the present embodiment weighs be 4.9969g, according to embodiment 1 determination step carry out gold, silver, copper and
The measure of tellurium element, measurement result is as follows with calculating process, obtains as follows：Golden content is in sample
23.2g/t, silver-colored content are 3918g/t, and the content of copper is 42.33%, and the content of tellurium is 26.62%.
m0=4.9969, sample size, g；
m1=80.5, gold and silver closes the quality of grain, ug in lead oxide used；
m2=0.5, the quality of goldc grains, ug in lead oxide used；
m3=19775.9, gold and silver closes the quality of grain, ug in institute's test specimens；
m4=116.3, the quality of goldc grains, ug in institute's test specimens；
C1=0.0425, the molal weight of sodium thiosulfate standard solution, mol/L；
V1=19.60, the volume of titration copper consumption sodium thiosulfate standard solution, mL；
V0=0.02, blank consumption standard liquid volume, ml；
M=63.55, the molal weight of copper, g/mol；
m0=4.9969, weigh sample mass, g；
r1=1/40, constant volume point takes ratio：1/40；
m0=4.9969, sample weighting amount (g)；
m5=16.4192, the quality (g) of glass sand core crucible；
m6=16.5504, glass sand core crucible adds the quality (g) of sediment after constant weight；
m7=0.0030, precipitate the total impurities (m) of recycling；
C2=0.000016, the concentration (g/mL) of tellurium in filtrate；
V2=300, the total volume (mL) of filtrate；
r2=1/10, constant volume point takes ratio：1/10.
Embodiment 3
The weight for the sample that the present embodiment weighs be 5.0012g, according to embodiment 1 determination step carry out gold, silver, copper and
The measure of tellurium element, measurement result is as follows with calculating process, obtains as follows：Gold content is 30.5g/t, and silver contains
It measures as 4438g/t, copper content 44.69%, tellurium content is 29.27%.
m0=5.0012, sample size, g；
m1=80.5, gold and silver closes the quality of grain, ug in lead oxide used；
m2=0.5, the quality of goldc grains, ug in lead oxide used；
m3=22428.2, gold and silver closes the quality of grain, ug in institute's test specimens；
m4=153.1, the quality of goldc grains, ug in institute's test specimens；
C1=0.0425, the molal weight of sodium thiosulfate standard solution, mol/L；
V1=20.70, the volume of titration copper consumption sodium thiosulfate standard solution, mL；
V0=0.01, blank consumption standard liquid volume, ml；
M=63.55, the molal weight of copper, g/mol；
m0=5.0012, weigh sample mass, g；
r1=1/40, constant volume point takes ratio：1/40；
m0=5.0012, sample weighting amount (g)；
m5=16.4192, the quality (g) of glass sand core crucible；
m6=16.5633, glass sand core crucible adds the quality (g) of sediment after constant weight；
m7=0.0031, precipitate the total impurities (m) of recycling；
C2=0.000018, the concentration (g/mL) of tellurium in filtrate；
V2=300, the total volume (mL) of filtrate；
r2=1/10, constant volume point takes ratio：1/10.
Embodiment 4
The sample of embodiment 1 is subjected to recovery of standard addition experiment, passes through quantitative addition pure copper powder (Cu% ＞
99.99%), pure tellurium powder (Te% ＞ 99.99%), proof gold powder (Au% ＞ 99.99%), fine silver powder (Ag% ＞ 99.99%), are pressed
Method provided by the invention carries out rate of recovery experiment, the results are shown in Table 3, experiment shows the rate of recovery in 99.31%-100.92 ranges
It is interior.
3 recovery of standard addition test data table of table
| Element | Copper (%) | Tellurium (%) | Golden (g/t) | Silver-colored (g/t) |
| Sample background concentration | 45.58 | 24.75 | 24.5 | 3759 |
| Mark-on value | 50.58 | 30.75 | 44.5 | 4259 |
| Measured value | 50.23 | 30.84 | 44.3 | 4276 |
| The rate of recovery (%) | 99.31 | 100.29 | 99.55 | 100.40 |
| Mark-on value | 55.58 | 35.75 | 64.5 | 4759 |
| Measured value | 55.42 | 36.08 | 64.7 | 4781 |
| The rate of recovery (%) | 99.71 | 100.92 | 100.31 | 100.46 |
| Mark-on value | 60.58 | 40.75 | 84.5 | 5259 |
| Measured value | 60.86 | 40.69 | 84.4 | 5231 |
| The rate of recovery (%) | 100.46 | 99.85 | 99.88 | 99.47 |
| Mark-on value | 65.58 | 45.75 | 104.5 | 5759 |
| Measured value | 65.29 | 45.98 | 104.2 | 5773 |
| The rate of recovery (%) | 99.56 | 100.50 | 99.71 | 100.24 |
According to table 2 with 3 it is found that method precision provided by the invention and accuracy are higher.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide range caused.
Claims (6)
1. the assay method of gold, silver, copper and tellurium content, includes the following steps in a kind of telluride copper：
By telluride copper sample, acid solution and the solution reaction containing chlorion, precipitation and the first reaction solution are obtained；
The precipitation is subjected to ashing processing, obtains grey slugging；The grey slugging using Fire Assaying gravimetric method is measured, is obtained
The content of gold and silver into telluride copper；
By first reaction solution and alkaline reaction, Kocide SD precipitation and the second reaction solution are obtained；
The Kocide SD is precipitated and is measured using iodimetric titration, obtains the content of copper in telluride copper；
Second reaction solution, sulfurous acid with hydrazine hydrochloride are reacted, obtain third reaction solution；The third reaction solution is filtered, is obtained
To filtrate and precipitation；
By the filtrate using the concentration of ICP emission spectrometers detection tellurium ion；
It is dry after the precipitation is rinsed, it is repeated several times, dried precipitation of weighing；By it is dried be precipitated and dissolved in hydrochloric acid with
In nitric acid, constant volume using the concentration of ICP detections wherein impurity, calculates the content of impurity；It is subtracted using precipitation capacity method miscellaneous in precipitation
Quality, then add content of the tellurium amount as final tellurium in filtrate；
The telluride copper sample includes：The copper of 25wt%~65wt%, the tellurium of 15wt%~40wt%, 10g/t~200g/t
The silver of gold and 100g/t~5000g/t.
2. assay method according to claim 1, which is characterized in that the Kocide SD precipitation is surveyed using iodimetric titration
It is further included before fixed：
Kocide SD precipitation is used into dissolving with hydrochloric acid, then constant volume, then reacts with sodium hydroxide, is then reacted with hydrochloric acid,
Obtain reaction solution；
Adjust the pH to 3~4 of the reaction solution, then with the solution reaction of fluoride ion.
3. assay method according to claim 1, which is characterized in that the Fire Assaying gravimetric method is specially：
The grey slugging with dispensing is mixed, obtains mixture, mixing coverture is covered in the mix surface, obtains fritting
Object；
The pre- fusant is melted, is cooled down, obtains lead button and slag；
The lead button is heated to black film to slough, ash is blown, obtain close grain, by it is described conjunction grain reacted with glacial acetic acid after with hot nitric acid
Reaction is weighed after dry.
4. assay method according to claim 3, which is characterized in that the dispensing is that mass ratio is (16~22):(8~
10):(7~10):(3~4):The sodium carbonate of (90~100), silica, borax, starch and lead oxide mixture；It is described
Mixing coverture is that mass ratio is (3~5)：(1~3)：The mixture of the sodium carbonate of (1~2), silica and borax.
5. assay method according to claim 1, which is characterized in that the acid solution be sulfuric acid, it is described containing chlorine from
The solution of son is sodium chloride solution.
6. assay method according to claim 1, which is characterized in that the lye is sodium hydroxide.
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| CN105842102B (en) * | 2016-06-22 | 2018-04-20 | 大冶有色设计研究院有限公司 | The rapid analysis method of gold and silver in a kind of silver anode slime |
| CN107505226A (en) * | 2017-08-22 | 2017-12-22 | 山东黄金冶炼有限公司 | The distribution of gold and silver in a kind of Fire Assaying enrichment cupel |
| CN108562576B (en) * | 2018-03-07 | 2021-03-02 | 苏州市宇驰检测技术有限公司 | Method for detecting copper element in water body |
| CN109580419A (en) * | 2018-11-06 | 2019-04-05 | 长春黄金研究院有限公司 | Golden measuring method in a kind of cathode steel wool of electrodeposition gold |
| CN113092305A (en) * | 2021-04-12 | 2021-07-09 | 北矿检测技术有限公司 | Method for detecting gold content in coarse impure copper and application |
| CN113466215B (en) * | 2021-09-02 | 2021-12-10 | 北矿检测技术有限公司 | Method for simultaneously determining contents of gold, silver, platinum and palladium in low nickel matte and application |
| CN115655958B (en) * | 2022-12-26 | 2023-05-05 | 长春黄金研究院有限公司 | Method for measuring gold and silver in bismuth-containing material |
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